{\rtf1\ansi\deff0{\fonttbl{\f0\fnil\fcharset0 Courier New;}} \viewkind4\uc1\pard\lang3082\f0\fs24 TABLE OF CONTENTS \par DISCLAIMER \par WARNING!

This book is intended for informational purposes only! \par It is currently illegal to attempt almost any procedure depicted in INTRODUCTION .................................................................. 5 \par this book. This book does not cendcne ner imply that any proce- EcsTAsY & AMPHETAMINES ........................................... 7 \par dure lieted herein be deed by the reeder \'a4r enyene else fer thel wi-IERE TO suv .................................................................. 9 \par meller- Even ll llle eliemlelrv were lege! Slrlke Wellld nel edvlee wi-in TO Buv ................................................................., 14 \par a"ll\'b0"\'80 *\'b0 \ldblquote >\rquote these l\'b0'\'b0\'b0\'80d"'\'80S *****955 lllel here 6 **\lquote\'b0'\'b0ll9ll \'a4"\'b7 i-iow TO MAKE .. ................... . ..... . .... .. .................... ..18 \par derstanding of chemistry, chemical reactions and methodology. ME.|.H0d\'b0|\'b0gy ' ' " " " ' 24 \par gr\'80atha'm\lquote V Pi-iENYLAcEToN'E\'a7'xxIii:3;;;:;;;:::;;iijzizicxziiiii2::;:;;;:;;;:;;:52 \par METHOD #1 .................................................................. 53 \par Copyright @1999 by Strike All righig reserved #2 .................................................................. \par METHOD #3 .................................................................. 75 \par METHOD #4 .................................................................. 82 \par Panda Ink METHOD #5 .................................................................. BB \par 2211 NW Military Hwy, Ste. 116 METHOD #6 .................................................................. 93 \par PMB# 115 METHOD #7 .................................................................. 93 \par San Antonio, TX 78213 METHOD #8 .................................................................. 94 \par METHOD #9 .................................................................. 95 \par AMPHETAMIES 8. METHAMPHETAMINES FROM \par r PHENYLACETONES ......................................................... 97 \par METHOD #1 .................................................................. 98 \par METHOD #2 ,,,...lll..........,............................................ 100 \par METHOD #3 ................................................................ 103

\par METHOD #4 ................................................................ 104 \par METHOD #5 ...................l............................................ 108 \par METHOD #6 ......................................................,......... 116 \par METHOD #7 ................................................................ 117 \par METHOD #8 .................................................,.............. 117 \par METHOD #9 ................................................................ 120 \par METHOD #10 .............................................................. 122. \par B-NITROPROPENES ....................................................... \par METHOD #1 ................................................................ \par METHOD #2 ................................................................ 131 \par -2- -3\par \par METHOD #3 ................................................................ 132 \par AMPHETAMINES FROM B-NITROPROPENES .............. 137 |N'|'RQDUc'|'|QN \par METHOD #1 ................................................................ 138 \par METHOD #2 ................................................................ 139 You have just purchased or Stolen the most Comprehensive and \par METHOD #3 ........................................................... . .... 139 detailed book on the underground production of ecstasy, metham\par METHOD #4 ................................................................ 140 phetamine and psychedelic amphetamines ever published Strike \par METHOD #5 .......................................... . ..................... 141 (your host) is an ecstasy and amphetamine chemist from Texas \par BROMOSAF ROLE & PHENYLlSOPROPYLBROMlDE.. 142 who used to be very frustrated with the lack of common-sense in\par METHOD #1 ................................................................ 145 formation about the produollon of amphetamines. Strike remedied \par METHOD #2 ________________________________________________________________ 145 this for Strike and now Strike is gonna remedy it for you, too. This \par METHOD #3 ...................................................,..,,,.,__,,_ 148 book is oeoked_witn_tne latest street jnethods for making am. \par AMPHETAMINES & ME-I-HAMPHETAMINES FROM phetemines - wntten in plain English with the detail that no other

\par BRoM0sAr=Roi.E & Pi-iENYt.ls0PR0PYLBR0Ml\'a4E.. 152 b\'b0\'b0*\lquote \'b0a" \'b0""'\'b7 \par METHOD #1 ................................................................ 152 Pius, this edition of -i-mai Synthesis marks the first Si/Sr C0iiabOia_ \par METHOD #2 ,........................ . .................................. ,...156 tion Of the ch\'80mioa| undorground_ Throughout tho book you will \par METHAMPHETAMINES FROM AMPHETAMINES -\'b7\'b7\'b7\'b7\'b7--- 159 find recipes, secrets and discussions contributed by the worlds \par METHOD #1 ................................................ . ............... 159 leading underground chemists. They have Shared their knowledge \par METHOD #2 ................................................................ 159 so that you may get the best education availab|o_ So gnjoyi \par METHOD #3 ................................................................ 160 \par ADVANCED SHRIMP PREPARATION TECHNOLOGY. 161 \par RHODlUM\rquote S CHAPTER ................................................... 164 \par PROMISING THEORETICAL METHODS ........................ 182 \par BUILD FROM SCRATCH ..,..........................................,... 205 \par PYROCATECHOL, GUAIACOL, PHENOL & \par SALICYLALDEHYDE ........................................,.............. 208 \par METHYLENATION ........................................................... 214 \par BROMINATION OF 1,3-BENZODOIXOLE ...................... 222 \par THE BIG CHAPTER ......................................................... 232 \par THANK YOU SIR MAY I HAVE ANOTHER? .................. 240 \par CRYSTALLIZATION ........................................................ 247 \par CHEMICALS .................................................................... 252 \par REFERENCES ................................................................. 285 \par EPILOGUE ....................................................................... 291 \par . - 4 - - 5 \par \par DISCLAIMER ECSTASY & AMPHETAMINES \par WARNING! This book is intended for informational purposes only! \par It is currently illegal to attempt almost any procedure depicted in

\par this book, This book does \'a40t C0l\lquote ld0l'le l'l\'a4F imply that Grill Pl\'b0\'b0\'80\lquote The reasons Strike wrote this book. The reasons you\rquote re reading \par dure listed herein be used by the reader or anyone else for that this book- Ecstasy is ins most benign dmg Sinks has ever 9n_ \par matter. Even if the chemistry were legal Strike would not advise s\'b0umsi\'bbsd_ ii is passive ysi powsi-iUi_ By pswsifui Siriks does noi \par anyone to try these pr\lquote\'a4GedUl\lquote 9S U\'a4l9S$ ll`l9Y h6V\'80 3 th\'b0l\'b0U9h U"' mean that it incapacitates or makes one dangerous. It is, in fact, \par derstanding of chemistry, \'a4h6mi\'a4\'a4| F\'80\'a4\'a4U\'a4\'a4S Bild m\'80thPd\'b0'\'b09Y\'b7 quite the opposite. Its power is in its ability to evoke a total sen\par Even the most basic chemical or reaction has the potential to do ssiy bath si issiiisi Visuai and mental enhancement One.?) pen \par great harm. - ception is perfectly clear. Halluclnations are nonexistent. The \par feeling one has is, literally, ecstasy, Plus, it is one of the few nar\par cotics in the world that is not physically addictive. Why this sub\par stance was taken away from the people is a question that only \par government-funded scientists can answer. \par And let\lquote s not forget Meth (speed, crank, crystal). Then again...why \par don't we just forget about them. Momma said if you can't say \par anything nice...etc., etc. \par Eml.Em.dlms \par \par G \par < Bos ties \par 0 \par MDA Anvhmmine \par 3.4\emdash M\'a4Irvyl\'a4neDI\'a4\'a4yAmphet\'a4mlns (Blnzodrlns) \par o cli, Hi \par V 0 \par < (Def \par MDMA Methamphetamine \par :1,4-MelhylensEIuxyI|ethAmphatami1\'a4 (Spud)

\par <O H;GH, Hz\'b0Hs \par 0 \par MDEA PEA \par 3.4\emdash M\'a4t1iyIsneDi\'a4xyElIiylAmphelamir\bullet n Ethyhmphetnmlne \par - 5 - . 7 \par \par The ecstasy molecule itself is just an amphetamine with a couple WHERE TO BUY \par of extra things attached to it. The chemical structures of the major \par ecstasy class drugs and speed class drugs can be seen in the \par preceding schematic: \par So how does one go about beginning an underground laboratory? \par MDA and its brother, amphetamine, are the easiest to make, in- The answer is: "they don't". You see that would be illegal. Hypo\par volve the least watched chemicals and are the strongest. MDMA thetically though, one would need 3 things: a combination heat\par and speed, although less strong and shorter lasting, are perceived ing-magnetic stirring plate, chemicals and glassware. The \par by many as 'better' because the highs they produce are smoother stirplate is no problem. The chemicals and glassware are sort of a \par and more pleasant. This is not necessarily true as the degrees of problem. But Strike is going to gc over how all of these things can \par differences between MDA and MDMA or amphetamine and speed be bought, substituted for or made. Good production can be had \par are very subjective. They are equally fine in their effect except with crude, makeshift equipment. But believe Strike, the most ef\par that MDA is better. The sooner the chemist accepts this, the fective chemistry possible is achieved with a good heating stirplate \par easier her journey through underground synthesis will be in many and a ground glass distillation kit. So Iet's see how the good stuff \par respects. S0, when Strike uses the blanket term of 'ecstasy' or 'X' can be had before we discuss the back\emdash up plans. There are basi\par throughout this book Strike may be referring to either MDA or cally four types of businesses out there that cater to people need\par MDMA (mostly MDA). Strike will let you know when a specilic ing scientific stuff.

\par difference is required. Anyway, if one were to look at that nitrogen \par atom stuck on the MDA or amphetamine core one can see that as (1) Little, local walk-up type stores \par more carbon groups are added on, the weaker the drug becomes. These kinds of stores carry hobby/craft supplies, gimmicky sci\par So MDEA and PEA are even weaker than MDMA and speed, but ence fair projects, ant farms and a low assortment of basic \par they do retain some pretty fair activity. And a few pages away you scienceware products such as beakers, thermometers, scales, \par are going to actually learn every excruciating detail of how under- rubber stoppers and most of the basic chemicals such as acids, \par ground chemists make every single one of these compounds! bases and solvents. These places are listed in the chemicals sec\par tion of any big city's yellow pages and are relatively safe places to \par get most of the basic lab necessities. The drawback is that they \par are really expensive and don't sell very large quantities of any \par chemical. It is possible to have these places special order a \par needed chemical as long as it's not a controlled chemical. \par (2) Local middlemen companies \par These places are also local businesses that can be found in the \par chemicals section of any big city's yellow pages except that these \par places have some big connections. By this Strike means that they \par are licensed distributors for some of the biggest chemical and \par scienceware companies and manufacturers. Those big compa\par nies would never sell a thing to a punk like you or Strike. Even if a \par punk like you or Strike was to present a fake business front or \par - g - \lquote 9 \lquote \par \par something they would scrutinize it very closely and would require \par proofs of clientele etc., etc. What the chemist is looking for are product companies that sell \par everything but glassware and chemicals. The reason for this is

\par lt's needless to say that this is too much to ask of a street punk. that if they know they don't sell anything that is watched then they \par That is where these distributors can help. They have the license have no reason to care who buys their stuff. In fact, they want to \par and authority to sell anything (both chemical and glassware) that sell the chemist stuff very badly. The other types of catalogues to \par the chemist needs and are not subject to the same policies that look for are those that accept credit cards and. money orders as \par lhs companies thsy sell fst smplpy- This is hst mssht as a put- payment. These companies obviously sell to individuals. All or \par dowrl but these dlStFlbUiOrS are like car S8|eSm\'80l\rquote l. The only way these Companies are excellent places to stock up on everything \par they msks mehey is lhi0\'a49h ths eemmlseleh eh sales- This the chemist needs, especially low priced magnetic stirplates, vac\par means that they tend not to care about whom they sell these other uum pumps, plasticware (great alternatives to some glassware), \par c<>mp\'a4\'a4iss' products to- Thsy lust wsht ts ssll stuff- A chemist electronic scales arid, in some instances, chemicals and glass\par Calls \'b0l'le sf llleee \'b0ol""Pe"lee and srdsrs $\'b0melhln9 elmple like e ware. These companies areiust like local distributors only bigger. \par thermometer or water and then pays for it promptly. Having then \par established an account (a foot in the door) the chemist will have (4) Big name science houses and chemical manufacturers \par Qellled lhel e\'b0m\'a4e"Y'e lluel ih kll\'b0Wll'l9 lhel She (lhe ehemlel) is e These include such names as Fisher, Baxter, VWR, Cole-Parmer, \par g\'a4\'a4<t custsmsr- Thsh- \'a4s><t time- s littls catalyst. sthsr sr. psr- Alltssh, Aldrich and Sigma. It is very hard to get a fledgling as\par haps, a distillation kit can be ordered. Having already established oount with these grants, but if one can then the sky\lquote s the limit, \par that the chemist is a good customer they tend not to ask for the Most enemists should pa happy getting these companies products \par required permit to buy glassware or as to the purpose that some through the dietriioutors \par chemical is needed for. And so the charade goes on. \par No matter what type of company the chemist chooses to purchase \par These ll/Pee pf bllelneeeee ele llle PVlme Cllelee e chemist Will use from it is a good idea to have some of the actual catalogues from

\par to ust lllel speslelly shemlsel or Piece sf Qleeewele Tllele srs the big name science houses and glassware manufacturers. This \par thousands of such places around the nation, Canada and Mexico. is haoausa ll Wlll help to havs tha sompar,y\'b7s aotual produol oata\par logue number whether one is ordering from a distributor or from \par (3) National dlsttibulets the company itself (looks professional, bubbal). These really big \par lf S Chemist were tv 90 clown to hsr i0\'a48i Ui`ilVel\rquote Slly 0i Qiedueie catalogues are down at the university or the chemist can request \par research school she could find science company catalogues in the prra from lhs oomparly ltselh They also make exoeiient reference \par library and in the divisional labs and offices of the research center. books ar-ld are just plalh lrltsrastlhg to read and daydream ot the \par Representatives of every conceivable scienceware company and day when one carl ardar sush_ahd_sush an apparatus as is da\par manufacturer like to drop off tons of their catalogues in the hope plsrad oh page Whalovar \par that someone will order some of their products. lf the library has \par \'a4\'b0l'le\'b7 lheh llle ollemlel goes up ts one of the labs ello eeks So with catalogue or list of items needed in hand it is time for the \par Someone ll Sho could lako o look ol some of lhell catalogues- chemist to order. The following is an example of how a typical call \par This iis not a problem because the labs are full of graduate stu- Wlll proceed aud how tt Wlll be hal-ldled by a ohemist no matter \par dents Who are dying for attention. Some have so many cata\emdash what business sha calls; \par |QgU\'80?* they don't use that, if asked, they would probably give the \par chem lst S0m\'80. __Rlr\'b7lglRlrlgl-\par - 10 - _ ll \par \par Customer rep: "Good morning, Blah Blah lnc." At times it may seem that Strike is implying that buying from these \par Evil chemist: "Uh, yes, this is Fake Name calling for Fake Com- companies is a catand\'b7mouse affair that leaves suspicions high \par pany Name and l need to order some items or possibly open an and traces put on one\lquote s phone line. This cannot be further from \par account." the truth. These companies want to sell their products. lf they had

\par Rep: "Does your company currently have an existing account with to file notice to the DEA or demand documentation every time \par us'?" someone called then they would be broke in a week. This does \par not mean that a chemist should be careless. lt's just that if a \par [They always ask this whether or not they werejust told that a chemist is Polltsi friendly and Sman than almost anything can be \par customer is a new one] had. And since, as this book will point out, most everything the \par chemist needs will be unwatched, there will not be a great deal of \par Evil: "No, we used to have an account with Rival Scientific Com- suspicion no matter what the chemist orders. Just remember one \par pany but they cou|dn't seem to get our orders on time." thing: the chemist never orders anything to the same place she \par Rep; "And what is your company's name and address'?\ldblquote cooks at. \par [They ask this tirst because they want to bag the chemist as cus- Science dealerships aren't the only places to get the stuff one \par tomer or at least get them on a mailing list so that they can hound needs. At those mega hardware stores one can find pure acetone, \par the chemist later to buy more of their stuff] methanol, ethanol, toluene, methyl ethyl ketone, DCM(as a con\par stituent of some stripping agents), sodium hydroxide inthe form of \par Evil: "Fake Company Name, at Address OfA Friend's House." lye, and some acids such as sulfuric and hydrochloric. These \par precious tools can be bought there cheaply and in great quantity. \par [ Delivery to an apartment address is unwise and there are very \par few companies that will deliver science products to a P.O. box] Then there are other places such as chemical waste exchanges, \par pool supply companies, electroplating companies, photography \par Rep: "O.K. Mr. Fake Name, what can we do for you today?" supply shops, agriculture companies, specialty gas canister com\par panies and just about any place where a chemical can be sold. \par Now the chemist rattles off the catalogue numbers of the things \par she wants and the quantity of each. After the order is confirmed Finally, if one simply cannot find the thing one needs then it\lquote s time

\par the chemist asks that the entire order be shipped by overnight ex- to hit the bibles of industrial and commercial sources; "Chemical \par press and has this added to the total bill. The chemist then asks Buyers Weekly", "Chemsource U.S.A." and the massive "Thomas \par for the purchase order number of the purchase she just made so Register". These three source books can be found at most librar\par that she can include this on the payment she's going to send. The ies and contain the listings and services of just about every busi\par chemist uses a reputable money order and sends this money or- ness in the country. No matter what the chemist needs, it can be \par der to the company via priority overnight mail. All this rushing ac- found in these books. Even if it takes going one-by-one through \par complishes two things: it shows that the chemist's company is a the listings, Strike can assure you that the chemist will find what \par professional, goal- oriented company, and it also gives no one any she needs and someone that will sell it to her. \par time to second guess a thing or establish a stakeout of the deliv\par ery site. The one source Strike does not condone is theft. If you steal then \par you are a weasel and a coward. \par - 12 \emdash - 13 \par \par Now, one is going to see most of the older chemical reci es call\par WHAT TO BUY ing for all reactions, solvents, acids and bases to be held lin Pyrex \par (borosilicate) type glassware because anything else will melt or \par degrade when exposed to \par all these harsh chemicals \'bb \par GI-ASSWARE and conditions. This is no ( . \par longer true! Any reaction, i , \par Ideally, the chemist wants a distillation kit with joints that are of the add')'\'b0" \'b0' m'X""9 in this it \par size 24/40(don't ask). This is the most versatile joint size for ac- b\'b0Pk (Wat does _"'Ot Ve' _. \par commodating both large and small flasks. Speaking of flasks, the qulre dl"?\'b0t haatlng can in; *

\par type one wants these days are flat bottomed flasks, not round be dame '\ldblquote 3 p\'b0| YF"\'b0F\rquote Y|' ' \par bottomed flasks. Flat-bottomed flasks allow one to heat on flat are (PP) \'b0_" F\rquote\'b0'YethY'S'j\lquote\'b0` \'b7 \par surfaces such as a heating stir plate. In the first of many beautiful, (PE) \'b0\'b0\ldblquote ta"\ldblquote\'b0"'\'b7 -I-ms '$ rj 5E\{O$\'a3;i\'b7RY \par hand-drawn sketches that will appear throughout this fine book regardless \'b0f the Chem" kssevxoki L \par one can see the components and proper configuration of a regular cms "\ldblquote\rquote\'b0)Ved\'b7 P\'b0|Yp"\'b0' FVNNE-'\par distillation set up in Hgure 1. Other pieces of glassware that are Wlene (PP) and \par highly desirable but can be lived without or made (as shown later) p\'b0'Ve)hY'\'80'\rdblquote\'80 (PE) _ are _ * l \par are shown in figure 2. very inert and chemically \par resistant to almost any\par \'bb\'a4\'b7;m\'a4m\'a4\'a4ia\\ thing this book describes. \par NEMOMETER I \'b7 Buckets, tubs, funnels, \par warren and all sorts of containers :\'b7,\emdash m=.ck \par \\ of this whitish, opaque, "\}\ldblquote\ldblquote \par ms in 3-,,,,, pliable plastic can be [Figure 2] \par "\lquote 3`IE'\\ *5 Amvert found for pennies at any discount or grocery store. These con\par \'bb.&\'b0-ii\'e9k \'b7t\'a7i.= I 'I tainers are stackable, easy to clean, never break and will save a \par I \\_ chemist a fortune in glassware. As was mentioned earlier, plastic \par VACUUM ER ` ware is starting to make its mark in biological and chemical labs. \par _, Asker-sa coseete Buchner funnels, side arm flasks, graduated cylinders and even \par separatory funnels come in PP and PE. These glassware substi-

\par N Immun X tutes are the absolute choice for today's chemists as they are un\par rmsk watched, versatile and 1/10 the cost of glass. lf the chemist is \par \lquote unsure what plastic a container is then she can look for the letters \par g PP or PE somewhere on the product. \par surtvciwe

\par . VACUUM \par #~ec=1;v.t.NG \par Fl.P\\5Y\\ \'b7 \par The chemist is going to need a source of vacuum. When distilling \par [Fl9UV\'80 ll high boiling stuff like valuable ecstasy free base oil, a vacuum is \par _ 14 _ - 15 \par \par applied at the nipple (tee heel) of the vacuum adaptor so that the \par pressure inside the entire distillation apparatus is reduced well HEATING AND S-IIRRING \par below the normal atmospheric pressure outside. This causes eve\par rything to boil at a much lower temperature. If high boiling oils are . . _ _ _ \par allowed to dlstlll/boil at their normal temperatures and atmospheric Tl\lquote a"a 'aallll '?\rquote "\'b0 g\'b0\'b0\'b0l S\ldblquote l?Sl'l\ldblquote\lquote a f\'b0' 3 \'b0\'b0"\lquote b'""*'\'b0" \ldblquote\'b0*\rquote **"9 and \par pressing than a considerable amount Of product could be lost dug magnetic stlmng plate. nor IS there any reasonable excuse not to \par to scorching. The other purpose for a vacuum is for vacuum filtra- ga? ana Tlgffj alabparlaclly lagal la buy and aan be mma at a"Y \par tion which is a very useful process and is described later on. salanaa Ou a Ol a alll 200400 a\'b0llar$\lquote lalalas \'b0"a araa that tha \par \rquote chemist should not sklmp on. Thls piece IS going to be the center \par . . . . fevery action in the laboratory so a really good one with as lar e \par Any commercially avaliable vacuum pump IS perfectly fine for the \'b0 . . . . 9 \par underground chemist\rquote s needs; but the best kind to buy is a dia- a sullaaa araa as passlbla ls a daflnlla plus \par ` ` ` t t th -h h h ' I . . \par 52;%?;\ldblquote rE\'a7.'2ie\ldblquote ;Efl\lquote .Li.?.\lquote ;iZ*gl?iisr23;.$a. $u$L\lquote i,'L...i'\'a7 .\'a7J;T.'\'a7S. ers was S~\'a4\'a4\'a4se\'b7.\'b7~y\'a4\'a4the\'b7\'a4\'a4\'b7\'b7yr that the ~r\'b7\'a4er\'a4r\'a4~\'a4\'a4 creme is \par $1OO_$2OO_ However the stronger the Vacuum the better. If 3 too stupld or unwllllng to get a stir plate. In this case a single unit

\par chemist is looking to pun 1mm of Hg (dom ask) like tha gms in the portableihotplate can work, but controlled heat using these is best \par chemistry papers do than Sha can be looking at a turbovac that accomplished by water or oll baths. Stlrnng can be accomplished \par can run WSH Over $5000 by attaching a shaft and paddle to a power drill or any gear driven \par ' motor. \par The other vacuum option is a simple little aspirator that attaches to \par ones faucet or hose. This $15 device pulls a decent vacuum; \par however, it is not an option at all in Strike's book. Running one of \par these babies 10-12 hrs a day is a despicable waste of a commu\par nity\lquote s water supply. \par WATER PUMP \par This is going to supply the cold water that courses through the \par condenser whether that condenser is set up for reflux or is part of \par a distillation configuration. The pump need not be very strong. In \par fact, the perfect example is one of those little, submergible fish \par tank pumps that one can find at any pet store for about $10. All \par the chemist does is attach a hose to the outlet, chunks the little \par pump into a bucket of ice water, attaches the hose to the con\par denser and there it is. An alternative source is that little pump \par that's attached to the windshield washing fluid reservoir of any car \par in a junk yard. The chemist removes the reservoir (pump still at\par tached). applies an adapted power source to the pump and uses \par the plastic reservoir to hold the ice water. \par - 16 - _ U _ \par \par HOW T0 MAKE The best replacement for borosilicate glassware is stainless steel. \par Stainless steel takes the heat, won't break, and, most importantly, \par is about as resistant to chemical degradation as the chemist can \par _ _ I hope to find. For those items that won't be subjected to direct

\par Strike is Sure that an lmeglhetlve Pel\rdblquote S\'a4h Feh t\'a4\'a4k \'a4F\'a4U\'a4d her eVe\'b7 heat there can be some steel/metal or steel/plastic hybrids. ln fig\par ryclay surroundings and think \'a4f S\'a4m\'a4tt\'a4\'a4\'a49 that can ast as 8 re- ure 3 is shown now riasks or any size can be made with two \par placement fOr S\'a4fn\'80 of th\'a4Se hefd to get 9te5SWel'e lteme and stainless steel mixing bowls welded together. Also shown is the \par other 9tZm0S\'b7 As it S0 hePPeh$ Strike hee th0\'a49ht eh_\'a4\'a4t this t\'b0\'b0- vacuum adaptor and condenser. For the condenser only the inner \par Here are S\'a4me 0f the m0Fe likely We!/5 thet theee thlhQe Geh bs pipe need be steel. The outside pipe can be copper or something. \par made. As for the other components of a distillation set up, well, they are \par made just as they look. \par EJ \par 6 A_;_, In figure 4 is shown how a separatory funnel and a pressure \par \par \par equalized addition funnel are made. The funnel part is just a PP funnel from the grocery store and what it is attached to is a stain` ` r less steel ball valve. See how the addition funnel is made by using a rubber stopper and an extra extension of tubing to the top of

\par \lquote\'b7

\par \'b7 the funnel? Well, that's how one can make a sealed addition fun\par nel out of the ordinary glass separatory funnel that one gets with a \par distillation kit or from wherever. \par , I , J MQ I `\\ "

\par , 1 . ` J: _ \par @2% la" Sb- \lquote \rquote . \par Q \rquote E \lquote "*\'b7~__\\ . \par Z \rdblquote F)g;\'e9_M ' "*-...,_, . / \par 13 Q3) . \'b7; \par gf? JZ? _ . _ _

\par U I /,2// // / f

\par r//\rdblquote 2* i ~ JY /\lquote r W r \'b72l\'b7~ \par 5/ )- \'b0 / at a . T

\par @t \emdash , in ~ \par [Fig 3] [Fig 4] \par _ 18 _ - 19 \par \par All of the pieces pictured here are not going to fit perfectly into \par each other and that's going to cause all sorts of leaks. The an- \'b7 . \par swer is teflon tape. Strike loves teflon tape! This inexpensive \par product is found in the plumbing department of any hardware ,

\par store and is the duct tape of the next century. Teflon tape is \lquote `\ldblquote ` l \par chemically and themially indestructible. This stuff is wrapped XQK " T` *"\rquote\'a4'\'b7\'b7~ \par around any piece of pipe or joint, said part then jammed into its xg; 1-/r=\'b7\\ hV_,rPr. _ \par appropriate receptacle and the tape will mold to form a perfect fit. _ 4 \'bb \par Hell, it can mummify a whole joint complex to make it absolutely giQ ? * \par impregnable. _ * " \par i \'b7\'b7 tf? \par So what's the downside of using a stainless steel distillation kit? ; \emdash \par The chemist can't see shit! There is a dehnite advantage of being \par able to see a reaction as it takes place and to see when some\par thing starts to distill over. All Strike can say is that the chemist \par must rely much more heavily on the readings of her thermometer \par and have a greater faith in the chemistry she is doing. By this _;\rquote Z_ \par Strike means that since there is probably going to be no more ` gg? \par than 2-3 different chemicals in the reaction flask, then all the \par chemist need be aware of is what thing comes over first , second _ _ \par and last. Strike knows. Strike knows. lt\lquote s a little more complex ` \par than that. But if a chemist gets the hang of distillation it really can \par be as simple as that. \par [Fig5] \par PIPE BOMBS -

\par A pipe bomb is not a bomb, It is just a device to hold high boiling \par or high-pressure reactions in an enclosed cell. The bomb should be GIRLS IN DA HOOD \par made from a stainless steel pipe that has as big of an inner diame- Some Of the reactions that the chemist ma _ . \par . . . y use will ust naturally \par mr F15 possible (w1dFh\rquote bubba!) Them argtwo good conngumtmns smell bad. Usually if something smells bad then it\rquote s probably bad \par wh\lquote\'b0i\lquote can be scm m Hgum 5* One em? ls permammiy sqalcd by for the chemist to smell it. Some reactions are, by design, sup\par Wcldmg Thc \'b0th\ldblquote\lquote "\ldblquote d\'a4 H0 matter Wh\lquote\'b0h_\'b0\'b0\ldblquote Hg\lquote\'b7\lquote\ldblquote\lquote\ldblquote P\ldblquote ls \ldblquote S\'b0d\'b7 posed to vent bad things that , when unchanneled, have nowhere \par Should haw as much end as HUG it threading as POSSlbl\'80\'b7 Also, to go but into the living room of the chemist. Sometimes there is \par when sealing up the pipe bomb, it is e great \'a4d\'a4\'a4 rb wrap at lor of he guarantee that a method Will go as piarmeti. There may be a \par teflon tape around the threads then screw on the cap. This will mistake or unforseen side reaction and some of the most deadly \par form an absolutely air tight seal. It is also possible to substitute a shit imaginable can be evolved. That is why the chemist will con\par stainless steel pressure cooker for some sealed, pressured reactions. Struct lh\'80 \'a4l\rquote l\'80 thing that may Bhd UD 59Vlh9 her life: 3 fume h\'b0\'b0d\'b7 \par _ 20 _ \'b7 2l \par \par ln professional laboratories fume hoods are big metal boxes rest\par ing on countertops and are connected by ducts to blower motors A fume hood is constructed in the manner shown in figure 6 \par on the roof of the facility. The blower motor is constantly sucking Strike drew the frame as being made of lumber but it can be made \par the air from the hoods to the outside so that chemists will not be of rebar or, preferably, from PVC pipes and joints so that it can be \par exposed to the vapors of chemicals they are working with inside assembled and disassembled with ease. The frame is enclosed \par the hood. The same precautions are taken by non-dead under- with plastic drop cloths or any semiolear plastic sheeting. The \par ground chemists. front face of the hood is halfway covered with plastic while the

\par bottom Vhalf is exposed to allow one to move objects in or out and \par to rganizulate things. On top of the chamber is attached some \par , -\lquote \} cot es ryer duct or some such crap which is led to a leaf blower \par my \lquote __r VV VV .... or blower motor. The exhaust from the blower is led away to the \par . \emdash a \rquote \ldblquote :\emdash\'bb\'bb \'a4\'a4*Si\'a4=~=-

\par V .\'bbT_`;VV y . .;V.W W .V Although a leaf blower is probably way too strong it may still be \par \emdash _V V = \par . V V in front of V . adequate at its lowest settings To insure that a correotairilow is gleing pujled the chemist; holdks 1 lit cigarVett: about a foot

V T QV.,

\par 1 Mx i \emdash - v VL Zi_q, Q V,\'b7\{ .5;;% e oo s opening an oo s o see i t e smoke trail is being \par VV I .\'a4 _j -~\'bbt pulled into the hood. lf so, then the hood worksjust fine. \par V Many houses have outside\emdash venting blowers over their stoves. Chemists in these situations can actually drape some plastic V \'bb\emdash ., V6, around their stovetop to make a perfectly adequate hood. ever, chemists who live in apartments never, ever attempt any ff chemistry at all in their pads. Why'? Well, not only do

\par \'b7 ~ \par "~\'a2~ How\par ;

\par _,Qt. . \lquote \lquote apartment \par --\'bbi \par

Qi- stoves lack an outside vent; but to vent a constructed hood through a chimney or out a window with so many close neighbors is ~._V \emdash > living about

_,,. g V V fi V

\par [ . . V \lquote \'b7\'b7\'b7\'b7 Vi_f \\_;.._ _ ;\rquote is just plain stupid. lt is also stupid in another very \par \'b0 \rquote \'bb \par \lquote V V \par . . \par

Q important way. If a chemist fucks up and blows herself up or

starts a fire then she is not only harming herself but is also going

V to put a lot of her neighbors out on the street, in the hospital Or in the morgue. No one making drugs has the right to jeopardize oth~

\par _ ey O ers in this manner. That is why drug making is always done in a \par I house, barn, mobile home (watch out for tornados), submarine or \par .\'b7.... *2 cave.

\par [Fig 6] \par - 22 - _ 23 \par \par M ETH0d0I0gy \par lf the chemist has done the appropriate thing and bought a heat\par ing stirplate then a magnetic stir bar is always stirring in the reac\par tion flask. lf the chemist only has a hotplate then the chemist is \par Just in case you are not familiar with basic laboratory procedures, Qeing to have to add Some boiling Stones to the flask. Boiling \par this chapter will explain them to you. These are the most basic lab stehes Gah be either little Chips of teflon. little wedded up balls of \par techniques and almost every method in this entire book will re- teflefl tape Of little pieces of a shattered porcelain countertop tile, \par quire many, if not all, of the protocols to follow. So pay attention! All ef these things have lets of ltliefescbpie p0Cl<etS of air in them \par that help to facilitate the start of boiling. Many of the solutions in \par |3|$T||_|_AT|0N this book, especially organic solvent solutions, need these boiling \par stones in them if they are going to be heated. If there are no boil\par You see that distillation setup in fig. 1'? Well, when one puts lhg atehee theh a Pllanemenen Called sul'-lel'heetihQ they e\'a40\'a4l' \par something into the reaction flask and heats it, low boiling stuff like Whel`ehV the eelutleh Wlll Stelt le Qet heltel theh its aetual beilihg \par Organic Soivohrs (pooioha oihph DCM prop) Vaporizp and than point temperature. Eventually it will burst into boiling buta lot of it \par condense inside the condenser. They then drip down into the re- will haVe gene spleeshl lhte the eehdehsel? Net seed. \par ceiving flask. Next (usually) comes water, then finally (as far as , \par drug ohomisiry is concerned) oompa high boiiihg drug oiisv DiStii_ Another thing or two to remember when distilling is to wrap alumi\par lation is the most preferred and reliable way to purify substances hum tell aleuhtl the leaetieh flask- This will help step heal less se \par from opp ahorhap that things will distill quicker and at lower temperatures. Some\par , times, if one is going to distill a solution that is just solvent and

\par There are three basic forms of distillation: simple, vacuum and Ptedueti all that pure Sell/ent that Comes over first is perfectly re\par fractional distillation, which oan toe an extension ofthe first two. usable and elleuld be saved fer future exlraetlens. \par Simple distillation is just plain old distillation with no vacuum and is \par used for purification of low boiling mixes or for removing solvents The laet thlh9 about dietillatieh that heeele lhel'ltiellil'l9 is the sWsP\'b7 \par such as ether. For vacuum distillation a thick walled or reinforced nine eut et eelleetlen flasks When distilling under vacuum it will \par hose is connected from a Vaouum pump to the hippie (too hooi) or be necessary to remove the flask that has collected all the solvent \par tha Vacuum adapfgn Application of a Vacuum graatiy reduces tho or crap and replace it with a clean one to collect all the product \par temperature or boiling and is a must tor most ofthe distillation in that Will be Pelnlns ever elleltlv- This swapping ef flasks needs le \par ~this book. Fractional distillation is merely vacuum distillation ex- bearlene \'80luleklY as seen as the Veeuum hese is diseehlleeted- By \par cept an addod oiaoswara oon-ipononr such as a Smaii Vigreux ooi_ quick Strike does- not mean lightning fast. Just quick enough so \par umn or a Ciaiaon adaptor packed with shards of giaoo is piaood that the hot solution in the reaction flask does not get too much \par between the reaction flask and the 3-way joint of a normal setup. hettet hem llie heat seuree it is elttihg ehi because it it dees. ehd \par Either of these additions create a gauntlet of extra surface area the Vacuum le leaphllet-l- it meV pull e little tellh etthel suPel\rdblquote heet\lquote \par elements that distilling liquids must pass through in order to con- ih9 etuht and Qe elsleeshl inte the eehdehseh \par dense. This affords a greater degree of separation between \par mixes of oils that have similar boiling points. However, it has been REFl-UXlNG \par Strike's observation that most of the bulk separation in this book \par using distillation ean be achieved with regular old vacuum distilla- Refluxlno ls all ever lllls beek and the proper annaralus le use is \par tion. pictured in figure 7a. The most general thing that can be said \par \lquote 24 \lquote - 25 \par

\par _ _ __ _ concern when refluxing large aqueous solutions such as acid or \par about refluxing is that it's lust plain old boiling except that there is bass nydrslysls seen lalsr lrl lhls book \par a condenser attached to the flask so that nothing escapes. The \par condenser must be supplied with really cold water, especially \par when refluxing hi9h b0iiihQ Sdiuiidhs- One side note about the drying attachment is that it need not be a \par vacuum adapter. Anything, such as a funnel, that can hold a plug \par ro., of drying material and tit snugly into the condenser will work. \par 2 \par I? EXTRACTION \par V A \'b7 In this book extraction is almost always about using an organic \par solvent such as benzene, DCM, ethyl ether (a.k.a. ether) and hex\par , *\'b7"?iS\'a5\} ane to remove (extract) product (almost always in oil form) from \par .l-n an aqueous solution. The most basic way to extract is to pour the \par .. ` water solution into a PP container, add some solvent and stir the \par . two as fast as possible for a few minutes. Most equipped labs use \par ,- a large separatory funnel to shake the two liquids. When using a \par separatory funnel it is very important to vent the funnel as soon as \par the stopper is smacked into the top. This is done by immediately \par V or _.=. _ inverting the funnel so that the stopcock end is facing upward, \par opening the stopcock to release the pressure then closing the \par . stopcock. The sep funnel ls given a quick shake then vented \par @ again. This is repeated a couple more times after which the pres\emdash \par . sure production will have pretty much ceased. The rule is to then \par [FiQ 73] [Fig 7b] shake for 2 minutes and allow the layers to separate for 10 min\par utes. And which layer is going to which? Ether and benzene are \par always on top of water and DCM and hexane are always on the \par You see that vacuum adapter stuck to the top ofthe condenser in oollom_ \par fig. 7a? Well, a closer look at it in fig. 7b will show that it has

\par Some drying agent sandwiched between iW\'b0 \'b0\'b0ii\'b0h haiis ahd ihe Most science papers call for things to be extracted 3 times (3X) \par nlppl\'e9 USG hed!) $98iBd With Piasiic Wrap O" f\'b0ii- The dU/ing ag\'e9ni with a solvent. Strike feels that this is overkill and that one or two \par can be either a commercial product called Drierite or calcium chlo- llmes is usually eufflolenf Sometimes one nas eo much product \par ride. This attachment is Didded on i0P of \'a4 condense" Wh?i`* i\'b0\lquote oil that it forms its own heavy layer (usually at the bottom). There \par fluxing solutions that have no water in them and must remain that ls no need to exlraol Such a large amount Wlln eollrenf ln Such a \par way during the time they are refluxed. All this is to prevent m0is\emdash Case one would merely draln lne oll from me wafer on if using a \par ture in the outside air from coming into contact with the cold sur- pp container, deeanl the wafer from me oll_ The wafer llseif can \par face of the of ih\'e9 inside walls Oi the C\'b0nd\'80h$9i\'b7 This will $ui\'80iY then be extracted once with solvent and the solvent added to the \par happen and the condensed outside-air water will drip down into oll_ \par the reaction flask and ruin the experiment. This is not so much a \par - 27 \par -26\par \par WASHING . \par ter free, bubbal) for some of the recipes in this book that call for \par Washing is almost always the act of taking an organic solvent auch IIIIIIgs\'b7 \par layer (most likely the one that was obtained from the extraction of _ _ l _ _ _ \par some previous aqueous solution) which usually contains product FIW'"9 '$"'I ? bS\'b0IuI\'b0IY \ldblquote\'b0CeSS?W\'b7 but ll 'S 8 9\'b0\'b0d Pet Illat tf 3 l'\'80\'a2\'b7 \par and mixing (Washing) Clean Water than discarding the Ip\'e9 SITGSSES ItS USB th\'80l`| Sh 6Vll Und\'80l`gTOUl"ld Ch\'80mlSl will do SO. \par water. A solvent layer is often washed with a dilute acid or base \par salt solution to neutralize anything the solvent may have absorbed VACUUM FILTRATION \par from previous extractions. These salt solution washings are then _|_h_ a _ a t l t "_ a a f \par followed by clean water washings. IS proce ure is use o separa e crys a ize pro uct rom sol-

\par vent or to remove crap and solids from a liquid. Figure 8 shows \par Since we\lquote re on the subject of clean water, this is as good a time as the tamper appafalus to USG. The ciollecting flask is called a side \par any to discuss what kind or water is used in ati this chemistry. By arm ask aud to that_e><tehded hibb e (tee hee-) le attached a vac\par dean water Strike means distilled water (dtizoi. All reactions are uum source. The thl\'a4Q that re ehoved through the rubber Stopper \par to use distilled water (daze) only. All setutiens and dilutions are to rc callad a Buchher fuhhel and re usually made of white porcelain \par be made with di-tzo as well. Distilled water sells rei about $1 a or. pre erably. PP. The Buchrier funnel. when viewed from above. \par gallon dawn al tha suaal-malkat Tap walal. la all abaalllla na_l,la can be seen to have lots of pin holes in the bottom surface of its \par in chemistry except for cleaning the glassware. ;\'a7;i'a';;ar2:;;L;'sl;;'v;?C\'b0 'S IaY\'80'\'b0d a $I"9I\'80 Sheet \'b0f munded \par DRYI G \par N To filter a solution one attaches a vacuum ilv \par Just as it is with laundry, drying often follows washing and is used gg? I'xIll\lquote IIli'll;h;aE\rquote 3g;lIlQ\'b0llIIl;.l;IIIcl; ElIlIl:aEI;;IPI?l$I I;Il;I` \par to rid the solvent of any water that it absorbed. All solvents ab- llaak laavlh what la aallail a llllar aah; lg lh; \'b0 ''\ldblquote\lquote \par sorb some water although you can't see it. lt is a good idea to rid fahhal Thg l, ala that has Calla lad lh lh \lquote \par the solvent/product of any water, especially before distilIation,_be- flask la haw Lcallad lha llllrala UC ll lhe .\'b7 \par cause it's one less thing to worry about and because there is an llllar k . lh h d .lh yh.l i l. \{ ,,, \par off-chance that water may form a slight amount of byproduct when alaahca E Is an was 6 WI EI I e hc; \par heated with product oil under distillation conditions. al/ar_klha_af_aalVahl_ll_Waa_laal_llllaraa_l\'a3ma ` lit \par . . That extra washing is then combined with the wi \par All one has to do to dry something is to take a sheet of filter paper . . . , \par or paper towel, fold it into a cone and place it into a funnel. About ?III\'b0\{ IIII2aI\'b0'a The mclgt SCIIEII II"; pI9i\'b0dIrII; ll

\par a shot glass full of sodium sulfate (Na2SO4) or magnesium sulfate .5 23:2 \'b0 S B Ig afclh IIa\'b0S IIIG \'b0k.\'b0IIIIS Iy a \par ls dumped into the filter and the solvent poured through it. It is Ish lhV\'b0I\'a5l \'b0II. ;I lleh IIIg`IIIa \{Il? pflmiss ..\lquote ` \par also a good idea to follow up by rinsing the Na2SO4 with a little gag? af .GlmIS fYIII l avekczyif $9 GC; . \par extra, clean solvent to insure that everything gets washed out of lh as SI ln \'b0 a matt TSI 6 a B t\'b0[mllaII \par the drying agent. The NHZSOA is a white crystalline salt that tastes lh\'b0" 'l\'b0\'b0 flh\'b0 s\'b0F\rquote ?'a P \'b0s\'b0 WS a S '\'b0'\ldblquote F. 8 \par like table salt. It binds water molecules without readily dissolving 6 S\'b0 Ven GY me III I Ig I \par and leaves the solvent water free. This way of drying is also an \par option for making some solvents and pure liquids anhydrous (wa\par - gg \par -29\par \par PRECURSORS thing easier for all involved the chemist informs the company of \par the fake name of her business and that she makes soaps, in\par cense, potpourri or is an aromatherapist (no kidding). Other \par places to order essential oils would be home care products \par SAFROLE houses, toiletry base companies, soap companies, flavoring com\par panies, aromatherapy stores and organic foodstuff companies. \par Where te eeehh Where t\'b0 baglljl Wa"- $*;**09 Vlftlintlgs Ghaptal is As of the year 1998. small quantities of sassafras oil are still being \par a 9\'b0\'b0d 'dea\'b7 Every awphetahhhe IS a e Emleg 2 elheelyglir sold on retail shelves without any scrutiny. Usually in 1-4oz sizes. \par geyerhmeht deeegt a ew lehe tgqewh eil ry . e el em ea 'le \rquote Anything larger is usually sold only through distributors and \par \'b0he has te. ge a eet hha 'hg e amp eahhheh rehh lega (er manufacturers. And as of 1998, the DEA has informed most of \par $\'b0ma*"\ldblquote aa "'agah \'b0*\lquote a'\ldblquote '\'b0a'a that alias F\'b0laa *\'b0l a lm? lhgeaa these distributors that they (tits DEA) want lists kspt or saiss rs-

\par p\'b0Sa'e'e\'b7 Fer e\'b0ataSy\'b7 that etarhhg e ehhea 'S a mee aways a` ported of most, if not all, sassafras oil purchases. Mind you it is \par hole not illegal to buy the oil. lt\rquote s just that you will be put on a list if you \par .Th t\lquote " dSbt \rquote . lt\lquote : \par Safrole is the #1 starting material for making X today. As a pure ggve sgmceasjleaeygetgcryllegci\'e9i Watche U S ance S0 U me \par chemical it is a schedule l controlled substance and, obviously, is ' \par mega! te ewh er buy yhtheut a pemht /\\O Strike has also been poking around the DEA and is getting the \par But, safrole IS. th? m\'a4l\'a4F \'b0\'b0ml$\'b0lqeht tel distinct impression that they will very soon reschedule sassafras \par the eeeeheal ee e essafias W Ie. Ie S I O oil as schedule I. Then one won\rquote t be able to get it at all without a \par quite legal to obtain. Sassafras oil has a pennll el Some Serleus decepllen \par strong licorice smell which is imparted to ` \par lt. eem the eaeele melecele Cemhlgee \\ All of the above safrole/sassafras oil sources are the more stan\par elahyx there are \{we klhee ef eaeea ras . - dard avenues to get these commodities. There are some rather \par oil being sold today: American sassafras (Sassafras albidum) and exelle Sources Of safrole for the desperate gel/elnmen_ \par Brazlhae eaeeaeae (oeetea eymearem) Plam. ele Ameeeah See` tally-challenged citizens of the future. Certain kinds of Asian cam\par safras contains about 80% safrole but the Brazilian sassafras oil is nner Olls esneclelly blown campncl ell cen eenleln 4060% \par ahheet ee`ee% eahele and eah pretty mech ee eeee as le safrole (another term to look for is \lquote Camphor 1070'). Sources \par . . ll` ' rt`f` ` l f `l' ll ll` ' f 50\lquote V \par So where does one go to get sassafras oil'? Well, if one werelto Zgnngelni ellgzozeiiirgeg eA;nl\'a7l:ec;\'a7t;?eae5;enlgeele;1\'a7i OApnle`; \par go down to one of those sickening hippie health food stores or in- eleble amounts of safrole can be found ln Slel enlse ell end \par cense shops there, on the shelves, will be small bottles of 80-90% smaller amounts can found ln the Olls Ol, elnnemen mace 'belel \par ecstacy starting material labeled as sassafras oil. Larger quanti- leaf and nutmeg (lots Ol fun lnlngs ln nutmeg)- Alec, lhelfe ls a

\par hee areereeree rather eheshly "\'b0'\ldblquote .*a:\'a4'a"\'b0a er pahuma eeplely spice bush that grows in India called Betel. Betel leaf oil can be \par eerhpamee that ehe eah he lh ahy ele clv yehew pagee New e found commercially and can contain up to 40% safrole depending \par people at these companies aren't stupid. They have a general On lne leglnn llwes eulllveled ln \par idea of what some of their essential oils can be used for so they ' \par mlght ask. But they still have no legal reason notlto sell these The sassafras tree llsell glows llke e Weed ln the Wllds and along \par thmge te the ehemleh After a"\rquote the Sams Stuff le eemg Sele ever disturbed fence lines throughout the south, southeast, eastern \par the counter to hippies just down the street. Just to make every\par - 30 - - 31 \par \par Qsual Components of Sassafras Oil \par seaboard, and Appalachian mountain regions of the United \par States. The trunk and root bark of older, mature sassafras trees Component range gf aaatam baiih-,gpO1nt@1a1m(OC) \par can be steam distilled to afford the safrole-containing oil. Another \par source of safrole would have to the be leaf oil of a little shrub that pihaaa 2-1g% 154 \par grows down in the low woods and swamps throughout the coastal phaiiandrano 2-1g% 175 \par plains from Florida to Georgia. The oil is more than 90% safrole d-ggmphgr 5-5% 2g4 \par [61]. The plant is known as Illicium parviflorum michx and Strike Safroia 39-99% 234 \par has no idea what the hell it looks like. eugenol O-10% 252 \par A new source of safrole that Strike has just stumbled upon is in [Table 1] \par Strikes back yard. Momma comes home from the local nursery \par with two plants that have these enormous leaves. They are suc- No matter what the safrole content is, even that of the Brazilian \par culents and grow like crazy. Strlkei `\ldblquote Whal l/8 90l there lVl0\'a4\lquote lh\lquote l\'a4?\rdblquote sassafras oil, it is always a good idea to try to get rid of as much of \par Momma: "Don\rquote t think I haven't notioed those filthy drug books you the other components as possible. The most basic way to do this \par write, you sick little mohkeyl" Strikei \ldblquote AW 0\rquote m0fl. lVl\'a4m\'b7 Lel'S \'a4\'a4l is to throw all of the crude sassafras oil into a PP container and

\par get into this again. Strike doesn't...\rdblquote Momma: \ldblquote WeIl I needed stir it with an aqua] amount or 3-5% sodium hydrgxjdg (NaOH) \par some new ground cover plants, ahd...Si9h...l know l/Ol-l'l\rquote e ll'\'a4t0 this solution. Little white crystals of eugenol anion will form in the we\par twisted licorice thing...so l bought these weeds that are called ter layer. The water layer is poured off and saved. That eugenol \par \lquote Licorice Plants\rquote ." is valuable, Eugenol is usually the main contaminant in safrole in \par more ways than one. lt is the only molecule in sassafras oil that \par Strike breaks off a piece of the plant and smells it. Oh Yeah! will react the same way as safrole so if it hangs around with the \par That\rquote s the bomb! The plant is called Piper auritum. Its common safrole it will compete with safrole in the conversion reactions. \par name is Hojo Santa. Strike loves Strike's mother. Also, eugenol is about the closest to safrole in both structure and \par _ boiling point so that trying to get rid of it by fractional distillation will \par Suffice to say that anything that remotely smells like sassafras oil be very tough indeed. Anyway, after the eugenol/water is poured \par or licorice or any of those strong rustic spices is going to have off the oil that remains is stirred with 3 washings of clean water. \par some amphetamine precursor, maybe not safrole exactly, but The cleaned oil will look a little cloudy now. Strike still does not \par detinitely something. There is just no other substitute in nature for know why. But it never seems to hurt anything. After the third \par the aroma these unique compounds give. washing is poured away from the oil, the oil is transferred to an \par ordinary cooking pot and boiled at 100\'b0C for a few minutes to boil \par The sassafras oil that one gets these days is not only going to off all the water. What would you think of french fries cooked in \par have the safrole but is usually going to have some amount of each that oil, huh? \par of the compounds seen in Table 1 [6]. \par Strike wrote the above paragraph relying on the few accounts of \par sassafras oil content that Strike had at the time. Since then, Strike \par has come across more substantial data showing that Brazilian \par sassafras has NO eugenol in it. This agrees with the claims of

\par many bees who have stated that no appreciable recovery of \par - 33 \par - 32 \par \par eugenol is obsenred when washed with the dilute NaOH. Strike . _ _ _ \par has also had commercial samples of both sassafras and brown top 10 recmes mscussee ieier The one p"\'b0b*em W***`* ****e **`*e***od \par eamphor analyzed for components and the results showed that Is that havmg Peer d*Stur*? ed\'b7 s\'b0me \'b0f the sa**'\'b0*e m\'b0*e\'b0u*ee' \par there Wee no eugenol in either. SO give it e ehet with NaOH er double bonds will tend to migrate or reform ln the more energeti\par eemv Smke nelenger feelememmetterei cally favorable position between the alpha and beta carbons. \par What was all that egghead shit Strike just said? Strike said that \par The above procedure Wee e good Step tewerde purity and mev be not only will safrole reform but there may also be a small amount \par all that one can hope for without a distillation apparatus. For Of *S\'b0Saf*\'b0*6 that f\'b0rms ee We"' A*_s\'b0i S\'b0me Very *n*Lt*t*Ve Bees \par those that have a distillation kit its time to get rid ofthe rest ofthe have s\rdblquote 99\'b0$*?\'b0* **is* '* Weil be Possible *0 o0\'a4\'a4e<=*_**ie ieoie*i\'a4s of \par stun by fractional distillation. This still isn\'b7t going to be easy be- ***e se*i\'b0*e Wi**i meieurie eoe*e*e eoo prooeed <*\'b7reo*iy with the \par ceuee even with e packed Cleieen edepter Or Vigreux column the complex into one of the oxidation reactions found later in this \par entire mass of oil is going to distill over with barely a 5 degree dit- i\'a4ooi<\'b7 o\'b0***0 be Could ee \par ference between the first drop of oil to come over to the last (this _ _ __ \par usueuv Occurs et ereund 17O_18O\'a4C under normal Vacuum) The After Strike wrotelthe first edition and started up the old web site, \par best strategy is to distill the oil at least 2 times; discarding the first ei *0* 0* new theories eeme io- The moei prorriieirio Wee \'a4 proposi\par few mLs (milliliters) of distillate and leaving the darker last few **9** f*`om ow io\'a4\'a4<i\'b7r\'b7\'a4 *\'b0e**\rdblquote e*` of ollbef o*'*sm*s**'Y\'a5 Elsiisls- This Weis \par mLs behind in the reaction flask (discarding them as well). me P*`oooee** \'bb

\par lt will be a little tricky but one can also try to purify by freezing! nPunfical\lquote i0n of Sassafras Oil v2.0 \par The sassafras oil is thrown into the freezer to chill. Safrole itself _ \par freezes at -14\'b0C so anything that starts to freeze prior to that can The Seeeefree P*e\rdblquote * \rquote s ep e\{\lquote Ge/lent source of Safrole. .8 Ilighly \par be cold filtered in a prechilled vacuum filtration setup. The filtrate useful \'b0o\rquote *Ypou"d\'b7 The P*e\rquote **V\rquote e*d$ UP to e%_ olt bl! Ws\rquote 9h*i Wh/Ch is \par goes back in the freezer until -14\'b0C is reached and the mother en eXeeio*t\rquote o\rquote Ze\rdblquote\'bbV good Weld- Sessefres ls mdigsnous **0 Vifgililsi \par Iode of safrole freezes up. This again is filtered cold but this time the Cerolme S\'b7 Tenneegeee end Pens of _Ca"*ede\'b7 The prefeqred \par the frozen mass of safrole crystals are washed with some ice cold meiiiod of eX*\rquote ee*"`*g o\rquote * o\rdblquote * of *`*`*e _P*o"* 's oY Steam Dls*l\rdblquote 6*l0'*\'b7 \par methanol or ethanol (preferably at -14\'b0C) to wash away the unfro- The most eomrnon method of oo*e\rdblquote '*\rdblquote\rdblquote *Q Sassafras Oil, U'*0UQ*'*. is \par zen high-boiling constituents. oV P*\rdblquote o*"ee"79 \rquote * J`\}\par lf one is absolutely serious about ultra pure safrole then it can be egg;g$r;t(\rquote\rdblquote ;n;I,E,i/iss/Qtlal OHS by GUS,-Ith\'e9n Sasse\par separated from the eugenol-free sassafras oll by treatment with \par mercuric acetate [1,2,3,4] which likes that terminal double bond 80% Safrole \par that only safrole has. The Hg(AcO)2 latches on to safrole at that o \rdblquote \par double bond bringing it into solution as a solid; sort of like the way 106 Phellandreng \par that eugenol was. The safrole can then be separated from its still 7% Cemohor \par oily buddies by vacuum filtration. Safrole is then regenerated to 3% Eugenol & various Sesquiterpenes (Cadinene el al.) \par its normal oily form by treatment with hydrochloric acid (HCI) _ _ _ \par which flicks the Hg(AcO)2 off the safrole and the safrole double I he"e derived e prooeoe for P\rquote efe[e\rquote **'e\rdblquote V sePa"a*"'*Q **`*e Safrole \par bond reforms. As it so happens, the mercuric acetate also re- ou* of Sessefres _O'*\'b7 This Process is based OP ***6 Physical P"oP\'b7 \par forms intact so that it can be reused again such as in one of those erilee of me Venous somPo\rquote 7e\rquote 7*`s listed above combined W'*h 8 \par /iff/e chemistry knowledge. The normal means of purifying Sassa\par - 34 -

\par - 35 \par \par fras Oil is through packed column vacuum fractional distillation. double boiler setup (especially since this will take quite a while \par This is an expensive, messy, and difficult process - in short, im- depending on how much you have to distill/evaporate). \par practical. My process that l am proposing takes advantage of drf- _ _ _ _ _ \par ferential solubility among the various oils in acetic acid to separate 5) Aftsr d'$t'//8t\rquote\'b0" t9\rdblquote [""atES (Ethanal bc"/S at 78-4C),_f6S? your \par the mixture down to only two components. The two remaining oils ggfmle PS"'? ms PhY$'\'b0a\rquote Pmpamas data be/cw tv COl'Wl'm purity. \par have sufliciently different boiling points to make simple distillation, \'b0\'b0'9t'\'b0a\rdblquote % Yourpmduct $,70**/d ba b\lquote -\lquote\rdblquote\'b0" than 99% PWS HOW. \par with or without vacuum, a feasible separation method. To wit: Sa- Th 1 f S r I \'b7 L . - - . . _ \par frole and Phellandrene are left, Safrole boils at 232C while Phel- S Sn ry Or 8 m 9 In angss mdlcatss the fo/lcwmg pmpgmes \par landrene boils at 171C. The difference of 61C is large enough to \par permit excellent separation of the two, though some texts feel that Safrole 3, 4methylenedioxyallylbenzene - Bielstein ref # XlX\emdash 39 \par there should be 8OC difference between distillants (see Vogel), it Molecular Wgight. 162 19 \par is generally accepted that fractional distillation is necessary only . . . _ l \par when the boiling points approach 25C of each other (see Zubrick). Svacrfrc G\rquote a"\rquote t\'b7V\'b7 1- 100@2OC \par However; with information newly acquired you now dont even Melting Point: 11C \par hlavzgoddoggesziztillation, since Safrole is soluble in ethanol, while Bojlfng point'. 233_234C \par e n e r . _ \par p A lnsoluble rn waten Soluble in Ethanol, Miscible with Ether and \par Enough of the arguments, let\rquote s take a look at what rs going on Chloroform \par here. . _ \par _ Note that this procedure has been modiried from the earlier ver-

\par Materials \emdash -\'b7\emdash -- Separatory funnel (2x volume to contain) Simple sion in that we no longer distill off the Phellandrene, rathen we \par Distillatron setup or pot on stove ,\'b7-) _ target its insolubility in ethanol as a means to separate it from sa\par . . . . . f . ' k \lquote \lquote \par 1) First wash with a volume of Glacial Acetic Acid equal to the mls Uhm We can all agmg that this IS a much betmr Wayr Sh? \par amount of Sassafras Oil being processed. This will remove Euge\par nol, Pinene and Camphorfrom the oil. This procedure, Strike believes, was not tried by Eleusis. But his \par 2) Wash with water to remove any salts made from other contami- $:1;,% Q; 21; afjrjfb\'b0aQ;jLS\'a7;.'*L*j;Q'*\{1(;S gigs \'b0'du agdl f\'b0\ldblquote\'a7\'b0\'a7d\'b7 \par nants and to crash out any partially dissolved Safrole (it might .1-DK. ymmracted 8 1,11111;) pine resggch ?abOraiO\'b0:yrtO\'80;V\'801 Hi; \par emulsify from the shaking, if so, add common table salt to help it proposal Here is what they said, ppy \par crash). ` ' \par 3) Wash with rectihed spirits (azeotrope of Ethanol + waten also Posted by TDK On December 28* 7997 at O1`.28\lquote -34: \par known as "grain alcohol') to dissolve the Safrole, leaving the Sassafras Oil separation/purilication \par Phellandrene behind. Of course, one should use only the amount \par of alcohol necessary to dissolve the expected yield of Safrole. 1:1 \'b7 - . . . \par seems to work, but could be an excessive amount. Zgglgfnp and IS WSH Swtgd for Someone Wuhout any \par 4) Setup for simple distillation, on the water bath, or if you don't \'b7 . _ . \par wish to recover the alcohol (shame on you) just heat gently with a Slamng Weight" 112 grams Sassafras O"' \par Placed 454 grams of 28% acetic acid in 2 liter separatory funnel. \par - 36 - - 37 \par \par _ recipe Strike knew of at the time. There are numerous basic refer\par Using 25% acetic acid allows the eugerw/, d-G\'e9imptwf Hfid Pili\'e9lw ences for it inthe literature and a couple of very convincing exam-

\par to form its own top layer. There was no separation using 99.5% ples in tha landmark book ~p|HKAL\'b7\'b7 by Alaxandol, and Am \par acetic acid, Shulgin. Pioneers in the research of amphetamines they are. \par Added 112 grams sassafras oil. Shake for a couple of minutes. ggygasa ?;V\'b03dShi;;ugh f\'b0r Strike SO S\'b0m\'b0\'b0"6 Other than Strike \par You get an orangish emulsion. Clears within 15dminutes f;:>r+m;2g \par oil, to la er acetic acl , eu eno e _ _ \par gvggiaggxb/gguggpggigd me ,5, fri\'e9m the Others) waghgd ma ci; What happens when isomerization is performed is that the double \par iayer 2x with fresh dH2O. Weight alter acetic acid & water washesi i\'a4<>\{i\'a4if\'a4i the aiiyibenzene safrole migrates to the more energat,\par 1g1_5 (-10_5 grams) Ga ill Hilurabi\'e9 p0Sltl\'a4n between the alpha and beta earbons cr the \par _ propyl side chain. Thus isosafrole, a propenylbenzene, is born. \par Added 100 grams denatured alcohol, no layer fomwed as the oily \par product is miscible in ethanol. Added 20 grams of dH2O. This \par puiied the ethanol and other product into the t0P /6VSH b0ii\'a4m To isomerize safrole to isosafrole one would like to have pure ea\par layer ccntaining Same ethanol and safrole. Sepafat\'e9d IHYGFS. frole to start with. This, usually, is not the case. Quasi-pure safrole \par placed the oily bottom layer into a 2-liter breaker Took the temp from sassafras oil is ok. Straight-up sassafras oil is probably ok \par right to 234 C. The ethanol and water came off <=10O C... The too, though not recommended. The safrole is then refluxed (boiled \par safrole started to boil @ 232C, then came to a full boil and main- under a condenser) in a saturated KOH/ethanol solution for about \par tained @ 234 C. Product was yellow orange in colon suitable for a day and that's it. The temperature of reflux is about 120-140\'b0C \par whatever purpose one has in mind! BTW after the safrole cooled, owing to the fact that the ethanol (usually boiling around 65-70\'b0C) \par she checked it with a 5% NaOH solution to see if any eugenol was is saturated with the halide salt. \par left behind noparticipate formed. \par . . . . Now, the ethanol used is almost always anhydrous, meaning it

\par Beautiful. `i`DKi B9\'a4UiiiUi\'b7 Strike, Suspects we wm be Seeing mma has no water. The closest one can get commercially to anhydrous \par from this Qifi\'e9d Gii\'e9misi i\'a4i\'80V\'b0" in the b\'b0\'b0k- ethanol is Everclear which is 95% ethanol and 5% water (190 \par proof). A lot of chemical supply stores will not carry 100% 200 \par i$O$AFROi-E proof) ethanol because it is a potable (drinkable) producto \{This \par / _ means that they would have to get a liquor license or some other \par At this point the Gh\'e9misi has what can be i\'b0\'b0$\'80iY 'wnsideied a? state permit to sell the stuff and that is a hassle that many don't \par pure safrole. She can use this for some methods or can convert it want to bother with \par to isosafrole for others. Isosafrole is the runner-up precursor for \par making X. lt cannot be found in nature but rather is made from al\par most exclusively safrole. The 95% ethanol of Everclear is not an arbitrary concentration that \par P O the producer decided to stop at, mind you. lf so happens that 95% \par Strike had previously written that about O ethanol and 5% water is a constant boiling mix that no more etha\par the best recipe for making isosafrole nol can be purified from. That 5% water is there to stay! There are \par was from boiling safrole with concen- ways to remove that water such as producing a ternary azeotrope \par trated KOH (Potassium Hydroxide) in / by the addition of benzene, but they are kind of a hassle and may \par ethanol. This was actually the only 39 \par -33\par \par not be necessary. Why? Because an alternative reaction for iso- _ \par mcrlzallon would bc to use a salulalccl aqucous lwalcll Zak) KOH still be dark regardless and washing this ethanol with water at this \par sololloo locloacl of an alcoholic ooc_ Thls wlll lalso loc lcmocla_ point cannot be done because water is infinitely soluble in ethanol \par ture of reflux to over 200\'b0C but is not too bad an can be used if (and Vlsa versa) $0 Wl/0 la!/GFS will not form. \par desired. So, if it is ok to isomerize in pure water, then the little bit

\par gicgil\'e9falggilhi@ll;SxE;$:;;;;ui;\'b0:L;Zt em thmgs t\'b0\'b0 greatly Filtered or not, the ethanol/isosafrole/(sometimes junk) is relieved \par \lquote of its ethanol by openly boiling it on the stove or by distillation. A \par . . . _ FW \par ethanol removed by distillation is saved because it is clean and \par What are some of the alternatives for this procedure? Well, one gzgjlgtlxgfugableo(rjl`nin\'a3l?\'80r\rquote il will stl\}? have that 5% Water\} One \par can use NaOH (lye) ih place or KOH out the yields will so down. ol all ll'l'\ldblquote\'b0`l\'b0f \'b0 E S0 Venti ls Wall b'=\lquote\'a4\'a49S\'80 things can \par Also, what about using denatured alcohol instead of pure ethanol? Q rc y \'b0 rea Y ast ast 6 last \'b0f the ethanol b\'b0"S awa!/\'b7 \par Denatured alcohol is ethanol contaminated with 5-10% methanol. \par The methanol is there because it is poisonous and prevents peo- .... \par ple from using the ethanol for drinking. This means that places like mgsljl\'e9tlily lin; YW" Bpld lilp W'th a dark \'b0'|Y la!/G" at the b\'b0n\'b0m Qi \par the giant hardware stores can carry gallons of cheap contami- be no ll ml cb IS pe GF 3ll1n\'b0rmaI\lquote Any S\'b0IV6"t mnt rnmmns wil \par plated oihoho. oo many of yoo heve dieeoveied. the eieiiuei c/-~ Olwiofm if ,,f\'a7Z\'a7?\'a7g 'Q i,..i.g\lquote\'a7g"O?\'a7\lquote i\'a7i;?6.i\lquote i'hi?Z\'b0i; '\'a7o?,31\ldblquote $oE,\'b0 \par be used 200mb of dark oily layer then a liter or more of water is pored in \par and mixed really well. After things settle one will see a nice little \par SO new that we have all the reagents out Of the way let'; see how l8yGI' of clear lSOS3fl\rquote 0i\'80 fOfl'T'l Ht [l`l\'80 b0[[0lTl, 8 mLlfky bl'OWl\rquote l lyikes! \par the reaction proceeds. There's the clear- yellow "safroIe" sitting in emulsion layer in the middle and a blackish water layer on top. \par the bottom if the flask and the clear saturated KOH solution is T|"l9 oil is Separated and the emulsion is dealt with in any way that \par dumped in The solution is heated to reflux etc_ and yes, some is best from the below mentioned strategies for emulsion tighting. \par brown byproducts and destruction artifacts will appear, Especially This particular emulsion is of very fine particulates and has a lot of \par if the safrole is not pure. These byproducts should be expected to lsosafrole in it. lf one is patient then one can add solvent (DCM is \par some extent because concentrated basic (OH) solutions can be good) to the remaining water/emulsion layer, shake then vacuum

\par as nasty as concentrated acidic solutions. One is mindful that filter. The crud remaining in the filter is the junk that was causing \par KOH is less intrusive towards the delicate methylenedioxy ring all the trouble. With it gone one can now extract the remaining \par structure ofthe safrole/lsosafrole molecule. water layer a couple more times with solvent, add the solvent to \par lhe isosafrole oil then remove the solvent by boiling or distillation \par - \'a4 _ 0 \'b7 \par After 12-24 hours of reflux the reaction is, for the most part, com- O get pure lsosafrole ( 70 B0 /0 trans' 20 BDA, cls) \par plete. The reaction mix will be a dark brown. So what does one do \par about all those brown particles and junk. Well, usually there aren't NO-l-El a lcally good oloooduro fol, bosllno up the omulslon \par any- The Snlnnnn Snould be \{\'b7'n'f\'b0n`n|Y nant- if anY $\'b0l\lquote dS can be caused by introducing the water is to slowly acidify the water layer \par Seen 't means that tn\'80Y a\rquote\'80_'n$\'b0'\ldblquote b'E 'n etnnnnl and can be \rquote\'b0' with HCI. As the water layer acidities one will see the emulsion \par m\'a4v\'a4\'a4 frm ==\'b7\'a4l\'a4\'a4\'a4\'a4 bv \'a4r\'a4v\'b7tv \'a4n vacuum tltr\'a4*\'b7\'a4\'a4 thi\'a4\'a4\'a4h \'a4 <=<>f- vanish. As ihie oeedie iiie water layer vviii light\'e9fl as particulates \par fee litter Or S\'a4m\'a4_l\'a4\'a4\'a4\'a4r t\'a4l~<\'b7=lS\emdash if \'b7t takes \'a4 dev t<> \'a4r\'b7_l\'a4 \'a2\'a4r\'a4\'a4\'a4\'a4 the ehli elim start to exit the water layer and go ihlo the ocivi layer. \par filter then so-be-lt. The ethanol with its payload of lsosafrole will Works cvcly tlmo \par -40\par - 4l \par \par Gee, that alls d f` dd d .B tStrik \par lf one is still having trouble then there is the old failsafe: just throw [ast. Without aosglugtl | 3l;ilIsalT;;t\rquote )Tas;sT snjggslzgltgqigrisj 2; \par the whole mess into a distillation set up and fractionally distill. Sol- lsomellzlng Safmle and other allylbsnzsnss ls le use CeOl_l \par vent comes first, water second and (eventually) isosafrole will Someone who is NOT Tim(Strikes name TOT hel.) smelled Srrlke \par Come ee We"- the Chemical Abstracts entry for the procedure:

\par Sound easy? Well. preeedurelly ll le- But the yield eerl reelly e\'a4\'a4l< \'b7\'b7cA 47;9a60. lsoearrole from earrore. yasnlnaru Ogata (Regen\par semellmes and lt een gel many messy. l-ele ef people have nel eration oampnar co). Japan. 5331 ('51), sep:. 15. Safrole \par been pleased with lt. Strike wasn t. But what can you do? b_132_40, 100, CeO 15, end KOH 1 g' are heeled 15 mln. at \par Well, someone named Osmium sent Strike a journal reference 243\'b75O\'a4 the Ceo a\rdblquote d KOH llllefed ell and the lillrefe disld fe \'a4b\'b7 \par about doing the exact procedure above but carrying it out in a mi- fain 95% isosafrole, b.240-8\'b0. K. Kitsuta" \par crowave [5]! A group of Brazilian folks tried both conventional and \par ' ht'.Th hdt lh`h'ld llb . . , . \par bggtlluveays. Seth SM asnlelautglile Iuwilgcorueilniraiitensaweug \lquote Not-Tlm said Strike was wasting everybody's time wlthvthe etha\par used in ethanol, propanol and butanol, They also found that add- ug!/FQTH regpe end Y\'b0u\'b7Wa"\rquote\ldblquote e knew What? He Wa$_k'"ua "9'lt \par ing 2M KCI along with the KOH helped things. The really cool ( u' eee rezueu Imerevememe ebeye elem hereluet te take \par things were that when they used butanol and 4M KOH they only up $l\'b0"\'b0"\rquote\'b7)The '\ldblquote\'b0**\lquote\'b0u 'S S\'b0\'b0\'b0\'b0\'b0 east \par dt l15' fb\lquote l` t t `ld f99\lquote VlS\lquote lth h . . \par Isacteareseeny prorgarlllcj arcidnegzhgnge oewlyneleeiied 2?5h;lf0FgCg+; All one does IS follow that CA reclpe to the letter. ln a small flat\par conversion. Strike would assume that the reduced reaction times b\'b0u\'b0u` flask pleee 1009 Sefrelel 159 CeO emu 19 New the \par erlerded by The lereer elsehels end such may Very Well help re_ flask IS heated directly on a stlrrlng hotplate (stlrrlng IS nlce but not \par duce tar and destruction and make for a better procedure. ueeeeeeuu lf ene hee e r\'b0u"u`b\'b0u\'b0m ueek er e lew Output heat` \par lng source, a shallow oil bath can be employed to get even heat\par Uslne The mlereweve lusl decreased the reeellerl llme le 3_ ing. The really neat thing about this method is the proof-positive \par somlnules The dudes ln The erllele used e heuseheld 500W Bre_ heat gradations that will occur. The mixture will rise to the boiling \par Zlllen mlereweve (Ylkesl) They eel e whsle ln the lee el, the ml_ point of safrole (232234\'b0C). And it will hold there for just a brief

\par ereweve le ellew the eerrderrser spperelus te pess through the second. Then it will start to bubble and the temperature will rise! \par oven. They then killed themselves most likely. But not before they Sur e e\'a4\'a4\'a4ell\'b7 eftei euly. 15mm ef the the temperature Wm reeeh \par were able to scratch down this procedure as they slowly bumed to the ueer beumg umm ef 'eeeefrele ("243'25e C)\'b7 And that- ee they \par seeth; say, IS lt. \par TGENERAL PROCEDURE. The A/eehelie elkslme selrmen ls pre_ The oil that remains is only slightly dark. Definitely translucent \par pared by prolonged stirring of 8.8g (or 4.4g) of KOH pellets in xlzhlch is ehflzys Ii?/ely\lquote dOue cer; lllgll ef? SOT; Weger le tekglgg \par 30mL of alcohol. The alkaline solution is placed in a round\emdash boftom f e uueeee eb S; ere; sepelge e e $0/rzuel ten euzul .5 \par flask provided with a reflux condenser (microwave or conventional Orme I can e Us e up mu Some \'b0 \lquote e 'Sese lrzefl \par systems). Then 4.0g of Safrole (or eugenol) is added and the so- clean eueugh le \'a4r\'a4\'a4ee\'a4 Wuh but u een el eeuree be diem e or \par rurlon neared? u te pu"*V\'b7 \par - 42 - - 43 \par \par Strike can\rquote t believe ' - \'b7 \par All of the above isomerization recipes can, in theory, produce al- \{That is so freaky!)]. lli:>rsl;i\'a4f\'80t?1resae:tll1?ngsqvgilltgglgke5 gwn bP\'b0k\lquote \par most 100% yields of isosafrole. But about 20-30% of that isosa\emdash that are much more potent than X It is also sslnfbletamlnes \par frole is in a screwed up configuration called 'cis'. This cis isomer around with some of the little side grou s on the; il e to play \par does not react the same way as trans and the drug that will be make X or some other interesting psy\'a7hotomime$csO ellflimuauy \par made from it will not be recognized in the same way as trans in exceptions these precursors are all substituted all lbenz le few \par the brain cells of USSFS. TSK. like safrole. They are all found in the same kind gf legalggilg \par /\\ O P O sold in the same kinds of places as sassafras. Finally, these pre\par cursors are turned into their own respective amphetamines using

\par O O the exact same conversion recipes used for safrole. \par / / ANETHOLE: Up to_90+%4in anise seed oil, 70+% in fennel and \par star anise oils, and in varying amounts in betel leaf, dill seed, car\par _ rot seed and coriander oils. \par trans-isosafrole cis-isosafrole \par H C \par The chemist can try to separate the two isomers by careful frac- 3 \par tional distillation but it will be next to impossible to do because . \par both the cls and the trans have practically the same boiling point. / \par There are a few things that the chemist can do or hope for to get \par rid of that cis isomer. The cis configuration is less stable than the \par trans and may switch over to the trans configuration with a little \par hel . The chemist can gentl heat the isosafrole oil to about \par 150llC for an hour or so. Sheycan also try the same heating ex- ANl$ALDEl'lYDEl ln Small 6l'\'a40\'a4\'a4fS (less than 5%) in anise, \par cept have the oil mixed with some acetic acid. Also, the isosafrole \'b0"ln`lln\'b7 lennel end slef afllse oils. \par can be fractionally distilled to ultra purity and then be allowed to H CO \par simply sit for a couple of days. Trans isosafrole \lquote may\rquote spontane- 3 \par ously crystalize out while the cis form remains as an oil. They can \par then be separated by filtration. O \par When all is said and done, the chemist may just wish to leave the _ ,, . _ \par damn cis isomer in with the trans. It's not really going to hurt g;lgl;]5`.23A\rdblquote jf celeryleef \'b0ll* upl\'b0 3)% ln pelelelfleel and Seed \par anything and if it goes unreacted in some of the conversion steps \rquote In sma am\'b0unls ln \'b0ul\'b0eb\'b7 dlll end fennel Oile\par it will be lost in the process long before X is made. lt might even \par correct itself during some of the conversion steps. /\\ O \par O CH3 \par OTHER PRECURSORS \par You people won't believe the potential amphetamine precursors H CO \\

\par just sitting around in naturally occurring oils and essential oils [6, 7 3 45 \par - 44 \par \par ASARONE: 70-80% of calamus oil. ln trace amounts in Asian car- 5,:-O5\ldblquote :;I;:t, $n\'80?;\'a3?ts6gZ; Egemssgfgilfill and 'in Vawing \par ~ . n various \par mt Seed amd \'b0'\'b0V\'b0 bud \'b0'|s\'b7 amounts in fennel and carrot seed oils. Sma \par HSCO CH3 /\\ O \par / O \par H3CO \par BENZALDEHYDE: The precursor for speed. It makes up nearly HSCO \\ \par 100% of bitter almond oil. _Not a very popular oil with the DEA. \par Some hints: Benzaldehyde is indispensable for the flavoring in- CH; \par dustry. lt is the flavor in almond extract and . \par synthetic benzaldehyde is used in all cherry ELEMICINT In V6l'Vl\'a49 \'a4lTl0\'a4\'a4T$ lll \'a4ltl\rquote 0\'a4\'80||9l \'80|\'80|T\\l. m6C\'80. nutmeg, \par flavorings. Also, there is currently a little loop- Paisley $\'a4\'a4k\'80l\rquote 00\'a5 and tafragon. \lquote \par hole in the system when it comes to a product HO OCH \par called \lquote Roasted Cassia Oil\rquote . Apparently, some \lquote 3 \par manufacturers take cassia oil and run it through some sort of in- H CO \par dustrial process to change it into benzaldehyde. No one wanted to 3 \par tell Strike the particulars of how this was done. But one company \par chemist gave me some hints (You can get really chatty with some \\ \par of these guys). HBCU \par Apparently, these guys are taking regular old cassia oil and simply \par running it through a series of distillations. This even happens in \par the Asian fields when the oil is harvested so it obviously is not a EUGENOLZ |\'a4 VGFV IHFQG amounts i\'a4 bay. \'a4i\'a4\'a4Bm0n, clove and \par complicated process. Cassia oil is made up almost exclusively of pimento oils. ln goodly amounts in basil. eucalyptus and tejpat.

\par cinnamaIdehyde.`Any of you girls have any idea what these com- Lots of trace amounts in many other oils. \par panies are doing to turn cheap cinnamaldehyde into benzalde- OCH \par hyde'? Might be beneficial for you if you do. 3 \par CHAVICOL: Up to 20% in West Indian bay oil. HO \par HO \par \\ \par \\ METHYLCHAVICOL: Up to 80+% in most basil, chervil and fennel \par oils. ln small amounts in star anise and wormwood. \par - 46 - _ 47 _ \par \par PHENYLACETIC ACID: Very important fragrance chemical. Only \par H C recently was it banned by the DEA. Fragrance companies still \par 3 can\lquote t believe they cannot openly sell it. It makes up 15% of jas\par mine oil (very expensive). \par \\ \par METHYLEUGENOL: Up to 60% in various parts of the basil plant. COOH \par Around 45% in snakeroot oil. In decent amounts in calamus, cas\par sie, myrtle, pimento, plstacia, pteronia and some forms of tarra\par gon . 2,3,4,5-TETRAMETHOXYALLYLBENZENE: In varying amounts \par in some parsley oils (hell, just throw parsley oil in a pot to get a \par OCH3 grab bag of psychedelic amphetamlnes!). \par HECO OCH3 \par HSCO \par \\ \par MYRISTICIN; ln moderate amounts in dill, carrot, celery, fennel, H CO \\ \par mace and nutmeg (no more than 10% tops). Makes up about 40% 3 \par of the oil of parsnip and can reach up to 50-60% of the oil of QQH3 \par parsley leaves and seeds. Give nutmeg a rest folks! It just don\rquote t

\par h\'a4V\'80 itwben Compared *0 P6V$l\'80Y 6\'a4\'a4l F>6FS\'a4\'a4P\'b7 VANILLIN: In vanilla beans of course. But never more than 2%. \par /\\ O This stuff is bought as a synthetic and is cheap and legal. \par O CH3 \par HO \par HSCO \\ \par _ _ _ HO \par OSMORHIZOLE: Makes up 25% of the essential oll of chervll. \par Very hard to rind this \'a4l|th0ugh. The standard way that scientists get these allylbenzenes and \par other goodies out of these oils is by careful, fractional distillation. \par Haco CH3 You can see from above that some of the more desirable allylben\par zenes do not occur in high concentrations in the oils they are \par found in. So that means there is a lot of crap one has to get rid of \par \\ to isolate the goods. This is not as big of a concern as one might \par think. \par - 48 - \emdash 49 \par \par sulfate intermediate with the elemicin causing it to migrate out of \par Essential oils from plants are technically known as \lquote voIatile\lquote oils. the ell laYet and Qc lntc the S\'a4lr\'a4r\'b7\'a4_e\'a4\'b7\'a4 la\'a7\rquote at- And Slhtie elemicin \par -l-hls means, among olhel, thlngsl that most even, component of is goinglto be about the only thing in elemi oil that has a terminal \par them will eventually evaporate if left to stand. So there is a definite alkehe\'b7 't 's Qelhg re hevahcut the \'b0nlV th'n9 that 9\'b0e$ into the aqid \par boiling range for these oils which, compared to other things in na- laYet\'b7 P'eatO\'b7 Alkene 's\'b0lateu\'b7 Well. alnl\'b0$t- What the Ghemlet \par ture, is relatively low. Strike means to say that when these oils eeee next la sePa'ate the aclu lever (stlll cold mlnd V0Ul). Pl\'a4\'a4e lt \par were extracted from the plants they come from, they were taken 'P SOmO Vessel and POut lh a hlg Olu excess ef Watah The taht \par by steam distillation where steam was the carrier. This leaves you getatute Wlll 9O uP anu the hYut\'b09en sultate Wlll be ln$tahtlY hY\'b7

\par with compounds that have relatively low boiling points with 300\ldblquote C FO vzed PY the Water tO_tOt!h ah Ol'l\'b7 One can else heat fer 5 \par being close to the max. And Strike can tell you right now that in mlhutOS re lhsute OOh"etOlOh\'b7 \par oils that carry allylbenzenes, those same allylbenzenes are almost Wh t ,d _ _ _ \par always going to be the highest boiling compounds. Usually the _ a . happens [mug ,hydr\'b0lyS'S ls thatthe OH tOrma and the \par bulk of the oil is constituted with compounds that boil well below Olem'O'h P'OPYl alOOhOl u"OPs Out ef sclutlen and ferme tts \'b0Wn 0ll \par the allylbenzenesl layer. Of course one won\rquote t see this because the solution is a big \par old brown mess, lousy with emulsion particles. Emulsions suck! \par People with or without distillation apparatuses can take advantage aut Oah be dealt Wlth ettectlVelV bv au\'a7?l'n9 a little acid Ol basal OF \par of this fact. Just boil or distill off most of the oil up to the tempera- tllttatleh eee the lrkeAhYWaY\'b7 atlet a llttle Walk UP Ona Qeta Some \par ture of your preferred allylbenzene and stop. There is a very good teallY PU\'a4'e Phenylpropyl compound. And if Strike had Strike s way, \par ohanoe lhalwhal le lefl Will be a malorlly of what le Wahleo Strike would have that OH stuck right on the middle (beta) carbon \par of the species. Work could then progress on using that OH to get \par -l-he above soooeellon le] of course, ralhel. loroaol lllloel oeoole an amphetamine (Sobl Strike had so much about that subject that \par would prefer a more specific solution. Unfortunately Strike has Stuke was Pl`ePal`edtO Put lh thls backu\par one. For over half a year preceding this second edition Strike was _ \par pouring money and time into the realization of making an isopropyl Bur that_'s hOt the eeee- What the Kctean lab found Out Was that \par intermediate out of safrole using sulfuric acid (please don't ask). when thls PlOceuute ls Pe'tOhheu\'b7 the OH stablllzes cn the @@1 \par So Strike hires this Korean research lab to work out the synthesis. ca'hOh\'b7 Ther la the Oal`OOh r\'b79r\'b7r_\'a4e><r re the phenyl rrrrs- lt che has \par won, things didrrt work out forthe isopropyl mtormsdisrs, out it uio ehv use t\'b0r lt ee *5 theh that re the aut What re meet preferable re \par confirm the following procedure as a nifty way of isolating aIlyl\emdash re teuuce the OH re 9et the prepenvlberrzene (s_aY lscelemleln tat

\par henzeneo (Son olrl ohemloally our example). Using the simple potassium bisulfate reductron \par recipe, one can get rid of the OH with no problems at all. \par The literature states that if one uses ice cold, concentrated sulfuric \par aold oh a lermlhal alkehe la_l(_a_ allylhehzehel ah aloohol (OH) Hey! That really wasn't a lot of work. Just a lot of talk on Strike's \par intermediate will form \lquote MarkovnikovIy' on the secondary carbon Pau- All Ohe ulu was mlx an err Wlth eeme aclu\'b7 auuecl water end \par (ooh\'bbl aekl_ What does this meah? l_el\'b7a lake ah example. Say ohe isolated. One gets some pure propenylbenzene without distillation. \par has some elemi oil and wants that elemicin that is in it. What one DOhe Oh a hlass'Ye scalel thls 's a cheap n'leth\'b0u fer 9ettln9 lets qf \par can do is chill, say, 500mLs of the oil to freezing and do the same Smell cOhcentl'auOn ellvlbenzene ccmlccunds cut ef c\'b0n'lPleX cu \par for about 100-200mLs of concentrated sulfuric acid (at least 90% "n'Xes\'bb And Since Strike blew so much dough on this glorified ex\par conc.). Next, one just mixes the two together for about 5 mll~l_ tractlon protocol, someone better damn well use rt! (ln an aca\par What will happen is that the cold HZSO4 will make a hydrogen uelhlc lah ef c\'b0u'se)\'b7 \par - 5g - - 51 \emdash \par \par A much more forgiving yet limited extraction method can be used PHENYLACETONES \par to isolate phenol species such as eugenol and chavicol. You see \par farther back in this chapter where one can use dilute NaOH to re\par move eugenol from sassafras oil? Well, why not use it to isolate S r , . _ _ \par the damn things for further research. It works like a charm! Ogpggiesixvi/?;;1ii:?;'; %g:a;a$;;m;:\'a7ra;g?;Lu"\'a7'c d\'e9d th? Exact \par I r, wn ea an go soma \par There are probably other methods for purifying the products one eqgipminh 6 \'b0\'b0upl\'80 \'b0f \'b0h\'b0m'\'b0?ls and S\'b0m\'80 Safr\'b0|\'80\rquote 'S\'b0S?fr\'b0l\'80 \par wants. But as this book makes clear, Strike is no chemist in the an Ort gpreculisor Ofthglr chmc\'e9 They may Very WGH declde t\'b0 \par real sense of the word. Strike has no real idea of the true applica- d\'b0 wmethmg t\'b0 It to get It farther a|\'b0ng the path to mia] pr\'b0du\'b0t\'b7

\par tion of chemistry and takes a lot of guesses (why is Strike telling W\'b0"\'b7 currently \'b0" the place caued Earth the 'fwst \lquote\rdblquote 'd\'b0|Y made \par you this?). But on the Hive, Strike gave it a few stabs. Things like pr\'b0\'b0U"S\'b0r f\'b0" X and \'b7amph\'b0tam'"\'b0 p'\'b0$iu\'b0t'\'b0" 'S_th\'b0 Ph\'80nY|aC\'80\lquote \par recrystarrization (dom ask), partial sorubiiities iike what Oui, friend tone. For crystal meth the precursor is called just that; phen\par Eleusis proposed above, freezing, heating,freezing-and-heating in Ylacelons (ak-a\'b7 ph\'80"V|`2'p'\'b0pa"\'b0"\'80\'b7 a\'b7k\'b76\'b7 _P2P)- For X The \par a two solvent system, solid phase extraction and alternative forms p"\'b0\'b0u"S\'b0r w\'b0uld b\'b0_ called 3\'b74'M\'b0thYl9"\'b0d'\'b0XYPh\'80V\lquote Y'6\'b0\'80t\'b0"6 \par of chemical purification. Or one can use any of the above in com- (a\'b7lF\'b7a 3\'b74'M\'b0t?\lquote Vl\'b0"\'80d'\'b0XY\lquote Ph?"Vl\lquote 2\lquote Pr\'b0Pa\ {\lquote\'b0\ldblquote\'80\'b7 aka- MD\'b7P2P)\'b7 \par bination. All of these are ways that an industrious chemist may St"!k\'b0 k"\'b0\lquote\rdblquote S 't Sh\'b0Pld t?\'b0h""\'b0a"Y be written as MDP\'b72\'b7F\'b0- Put \par wish to further Study and ahhh) SO hit the hhraryr Braq Strike has always written it incorrectly as MD-P2P and that is just \par how stupid-ass Strike is always gonna refer to it. \par And now for the hardcore chemistry you've been waiting for... P O \par O \par \'b0 CUL \par MD-P2P P2P \par That double bonded oxygen (a.k.a. ketone) is very amenable to \par attack and replacement and is the ideal stepping stone to final \par product. There are a variety of methods to accomplish this inter\par mediate. Many of which Strike is now gonna lay on you! \par METHOD #1: Strike's sentimental favorite. The one Strike has \par dreamt about so very often. This method involves taking hydrogen \par peroxide and formic acid to form a temporary intermediate which \par is subsequently hydrolyzed with sulfuric acid ,to give the ever\par lovely ketone. \par \'b7 52 \'b7 - ss \par

\par This method is a little labor-intensive because it involves a lot of I \par distilling, but it ls so easy to do and the results are absolutely pre- The color of the solution will start off clear to pale yellow, then will \par dictablel The production of MD-P2P or P2P using this method has ttlrrt orangy as the dripping continues. After about zooml_e er ad\par been previously described [8,9] except that Strike is going to de- dltlon the chemist will notice that the temperature won't rise so \par scribe the little things. You know, those little bullshit things that much lf the dripping is increased. When addition is complete, the \par never seem to work their way into official accounts but always thermometer and separatory funnel are removed. A piece of foil is \par cause a lot of stress to the novice chemist. placed over the opening of the flask and the solution is allowed to \par stir overnight. The solution is reddish orange after the addition. \par O P O No more ice is added to the ice tray and the solution, as it stirs \par /\\ ovemight, will eventually come to room temperature as the last of \par g O the ice meltsaway. \par Formic acid/H20, O \par l-lzso, The next day comes and the hung-over chemist wakens to see a \par \\ dark red solution stirring away, In some cases where the chemist \par S f I MD-P2P had made an enormous batch of this stuff, there may be seen a \par a me small mass of crystalline precipitate at the bottom of the flask. \par a - \'b7S laced in a tra of ice On to a This is no big deal and will go away in the next step. If the chem\par Q ggtgtaigtgih\'e9fa\'e9k Q pwed 3409%, 30% hyd,O\'a7\'80,, lst had made this in a itathottoinetl tlask_(which she really should \par peroxide (H20; always store this chemical in the fridge or it will h\'a4Ve t\'a4l\lquote \'a20hVehtehCe) then the ice tray is removed, the flask re\par degrade over time) and 1500g of ttlmefi tothe Stir plete. a dlstlllatlon setup attached, and the ace\par 88% formic acid. The formic acid ,. \'b7 V! tone IS V\'a40UUlTl dletllled from the flask. After all the acetone has \par fumes are immensely overpowering come over the chemist can proceed in two different ways. One

\par when the stuff is being transferred to .' way IS to lust keep on dlstllling the solution untll all of the formic \par the flask but as the solution starts to t a acidhas been removed. The chemist knows that just about all the \par chill the formic won\rquote t evaporate so \'b7\lquote\'b7`\lquote\rquote r """"'*\'b7 \'a4\'b7\'b7' t\'a4FmlC here been Iremot/ed when there is about 300ml_ of tl-lick \par much and will barely be noticed. V black liquid remaining ln the reaction flask and hardly any clear \par 324g isosafrole (or 236g propenylIf one were to formic acid is dripping over into the collection flask.

\par benzene for meth) and \lquote lOOOmL / swirl the reaction flask, the liquid will appear syrupy and kind of \par acetone are mixed in a PP container coat the sides of the flask. This is more evident when the flask \par and then poured into a separatory cools. A quick sniff of the flask may indicate that some formic is \par funnel which is situated as shown in xi, Still lh there, but it Should be too minimal to be of any c\'a4nr;ern_ \par ggzlgj gdroprhsy i;\rquote ;?rt?1tC?c1tltgOrgOt<\'a7 \'a7 The problem with removing large amounts of formic acid by distil\par formic solution so that the ternperabatches can lation is that it takes a long time to do so. Really pig

\par ture stays between 10-20\'b0C. The take eh entire dey to distill. So a second optiorl [10] after removal \par temperature will start to rise a little t - \lquote \lquote\rquote\lquote\rquote of the aC9t0\'a4\'80 would be to cool the formic acld solution then ex\par but the ice bath is well stocked and tract the Wh0|e thing with ether. The black ether layer IS then \par the dripping is controlled so that the . washed with an ice cold 5% sodium carbonate (Na2COe) solution \par temperature stays below 20\'b0C [Figure 9] to heutreltze any formic acid that was carried over, then washed \par - 54 - - 55 \par \par once with clean water. The ether is distilled off to give a black Tachnlcallvl ll lhs chemlsl wanted to do lhlhgs by the book, sha

\par heavy mess just as would have been attained by removal Of fer, would extract the whole HZSO4/oil solution with ether, then wash \par mic acid by distillation except that it was done in a fraction ofthe the alltel wth Walai $\'a4 the \'a4ll lwhiqh is now MD-P2P, by the \par time. One thing to add about this alternative is that it does not al- Wal') ls llallsfsllsd Y0 a small flask U$ll7Q_\'80th\'80l\rquote and vacuum dis\par vvevs work for evervbedv There een he seme heevv emulsiehs tllled (The Oll IS still very black vlnth contaminants which need to be \par and, sometimes, the product forms some weird, heavy ball of tar. f\'80l`l'l9l\{\'80dl- Aflal all the Ether and water have Game OVGF and the \par This is best tried under strict adult supervision. But it may not all fecelvlllls flask has _l3\'80$h Tschalrgsd Wllh a Glaah, new One, it may \par bg bggl_ The following is 3 l-live post by \lquote Ql_lirk5' letting pegplg seem l S all 6 9l`lll Y OT 6 Ol IQ QGI hOt enough to come OV\'80l"_ \par know what the goods are regarding a successful (Strike guesses) Sgt- evenluall\'e9l lhts algal vallgw \'b0ll fl`\'b0lllbWlll slal'f Clsaplhg up the \par etherexheeh ssware an lno e con enser. A out 250g (60%-70\lquote V) of \par l\\lllD-P2P will come over. The chemist knows its time to stopndis\par "lf you netralize the formic acid mix with 25% NaOH the layers lllllllg when the Oll flow Stalls to gel a lmle \'b0lall9V\'b7 \par separate out nicely. lt takes ~. 75 I of 25% NaOH to neutralize the -I-h _ . . . , \par $8,8 88, 8589,8. 88% lamlc. 88 youll need 8. big Sep8ttn tunnel. 8,,5 2\'a2'i\}.E\'a7E8i\'a7?,?lZi?8l\lquote 8\'b0l$;?8t,'i\ldblquote\'a3sll\lquote ilZ.8a"\lquote l 'S S\ldblquote 'lal"\'b0 '\'b0' "\lquote \par After you hit ph 4.5 add it very carefully cause itll run away to 9+ p ' \par real quick. You can then back extract the water with DCM, or l *,,,,HOT TIP #1*,,,, \par guess preferably ether lf you use too much DCM when extracting \par gnzngs Z/\'b0itl;l?hl;);f$gly;_;d Sgggihzfcgcflggigfegnewi\'e9hpvni? 5;% Distillation is always the most reliable way of separating things \par hd egeke in H/egelecnvines _p,, V \lquote\'b7 from complex mixtures such as relieving our P2P from its annoy\par p \'b7 lng black contaminants just like what was done above. But \par _ . . . . . wouldn\rquote t it be nice if there was another way to do it for those with\par &;lli);n"l\rquote ;"nlQ\'b7 gl;\'b0h;l;l$|;l\'a7f lslgtlglz? gebesbielfggiegnei gliigeilgrgng out a distillation apparatus or who just didn't have the time to dis-

\par D . \lquote . . p . till'? Well, there actually is such a way, and it works fabulously! \par 2500mL 15A sulfuric acid solution. lf the chemist does not have a \par big enough flask the stuff will need to be halved or thirded and Fer years chemists heve been hem . . . \par . . . . g sodium blsulllte (that IS \par l\'b0'\'b0\'b0\'b0SS\'b0\'b0l lll ba*\'b0l\lquote\'b0$\'b7 AS $\'b0\'b0\ldblquote as lhs S'\'b7llfl\rdblquote '\'b0 _s\'b0lllll\'b0ll lllls lhs BISULFITE not BISULFATE) to actually crystallize a ketone out of \par methanol/product (oxlme) layer the heavy black oll wllllform beads solution ih Order te seperate h Ae it se heepene Our nee lime \par and sink to the bottom. The solution itself will get kind of milky MD_p2P is e ketehe And when en eu mixturel eenteinhlg it ie \par and llazlh , NOW all llle \'b0ll\'80l\ldblquote lSl "l\'b0\'b0s ls slap 3 \'b0\'b0ll\'b0l\'80lls\'b0l llll\'b0.lh\'b0 mixed with a saturated solution of sodium bisultite (Mal-ls03) the \par tlaskjust like fig. 7a and reflux for three hours. After such time, MD_F,2P erystemzes out es e Usumte eddmen reduet, It een \par the solution is allowed to cool down to room temperature. Now, in then be eesih, seperated hy hlhetien Here,e h W np eee \lquote \par large batches like this and those that are even larger than this ' \'b0 g \par one, itsjust not feasible to extract all that liquid with solvent to re- vvheh the MD_P2Fveree eu hes been ieeleted end is et the eeint \par glolf Egl U2: \'b0'lneJll$lt\lquote iljbe\'b0l\'a7n?llEl\ldblquote ;ul;;linglf;lQl;nl;lel1l\ldblquote ;fli$1l;\'b0:Ile$;rf;; where one would nomlally apply distillation, this is the point where \par as ;bI \'b0 dee': fm'; 'E SUP deems the Water adds new the chemist Will use the bisultite. one should not tty this method \par l\'b0\'b0s;l \'b0\'b7ta i lf\'b0STnWf\rquote l \'b0f\'b7 SnlS\'b7 ef eve eheuld \'e9emeve en unless the oil is rid of most solvent. In the Method #1 above. one \par rss WZ; \'a7l'egCv. ft. 2:9 visas lhgs W T Y would apply it after the ether from the final eXtraCti0l\rdblquote l has b\'80\'80Vl \par l'6\'b0\'b0$\'b0 = 4 6 "\rdblquote \'b0\'b0l- removed by boiling OT distillation (Yes, some distillation still ap\par _ _ \lquote ' \par \par . , Strike will let you know when it chemist felt that it may have been due to the solvent solvating out

\par pges\'e9g Qrgrgr\'e9e methods to come the isosafrole which gave the P2P a chance to form more clystals \par c n \par 2P/ oil, ri ht? Right. Next one makesa Strike. sees a point to this in Vogel's ltext \lquote Practical Organic \par Anywiyidongdlssttggtllnte Cstilztion bg dissolving as much sodium Chemlstry\rquote (3"\rquote ed.)[37]. In lt, Vogel crystalllzes his ketones using a \par STM"? Q Swill dissolve in a given amount of water (Say. iOOOm_i\emdash l\'b7 saturated Sodium bisulfite solution that a/sor contains a little Sol\par bisulfite as dds the |\\/lD-P2P oil into some of the saturated s<>l\'a4t\'b7\'a4\'a4 vent. This is in contrast to the straight up aqueous (only water) \par NOW OPS at 30 minutes. The temperature of the reepripp will rise solution that Strike described above. Here is what Vogel Said on \par 222 gg; old mass of P2P crystals will form. People often say that page 342: \par \lquote h' k fat. Those crystals formed because l I \par the ciysliiis loglrrililhi (sdgiti: bisulfite Iatched onto the ketone of \lquote Prepare a saturated solution of sodium bisullite at the laboratory \par the bg; i Bforrm a precipitate. And since the P2P is pmbably the temperature from 409 of finely powdered sodium bisu/pnite; about \par the P .l \'b0 ment with E ketone, it is gonna be the only thing of 70m/. of water are required. Measure the volume of the resulting \par only Oi comznee that crystallizes. Solution and treat it with 70 per cent. of its volume of rectined Spirit \par any pppspqu _ ft (or methylated spirit) [ethanol or methanol or both, dude] ; add \par _ . t I d the crystals ofthe P2P\emdash _blSul l e sunicient water (about 45mL.) to just dissolve the precipitate which \par Z\'a7\'a7l\'a7\lquote\'a7i\ldblquote\lquote i\rquote\'a7.li.\'a7i\}Zt\'b02.\'a7 iiiflepaaa by t\'b7\'b7eg\'a4\'a4\'bb \par \'b7 \'b7 l dH2O then washed with a couple un\par Washed [libc? ISE; EESCM O,. benzgng The filter cake of Either pure aqueous or aqueous/solvent solutions work. lt is en\par dr9dP2nl; liisulfate is processed by scraping the crystals into a tirely up to the preference of the chemist as to which one they use. \par MD- cl then 300mL of either 20% sodium carbonate solution or Just to make one feel more secure, there is a little test one can do

\par Hark artll Iution are added (HCI works best). The Solutlen ie with the bisulfite solution to see if they got it right. Just put a little \par 19/\'b0 H fso another so minutes during Whioh time the of that ketone known as acetone into the saturated solution and \par \'a7ig?2P-lgigultite COl'Tlpl\'80X will be busted up and the P2? WlllhI\rquote\'80\'b7\'b7 Watch the grygtalg gl\'b70w_ |5n\rquote t it mcg how chemistry WO;-KS?] \par - \'b7 \lquote . Th P2P is then taken up with et er, \par turn to '\'a7\lquote hapglyegigcmg Solvinl to give pure MD-PZP. Whaddya Now then, there are some chemists that rely on bisulfite as a tool \par dread anh rg? to physically separate all of their ketone from an oil mix. But some \par think \'b0rt a " _ H chemists, using some methods, are rightfully sure enough that \par . l\'b7 dt ost P2P mixes but is espeola y their ketones were produced in such high yields, and so cleanly, \par This Pmcedlillii;tE\'a7t~?spi)o|$0lIc?wrTiHoweVer. in euper \'b0l\'b0ar\lquote _ men" that Separation isn\rquote t necessary at all. But even they, like anyone \par Effective En the PdCI2 below, where lotS of ieeearrple 'S Pr\'b0' elSe. Would Still like to know for sure that what they made was \par ods, Suih aio b peduct can interfere with CrY$ral f\'a4rmat\'b7\'a4\'a4- P2P. This bisulfite procedure works in this regard as well, lf one \par duCEd` $A;li,0-lS-i/xii;t-stnke once found that when an appreciable Wants to know if what they made is P2P all one has to do is just \par S\'b0r"\'b0\'b0"e\\Q. afmle was formed to the detriment of MD-p2F\lquote . the drop a mL or so into the saturated bisulfite solution and see what \par aiiioglgvgeclsigg the crystal matrix disallowing it to tonn- C\'b0nrU$\'b0\'b0r\'b7 happens. lf crystals form, one has ketone, it not, one nee fucked \par 'ilteschemist tried to rescue the uncrystalliged trail from va\'e9l\'e9lreolug up. \par - \'b7 `l t t ot er ings. \par Solumli bytigrggilitgslsuihtgepgp gryg\'a4iiiZed Our- Gp rigure? The 0ne can even use this test as a quantitative measure, The chem\par S\'b0lV\'80" hn ' ist can weigh 5g or so of their P2P product, crystallize it and weigh \par - 58 - \'b7 59 \'b7 \par \par the subsequent P2P oil that results to get an idea of how much of \par their product is honey, and how much is not. Get it?! As Strike

\par hopes you can see, this simple sodium bisulfite tool has an enor- /\\g \par mous amount of potential for helping the evil chemist out. O \par One final thought. Strike found that there are a lot of companies /\\O O \par that do not sell sodium bisulfite (NaHSO3). ln fact, a lot of compa- _ t \par nies list \lquote sodium bisulfite' in their catalogs but tell the reader to see O / MD_P2P \par \lquote sodium metabisulfite\rquote instead because that is the only form of this \par compound they carry. ln other words, a lot of companies sell so- \\ \par dium metabisulfite (Na2S2O5) as an acceptable alternative to the \\ /\\O \par other. The Merck Index even says about sodium bisulfite that \ldblquote the Saiioie O \par [sodium] bisuliite of commerce consists chiefly of sodium metabi\par sulfite, Na2S2O5, and for all practical purposes possesses the \par same properties as the true bisulfite". What this meant to Strike / \par was that metabisulfite would work just as well. So some was pur- Isosafmlg \par chased and tried. And it really does workjust the same! _ \par The reaction proceeds via the above schematic. And as one can \par METHOD #2: Without a doubt, this is the current world favorite for $69 in the above schematic, the major Side product Of the reaction \par making P2Ps. This method is known as the Wacker oxidation and is nai tal 0F junk but is the very useable isosafrole This is `ugt \par involves mixing safrole (or any other allylbenzene), palladium another illustration of the desire ofthe safrole double bond tojmi\par chloride, cuprous chloride and dimethylformamide in an oxygen Qiaie to iiia is\'a4s\'a4fr\'a4le l\'a40Siii0n When given the chance The cu\par atmosphere to get MD-P2P very quickly and in a totally clean PVDUS \'a4i'\bullet i0Fida (cuci) and 0XVQ\'80\'a4 ale there to promote and kee \par manner [11, 12]. There\rquote s also a very nice review in ref. #13. tha F\rquote dC|2 in 3 +2 state (don't ask). There are two different a ag \par ratusl setups that a chemist can use to complete this recipep\'a7e\emdash \par Strike ranked it #3 in the Top Ten from the first edition because Pending on tha aquipment available. Figure 10a shows a setu \par Strike didn\rquote t think people would bite at the idea of using such an Using a ihfaa-neck flask and figure 10b shows how the sam;

\par expensive catalyst as PdCl2. Street chemists are often tightassed System can be attained using a single neck flask. Also one can \par when that is the last thing they should be when it comes to pro- USG. the single neck flask by placing the Claisen adapter from \par duction. But this has not been the case with this procedure as \'b0'\rdblquote 'aS distillation set into the flasks heck \par Strike has happily found out. At $7.00-$9.00lg. PdCl2 is still pretty \par pricey but this has not been a deterrent as many chemists have N\'b0 iiiauei which iiask is used, ai" addiiian iiinnai is Faquifad An \par found. Nor should it be. This procedure works so well that it would, add'i'\'b0" iuiinai is liiai iika a Sal>afai0ry funnel except there is an \par in fact, be stupid not to do it should one happen to work in an ae- extra side arm that allows for addition into a system that has pres\par credited, licensed research lab. The following is what Strike first Siiia (which this one is going to have). Strike knows: Strike \par wrote about it. k\ldblquote\'b0W$i Pressure S\'a4\'a4n\'a4s Complicated but this one isn't. You'll \par see. The addition funnel can be bought, made from a separatcry \par funnel as explained in the How to Make section of this book, or \par - 60 - - 61 \par \par _ DMF is a common, legal solvent. lf a three-neck flask is bein \par een be made entir\'e9iy fF\'a4m scratch as s\ldblquote 99\'b0$t\'b0d \ldblquote " th\'b0 same s\'b0\'b0` used then the openings on top of the addition funnel and the un? \par tion. used neck of the flask are plugged with stoppers and the stoppers \par , . secured in place with wire or strong tape. Vihth everythin all set \par The pressure is going to \'a2\'a4m\'80 fr\'a4r\'a4 \'b0?\lquote V9\'b0" that 'S apt;:'\'b0d':\'b0n:?\'a7 the chemist fills up a balloon with oxygen, pinches it cloged with \par eystem using a ba||00lj\'b7 Pure \'b0XY9\'b0't '$ easy t\'b0 9\'b0t\'b7 T \'b0 \'b0 6 n her fingers, wraps the end over whichever opening is appropriate \par can get it from the n6\'a49hb\'a4Vh\'b0\'b0d $F\rquote\'b0\'b0'attY gas \'b0yt'"d8r \'b0\'b0mp;cy and releases. This setup can look pretty cool depending on what \par er ehe can plovn through T6 Qgazmgg gggg atggg :\lquote ;5\'e9\'a7:?g?hE: kind of balloon the chemist chose. Maybe one of the three foot \par ersona us o . \'b7 - \'b7 - - \'b7

\par Eggdgg fil ?IrgiJI'tBpOf those thick walled camival balloons that can Smptlcal kmd \'b0r me wml a ducky pnntcd \'b0" It \par be bought at anytvy store- Anyway, all that pure oxygen has infiltrated every part of the en\par V _,_ \'a7_ closed system and the solution in the reaction flask is allowed to \par stir, exposed to all that oxygen for 1 hour. At first the solution is \par Q brownish black, but as it absorbs the oxygen over that hour-'s time \par it will turn an olive green. After 1hr it's time for the chemist to add \par \'b7\lquote r if ,l the safrole slowly over a 30min period. As the safrole is being \par / added it will start to take up all that oxygen causing the palladium \par ____ _ to turn black again (shows that things are working) but after the \par _' \rquote "" _ addition is complete and the safrole has been converted to \par L z= = MD-P2P the palladium will again start to soak up the remaining \par nin jg, i oxygen and turn green once again. The solution remains stirring at \par "*\'a5 _ `\'80"j" T room temperature for 16-24 hours. lf the balloon loses significant \par ( T _ t e\'b7`\emdash\lquote " , volume during the reaction, one just fills it up again. Nothing bad \par it ~ w _ J will happen. \par \lquote L The next dey the chemist takes a PP container of 1500mL cold 3N \par _ _ HCI out of the fridge and pours the contents of the reaction flask \par _ into it. The mixture is stirred a little and extracted 3 times with \par \lquote\lquote\lquote\rquote 'U 100mL portions of either DCM or ether. The one thing that needs \par to be added here is that the DCM extract needs to be washed 2 to

\par 3 times with water. Many bees have reported that this re\par _ [Fig 10b] duces/prevents an emulsion from happening in the next step. The \par [F'9 ma] solvent is then washed with 200mL saturated sodium bicarbonate \par _ . . \'b7 _ (Na CO, 2 solution then with 200mL saturated NaCl solution. \par The td\'b0a 'S t\'b0 have Bv\'e9rythtng- In rt;IaCZgzfonefglni,;x;?\'a7net?rr?:g Tecttnicatllgi the washings can be skipped, but either way the sol\par Pt'E\lquote\'b7d\'b7 SP- 1009 \'b0f $afr\'b0I\'b0 Is In t 6; If Opdcl 609 Cuci and vent is going to be dried through sodium sulfate in filter paper and

\par atm-"td '" the t\'b0a\'b0t'\'b0." flask are 1Q' g O d b2' mixing G2 5m|_ the sodium sulfate washed with a little extra solvent just as is de\par 50OmL \'b0t aqu\'b0\'b0us dlmethylformawl? (ma 56 \'a5DM|:) is nnt the scribed in the methodology section of this fine book. The solvent \par UHPO andt:;7\'a3;:;\lquote h5gM;kBr3;;?tkzO$T;? N_mBtny|fnnnam;dE_ is then removed by distillation leaving what should amount to \par same as \par - 62 \emdash 63 \par \par about 70-80% MD-P2P and 20-30% isosafrole oils still left in the it usth . _ \par distilling flask, Weye tt?) eizziigehgeile xeteggfii titlzaref eia, tleen there are \par that us- \emdash _ \'b7 ten emonstrated \par Oh boy! Here's another case where there is a couple of similar [12]. Tenetgttliignsngbeqngoqttleeeet \'b0an_a\'b0\'b0\'b0inPiiSh the $\'a4metl1ii\rquote iQ \par ooiiing oils that the poor chemist is going to Want t\'a4 Sepafate- and quinone stirrin inetna he\'b7mgred|ems\rquote teetuetttg the $ati'\'b0ie \par Again Strike is going to say that the best way to do this without was mixed with thegDMF e reaction tteek \'b0\rquote $\'b0ePt t\'a4r the water that \par tangy soparation columns is going to be to \'a4ll\'a4W that the filet is placed in the additio I \{That Water Is going te be the thin9 that \par 5-1grn|_s or oil that distills over is going to be mostiy iS0S\'a4tf\'a4ie and Another oxygen soot n umel and added te the 'ea\'b0tt\'b0n mix\par the rest of the clear oil that comes over is going to be the ti4]_ -i-his pmceduretcedcen ee that et 30% hydrogen Peroxide \par MD-P2P. Strike has never been a believer in predicting the pre- that the aqueous DM; .\'b0tte \'b0Xa\'b0tl_Y as the ie9\'a4i\'a4f method except \par cise temperatures that something comes over at relative to the stead Ot ptath dH O te made wtth 30% hYdf\'b09e\'a4 Daroxide in\par pull of vacuum or the size of the distillation apparatus. It varies 2 ' \par too much and is never applicable to any given circumstance. - . \par Strike knows three things in instances like this; 1) solvent always gtttgr tttieegtsgeiieeththis procedure een make it Even m\'a4re Ver\par comes over first at low temperatures and in a very rapid manner, mh the entire ree t, at 24hr stlfan Ot incubation/stirring ono ooh

\par 2) the isosafrole starts to slowly roll over at about 170\'b0C at regular -t-he reaction nee; tt)? at 60'7O C from the beginning of addition \par vacuum (who the hell knows what that is?), 3) after about a 3-5 te that a three eketty \'a4'\'b0\'b0ee<\'a4i tat about 3 hours. The downside \par degree increase in temperature (usually no increase is noticeable) memeter end ree \lquote\rdblquote 'il have t\'b0 be used to accommodate a tho,. \par or, more importantly, after about 5-10mLs of oil has collected then usthg eu tie em eetteetteet At-tether Switch can be made bY \par it's time to switch flasks and start to collect what is assumed to be Beth were e tert e (Ouch) instead of Cuprous chloride (CoCi)_ \par the MD\emdash P2P. In the end, the chemist should just follow her nose. ttnete the rgge tttftett exeettt that CttCi2 has a i\'a4\'a4\'a4\'a4\'a4\'a4v t\'a4 \'a4i\rdblquote il\'a4\par Does the first few mLs of oil smell strongly of licorice? Does all the et these gte ue. S tgt'tty\lquote Strike has Since learned that ani! and all \par rest of the oil not? Strike cannot answer this either. The isosa- che ter f Ittttit Wes \lquote\rdblquote\'b0'k _\lquote\rdblquote eiii Keep reading farther down tho \par frole fraction will smell like licorice but MD-P2P always smells dif- p et tt t e g\'b0\'b0ds On 'ti \par ferent relative to the type of reaction it is borne from. Pure SO an we th t _ \par MD-P2P doesnt have that strong a smell and can usually be pee tethgh e wee what etttkemid eVe"Vb\'b0dY in the first edition, \par overpowered by impurities that will always carry over with it from eettr? ebee tat) with the ieee and eame up With $0me Vei'V inter\par the reaction it came from. So MD-P2P that comes from a reaction aeceght Ot tttyetgzttg et thett \'b0W" e'"\'b0\'b0 then- The t\'b0li\'a4Win9 is an \par using formic acid or mercury compounds is going to smell a little From what SEK K 2 m\'b0th\'b0d Contributed by our good friend TDK \par differently than one that came from a reaction using palladium. pttehed cer ttl e dtt\'b0We.\'b0t TDK eheeeems t\'b0 be a Veil! accom\par However, the distinction between isosafrole/safrole and MD-P2P get et eee E tt Sn lntutttve Chemist in het Own 'i9iit\'bb N\'a4ti`ii\'a49 ille\par is quite evident. In the end, a little of one in the other is not going methedel t.e\lquote ut she always Seems t\'b0 be \'b0\'b0inin9 GGYOSS evil \par te hurt ththee much ogies that others produce. \par `Of course the chemist may wish to forego purification and separa- J geegtefted my Sisters friend and went over to her compound for

\par tion of the two remaining oils by distillation and opt for the sodium edueeg e elrun down On what She dreemf". Her dream was of an \par bisulfite procedure described earlier. That particular method is het th tene nature and SO Shetlld the fo//owing be construed os \par perfectly suited for this situation. Perfectly. J e \par 64 The Wacker Oxidation a.k.a. #3 of 10 (most fool proof of the lot) \par . 65 \par \par CuCl added. Insert the claisen head adapter into the flask. Be \par _ _ . . . -- T MOST BASIC sure to apply some vac-grease to the joints. Place the addition \par The f\'a4/i\'a4Wi\'a4\'a4 T her \rquote "\lquote $Z;Zr;t;?\'e9\rquote ;;p;;;;ggZed to IS funnel in the center hole. Add the 500 grams of safrole to the fun\par FORM fer the eymen ' nel but don't start adding it to the stirring solution. Next Hll the \par - - \'b7 __ Al , t d are balloon up with O,. She said that she hlled it up pretty tight, but \par First Shi.\rdblquote Sfaz7;t;ggg7z1;n\'a7r;\'a7,;!g?; giagfg\'e9sup. SO no S don't blow it up. Carefully attach the balloon to the remaining \par the bee 5 q open hole on the claisen adapter and then TAPE or wire it to pre\par _ 5 I _ vent any leakage. For those of you that don't have access to vari\par EqU'Pme\rdblquote t fer X See e\lquote ous pieces of glassware, placing the balloon on the addition funnel \par Ph One Equipmenl will work as well. This was described in the book Total Synthesis, \par ase \par a-liter not bottom riosk (single 24/40 nook) Pages 52 *0 55\par 1 claie\'e9n heed adlepter/(egitcg) You let the solution stir for 1-1/2 hours so it absorbs as much O2 \par 7 1-li\'a2\'a4ta<?d**\rquote\'a4\'a4 "me ( as possible before you start adding the safrole. Everything is kept \par 7 Te'7\'b0"\rquote St" bar at room temperature for this procedure. The stirring solution looks \par 7 h\'80e"V d\rdblquote tV eel/i\'b0" very dark, almost black in colon Now slowly add the safrole from \par 7 mu eeeleetncal ape the addition funnel so that it takes about 60 minutes for the 500 \par Ma9\rdblquote et'\'b0 stiffer I grams to drip in. There is no noticeable reaction as the safmle is

\par Suppen etend end C alrps dripped into the stirring solution. Once this is completed let it stir \par OheU$_""p/e beam See e away for the next 24 hours. Note: ln her dream, she checks the \par 7P7eS7\rquote e funnel balloon at the 12\emdash hour mark. lt has gone down in size as O2 is \par _ T t I S thssis being absorbed by the stirring solution. She inf/ated another bal\par Phase O\rdblquote\'b0 x ex eeeleup 0 a yn lcon, removed the one that had been on there for the past 12 \par chems 500 rams 100 grams hours and placed the new full balloon on the open hole. Tape or \par safmle .0 53 slams 106 grams wire it so there's no leakage. This ensures an adequate O2 at\par Pe//ed'\rdblquote m Ch/en e 3009 rams 60 grams mosphere while the process hnishes (excessive, yes, but cheap \par Cuprous Ch/Onde 218795 mLs 437.5 mLs and simply). She noted that after 3-4 hours of stirring the solution \par DW 312 mLs 62.5mLs changes from a dark almost black color to a dark sea green or \par D/Stlli\'e9d H20 \lquote dark olive green in colon \par 1 cy/ihd\'e9f of DWG Oz After 24 hours, the stirring is stopped. Now it's time to 17/ter out the \par O T ma 800 are Cuprous Chloride, which is one of the two slight nuisances re\par The ebeve reagents (ek me eafroleriyndrll-gk isefszleurelygclamped Qardihg this Procedure. Note: forget about Palladium Chloride \par weighed Or measured 5\'b0\'b0F\rquote rd'5'gIyi e e F d H O Start recovery lt's too complex for the simplicity of this procedure and \par into place on the niagiietiez\'e9kstgen giddy; 22700;; ang \'e9upmus purchased from a photo supplier it shouldn't cost more than $6. 50 \par t" . dihS\'a4S0WVa ep . . . .W'll llth' t Ph T . \par 2/Zgggglazf you add the powdgrs mst than the liquids you H have per gram e ca is nex process ase wo \par problems with the stir bar finding a place to SPIFV- Phase Two - Equnnment (Vac tiltering) \par _ _ . Vacuum pump \par Now you have the DMF and H20 stirnng away with the PdCl2 and \par - 67 \par - 66 \par

\par Vacuum-Trap set-up The extracts are oo/ed. Wash onc ' \par Buchner funnel $0dium bicerbvh\'e9iie. This washing Eiswahbqsgljglyrrzgggeioluhorihof \par Whatman Hlter paper book says it can be skipped \emdash DON'TO The prob/em witiialiif (E \par 14-liter nltenng flask (Heavy Walled) ihis is the other nuisance of this process) is they e Scugfand \par Support stands and clamps emulsion develop from the wash neutralizing the acidic naturgnci \par the extraction. The easiest way to deal with is to vac-filter th; \par Phase Two - Chems mess. Your rid yourself of the scum and breakup the emuls'o \par 3N HCl Book calls for 1500 mLs, on the 5x scale up she used into a fairly easy to separate liquid. One washing with sodiumlbp \par 3000 mLs \'b7 H carbonate is sufhcient, then wash once with a saturated solution of \par Silica sand (white, sterilized and washed) or sodium chloride, then once with fresh H20. Now the extract i \par Celite dried with sodium sulfate. Your are ready for vacuum distillations \par Methylene Chloride The DCM extraction should be golden to dark brown in color U \par There are two ways one can try to filter this solution before acidifi- Phase Three Equipment (Vae distillation) \par cation. First, set-up your vac-t7/ter tlask with vac-trap, Buchner Vacuum pump \par funnel & vac source and start the littering process. A 5x scale up Vacuum- Trap set-up \par will take about 6-8 hours to filter The cuprous chloride is in sus- Heat Mantle with heat controller \par pension and it almost completely clogs the hlter paper making the Or hot plate with oil bath \par process painfully slow. She found a method that works fairly well 1 3-liter boiling flask (round or flat bottom) \par and reduces the Hlter time to about an hour Set-up your 3-way adapter (still head) 24/40 \par vac-littering as usual, moisten the litter paper with a little H20, then 1 West condenser \par pgur a % inch thick layer of sterilized and washed white silica sand Vacuum a\'a4ial\'a4fen\lquote Condenser to receiving flask (24/40) \par on the filter paper. Moisten the sand with a small amount of H2O. 1 1-iiferreunci OT fiat flask (used for receiving ketone) \par Apply the vacuum to the set-up and then start pouring the solution 7 Thermometer adapter (24/40)

\par right into the sand. The sand will keep the cuprous chloride from 1 thermometer-10 to 400 C \par totally clogging the paper up. Celite can be used in place of the Tubing for waterin/out \par sand. Celite is a 'tilter aid' is available wherever tine chemicals are Misc fittings to hook water lines up \par sold. /t's a standard and unwatched laboratory item. Celite works Aluminum foil (to wrap flask & still head-insulation) \par in a similar fashion as the sand. White silica sand is readily avail- Support stands & clamps \par able without having to deal with a chem/lab supplier Place the \par hltered liquid into a PP container and add the appropriate amount \ldblquote ""\lquote **************\lquote **** \par of 3N HCl. She stirred it with a wooden paddle for a few minutes. \par The solution is ready for extraction. ln her hrst dream she used Phase Two \emdash Chems \par DCM and broke it into 4 extractions of about 1500 mLs each (she Washed & dried DCM extractions \par had a 2-liter separatory funnel). Since DCM goes to the bottom, a \par ggparafgry furmgl ig 3 must Buy gr mgkg Ong The gxfragfigng Set-up for VECdiSiiiiaflOfl. Si`lE' Wraps the flask and Stiii head with \par Shgufd gg wjfhgut any prOb[gmSl as [hgrg [Sn? any gmufgjgns [O 6/Uf77II7Uf77 foil to act BS BU iflSUia[OlZ Speeds up HTG diSti\rdblquote 3tiOn \par cgnfend w/[h_ Shg used 100 mLS Of DCM fgr gggh gxfracffgn PTOCGSS. B\'e9gifl to hS8f HIS DCM extraction slowly UI7d6'T maximum \par - 68 - - 69 \par \par vacuum. Her vac\emdash pump would only pull 100mm Hg, so the temp at color of the reaction after 72 hours was a richen darker green and \par which product hrst started coming over was 198-200 C (approx 60 the hnal yield was 362 grams ketone 72.4%, 51 grams isosafrole \par g,-ams Or isgggfmle - 12%), then again at 204 C. (*yiS/d of k6\lquote f\'a406\lquote VO2%\} N0! bed for very little work and it is very dif/TCU/( \{O Screw \par was 308 grams 61.6% + ). The plus being residue that could not this up! Once the safrole is added, you can forget about it until it's \par be distilled as there was not a small enough flask to hnish the drs- time to check the balloon." \par tillation. DO NOTrun the larger flask close to dry lf you do, upon

\par cooling the residue will carbonize and push black crap through the Note TDK's appalling pronoun use. Actually, niether TDK nor \par condenser and into your clean, yellow ketone. Or worst yet, rt will- Strike can be held accountable because this was written by \par expand so rapidly that the carbonized mass will cause the flask to someone else who addresses the audience in a normal way. That \par push away from the condenser and possibly break a valuable aside, look what happened in that account. Seems like the tradi\par piece of glassware. Vl/hen you get to 1/4\rdblquote of material to be dis- tional. reagent proportions of PdCl2 and others may have been \par lilled it's time to stop. Either save to pool with other similar mate- overkill. Given enough time to react, very small amounts of PdCl, \par rials' for future distillations or use the bisulhte procedure to can do the Job just fine. That certainly makes a difference ln one\rquote s \par separate and purify. This was explained from experience; she ran wallet! \par it close to dry and had the worse happen. Black crap shooting \par through the condenser into 330 grams of clean ketone. Two dis- The next example was a post on the Hive by a bee named TaRa \par tillations did completely rid it of the discoloration or smell. (Could be an alias of TDK. Strike ain't sure.). It is essentially the \par same old song except this girl proved that CuCl; (cupric chloride) \par *\lquote /ield; isosafrole, 60 grams (12%) TOTAL-MDP2P, 338 grams can indeed be used in place of CuCl (cuprous chloride). lt also \par fb`7. 6%) The smaller portion was distilled in a 500 mL flask and gives you more examples of technique. The more of this one has \par yielded another 30 grams. Total yield 79.6%/ 67.6% (MDP2P) + the more confident they will be in their \lquote understanding\rquote of the \par 12% (ISOSAFROLE). method. \par The above dream was scaled up irr46>\{\'a4\'a4F P0FU0\rquote 1S\'b7 as lt Was hel "lnteresting results for something that was thought to be a lost \par mst Her next dream had SOITIS Vaflat/005 tv W\'80"9ms md mB\lquote\'b0S' cause [Lost Cause'?!]. Dreamt about using CuCl2 for process #3 \par ures, plus a longer reaction time... as fo//OWS', \par Noted are the changes to the above dream: ln this dream the book writer's chapter began like thr's - lt took 800 \par Phase One - Chems g lsaf \{4 g PdCl2, 240 g CuCl2, 3500 mls DMF + 500 mls H20,

\par Safro/es 500 grams (same) stirred rn O2 atmosphere with balloon for 96 hours in a 3-neck 12 \par Palladium Chloride.\'b7 26.5 grams (50% less & big saving in $$) liter flaslq yield was 6977%, (distilled did bisulfite and then re\par Cuprous Chloride\} 300 grams (could have cut this to 200 g) distilled the oil from the bisullite procedure).. Note better lab tech\par DMF (n,n-dimethylformamide): 1500 mLs (31% reduction) niques would. get better yield. Materials lost in washing and Nitra\par Distilled H2O: 300 mLs tion, punfrcatron disti/ling,. etc... This chapter followed the book's \par 1 cylinder of pure O2 (TS) outline, but a few simple variations were applied. To elimi\par nate the nasty emulsion from the sodium bicarbonate wash they \par Do everything else the same except; let the solution stir in the O2 washed the initial solvent extracts (right after acidihcation) 3x with \par atmosphere for 72 hours. You'll need to check the balloon every H2Ol\'a7 Used DCM as extract solvent. Removed a good deal of \par 12 hours or so. Replace as needed (when it starts to sag). The CuCl2+ some PdCl, with those H20 washes. Note, don't know rf \par . 70 - - 71 \par \par this helped but they dissolved the catalysts in 400 mls of DMF + funnel was coupled to the flaslg a \par 100 mls of H2O before they were added to the vessel. The cata- rr'rd rr Thermometer Was attached l\rquote :s?\'a2;\'b7/tzlbghgr Wits mgasured \par Iysts remained dissolved for the complete rxn' Maintained as \'b0r hzd Wee eddad temp went to 70c.Brisk stir rate\rdblquote 75mt?' One ml \par much pressure as the balloon would hold as they feed the flask 8li0lhaf ml of /120 added. External heat if needed is u mm Bt and \par directly from the O2 cylinders putting the balloon on the top open- another ml was added, and temp heldlat 70c at 2\lquote 30i?1d' dr 1:00 \par ing of the addition funnel. Used a ground glass 3-way joint with a was added, and there should be a trace left but ok. if 't gtnnal ml \par hose from the regulator to feed O2 into the system. Was easily at 70c for 30 more minutes, allowed to cool to room tl am nmhgld \par able to keep flask as full as possible with O2. BTIM balloons will ~ W/ chilled h2o, and extracted w/ startin gms, flooded

\par burst when filled beyond capacity and it will give you a rush that's Q) ---- BOOOOOM! yield- over 70% \'b7\'b7 g U, (md rd \par not forgotten easily\rquote . (makes you think you blew you rxn up)" \par interesting note, using CuCI2 for the first time.. NO OLIVE GREEN ggiefgks. griat SPl\'b0\'b0b\'b0Y\'b7 Thar\lquote KS\'b7 Brell And td shew You that \par color appeared. Stayed slightly yellow -dark brown... All the way mm .t y.nl?n mdk'r\lquote 9 this UD, the f\'a4ll0Wi\'a49 expeflm\'e9ntal will \par through the rxn. Never came close to Green (light, dark or olive). gcctcrl ,,1 t IS was taken rrdm the review [73] written by the same \par When rxn finished solution was very dark reddish-brown, even from to fa a":h\'b0r9d_the Pr\'b09e"\ldblquote\rquote\'a4\'b0l_l\'b0dC|z article that Strike drew \par when acid washed it stayed dark reddish brown. there is :gn:;;I_1\'80f;l;';|;$C;r\'a3)\'b0\'b7 grid lust as fpleebdll $8VS ab0ve, \par r com \par The reduction of catalysts warranted the additional Stir lima. 96 reaction time is serleuelll eh\'a4?\lquote %i\rquote and tllrglerrnoghtbgllgzrglgl Fha \par hours maybe excessive, I believe they were hoping it would turn needed is drastically reduced; a rst \par green and the longerthey waited the more they thought it was a U \par lost cause. Fortunately it worked out on the +++ side ,\'b7) " pIg1c;d1t;0zb ;\'b7ound\}bottomed flask htted with a magnetic stirrer is \par U IX ure o palladium (II) chloride (89mg, 0.5mmoI \par To read more about the use of CuCl2 read ref #15. ?.'\'a7gr;1%7ulqr?t,l? e(go?:gon55l\rdblquote d;2g in? 7\'e91t(:ir\{""d\rquote V/fafmamide/vliatgr \par , \'b7 . _- n su s i u e safrole for this com\par Now here is a post from a very influential chemist named Spice- agglg fommdd \rquote s edded l" 70 min and the mixture is \par boy who has contributed quite a bit to this science thypothetically 3 normal h OCWO irrperarure rdr rh- The $0lUii0h is poured into cold \par of course). She decided to go ahead and apply the idea of using Of gms], TZE Efdrgrf amd (1OO'l\'b0L) a"d exrreeied with 5 P0l7lb\'a4S \par benzoquinone as the oxygen source. If this works it would mean tions Of\'b710% a ue C S are lcombined and washed with three por\par that one would not have to use a balloon of O2 at all, thus making b - q SWS S\'b0d'um hydroxrde Sdrdrlen and e POYUOI7 of

\par the entire apparatus much more simpler and causing an increase rm? and than drled Addr r emdvel or the $0/i/ani the resid ' \par . , distilled to ive 2-decan P2P\'b7 \lquote \'a4 ' US ls \par in the efficiency of oxygen uptake and transfer by the system. So g drlel I Yield 6-79 (78%). \par Iet\rquote s see what S icebo dreamt mi ht ha en if this were actuall . . \par applied; p Y 9 pp V The last variation we should discuss is about the use of solvent. \par E;$g\'b7gLi;l;?gh;b;utg;hetr:rityD:;|\'b7;1 price of chemicals, the bees \par \'b7 _ _ n r a e used in this method. TDK sent \par Holy Ketonel Whata dream ..... I V \'b7 \'b7 Strike an article that gives some credence to this [16]. In it the al\par Dream setup; 100 ml of DMF stirring rn a flask equipped w/ a \'b0\'b0h\'b0lS metherleb erherlell 7\'b7Pl0P\'a4\'a40|, ethanediol and others were \par sidearm 34 g of safrole was added in 4 portions of about 8 g each. Used in Place of DMF with beautifully high yields. Below is the \par Mixed intimately. Next, 11g of p-benzoquinone was added. Stir semlele expeflmanlal item the ailicla (lust Pleluie Using Safl'\'a4l\'80 0i' \par rate was upped. Finally, 7 g of pdcl2 was added. A dry addition alwlbenzerle ln Place \'a4ffl1a T-hexene): \par - 72 \emdash - 73 \par \par H2. and 3_Hexan\'b0ne.__A 5O_mI portion of 0665 M Lh\'e9x\'e9n\'e9i Zee bZd1gressurrze agarrr, allow to stand overnight. MV time \par 0.020 M PdCI2 and 0.100 M CuC/2 \rquote 2H2O in 1\emdash proPano/ was timtesilit it /h;\'a7rS at bedtime + 8 hr Sleep = 21 hours reaction \par Shaken for 120 min at 50C under 3 atm oxygen. The reaction eO%\lquote + Hunt"; HCL arld extract PGF usual KA\'b7FUCK/N' BOOM; \par mixture contained 2.0% water from all sources (salt hydration, im`''\rquote\lquote\lquote\lquote \par purity in thi alcohol and water of \'e9zrxidation). Of the hexene \par charged, 13% (by gc area) remaine unreacted and 86% was H, \'b7 _ _ \par converted into hexanone and 1% into side products. Resolution of nzirsgrmeeiiis Some serious psychotoglcal hetpt \par the hexenone peak showed 75-76% 2-hexanone [or MD-P2P for tee e \'b0t'em'st"Y\'b7 NO WQV!

\par the likes of us] and 24-25% 3-hexanone, both identified by means \par or residence times and infrared spectra in comparison with We"- that sh\'b0Uld b\'80 \'e9hvugh examples to give you o good jdee of \par euthenticsamplesf how this Wacker oxidation method works. There are a lot more \par interesting variations that bees have been posting on the |-live jf \par Whaddya mean it won\rquote t work for things like safrole just because yeu wtsh to lead m\'a4l'\'80\'b7 \par the substrate used was 1-hexene?! The only thing Strike had to go , _ \par on Years ago was one article [11] which had as its star 1-decene. Fmetty' tt meet ba restated that the biggest plus of this method is \par And yet the method translates! This last contribution (by Spiceboy that tt pmduces 70*80% MD-P2P or P2P, and 20-39% isosafrole \par again), shows that using methanol as a solvent works just fine \'b0" P'\'a4P\'80\'a4ylbehZene as a side product. So if the chemist were to \par and, as has been suggested by others, can lead to a reduction in turn afvuhd and process that isosafrole using, say, the fomaic acid \par the amount catalyst needed. Strike doesn\lquote t know what the hell is mettt\'b0e_#t\'b7 then the Pm\'e9mlal P2P production from this method \par up with the bicycle pump, but to each her own; \'b0\'b0Utd cllmb t0 well Ol/BF 90%l \par "Welcoma badk...now, before I give up dream details, I want to ::5 1eI;I<\'a7;r?1:;.n\'80j gt the p\'e9mttttg ettttte b\'b0\'b0k\'b7 this m\'80th\'b0d l$ Still lh \par thank Osmium for_ his inspiration. You got me to thinkin' man. I the Wacker Oxidaeoelge d Uett tepteeettte tha nettt Q\'80\'a4\'80\bullet\rquote\'a4tl\'a4\'a4 of \par want to say that this is another offshoot lguess, of #3,but with Old ene in beth - Id an S Outdi tt ptepetttt teetteett e\'b0\'b0t\'b0t\lquote the \par some twists. Such as .... process ONE HUNDRED GRAMS of olefin Work ef Oemiu,.z|EI-bgost and tlme Thts. ts entttety due te the \par with 2 got pdcl2, and 8 g of cucl2. There will be no oxygen tank. ehemist named SG I. h jfd an a99l`\'80$$lV6\lquote ly active European \par FUCK THAT SHIT? The reference I based this on indicated that air del reference eentn Ig IL T ey\rquote and maybe Others? teund tha tm"' \par will work. Whaddya know? Theyre right. The air comes from a pueation All emk\'e9 ett2jp_etett ttend Started dreaming ebout its ap\par l4.95 piece of shit tire pump from wa/mart. It will pressurize the and bee;] told 'S \'b0'"9 ts t'tt""9 YOU lll 00 what Strike has seen \par SRV in about 10-20 seconds. Here we go: \lquote

\par The mett"\'b0d 'S baslcalltl an application of the Wacker oxidation \par preserves g cucrz in so mr rvreor-rprssarve 2 g pdcrz intro mr except that *h\'b0 \'b0\'a4*\'a4'YS* uaad is palladium acetate ( PdcA<=0>2 or \par MeoH_ Dissolve mpg or Sarroio in gpg ml Meg;-i_ pour]; ei; in and Pd(OzCCH3)z ), the solvent is acetic acid or tert-butyl alcohol and \par ddd MeOH to make 500 ml MeOH total. Swirl and gently shake. the Oxygen s\'b0'~*'\'b09 is the PF\'80Vi\'a4US|y suggested hydrogen peroxide \par Pressuriza the SRV to 37 psi. A tire gauge works great. After one (H20!) [17]\par iiour, release the pressure and immerse in warm water for 2-3 \par mins, Snake. Re-pressurize. Repeat process hourly. At night be\par - 74 \par -75\par \par P O action time = 6h. [or in other words] O.5x103 M Pd(AcO)2; 0.75 M \par P O 1-octene; 3. 75 M H2O2 (30%); solvent AcOH,\'b7 temp 80C." \par O \par Pd(OA\'a4)z/H2O2 The experimental procedure: \par \emdash ) \par \\ "The olenns were oxidized in a three-necked 1L thermostated \par MD-P2P glass reactor equipped with a magnetic stirren a condensen and a \par Safwle \\ 100mL glass funnel (for introduction of H20;) and connected \par _ _ , - ixed feet through a gas counter (for the evaluation of O2 evolution) to the \par in-"S amcle was Kmten gg zirgjzcgnirzgadigckfaugsugiaiiy quite atmosphere. H20; solution was introduced dropwise into the mix\par mgs altqmtgringheigiigg \'b7On the other hand they are always toc \{Ure of 0ieWn, Solvent, and catalyst during 30 min at the rgagtfon \par Cmec mt 6 the deteltie in a comprehensive and detailed man- temperature. When the reaction was complete, the mixturg Wes \par lazy ni ettgp W ntto te|| ou how great they are but they dcn\rquote t 000/66 and Water Was added. The yellow upper layer containing \par ner. Its I T 5-izreain it Strike can say this with confidence be- the catalyst WHS Separated and passed through a eoiumn gf ciu.

\par wgggeygtrise has yet to have anyone from France buy any Gi mirle in Order ic eliminate the catalyst and reduoed under reduced \par Strikes books, so Strike knows they won't see this one either (tee pressure. \rdblquote \par h\'b0\'b0l)\lquote Yeesh! What the hell did all that mean? Well, let\rquote s see what Sun\par . \'b7 ut the results are light\rquote s preliminary interpretations are as were secreted to Strike \par Anyway' the dams are E me hard to process b via encrypted messages. lt is interestingly voyeuristic to see the \par Very clean first machinations of a recipe come to life: \par \'b7\'b7 - \lquote `e t catal ic rocedure for the \par oiiditliijvpgli gtmtigisolgnnirtie\'e9gfaitoie] to mgthyli ketones [ie MD- "WelL l've started to work a few days ago with palladium acetate. \par pgp] by hydrogen peroxide using a palladium catalyst and oper- Norma//y / Start with quantities of 10 - 20 cc or eerroi but tnie time, \par ating in the absence of ha/ogens and co-metals [ie no CuC| or animated becuase you [not Strike!] said there's someone who said \par CuCI needed]... This reaction is carried out either in biphasic me- this way is good lmake a direct production test with 150 grams of \par diumz using solvents such as ethyl acetate or dichloroethane, or in safrol. We/L at 80 C, and after 1 hour or so, l go out from home 10 \par homogeneous solution, using tert\emdash butyl alcohol or acetic acid...a minutes, and when Ilcame back, rxn was no controllable, a exho\par quite complete conversion of 1-octene (90-95%) was obtained af- termrc n<n started with a lot of evaporation of acid, l did another \par ter ~3h or reaction time... mistake when trying to stop rxn and a lot of acid whas rn the at\par dium was found to transform *400 tTlOi of i\'b7OCi\'80l7\'80 ink? 2' i770$Pijl\'a7\lquote i'\'80. ii WGS hard Hear Intoxication. Other test with small \par quantrtig shgws me 80 it's tgt) myCh_T/tg pmdugt Obtained was \par \'a3* only a clear brown tar with no ketone. The problem was the temp, \par That folks is an incredible reaction rate! They are essentially it's too high. l\rquote ve started again with my classic tests. l put yester\par saying that, less than a gram of Pd catalyst will turn 100+9 of sa- day 10 cc of safrol with mg of Pd(OAc)2 and 35 cc of H20; 30 \par frole into MD\emdash P2P in less than 3 hours! The cryptic optimal reac- %'and 70 cc of acetic acid at room temp (30 C). After 16 hours,

\par tion conditions and procedures are as follows: this morning before go to wcrlc rxn was not complete, (in the night \par temp goes down), and l think in 24 hours it will be done. I put e \par " temp = 80C; H2O2 (30%): 1-octene = 5; 1-octene:Pd = 1500; re- piece of glass in the flask and wait to acetic acid is evaporated \par - 76 - - 77 \par \par then I smell if there's safrol I smell Hrst safrol but like safrol is Then add a bit of NaHCO3 (4 grams) and salt to saturate solution. \par more volatile than ketone, after 5 minutes (or more depending ra- Stir a bit more. Separate layers, Extract one more time and distill \par tio safrol:ketone\} start the ketone smell. I can now smell the ke- Time depends on reaction speed. Reaction speed depends on the \par tone in my hngers. ldon'l know how yield can be achieved. Other amount of catalyst and temperature. 60 C seems to be good \par probelms are if temp is not used it's necessary more solvent, may more catalyst, less time. More temperature ? May be more by\par be 1 liter for 100 cc of safrol, what is too much, it will complicate products, this is what happen when acetic acid is the solvent. \par extraction, although in my test there are 70 cc and it seems to Probably a good way will be also acetic acid and 40-50 C, but dual \par work but it is not an homogeneus solution. In JOC they say the phase is easy to extract ans uses less chemicals. \par reaction can be done in dual phase, this will be my next try rf it \par runs, it will be the best just stir safrol with H2O2 and solvent (l'l/ try I hope my reaction success and I can run the 100 grams batch \par with toluene), when done, add some NaHCO3 and stir and then tomorow. Another difdcultie is now water tap is at about 29 C ( to \par separate layers, distill. Perfect simplicity, will it work ? It seems distill ) , may be III use a refrigerator compressor; I think it will be \par best temp will be 4050 C, it will increase reaction speed." enough to distill ketone at about 180 C. \par A few days later: Couple of questions for me: \par \ldblquote l' m working now. Best results were obtained with dual phase with ?>Add the toluene + safrol into rxn vessel, then add acetic acid +

\par toluene at 50-60 C 24 hours stiring. The isolated oil smelled a lot >Pd(AcO)z then start stirring, then start dripping in HZOZ? \par to ketone, and when two drops were added to a saturated solution \par of sodium metabisulphite and stired, practically all reacted fomring Well I think it's better to add a bit of H20; to the toluene + safrol + \par the addition product that precipited to the bottom. I think its about catalyst to prevent catalyst decomposition, for example, with 100 \par 80 % yield but it's only an impression, may be less. Now Ihr re- cc of safrol 10 cc of HZOZ, and then add the rest dropwise. \par peating the experiment to detemrine conditions and then, /7/ do a \par >100 grams batch, so I'lI determine yield. The problem has been ?>A/so, is the amount of acetic acid exact for example would 5 cc \par is needed a good stiren and I was working with a motor cassette hurt \par with two magnets, I realised only 300-400 rpm. Then I bought a >the rxn or help it (in your opinion) .... ldon\rquote t think more \par more potent one, but now my problem is the noise of it, because it >temperature would help, probably create more by-products! ? \par must run 24 hours... \par Well I thought previosly a bit of acetic acid can help reaction to \par The recipe will be something like : prevent decomposition of catalyst. Now Im thinking after re-read \par 100 grams of safrol JOC article 1425 times, acetic acid is not needed at all because if \par 150 cc of toluene. catalyst degrades to Pd metal is not more dissolved so why add \par 100 cc H2O2 30 % added dropwise acetic acid ? My last test with 10 cc of safrol had 0'4 cc of acetic \par 100 cc H2O2 30 % added dropwise at 6 hours acid but /7/ omit it in next rxn. \par 100 cc at 12 hours \par 100 cc at 18 hours... \par 2.5 cc of acetic acid I've found that unfortunately, there is a hyper oxydation of oleohn \par 0.5 - 1 gram of Pd(AcO)2 stir about 24 hours .... thats all. as side reaction, and gives organic acids, probably MDPhenylace\par tic acid and may be a bit of piperonylic acid. its easy to realise it, \par - 7 S - - 79 \par

\par just measuring ph after reaction. l suppose this side reaction is `\'b0200 Q Soffol + 7 Q Pd(A0O)2 + 500 mls tert butyl alcohol + 400 mls \par more important when temperature is high. My last try was dual 35% H2O2. Added everything but H2O2 to a 5 liter two neck Hask \par phase, 10 cc safrot 0.7 Pd(AcO2), 20 of toluene and about 45 cc equipped with a reflux condensen themrometeh and dropping \par H2O2 in three times and at 60 C, may it's too much high. So if we funnel, mounted in an oil bath on a good magnetic stirrer Started \par decrease temp reaction, we must increase time or catalyst. lf we stirring while bringing the temp to 80C. At 78-80C start to add the \par increase time, H2O2 degrades in time, so we must add more, and HQOQ. lt was added over a 30 minute time frame. As this was \par H2O2 concentration decrease, so reactivity decrease also a bit ( l added, they noticed an evolution of bubbles coming from the rxn \par think ). Best solution will be increase a bit` catalyst. BTl/it in my (O2 from the H2O2). Monitored stirring and temp with no unusal \par next try l'll use PdCl2, as l said you in the first samples l saw PdCl2 occurrances until hour 4... Initially solution was a light orange \par yilds also ketone. So lll do a sample with exact conditions to brown, after 4 hours in started to turn a very deep orange, almost \par Pd(AcO)2, and lll compare results. lt' would be better to work with reddish color Also the smell of safrol was completely gone and \par PdCl2. Now, when l come back to home, lll extract my last 10 cc was replaced with a unique aroma of ketone. One that is attribut\par reaction, and lll see the lose of material in carboxylic acids, be- able to this rxn as it differs from the smell of the wacker oxidation \par cause they will go out in basic wash. lm afraid my last yield will be ketone. Continued rxn for a total of 6 hours, maintained temp at \par about 50-60 % only far from desired 80 %, but not bad having the 79 to 82C. Color at the end of rxn was deep orange- reddish, pH \par nature of chemicals (toluene and H2O2, OTC ) and the little effort of solution was 2. \par that supposes. But l would prefer 70 +. So try to send me the in\par formation of your friend's friend may be there is some key in it im- To separate the oil added an equal volume of fresh cool water \par portant for me. lll hope improve this method to make a simple, (note; waited until solutr'on cooled before adding the waten. The

\par elegant, cheap, OTC, high yielding procedure. l have only a bit oil started to drop out perfectly, used DCM to extract all traces of \par more than 100 cc of safrol Ill do one or two tests more and then the oil. This work up is by far the cleanest easiest and simplest \par l\rquote ll process the rest. And Ketone research will linish for me. May to dates. ( This dreamer was tried all method of ketone synthe\par be lll have your post tomorrow ? sis)... Once the oil was extracted, the extracts were pooled \par Thanks" i washed with sodium bicarbonate 1x, saturated solution of NaCl \par \lquote 1x, and two washes with fresh dH2O... Some time was required \par See how things happen when a competent, energized chemist f0l' tho Work Up HS fhofo was a little emulsion from the use of the \par gets ahold of a new recipe? Well as it so happened, Sunlight was MSG wash and then with the lirst water wash. The JOC ref Sug\par getting a little uncomfortable with the results (as was communi- 998iBd Using an alumina \'a40iUmn tv lomvl/6 the Catalyst (could be \par cated in later emails) and decided to contemplate the alternative 8 bnii\'e9i WHY to 90)\par use of tert-butyl alcohol and other solvents- as was discussed in \par the French journal article. But just days before this book went to Sv n\'a4W W9 iiaV\'80 ii7iS SO/von? Containing ketone, dried with \par print came the nevve that vviii change the production of phen- MgSO.,... Not being able to vac-distill today took about 50 mls of \par ylacetones forever. TDK, bolstered by the reassurances from a S0iVi=\lquote nVi*'6\lquote i0n9 and lJiO\'a4`\'80\'80i in boak\'e9i OH Stifp/ate and boi/ed Off the \par Secret group of oherniste that have apparentiv peen using this solvent. The resulting oil was a nice reddish-orange color Had a \par recipe for years but forgot to tell everyone else, came through VBW Uni<7U6\lquote $/176// iO\'a4\'b7 TOOK about 2 grams worth of this cit \par again The foiiowing ia the proof positive definitive appiioatipn of added to a test tube containing a saturated solution of sodium bi\par thig reoipe; sultite... ln less than 60 seconds the oil precipitated into a whitish \par yellow mass (very similar to what acetone would do if added to a \par bisulhte solution). Never had this quick of a crystal/ization. Not \par - 80 - - Sl \par

\par having access to HPLC or other more accurate method of analym9*\'b0hVI\'80N\'80di\'a4XVPh\'80NY/\'b72-Pro anone/M \emdash - \'b7 e \par sis, I would say the purity of this ketone is >90% and the yield will 700%\'a4l\lquote the reactants con,\'b7,\'b7u:;ed_ DP 2 P) IS .95% with \par be minimum 78% and probably as high as 86%. No isosafrol ei\par theh as this rxn is highly selective. Exam Ie 51_ Add 1 \par U I I eng Z5 . . mole of 8-(3,4-methylenedioxyphenyg propyl\par This is the best method, easiest and most fool proof process to \'bb \'b7 l\lquote N0ie of methyl nitrite, .5L of methanol 36g of water \par date!. A .00025 mole of tnmethylamine, and .0005 mole of palladium chloi \par nde as a catalyst to a flask. Stir magnetically for 1.5 hours at 25C \par Strike wants to believe that, but right up til the last day this book Tha \'b0\'b0"'V\'80"S\rquote O" Of the sia/'UNQ material was 92%, the yield O\} \par had to go to press, the ball was still up in the air on this one. Con- MDP'2'P was 83% and the Pd Turnover Number was 156 \par flicting, odd results have been seen from many different groups. \par This method has a lot of advocates and proof of its efficacy. But it . _ \par Seems to be a little fickle at times; the causes of which are Siiii 5h(gmg?rggleAdi\rquote lid;tlT?ISitOi CH2]4-mgthy/gnedloxyphenyo pmpyb \par being debated to inte dey. \lquote \lquote . , Y \rdblquote \'80\lquote\'bb -_ L Of methanol. 36g or wateq me \par m e o \par fl olk bis(benzomtn/e) palladium (ll) chlonde as a catalyst to a \par METHOD #4; This is a P2P recipe that Strike has no hand ihs;itir\'a7,;nrZ;i`Zi,i;th$gg\};h(gJ.ihhmiri at 25C' The conversion Ofthe \par Strike never even knew about it until Strike saw everybody talking \'b0\rquote ey"? d \'b0f MDP\lquote 2'P was 88% \par about it on the net. But it seems to be extremely popular. Shulgln \par has written about it. Uncle Fester, Strike understands, has written Example 86: A 0.10 mole amount of the startin 3- 4. \par about it. And there seems to be a lot of posts regarding its high hydroxl/phenyl) propylene, 0.25 mole of methyl nitrite Og liter(of \par success rates. Most people get started from the method descrip- methyl alcohol and 0.006 mole of a palladium chloride Gere; st

\par tion in the patent literature where they were first published, The were Charged into a reaction vessel. Then the reaction was ciar\par following are some representative examples from the U.S. Patent Ned out ata temperature of 20, degree, C_ rdr1_5hOu,S ~ \par #4,638,094 \ldblquote Process for Producing Phenylacetones": ' \par X O Those 'propylene' species that the author \rquote \'b7 \par /\\ O P ferent than safrole or allylbenzene. ln fsciyesgfhlaiengisage lggrfggt \par O MBNO2/EEN Q O Subetliute. YOWZa! Those recipes look awesome! Now as Strike \par ______ understands it, there has already been a detailed writeup of the \par Pdclz by-the-numbers application of the above patent as written This \par \\ Strike believes, can be found in Uncle Fester's "Secrets of LSS \par Safmle MD-P2P Manufacture andlor "Secrets of Methamphetamine Manufac\par gu; our adventurous chemist Sunlight came thru again \par UE I _ a new, hybrid form of this method which she seems \par Xdmple 24_ Add _1 mole or 3-(3,4-metnylenedioxyphenyl) pro- *0 here i\'a4rrn\'a4|ated after a lot of thought on me metre; Se here \par pylene, .25 mole of methyl nitrite, ,008 mole palladiumbromide as again is Sunlight: \par a catalyst, .5L of methanol and 36g of water to a flask. Stir mag\par netically for 2 hoursat 25C. Yield of 3,4- "This is a new ost in the Hi ' \'b7 \par methylenedioxyphenylacetone (also KNOWN 88 3.4- [$h\'80`$ jUSt kiddiriig folks!] with the Invgwpgxmgig iijtvh Ehiiigrh \par better than the other Darkness part is extraction (yes, a lot of dark \par - 82 - - 83 . \par \par brown product), so may be it's better to do it as your procedure top and bubbled In 6 Solution of Sefrol in methanol gonfalnmg pdcle \par #3 , sometimes is really hard to make the two layers different in Cara/VS! (A\} \par colour. lhope we are in time to include in your bood if you want. \par This example has been done with good yields J \par This is real. A. 50 cc of safrol 300 cc of methanol, 2,5 grams of PdCl2 \par B. 100 grams of NaNO2, 60 cc of methanol and 200 cc of H20

\par C. Chilled solution of 38 cc of HZSO4 and 85 cc of H20 \par The present post is an adaptation to kitchen chemistry of \par Japanese patent #4,638,094, process for producing . . . . \par phenylacetones, and is the result of a large battery of dreams. ln C Or ? Pa"! Of C]-? PU? in 6 \'b7\rquote >`6P\'b7 fUrme/ wich IS connected to flask \par SOMM (Uncle Fester), we have three versions of this patent, one \'b0\'b0\rdblquote ta'\rdblquote '\rdblquote Q B ( WIC\}? C60 U6 6 bvffl\'e9 l, and a tube connect this flask \par uses PdBr2, other PdCl2 and the 'prefered" uses PdCl2 and to the bubbler W9 flask 00l'l? 6i\'a4l09 A, wich have other tube to redi\par CuCl2. Last one doesn't run. Also SOMM version be dangerous rect NO and 'lltm`9 96365FI6-Sk A is in water bath to keep rxr; \par neeeuse in ine scheme ef em, Fester isis 6 mais ei NO end temp between 20 - 30 C/reaction is slightly exothermic) and stired \par niinies te ge Oui free of Dm Vessel (see Eieusis vs_ Fester; magnetlcalg/. MeONO is bubbled in A with a bubbler that provides \par Rhediunfs page, eieusis has right) Weii both gese s ere Very toxic, little bubbles ( not necessarya gas difuson but a single tube is not \par good ventilation is not enough and these gases must by carried ?\rquote Z\'b0\rdblquote 9h\'bb YOU mus? l\'a4\'80F\'806$\'80 their B and C ). Bubbler is all deep as \par out of the window through a tube (use a two hole rubber stop or a '*` 'S P\'b0$$'b\rquote 9\par two necked flask). Also in this sample a precipitate that is taken \par ' st be do \lquote ` . \par \'80li;\'a3"?\'a7?l2'%5,73iZ'G?\'a3\'e9ia?\'a7\rdblquote\'a7\'a7\ldblquote l$\'a7\lquote Z\'a7'E\'a7S;$2iT\'b0$.\'a3\rquote Z,"t.x,,l.,Sl.,Zi gg; ;g;iggg;n;~;hgi;;\'a4ie;i\'a4g;ggig c l~ B. Svmetimes we me \par have been reported when distilling, may be because this reason. denereiien A ddidd n Speed is nmnggeba \'b0\'b0"$$;\rdblquote\{ rate gf MGONO \par Also in this procedure we spend much less solvent, minimizing between desks if ii is me much ui\'e9ifziu" ';5mOi?iOp'\'80SSU'\'80 \par evaporation time, less catalyst and less NaNO2. Otherwise, l inrengn Sep fdnnei then We eiese ing Se \rquote f En I Gd _ gas, 99 \par agree Uncle Fester his work because he have shown me a loFof denereden ie iew Zine eddidc f C . Bp Lime a" Wa"` a M "'\rdblquote \par things I r\'80\'b0\'b0g"iZ\'b0 aIS\'b0 the g\'b0\'b0d pad \'b0f his Work sep funnel and shake a bit Brtoofinishv reagtigri ifhn(Zrl\'b7in(A,)\'80ciihhg\'a7 \par U U _ _. _ temp too much, we can add ice in the water bath. l've monitorized

\par Interest of this reaction is that uses. OTC chemicals or non suspl- temp touching a part of solution that was out of water bath. At the \par cious, as NaNO2 (it's used in food industry as a conserved , and nnal part may be water is to much cool so we can take it out. After \par it's really easy. Methanol used is drugstore methanol PdCl2 is the addition of C in B we wait one more hour. \par from photografy supplier in the net or elsewhere... \par _ Now we open flask A. We can put a piece of glass and smell it \par Procedure is as follow: once methanol is evaporated. There is no safrol smell it's differ\par ent, it's the dlalkoxy derivative of safrol, nm is completed perfectly \par A solution of chilled dilute HZSO4 (C) is dropped in a solution af We edd \rdblquote 0W 75 CC Of W6T\'80F 60d SNF 45 minutes more. There 's a \par mgthanoii Water and NENQZ then nitrite is ggnerafgdl PFGCIPIFBFG. I/V9 [,79 IEHCHOH, IdOI7't know what is this, may be \par also black tan l thought this may be palladium complexes, this is a \par - 84 - - 85 \par \par organic compound that burns easily and may be contains Pd. This Weld. _ _ h \par will forme tar laten now we don't have it. We can now smell an- lh \'b7\'a4g1t.Wt~ 8 flame (BUnS\'80\lquote n). When done, you can bfgw \par other time rxn. This smell is ketone, we have more than 80 % of mug 't '" Wafer to $96 there ere many bubbles. lt\rquote s enough \par MDP2P (patent says 91 %). Good extraction procedures will give \par EH E j E h E' i flasks;] iash Chmahitng B Gan be a bottle. A is a d h pt \par flask; its better because in a bottle or a flat bottomntilagk gag;] \par This is my version, but may be better done. First one, evaporate ggigels Q? glissqlved '" m\'80\rquote hah\'b0\rquote Uhh\} it reacts, could be in the \par methanol, better with vacuum. Then we have two layers similar in r \'b0 a W\rquote thOUt"9a\'b0hh9\par volume, we add 100 of solvent and 50 cc of basic solution (sodium \par carbonate, bicarbonate or 10 % NaOH). We shake it and may be Hazards. lf dd t \'b7 . \par We wil\} have little more precipitate or tar A/so may be we Gen'? $96 through sep. yifiilhnzl. Sowgoszufge ilgckg [Fifa; B, MGONO goes

\par Separation, then we add a bit more so/vent Without shaking to $96 addition or you shake immeoieh (hgh U (gre Yvashmo much \par separation, We make two more extractions with 50 CG of solvent. the possibilities of bubbler and hihb gehmra [On IS higher \{han \par Even if we can'! see separation, we can add enough HCl and [Qt Qi mam and SDM-E, E\rquote U . at OC', ask B Canlump with 3 \par shake, this will forme some tar and layers will be distincts, S0 we dissolved t ( ' \'b7 \'b7 \'b7 8 . 2 \par can Separate and make a basic wash. Sometimes l've done first and shake. goIiiC?\'a5:;;yeil;e\'801hIl;(;i'lxzigtggtiyritygitcgssa/V. B9 patient \par an ac/d wash, but l can't sure it's better l'm thinking now may be W;,,dOW_ G fumes OU? \ {O the \par is better to do all extraction as Strikels top #3. Add acid solution, \par like 250 cc (less PdCl2 and no CuCl) 15 % HCl, extract and make \par a basic Wash Cleaning flasks. Flasks, specially distilling tiask are really dirty \par a brdwn blaclls semisolid tar lt\rquote s easy to clean them. Make a \par or s ' . \par This procedure has been tested for a lot of bees and conditions in rh; ,qaS,;0gg\'a7rh\'80;\'a7)C\'a7[Isg;l;Z,?n gig; drugstore, Of C\'b0\rdblquote 'S\'80\}\'b7 PU? it \par are similar Distill solvent and distillketone with a water pump. My USB 9,0,,681 please. ' 9 Gssam all ter 90 Out 666% \par have been done with 150 cc of safrol, but with 1'75 l of methanol \par with simialr yields, so l\lquote ve prefered to present this version wich is Bisuiphite. My personal nightmare. I use metabisulphite what l \par better (less so/vent, less time) Addition of nitrite was done in 2,5 think i't's the same. Sometimes product is umilterable other one \par hours. When scaling, water in B can be decreased if we have couldn't be recovered with NaOH solution. Investigate l'm not a \par problems with our volume Hasks, but this means a lot of NaNO2 is great chemist. Solvent, NaNO2 or PdCl2 may be can be reduced \par not dissolved, so each 15 minutes, we close sep. funnel, and but I think the quantities in this sample are really good Solvent is \par shake B a bit, and when there is no foam, we can open sep. fun- easily evaporated, NaNO2 could be o l l' htl \par nel again (1 drop or abit more lsecond). My opinion is 150 is ok, PdCl2 is about 4,5 % versus 6 % in partehvts gut it'sr;nLbC1.?;w Zig

\par but theorically you can scale more. More time nm is not a problem Cause 3/i Sefrol reacts. Well, Ithink its ali___\'b7* I \par \par Bubbler l've done it widening the end of a glass tube, then puting \lquote \par in the hole with pression a piece of glass sponge ( for feet) and , \par - 86 \par - 87 - \rquote \par \par METHOD #5: Could Somethin this easy really Work-? Actua"y_ dH2O and 32g lj|gOAc. This is stirred a little, then 82g of safrole is \par yes! Well, ya wanna know sgmething'? Actually Strike doesn't Sl\'a4-lv P\'b0l-lied lh- The S\'a4|\'a4i\'a49h Sh0uld be bright yellow. Now, \par fin _ A A; vwi _i _; .\lquote _y_ i AA`U _ j A;i =` \'b7 . .~\'a4 e **.:\'b7* *.a\'b7\'b7 \lquote ; \bullet s\bullet \bullet\bullet\'a4 \'a4* " . `\'a4 f p \par read the following which was what Strike wrote in the first edition 9V\'80' 3 P\'80V'\'a4d \'a4f 4hF$\'b7 The Chemist will keep chunkinkg neces of \par \par watched chemicals and a yield of 70%-80% [19]. The reaction is $0|Ut\'a4\'a4\'a4 Will thlm dark greenish brown. After addition is complete \par shown in the accompanying diagram. the solution stirs for 4hrs more. \par t-, Hgw \'bb \'a4 OH When completed, the solution is merely dumped into 1L of dH2O \par < \'b7\emdash\'b7 < and extracted 3 x 100mL Et2O or DCM or benzene. BUT when \par O \\ \'a4 cri,H\'a4\'a4M that solution hits the solvent, the biggest, ugliest emulsion Strike \par Smit . has ever hypothesized occurs. It is wicked! The chemists can try \par O . all the usual tricks to get rid of that bitch, but when it comes down \par to it, there is only onelway that works. The chemist is oin to \par \par o n\'a4.g...i /r MDJW The idea here is to saturate both the aqueous and emulsion layer \par < \emdash -\emdash\emdash - with so much solvent that a separate solvent layer can form. Once \par 0 eH,H,oM \\. \'a4 saturated. the entire mix can then be properly extracted, \par _ The solvent is then washed 3 x 50mL dH2O and, if desired, can be

\par ,ma,m,_ washed once with 100mL saturated NaCl solution. Finally, the \par . solvent is dried through Na2SO4, removed by vacuum distillation, \par This will work for conversion of allylbenzene to P2P. And the bo- and the first 5 to 10mL of oil that distills over is saved because it is \par nus is that the major side product is isosafrole.- The mercury (Il) isomerized safrole (iososafrole), which is suitable for reuse. The \par \par \par and acetic acid (why anyone would do that is beyond Strike since this book. \par the stuff is easily purchased), or mercuric propionate made from \par HgO and propionic acid. The oxidation of the intermediate alcohol What you have just read is what Strike wrote in the first edition. \par is achieved by using Jones reagent [153]. An SM solution of Strike laid down one day just before publishing and had this bad \par Jones reagent is made mixing 267g of cold chromic acid (CrO3) ass premonition regarding the recipe. But most people since then \par 230mL cold HZSO., and 400mL cold dH2O then the solution is have not. Let's see what the problem is. \par brought up to a final volume of 1L with dH2O (or can be pur- _ \par chased). The working concentration that one wants is 2M, so the Strike got the journal article for this recipe as literature citation \par \par . ln it both mercuric acetate an e \par \par propriate sized flask or PP container is placed in a tray of water on got a certain ketone. But maybe they were lucky or just plain \par the stirplate. Into the flask is dumped 800mL acetone, 25mL wrong. Most people on Strike\rquote s site say this mercuric acetate thing \par - gg - - 89 \emdash it \par \par just ain\rquote t happening But some say that it does, Funny how Strike Oxidatifm requires NO QXCGSS to be present during the oxidation \par only happened to save those positive p0sts... That's why one has to dnp in over a four hour period A/so after

\par "Posted by Dr. Quack on March 08, 1998 at 16:53:53: temp should remain stable...QuaaaaaacK 9 \par Quaclg Quackllllllllllllllll B. Big secret...Quack!l!l!!, Use approximately a total of 600 ml \par (twice the amount prescribed) for the three extractions. Don't \par So there's this little duck and round and round she struggled with quack at me...its starting fluid. its cheapllll Quackl Here it is: Let \par this method. But here is the report for all to benelit from, Quaclg the Hrst extraction sit for several hours (or overnight) and the \par Ouack... seperation will be VERY clean. Howeven there will still be an \par V emulsion present in the ether layer. Novig the Quackload of prod\par uct will be in the lirst extraction, so the emulsion and settling of the \par So for all you book owners out there, boy did you get following two will be much quacker (faster). Combine ALL three \par your money's worth. Check this out (btvm Dr. Ouack has NO idea ether extracts and note that there will be a little water that will \par \par Dr. Quack - promise): \par I I I C. Big secret #2...Quack!l!ll...One MUST Hlter this 600+ ml of \par For top ten #2 (Mercuric Acetate method) use the following ln ethen..but a duck can't do this all at once...so one must Hlter in \par place of reagent grade materials: vacuum \'b7r7lter in 200 ml portions...changing the duck paper every \par . time and wash the lilter cake with ether..Dn Quack thinks a vac\par 1. Ether - Starting fluid (works great- Quaaaaack!) 2. Home made uum Hlter (apirator) at this stage is a must...Quack!!l!!!! \par mercuric acetate (Now this stuff can be special ordered from ones \par chem supplier but there's a delay, may look funny - Quaaaaackl, D. Now the ether will be a deep reddish yellow. Distill off the \par and is more expensive. So what is the solution to this? Make it ethen..quack...and take the temp up to 170 C to drive off an \par \par \par same procedure for Mercuric Propionate except use glacial acetic hours...Quack!lll!l.l Vacuum Filten the duck fat crystalslll Wash

\par acid...quackl). Youil need to use 20 to 25% more of the home with water and ethen yield dull Une ppt in the H/ter cake...stab/e \par brew mercuric acetate since it is a little contaminated with acetic bisulfite addition product...can be stored forever...Quack!!l Yield \par (ducks can't get it totally dry without a vacuum oven). 3. NaOH \'b7-50 to 80% depending on a ducks techniquellll \par washed Brazillian is finelll Quackllll No need to purify further for \par starting material! Du Quack thought ole Strike had a screw loose at rirst but after \par continual quacking and persistence, Dr. Quack is convinced...this \par Now here is the secret(s): method is great as wellltll Quaaaaaaaaaaaaaaackllllllllllllllll Ho e \par \par \par ther add tepid OR cool ice to the water bath to keep it in this . \par range. Maintain drip at 1 large drop every 4 to 5 sec- Now as you can see, Dr. Quack is half nuts! And his description of \par on_ds...Quacklll This is imperative since the mecanism of chromic WFIQS and outcomes are right in line with what Semeone-whO.|S\par - 90 \emdash - 91 \par \par Not-Strike ma have seen. But what Dr. Quack did that SWINS .. _ \par did not was use the bisulfite test with positive results. What does WSH the gospel a\'b0\'b0\'b0rd'"g to Sodium Biallifaie conhrms it is a \par __ _____ _____ __ ____ __r_e_____ !__:_ ketone. Whetherthatisallitis .I\bullet l IIIO \par formed, unless Dr. Quack was fibbing to us. lt cahhot have been a Seem I _ i - ~ _ - , _ \par \bullet\bullet\bullet \bullet\bullet \'b7 \bullet \'b7 \bullet\bullet . ' \bullet\'b7 .I \'b7i\bullet i \bullet n \'b7 \bullet \lquote . `\bullet fm -r:. =' -YA-Mir s nsa OW[`la|']d \par the bisulhte addition product. Could an aldehyde have formed gqolglsenglprlifijeticfegfi \'b0fth\'b0 P2': "\'b0th"l9 l?\'a4tmlse_ry followed. This \par (don\lquote t ask)? Maybe. But highly unlikely considering the mecha- rurrherstud rYeeShHr\'80\'b0auS\'80 lis Petehtlel is massive. But it needs \par nism of the reaction. y` \par ME1\'b7l\emdash l0\'a4 2 \'b7 \'b7 . . . \par Later on Strike noticed a few posts from Dr. Quack grumbling for meking#;2;hIi1g;] i/llgfgggmh \'b0\'b0\'b0kS \'b0\ldblquote i_Y as 'I is ehhl Dtaetlcal

\par about how things did not, in the end, work out with the products of erle can ger . r' erm r ` , _b9\'b0aUS\'b0 Strike deh'! knew where \par this procedure. ls Dr. Quack cwazy? Yes! ls she a bad chemist? Works really Wslhlzel \'a5.L\'b0er;$gre til: ha: b?\'80"' amund awhile and \par NO! So what gives? Well, the following is a personal communlque restricted fer quite Seme tr B ? C elmceie heeded have been \par from Merlin: a chemist that all of you will thank when you see the the hell me ut 'f me can Qet them then what \par . . . . O \par "#2 wlthout water- proceed as follows. After the 4 hours stirring IS COOH \lquote *\'b7> \par complete extract direct with Ether A normal amount of Ether will \par do nothing so add more till a layer forms. This is due to the need Phenylacetic Acid \par to drag the acetone out from the water Water and Acetone mix, PEP \par the Ether needs a hell of a pull to drag it out. The layer will be This is a way to do th`s d \lquote \'b7 \par huge as it includes the Acetone. This will leave the muah which those crazy tube furnaloe;rgtsfiel\'e9ewviilzhfhugriziz/Iggdo use one of \par Wants to form an emulsion in the water layer which can h\'a4W be h\'a4US exide catalyst [21]. The key here is to use gnxl 6 or manga\par \par whicn will extract the acetone from the etheli leaving a small ether insure that the reaction proceeds in the right direxliensggcl ed Wm \par \'b7 I I II. I I-III ' . - ' I- I--. -I' t r, _ \'b7 ' I"-\bullet \par ,.\'b7....- - ~ .--- \emdash -\'b7 -- \'b7 \'b7 \'b7 \'b7 -\bullet m lqrlgee lk \'b7 \'b7-. \par colour After three washmgs (leaving the boogers lh the /0Wef (don't ask). 18g piperonylie aeid\'80l;z\'a53_g:dO;?,e:"l|a;iicrglrignzgzed \par watgrlayer each time) dly with sodium sulfate. Only a tiny amount acetic ahhydfide and 50mL pyridine are refluxgd ter 6 hcl ` mL \par erisosatfy will come over beforehand (a couple of mils) which will the Sdlveht removed by vacuum distillation The rg Furs ang \par float on top or the product (which l hope is MDPZP as this lhethdd due is taken up in benzene or ether washgtj with 1O$ai;l1 Hgrlresl\par is so fucking quick and easy compared to lsosaffy bastards and lutieh (discard the water layer) and vacuum distilled ll a so\par that palladium chloride method). This extraction method would P2P (56%)_ ' \'b0 get " 89

\par take 3 hours in total including purification, no need to fuck about \par \par (rather than 50%) giving just less than 60g product from 829 of [22. 23]- 709 piperonylic acid or 65g phenylaeetie aexidwil gzrgl? \par A I I I solution is heated to reflux until no mor; HCI gas is reieaggd trol: \par And a later email said this. the solution. The chemist should have a tube leading from the to \par of the reflux condenser to a glass of water to catch all that HCFi \par \emdash 92 - - 93 \par \par gas. What the chemist now has is a chloro-intermediate oil that is ilggsgzcufgeddtn the b\'b0\'b0k\'b7 The P'\'b0\'a4\'80d\'a4r\'80 can be scaled up to \par fractionally distilled to purify. 65g of this oil is added to 100mL p po '\'b0nS\lquote \par sou lon IS s lrre ovemlg a room empera ure. poure In 0 ICG - . \lquote _ _ _ 3 S rms \par water, aciditied with HZSO4 and the toluene layer distilled to give g;\'a7r\'a7;;L\'a7rFB? AZSI;\'b0hVdG '\ldblquote t\'b0 a qua$l\'b7\'b0V\'a2ll\'a4 Intermediate that will \par P2P in yields or about 40-50%. V \'b0 \lquote ZF \'b0"\'b02'\'b0l25l\emdash \par METHOD #8: Check this outl This uses benzene or \par 1 ,3-benzodioxole (for X) as the starting material [24]. This method \'a4 \'a4 O \par is better suited for speed makers because the NCI; catalyst can < me \emdash\'b7 < \'a4 ____ < Q \par tear up that methylenedioxy ring structure of the X molecule pre- \'a4 so o O \par cursor, Chloroacetone can be easily purchased. P\'b0\rquote\'b0'\'b0"'\rdblquote O mans Mncpgp \par O OVBF 6 4 hour period 23g of powdered sodium ethox' \lquote \par $ Q to a stirred solution of 50g piperonal (40g benzaldehygg) lgnildxg \par bromopropnonate which is being chilled to below O\'b0C with a bath \par Benzene p2p of lce and rock salt. After addition the solution is stirred for 12 \par hours at room temperature, then for an additional 6 hours at re\par 41.3g AICI, and 100mL anhydrous benzene are stirred in a 500mL flux. Ice water is added and the solution acidified with dilute acetic \par flask fitted with an addition funnel and reflux condenser. A tube is acid. The solution is extracted with ether the ether washed with

\par attached from the drying tube atop the reflux condenser to a water dilute sodium carbonate solution and dried through Na SO Dis\par trap to catch the noxious HCI gas that is going to be evolved. The tillation affords about 50% glycide ester intermediate gdonft ask) \par |I I \lquote .`I O \lquote I' . I *I I II-l*'l ' .II'I "\'b0 P \'b0 ':"\lquote i .\'b7 - *-6 \'b7 O. \par After addition the solution is continued to reflux for 5 hours to give _ U" 2 IS 8 ded to the residue and acldifled with l-lgl This \par a black solution. While everything is in the same position, water is acldlied solution is extracted with ether and the ether layerrse a\par added from the addition funnel to destroy any remaining AICIE, rated. Remember, this is not an MDA or amphetamine we gre \par This will cause more HCI gas to be evolved until all the catalyst is ta'kl'lQ abdut S0 ecidifylng is not going to bring this ihte the Wale,. \par gone. After such a time 20mL dH2O and 20mL concentrated HCI The ether is removed by simple distillation to give a residual oil\par are added, the benzene layer separated and the aqueous layer is This oil remains alone in its flask and about 0.2g of copper powder \par extracted once with benzene. Both benzene portions are com- 'S add\'80\rquote d\'b7 A \'b0\'a4\'a4d~'=\lquote\'b7nSer is placed on the flask and the eil is heated \par bined, vacuum filtered, dried through Na2SO. and vacuum dis- to .1SOf\rquote C for 18 hours. The procedure claims reflux occurs but \par _ - . an nv- \bullet\'b7 \'b7 , \'b7 .\bullet\bullet u \'b0\bullet\bullet Z r : "\'b0"`\'b7 `: ' I "" \bullet 'r VV 3 \'b7' : \par low boiling oil which will be the P2P and then 10g or so of black, h\'b0UV$ the MD-P2P or P2P is vacuum distilled dieggtrrl fron?. h \par \par flask. The P2P can also be purified by making a sodium bisultite intermediate. \par addition product out of it which is outlined in this reference and \par - Q4 - \'b7 95 \'b7 \par \par AMPHETAMINES AND \par Well that's the end of Strike's section on MD-P2P/P2P synthesis. METHAMP \par \par gc and check out Rh0dium\rquote s Chapter. You wont regret it!

\par Vlhth all of that MD-ISZP and/or P2P lying around, there\rquote s a good \par possibility that an evil underground chemist might turn it into tinal \par \'b7 product. Dear God! The thought of it just sickens Strike! But what \par can ya do'? And what again were those final products? Why it'S \par these suckers right below: \par \par \par O \par < Ilya \'a9V~& \par 0 \par MDA Amphstemlne \par 3,4-Metl1yleneDi\'a4xyAmphetamine (Benzedrine) \par HN \par O \par MDMA Methamphetamine \par ~ 3,4\'b7Metl1yIeneDioxyMethAmphetamine (Speed) \par \'a4 cum CH cn \par < O i~\rdblquote O ~~\rdblquote " \par - Q6 - - 97 \par \par A _ . . i k-i.i igii solve any polymerized mass (No, Strike still ain\rquote t gonna tell you \par So without further ade- here S the reclpes you VS been O0 I g how to calculate \lquote 3N'. You really need to learnito calculate Nor\par _ i . _ ____ _ - __, mam &M \'b7 ,, ; \'b7 , 7 __ _ _ __

\par , ee . ; - \'b7 \'b7 ==- \'bb \'b0 V _ ' . \lquote ly a 10% HCl solution). The entire solution can if \par \'b7 his is the cleanest, highest p'\'b0\rquote F'\rdblquote\lquote ate _ _ \'b7 \par t\'80\'80d[Opl_|tth\'80$lHl`Chln l/0Ut$0 SlT '_ =_= I \'b7_ _\'b7A e- -e e- ee, ei 7 o_ ee o _ _ ereiswere Sch\'80m_ \par yisiding prooe ure or ma IUQ ' bi t mc up ist comes to a slight variation in what is normally considered

\par eyer known. lt is abeoluielll 'h"p\'b0Ss' 9 \'b0 ' washing and extracting. The MDA is , at this point, an acid loving \par O species and is actually going to stay in all that HCI solution even if \par /\\O ` /\\ that solution is mixed with an organic solvent. This gives the \par 0 chemist an excellent chance to recover all of the valuable, unre\par 0 O N,en$cn1cn,cooNHi NH2 acted MD-P2P which is not acid loving and will go into the solvent. \par Li" So the chemist extracts the HCI/MDA solution with a few hundred \par mLs of DCM (a.k.a. methylene chloride, or dichloromethane) and \par MDA saves the DCM to recover the MD-P2P for later use. Technically, \par MD-P2P ' ' ve in an en ex\par Q-ililggpicglillgfsil lsniigt iery common but there are few `Dl\'a4Ce$' thiat way worksjust as wel|_ \par 3 \'b7 ' \par . . - t routofthe airsote \par stm sen IL It Is Vary Qiggililig ljaofshlglggvz it sitting out all \'a4iQltt\'b7 After the DCM is Separated from the HCI/MDA, it\rquote s time to release \par chemist mehes eu'? .t iiseii the MDA from the water. To do this the chemist has to make \par The method 'S Slmp ICI y ' some saturated sodium hydroxide solution. A saturated solution is \par \'b7 \'b7 qi d 200g MD-P2P (or made by dissolving as much sodium hydroxide as possible in an \par T\'e9g 8 Egg? ngik ggozlaismtrizrlhligrilsaezteitg 2000ml rnetharwl amount of Water (say. 500mL). This NaOH solution should be \par 9 \'b7 \'b7 ` o h dride chilled in the freezer. So, the chemist is going to place her \par and s l y p r all - " ! '\'b7 \'b7 \bullet e \'b7 e' U P \'b0\'b0 \rdblquote\'a4 h \lquote \'b7 _ I h I HD ICG 3 [By \par . . \'b7 ii o ofthe flask to dispel with stirring. Next she starts adding the cold NaOH solution i \par the an and t $\{8; stirs gt room temperature f0l' 24l`li'$\'b7 tion will start to gel Warm and slowly turn basic. At around pl-i 9 \par l'Qht Yellow S\'b0u '\'b0 beautiful, clear-amber beads of MDA freebase oil will appear all \par _ . o V Thesolution is com- about the solution (most of it settling at the bottom) and the

\par Thats It! The gaznzclxiigeg? gra pioduced, and all of this Ghernist adds a little more base to insure an excess so that all \par pletely Zileiriglgm rczmpgraturg with no pressure needed. Strike MDA will separate out. This is one of the more pleasant events of \par ?;3I$;i th?s was gooo_ The solution is now cleaned up a little and drug chemistry. \par the MDA isolated. . - 9 Wa ei, \par il-he mGt;a;\'b0;i;;r;aS:|um ms\}! G mm 9 . mis merey pours a out 4 0mLs of DCM into the con\par . - i o r r will polymenze lnt0 a tainer and stirs it really well for a few minutes w ile s e watches \par Hines Liiggn E3-$:3,9;:1;;; Onizligtlvirill ggl Evra? in the next $leP\'b7 T0 TV. As much of the water as possible is poured off or separated \par elerlcerilrate is added 2000mL 3N HCl solution which will dis- - 99 \par = - 98 \emdash l \par \par in e eeparatory funnel and then the DCM layer is dried through aluminum foil i\'a4 reduce ketones, Strike thought that it was b \par toog of sodium sulfate ( see methodology chapter). The DCM is bil! 8 bunch \'a4f baioney because this procedure was \'e9iisaiz \par .\emdash . \emdash ..\bullet \'b7\bullet\bullet in-\bullet - ur -\bullet\'a4 \bullet -\'a4\bullet\bullet - \lquote - ' ""\rquote * *' \bullet --~-\'b7= =\'b7\'b7er \bullet --, .- , \par light-amber MDA freebase. This oil is so clean as is that it can be BS if it merited much Cgngidgrationl iii fact, this riz\'e9dui nt ook \par \'b7\'b7 ; oi\'b7\'b7`o\bullet s` ;i\rquote \bullet\lquote ~3"i i \'b7r \bullet l\bullet\bullet """ \'b7\bullet suefggs utt ' \'b7 \'b7 x \par to get rid of the color impurities, but there is so little contamination But since the catalyst is 'pxlain olldgaxlfriilritirg |i\'b7;Vcg.u_;O%ii \par and, besides, what little there is will separate out in the process of prove to be the perfect 'foiI' (ha hal) for those who Fcan't et thwi \par crystallizing the product for consumer usage (see Crystallization hands on other highpowered catalysts. Strike did sa ighat tl? \par chapter). method will produce methamphetamines but the trayde-off fos \par those spoiled babies that just have to havelthis kind of dru 's th i \par The yield here is 80-90%. No, that is not bullshit! This method they are going to have to use a watched chemical the ri I d 8

\par has not been given the proper credit it deserves and sometimes m6lhYl\'a4mirls. lt's pretty groovy that this book has. gng \{sa ed \par has been dismissed without due process. Does Strike sound de- without having to rely on any controlled substancei e Ii lar \par fengivg? You bet! Strike has been in the science game for a long precursors. As one of the most watched cherniceie or X or \par rro:*i \lquote i\'b7\'b7\lquote \lquote : i""" ii\bullet 6 2\lquote i\rquote i\lquote "'\bullet Zi|\'a4'i =I . I ` g ln O aveto . 1 _ l \par that's ok, because those who do not use this method simply get this book is ar? easy methoctii\rquote oT?r?;kinrg ih; i:di\'b7inm\'a7ai:ei:y$ita?\'b7h1in\{g \par hammered by those who dol that is required for this method which is methylamine h d \par ride ci-limi-i .i-ici. V i\'b0\'b0hl\'b0' \par For those chemists that prefer MDMA or meth, this method can ( 2 ) \par work for them too [27]. Everything about the catalytic reduction \par remains the same except that instead of using ammonium acetate /\\O \par as the amine source, one is going to use 1000g methylamine hy- /\\ O CH \par drochloride (see the Chemicals section on how to make). The O O Ainwenn O / \ldblquote \par screwier thing about this procedure is that someone is going to O __ is HN \par 'iv\lquote ii:iv\lquote *2 \lquote\bullet i5\rquote i G s i`i\'a4' ''`' 'i "G v \par every now and then. The reaction has to remain neutral (pH 6-8, ` \par \par dissociation products from the methylamine are going to start to ih . G qhamlsl pl\'b0\'b0\'b0\'80dS\'b7 Nexl in lhs Ghseios, the pa\par turn things basic. So someone has to keep it neutral by checking ellcqlly unemptled a$hll'aV iull of Cigarette and joint but-te, the \par the pi_i with pi_i paper and adding 8 coupie of drops of rave fliers and the decomposing cat carcass the budding chemist \par Siraighi_fr0m_ihe_bOiii\'80 concentrated i_iCi> Aside of the two may find her roll of aluminum foil. 50g ofthe foil is cut up into 1in \par changes, the reaction, cleanup and yield remain exactly the same. X lm Squares and Chunked into G big flask or glass sun tea ing \par Older methods suggest that those pieces of aluminum foil be

\par METHOD #2: By far the most popular method currently available. ;'ij_';\lquote\'b0r;l1OV;'gh_S\'b0m\'80 Fliluie \'a4\'a4lu\'80\'a4us NBOH, drained, then washed \par , . A -- _- _. _ __v__ . F = Mi!. . _= ll` t I \lquote no-A! \{ ` --\emdash ;\'b7 ' -_ A \par meih and MDMA (.\'80cSiacy.)\'b7 it is a Very clean procedure, akin ic surface ofthe aluminum before itris amalgamated. This really isn't \par \par catalyst made from ordinary household foil [26, Z8]. When Strike _ _ _ \par was reading all the underground literature on the use of household lgihsr Way\'b7 the i\'b7\'a4\'a4r>v iliils full Pl\'80\'a4\'80S snd up lying at the bottom of \par 100 t e flask ready to be turned into a catalyst. To do this the chemist \par ` ` -101 \par \par . \'b7 hloride (l-lgcl) dissolved in this way f0r3 hours. Usually, the temperature never seems to rise \par pours 8 gsllgloldogtllrgqg it;$t;il.CThe Hg $t6l`t$iO lnlnledtatetY over 30\'b0C no matter what one does. Some folks sa tn , - . \'b7 \par 1700mty 3 n l n I_._ _. L" ., \'b7 .- \lquote -..\'a4 -- . \'b7~\'b7\bullet\'b7 in itis.Thesolutionlooksveryhet\par \'b7 \'b7 II h t. This is allowed to continue erogenous. B this Stnke \'b7.\bullet \bullet - s .- - H . \par tha S\'b0t\lquote\'b7't \'b0" 'tt a t9 \'80 Ej y\'b7 . \'b7 ~s -i . \'a4\'b7 \'b7\'b7 we aroun in the flask. Amber beads of P2P go flying by as do \par d -g \'80y wt h metal particles from the degradation ofthe at\'a4tnt\'b7 chunks of foil, grey dust, and frosted beads or oil_ \par cou y W \par hum- After 3 hours the stirring is stopped and the solution allowed to \par 'd here. Just about all of that settle. By this time just about all the foil will have turned to dust, \par There arg Z CcxglglggEygtfnitgdcggtglyit, which is great except that which is going to make the next step of vacuum filtration very dltti\par pOWd\'80r\'80|| \{ui ill bg lost in the next cleanup step. One can maka Cult because it will plug up the filter paper in a seoond_ 50 the \par almost a ti I Wf Catal st t[]Cf'\'80aSil']g the aluminum batch stzev chemist tets settle, then pours OH thB through the Vacuum

\par up for mg Origcgeeery ltn doing this. There is a dengef point in ttltfatlon Setup (see methodology section). The flask is rinsed \par butkgari I; bl a batch of AlHg. Beyond the size of a 1509 of At. with 100mL methanol th ii \'b7 . . ... ,, . s , . s ,, . . s , . , -i \par ma 'h9 9 9 _ _ _ - - \'b7 \'b7 _ . - " , \'b7\'b7 cake andthe Hlter cake discarded. All of the filtrate is placed in a \par \'b7 \'b7. _ \bullet _ v V * U . . . \par \'b7 . t tfeakyl Also, the amount flask and vacuum distilled to remove all the methanol, isopropyl \par Camc Steer\}? Cllgugcltnlig itrgrrgashgizgsndrthe ratio given here t>a\'b7 alcohol and water which will leave the chemist with oil and junk in \par ggiiiigtzifriltmplulverize all the aluminum very quickly leaving moth- the bottom ofthe flask. \par thg butdust The cleanup of this oil is exactly like that which was done in \par \'b7 ` d nted from the catalyst Ieav- Method #1. The oil is dissolved in about 500mL of 3N HCl and the \par After 15-30 ml:uggsegcirmtzfrmztatiiunks. lf the catalyst is eX\lquote Solution extracted with 100mL of DCM. The chemist remembers \par mg Just Snpq? meld degrades. The aluminum is then washed 4 that in this particular case the MDMA or meth is going to stay in \par posed tghatresg dl-l \'e9 decanting each washing so that a little Wa\'b7 the HCI/water but that . -, -. . __ , - e \'b7 - _ a a - _ _ \par tlma \lquote\rdblquote '_ t ___ _ __ ,,_ - - _ , \'b7 ..\'b7 \bullet \bullet\'b7 ing to be in that DCM so it, ofcourse, is saved. The HCVMDMA \par ` ' . \'b0 ` \'b7 d for the big reaction. Attef ` ` " ` e a so that at around \par the taat wan Qgms imo the ftask holding the catalyst in the exact the solution. As usual, the oil is extracted with DCM, dried \par t\'b0tt\'b0W'"g "fte _ through Na2SO4 and the DCM removed by distillation. The final \par Otdst as t\'b0 \'b0wS\lquote product here is usually a little darker in color than the product \par \'b7 - \lquote L dH O achieved in Method #1, but it is still remarkably clean and may be \par (1) 769 m\'b0thytamtn?at;L%u2|76m 2 crystallized as is with the crystallization process removing most of \par (2) 23OmL tgggogyueous NaOH solution the color impurities. Of course the chemist may wish to vacuum \par (3) *83 mlb P2.; O? 50 P2P distill to afford clear r ` ' '

\par \par The flask IS pctasienqign ; g\'a7;ntlcstaartIed?(ice is added as neeeeeaty cept that ammonia is used instead of the watched methylam\par necgziatrg/Bapempemtire stays below 50\'b0C and the solution attrs ine.HCl so one can make MDA instead of MDMA [29]. This is \par so \par - 102 - -`103 \'b7 \par \par pretty low yielding and can get messy. lt is strongly suggested that "\'b0W\'b7 M\'b0\lquote\rdblquote\rquote Yi6mi\rquote\{6 is N0 IOOQGF 6 Stumbling block in the aluminum \par ohe eohsider doing #2 above betore tryirto this method 549 amalgam reductlve alky/ation method of producing MDMA as this \par e -\'b7.\'b7 \'b7.\'b7e \'b7 \'b7 s as \'b7 i as-- - -.\'b7s as-- - . .s--s. VO \'b0 -1\'b0 \bullet\'a4\bullet \lquote Mun a c e ee .\'b7\'bb \lquote - 6 --; r \par ammonia solution (ammonium hydroxide), 40g aluminum grit m8i9"\'80\lquote ?\rquote\'b7 in Sliut during The reduotive alkylation of MDPQP fg \par +(_lFa. .a. powdered auT m or iney mT auminum n _ _ e. iromethane when \par 039 t.tgCt2 ere stirred together -t-he mixture Witt heat itsett up subjected to the simplest of reductions forms methylamine, so why \par pretty good so an ice bath can be applied to insure that the reac- \ {\rquote\'b0i\rdblquote\rquote 8k\lquote\'b0` \rdblquote\rquote\'b0\lquote ihViam'\rdblquote 9 at ih'? Same time MDMA is being produced \par tion doesn't get too violent. When the reaction has simmered \rquote "$i\'80ad Ofgomg ihmugh the #858/G of making it separately? \par down, the solution is refluxed for 2 hours; then the solution is vac\par uum distilled to remove all the ammonia and methanol. What's left N-r th . _ \par is water, MDA and particulates. This solution is basitied with \lquote l20g toggingtiagagzoseirdvziidkcggirg2;;,73\{ifi;/dj gg ggwn to \{Fur \par KOH or NaOH to release the freebase oil which is then extracted . . p g \'b7V\'b0"\{ \rquote gh \par _ . . . . performance cars fuel. Its also available up to 40*7 ure rn RC \par with ether. This ether is then itself extracted with 3N HCl, the modettuets Simpty fractional] disrrrrrhe nt rh \'b0 p C, \par ether discarded and the freebase liberated from the HCI by basl- euro I: u u _ _ H. _ _ _ _ __ _t Om g ne p

\par r\'a5;%r;g;Kr 2%% ` \'b0 - \'b0 9\ldblquote\rquote\'80 Cean ree ase W' a we ' \'b0 ap` prerseht in the fue-it formulation, some will azeotrop ally sti l ver \par \'b7 wi e ni romet ana lowering its boiling point slightly but this \par ir r ' \par METHOD #4: This here method was contributed by a scholar OES no prSS9mapmbI9m\lquote \par named Ritter. She is adamant about this method and considers it \par a major breakthrough. Ritter wants to do what was done in So, how does this whole thing work? lt's as simple as it sounds. \par Method #2 except without the insidious methylamine. An alcoholic solution of nitromethane and MDPZP is dripped into a \par mass of amalgamated aluminum immersed in alcohol iirst reduc\par /\lquote\\O /\\0 ing the nitromethane to methylamine, allowing the Schiff base of` \par _ _ A CH3 the amine and ketone to form which is then further reduced to the \par ' Is O A|Hg/MsNO= Ts HN esrre VI V _ \par \par 'Z? VY \par Set up a 2 liter two or three-neck flask with an addition fun I cl \par MD-P2P MDMA a reflux condenser and provide with a heat source. Not mug; h\'e9erat \par _ _ is needed here so anything from a water bath on a buffet ran e to \par Who i\\leeds Methylamrne Anyway? a heating mantle is line. Stuff 55 rams of one-inch u g \par _ _ Q sq ares of \par by. Ritter edited by The Professor aluminum foil into the Hask. An important topic must be addressed \par Dgdjcafgd rg gidusjs here which has been formerly neglected to a confusing degree \par the proper type and thickness of foil. The problem with aluminum \par The fo/lowing procedure may proveito be. one of the largest 8d\'b7 three major favfors, and depending how you play these factor; \par I _ _ _ _ ou may either have a complete failure or an explosion, or better \par dissemination of the Wacker oxidation procedure for producing yet lf_you follow this advice a perfect yield! These factors are the \par MDP2P. This reaction is based on a published process that mentioned foil type, the degree of amalgamation allowed by HgCl2

\par somehow has escaped discovery by underground chemistry until \par ' - 104 - \'b7 105 \'b7 \par \par solution before ketone and amine are reacted and Hnally the \par temp the reaction runs at. Thick foil tends to react slowly at a low . \par \par tends to react so-fast and exothermically you can literally shit your five features_ Ot this new Synthesis is that the standard AU(\}-ig) \par ,, _ -.- . I . , ..... 5 !: !:. :.. I _ ~5: \'b7IlI\'b7 II I! _A: u__ g; :5:, _ -.-; G -i;;; ,;.\'b7. \par available to the industrial biological community in the fonri of 4" x uct from the spent aluminum hydroxide sludge at this point 77-,6. \par 4" sheets .04mm thick neatly separated from each other with a f\'a4ll0Wi\'a49 remedies this most frustrating step and will probably give \par sheet of tissue paper. It is used for sealing tiasks and the like be- many a new outlook on the potential of the Al(Hg) reduction. \par fore they are autoclaved. For those of you who can't get this, don't \par worry. Heavy Duty Reynolds Wrap will work nine, only a more , _ \rquote \par careful eye must be kept on the reaction rate. Others have re- M'X up about 1-5 Ur 2 liters \'b0f_35% NBOH SOIUUON and ellow to \par ported success using cut up pie tins. The main idea is don't use ggzgnsigvyli wg\'e9zesgcgzotzimgum QQ0;< Pl'7dUC9d in the Hrst re\par \'b7 fl n pour in o a a e se erato fun\par mal mm fo nel. Two distinct layers will appear after sitting fgr macbe 8i'?iIOUlj \par \par Fill the seperatory funnel with 50 grams of MDP2P and 50grams tom garbage NaOH/Al(OH)3. Simply separate off the garbage \par or 39ml nitromethane dissolved in 200ml methanol. ln another 1 bottom layer and discard. Don't worry there's no product tied up in \par liter vessel add 1.5g HgCl2 (mercuric chloride) to a liter of metha- it, and remember that no Hltration is needed anywhere in this re\par nol and allow all solids to dissolve. Very carefully (HgCl2 is deadly covery process compared to other synths out there! Take the top \par poisonous!) pour the methanolic solution of HgCl2 onto the alumi- layer and evaporate off the methanol to give an amazing yield of

\par num foil pieces in the flask and stand back and watch the magic impure amine and a little bit of water Unscrupulous souls not \par begin. lf all of the foil isn't covered by the methanol just add more worth their weight in shit can take this product and crystallize it \par until it is. ln a few minutes eifervescence will begin and the reac- directly but there is a lurking deadly poison in it at this point--- sol\par tion may be started. After about 5-10 minutes the bubbling should vated mercury salts! These can be easily removed by dissolving \par \par nitromethane and MDP2P drop by drop from the seperatory fun- several portions of water in aseperatory funnel and i7nally with a \par !: *_ urge! 3..:, I: !f=H!! He Ita .! ! If QQ! Q 4 \'b7'| Ia- .!. 5! Q! I: e,\'b7\'b7\'b7 .-. -,;;, -5; ;\'b7-, \par boiling and refluxing of the alcohol will occur. This is no problem drous MgSO., made by heating drug store epsom sa/ts in the oven \par as the 65\'b0C boiling point of methanol is perfect for this reaction (I at 4007: for an houg cooling then powdering. After sitting for an \par know many disagree, but dream about this and youll see!) The hour or until the toluene is no longer cloudy, chill the dried toluene \par addition should take roughly one hour and the mixture should be solution of freebase in the freezer and bubble away with HCI gas \par allowed to react for at least 4-6 hours after or until all pieces of to produce beautifully pure MDMA hydrochloride crystals. lf they \par aluminum are reacted into a gray suspension. Temperature con- are a little discolored they can be easily cleaned up with an ace\par trol needs to be addressed here. lf the reaction proceeds under tone rinse to pristine purity VWTH NO MERCURY \par \par ideal and more comm-only, the reaction will start to Slew d0Wn [ses ret CA, 51 11278 (1Q57)]' \par \par action rate. lf the Greater Powers really are against you, an addi\par tion of another gram of HgCl2 in methanol solution added to the \par mix will kick it back in. \par - 106 - _ 107 _

\par \par _ . ` ly an aluminum sauce pan with enough corn oil in it to \par METHOD #5: This method is extremely easy to- dotbut can be 'S mere _ _ _ _ _ \par messy. One needs to read everythi trike sa i his se t n 0 qu a etn e g h f t lq i ln t e s . t erm m ter I laces; \par action and it converts P2Ps into amphetamines or methamphet- setup |\'b0\'b0kS hke n9L"\'80 11\par been \'a4r\'a4SS.'v m'Sr\'80p\'b0r\'a7ei\'80dLrii;pnit;:,:1;\rquote d`IiIiL`e;l:g ggezpffglgzggltgtgghi mix achieve a temperature of about 120\'b0C in about an hours time. \par l\'a4F\'a4d\'a4\'b0t'\'b0" IS \'b0\'b0"?e""\'b0 \'b7 f U d in ehemieei Abstrecte tgt This It is at this point that CO2 bubbles will begin to emerge signaling \par the l\'b0"l9\'80$t f\'b0'X 'S the me \'b0 n ee eee the yieies suck (about that the reaction has begun. Some amount of ammonia will start \par \'a4'leth\'a4d W9'k\'80 but_'t 'S gr? Wythie metheei Werks but e few to be given off at this point so the apparatus, if not already in a \par 20%)- Stllke 'S gm"? t\'b0_ 6 g' \'b0 i d We iets et weiis that this hood, should be placedin one. It is from this point that the solu\par Pal'\'a4Ql`aPhS 3WaY Smke 'S gmng today od reduetieh tion will start to turn from its clear yellow color to that of a more \par m\'80th\'b0d can be better f\'b0" b\'b0th X an spas p ` orangy hue. The temperature of the solution is allowed to slowly \par O climb until it reaches the blistering temperature of 190\'b0C. It is \par \par rg < " E; < the chemist will have at this point is a thick, gooey mass of black \par < 0 "\'b0' U tar that has probably gotten so thick from polymerization and \par \'b0 MD-me N_i\'b0m_yi_MDA MDA evaporation that even the magnetic stirbar has been halted. \par 23g of MD\emdash P2P or 17g of P2P that was made by any method and When cool, 100mL ether is added to the flask to dissolve all the \par 65g formamide (HCONH2) is poured int a small Pyrex flask (sorry. tar and then the black tar/ether is poured into a separatory funnel. \par eieee ie e he_he The ether is washed once with 100mL dH2O, the upper ether layer \par here) if eee Wehted separated away and the water extracted once with 100mL fresh \par te nieke meth et t t ether. The two batches of ether are combined and the solvent

\par i _A- i\emdash i - \bullet\'b7\emdash ysiimpeb esi a ion eaving the chemist with a black \par ma$SO OI In he OOITI |' a- . L`! nt .\bullet s\'b7\'b7 as. \par Z/igeligeiie Goielifeg i _, 1 8mL of methanol into the flask, swirls to mix the tar with the MeOH \par Mmeihyifermemide \'b7 then adds 75mL of 15% HCI. This solution is refluxed for three \par ineteed et tem.iam_ hours during which time the whole solution becomes black. The

\par i e e Hewevee this .\emdash -a i \'bb . J ;\'b7\'b7 chemist is using HCI to hydrolyze the formyl intermediate. The \par ehemieei is eX_ eg at " solution is allowed to cool then is basitied with concentrated \par tremeiy Wetehed \rquote NaOH solution until pH -9 is reached. The chemist won\rquote t really \par beeeuse ef its use need to check the pH with litmus paper because, as usual, dark \par in this recipe se it is _ drops of MDA oil will appear all about the surface of the solution \par _ ,_ _ U s . . \'b7 \'b7- an m ica ion. \'b7 a is eftlis forthe chemist to extract \par \'b7 the MD/-\\Wllilt \'80thS|\rquote 0r'DCM nr \bullet \'b7\'b7- \'a4\'b7 .e r- -=\'b7 \par Sigma V\{i?\'b7iLggr\'a7:\'a7i$1 ever, Separating the solvent layer from the water layer ns e bit \par ehemist Weuiet use . . . _ tricky in this case because the two layers are so equally black that \par This flask is placed [Figure 11] ll may require a lot of squintmg and a flashlight to spot the inter\par ln an oil bath which 08 _ 109 _ \par - 1 \par \par face between the two. Needless to say, the oil obtained is way to \par filthy to use and must be vacuum distilled to afford clean yellow \'b0 is _ ,.,,,,_,,,_,, \'a4 ts 0 A /ii\\ \par \'b7\'b7E* \'b7\'b7a:\'b7\'b7 \'b7\'b7s\'b7 =a scare s ez \'b7i\bullet , an \bullet i l i N ` -+. ` \par the effort to get this sorry yield is not worth it, especially if this is \'b0 vt *\lquote\'b0\'b0\'b0"\rquote *\'b7 \'a4 U F2Li'2'\'b0 0 U \par \par conversion of at least 200g MD-P2P or P2P. _ _ \par it one is using formamide or N-methylformamide then one is not

\par If ever there was a reaction that was batch size independent then 9\'b0'n9 t\'b0 have the advantage of creating formic acid as e break \par it has to be this one. A chemist can try to process 200, 500 or d\'b0Wn Preduet. S0 the idea is to have formic acid already in the re_ \par even 1000g of P2P using this version of Leuckart and never re- eetien mix- To do this one takes the 65g of formamide and mixes it \par cover more than 100g no matter how careful she is. This proce- with 309 of 88% formic acid, plaees this flask in the OH bam and \par dure is more in line with those who wish to make steady ettecnee e eimpie diatiiiation set up to it as shown in figure 12 \par reasonable supplies of X and should not be used to process more Since the formic acid has some water in it the chemist is going re \par than 100g of P2P at a time. In fact, it shouldn't be used to make remove that Water by heatin the oil pa h _ \'a4 \par \par water distills over the chemist allows the reaetieh flask to COO. \par strikes mission with this book is to provide as many methods for a adds the 239 of iViD\'b7P2P, reattaches that distillation setup and ei; \par conversion as possible. Slight corrections to a recipe can make a t\'b0"\lquote\{e the mix to slowly rise in temperature to 160-170\'b0C_ The re\par great difference; and to become a truly great chemist one should e\'b0t'\'b0n SteVe at tnie temperature for 5 hours, any longer n-lakes \par be aware of both the good ways and the bad ways and what it ttttte difference. Aiee. it the temperature rises above 170%; iheh \par was that made one recipe a poor one and another a good one. destruction- not production. Wiii occur. The distillation setup is \par Tnen_ when a chemist comes across other or future experiments, titer e te condense any Product that happens to exit the reaction \par she can make a more educated assessment as to its worthiness. tteek- inte dietiiiete is returned to reaction while things are still \par This whole Leuckart business is a good example. The Chemical n0t- Using termic acid effectlvel doubles the \lquote \par \par \par illegal chemists in the face. Not until very recently has some cor\par rection been made in some of the underground literature. Folks

\par interested in speed manufacture should read this closely. It all \par relates in every way to the betterment of methamphetamine syn\par thesis. \par The Leuckart reaction was originally conceived using a chemical \par called ammonium formate (HCOONH.,) which is very similar to \par \par \par mate part turns into formic acid (HCOOH) which then acts to re\par duce the intermediate into its stable forrnyl derivative (don't ask). \par - iii) - \emdash lll \par \par are more amenable to production. Whichever way was used, the \par I chemist is going to have a cooled solution of formyl intermediate, \par .|| IIII.I! l" l"-T- !.!C! 1, _ !!!.;-, . _ \par \\ stuff from here that are better and more convenient than the origi\par \{ _ Il , V - - I - _ \par I \par A Instead of washing the reactants with water, extracting the product \par with ether, removing the ether then hydrolyzing, why couldn't one \par * just hydrolyze right off the bat in the original reaction pot? As it so \par - happens this can be done. The chemist can put 200mL of 30% \par \{ Ill aqueous NaOH or 200mL 30% HCI right into the flask and reflux \par for 5 hours. Using NaOH to hydrolyze has two advantages: it is \par _ _ _tg_ t___ gentler on the methylenedloxy ring structure of the X molecule and \par I g = it is faster to process. After hydrolysis is over and the solution has \par V \bullet\bullet\'b7i\'b7 0 \'b7 \'b7\'b7i O I \lquote T3 wi G SFOO EITI VI' \par my oil because using NaOH means that the MDA stays as an oil \par _ _ throughout. A really frugal chemist can do one extra thing to help \par 1 \rquote herself out. She can take that ether/MDA layer and mix it with a

\par I `ci \lquote \'b7 \lquote few hundred mLs of 3N HCI. This, as usual, will cause the MDA \par _ _ f to go into the water layer but what is going to be left behind in the \par gs ether besides tar is going to bea lot of unreacted, valuable P2P. \par The chemist saves that layer to deal with its P2P payload at an\par other time. Meanwhile, all that remains is for the chemist to re\par F? lease the MDA from the water/HCI by basifying and extracting with \par r. \par [Fig 12] \par _ _d Of course, there are a couple advantages to using HCI as the hy\par Other ways to dcthis l\rquote\'80\'a4\'a2\'a4\'a4\'a4 W\'a4U*d \'a4\'a7g> W*\lquote a***l1\lquote ;;\rquote ;*d\lquote i?[fgd;)f drolyzer. Since using hydrochloric acid means that all that fat \par in tho old days: ammonium fefmete - \}$_Wa\'a5 MDA or amphetamine is in the water solution, the chemist can \par ammonium formate, no f0l`mt\'80 BCI? and"; d'$tTit'\'b0"_s\'80;g% vacuum filter the solution to get rid of all the tar and crap which will \par other combination that works SQUB IY W6 'S T \'b0\{m'c give a remarkably clean water solution. The X is released by ba\par ammonia in place of formamide. It is also perfectly fineto remove sifying and extracting with solvent \par the water under the distillation setup. then replace It with 6 FSVIUX \par Condenser and conduct the FGGGUON under VGHUX for the 5 h\'b0u S Since the formamide reaction solution is going to be a lot cleaner \par , na,r ` \'b7\'b7\bullet\'b7\'b7"*""\'b7\lquote \lquote "` Q \lquote\lquote\lquote\rquote ' ` n e meso or' i reip , c mi A ye n\par actions. other option to explore. Instead of hydrolyzing in the reaction pot, \par These mgm me amount cr tar M-ns-\'b7y and kegpi LTSp\lquote ;T$'I;2\'a7\'a7"\'a4$\'a7?.\'a3d\'b02'\'a3Ci\'a7I ?ii??h?5i.?.\'a7ISSELQEEJIEE SOEES \par the reactants together B |0\'a5 |0\'a4Q\'80*' under \rquote\'80\lquote 8\'b0t'\'b0" \'b0\'b0"d't'\'b0"S E to look for a heavy oil layer that will settle at the bottom. The up\par - 112 - - 113 \par

\par per water layerlis decanted from the oil layer. That water,. by the flask with the formylMDA residue, the condenser from the distilla\par way, can be acidified with HCl to forml crystals of formamide that ti n s-et is plopped in vertically and the solution refluxed for a mere \par rl O` I-`O I l` \lquote l'|\lquote - I - ' -II'\'b7 I` Oi lll III C. *2 -5. 5\lquote "\lquote :` i \lquote i" l G` ." -7 \par of the flask can be hydrolyzed as is with either 10% HCl or 10% solution, the distillation setup reattached and all the ethanol dis\par \par and outcomes of hydrolyzing with either of these two compounds. from this the MDA is liberated, as usual, by basifyln;OxiihHl$a3Ld \par extracting with solvent, drying the solventand distilling to get MDA \par By utilizing the improvements stated above in any combination in 70% yield. \par preferable to the chemist, convenience will be enhanced and yield \par will jump from around 20% to that of 50%. Not bad, but there is Dear readers please take notice: Not once has e \par one more oddball fom\'b7i of the Leuckart reaction that was devised stirplate since the formamide and P2P reaction sgartggsxplig th.; \par specifically for X production and produces a yield of 70%! This last point where MDA freebase was liberated. That's pretty damn \par little procedure [32] has been around for 40 years and has, until convenient. Technically, the Leuckart reaction can continue as a \par recently, failed to be reported as a superior Leuckart conversion one pot synthesis from the last part of P2P cleanu ri ht u to ri\par \par trates Strike. \par The last thing that Strike has to say about the Leuckart reaction is \par This procedure works equally well for both X and speed produc- the use of LiAlH4 as a method of making the final freebase out of \par tion. The set up used is the same as fig. 12 (remember, no vac- the formyl intermediate. What we have gone over so far is the \par uum) and into the reaction flask is placed 275 mL formamide, 80g method of boiling the formyl intenrnediate one gets from the form\par MD-P2P or 70g P2P, and 55mL of 9% glacial acetic acid (50mL amide reaction with HCI to hydrolyze the species. What happens

\par dH2O and 5mL glacial acetic acid, bubbal). This is slowly heated when one does that is that the bond between the nitrogen and the \par to 140-150\'b0C inthe oil bath and kept there for 5 hours. The lower N-carbon gets ripped apart allowing the amine to form. But if one \par the temperature at which a sustained reaction (bubbling) can oc- uses LiAlH4 instead of HCI, what happens is that the double \par \par \par over and can be discarded. MDMA instead of MDA! And without havin to use the est ' \par N\emdash Methylformamide to do it. g r noted \par After 5 hours the reaction is stopped and the flask cooled. The \par formyl-MDA can be isolated and hydrolyzed by any of the ways /\\O O /\\O \par Strike just mentioned a few paragraphs back, but this method of- g;H3 \par reps a third, very convenient way which should be tried. What lh\'e9 O HN)LH ,_,A,H,, O HN/ \par chemist does is forget about letting the flask and its contents cool. ?\'bb \par instead, she removes the oil bath, places the flask back on the \par \par myl-MDA precipitate that is allowed to cool down while the chem- TO make MDMA f th f ___ \par ist makes up a solution of 150g potassium hydroxide (KOH), Leuckart reach) thmmh e tqrmyl. 'msnnedmte qbtfmed bv the \par 500mL ethanol and 125mL dH2O. This solution is poured into the Cleamy\'e9uow 0:I grsteghgpgi\'e9i ggggoazziig ;:\rquote D:;SE\'a7;';g?n?\'a7$1\'a7;; \par - 114 - - 115 \par \par reaction is too dirty. 50g of cleanish N-formyl-MDA or ampheta\par i , qj gg v d i to rri ri y o s ( _ u b ba! the . hi E H = 341- ls ms 2 i t i te diate sailed s \par 200mL anhydrous lether and the reaction mix refluxed hard for 4 solution of 25g MD-P2P or 18g P2P in 40 L th nol Og ydr x \par rs, \'b7 \'b7 - \lquote " \'b7 " \lquote\'b7' " ' "' \lquote "\'b7 "*" *" lSa e as0utiono 6g \par coursing through the condenser and that there is a drying tube NaOH in 20mL dH2O. This mix is then refluxed for 2 hour d`

\par placed on top of that condenser. After four hours have passed luted with 100mL dH2O, acidified with I;lCl and extracted with Ethe\par 100mL of dH2O is poured into the flask to destroy any remaining to give a thick, red oil upon removal of the solvent 10 of th\lquote r \par LiAlH.i. The ether layer is separated, vacuum filtered and ex- ketoxime intermediate, 100g acetic acid and 50mL dig O ari; \par tracted with 3N HCI. The MDMA or meth is, of course, now in the stirred together, then 300mL of 3% sodium amalgam catal st (see \par HCI water, not in the ether. That water layer with product is sepa- chemicals section) is slowly added, then the solution stirrgd for 6 \par rated from the ether and the MDMA is liberated with NaOH to give hours. The solution is basified with NaOH extracted with ether \par MDMA or meth (90%). and then the ether is extracted with 3N HCl.| The free base is re\par A leased from the acid water, extracted with ether, blah blah blah \par e_ asa ou \bullet l\rquote\'a4\'b7\'a2\'b7 \'b7\lquote\bullet\bullet - \bullet \bullet \lquote\bullet `\'b7 `\'b7 ' ' A '\bullet `\bullet \bullet\bullet \lquote\bullet " Hve eehrepole as igri \par as Strike can give. Strike feels that after reading all of those as 90% [35]. However, these results are from a group in the \par similar, repetitious steps, one can start to get a good feel for Netherlands which happens to be right next to Belgium And from \par where a product is at any given moment. Stuff like what happens Belgium there came a punk that did Strike dirty. Yeah. you know \par to MDA when its mixed with acid or base, or what happens to ke- Wh\'b0 Y0U are y0u piece of shit! lf Strike doesrrt oaton np with Ou \par [Ones (PQP) under the same circumstances, Orig can gee now before Strike dies th\'80l"i Strike will d\'e9tihit\'e9ly be waiting for O3 in \par that it is possible to not only isolate safrole and P2Ps chemically h\'80ll\'b7 Y\'a4\'a4 \'a4\'a4W\'a4rdl Anyway, there has also been proposed a we in \par but that the same can be true for the tina! MDA or meth freebase reduce that ketoxime intermediate using NaB|-[4 instead Of \{he \par oil, Repeated washlngs with acid or base and solvent can effec- harsher S0dium amalgam [36]. \par tively clean up a compound to an almost presentable state without \par \par guy came rom. lut one day a care package with some very star-

\par METHOD #6: [33]--17.8g MD-P2P and 300mL 40% aqueous tlrng research articles appears in Strike's mailbox from this Feck \par methylamine is stirred at reflux for 30 minutes then 15g NaBH4 is character. This one was the best because it actually used P2P as \par added over a 10 minute period and refluxed for 1 hour longer (an an experimental subject [54]. So you already know the method \par even longer reflux time than that would be better). The reaction works on our favorite ketone species! \par mix is cooled on an ice bath and carefully acidified with concen\par trated HCI yielding a thick white precipitate. The aqueous acid The article was a complex read for such a simple process Strike \par layer is washed with DCM or chloroform (discard the solvent) and has done Strike's best to interpret this article correctly for you \par asiie wi * \bullet ' oreeas \rquote\'b7 \'b7\'b7\bullet\'b7 , "` ' \'b7\'b7 " I " "" \lquote\'b0\'b7*` \lquote \lquote\'b7 ` ` ` * ' \bullet , \emdash au ors \par \par see how all this chemistry is just the same bullshit over and over in ing a e p must remain between pH 7-9 or nothing will \par again_ with the only differences being an odd chemical here or h?PP\'80h- Next. lhe granulation of the magnesium was round to bg \par there? critical as well. Chunky old magnesium turnings were found to \par - 116 - - 117 \par \par give much higher yields than the finer powdered magnesium. The bined SXTFSCTS WSFS dl'lSd (KzCO:<)l fl/FSfSd and evaporated on 8 \par purity of the particular Mg used was 99.5%. The last note is that VOYSTOVY SVSPSTSTOF-" \par Strike is stopping the quotation here because the chemist is a \par \'b7V\'b7 . Y\bullet \'b7. \bullet \bullet | -.\bullet\bullet .\emdash _ - . | -. - S" l\'b7"" " \lquote ``' ""i\'b7\'b7\lquote\'a46 i" \'b7\lquote\'b7\lquote : \rquote e"=" ' \par mgnjum acetate ta make MDA ar amphetamine, gr mathyjamtrta has left after evaporation (or distillation) is freebase residue with \par in methanol for MDMA. But methylamine is optimal because it SOWS C\'a4\'a4lSml\'a4S\'a4l$- The chemist Sail W0i\lquote l< lhls Up 85 USUGI which \par gtvaa higher yteld and lege byprOduC\{5_ A|sg\rquote tt ammonium acetate would be to do a little more acid/base clean up like has been done

\par js used, Ona must use etthar ammama (NH3) gr a primary amine with all freebase recipes. Or crystallize the final product for rec\par (any of one's choosing, `Strike supposes) in place of the triethyla- feallvnal USS. The authors continue by making an oxalate salt out \par mine in the reaction. of their freebase. One can make whatever salt they want out of an \par amine freebase. Making an HCI, like what naughty chemists nor\par ln articles like this one, the scientists don\rquote t have the time nor the mall\}! d\'b0\'b7 ie lust 006 Way pf d0l\'a49 lhl\'a49S\'b7 Here is The rest of the \par space to write out the details and amounts or reactants used for experimental. We're continuing right where the last sentence \par of the precursors they tried and use their numbers as an example \lquote \par of how the reaction typically goes. All one does is just substitute " The residue WSS dissolved in MSOH (20 cmg) Sfld \'a4ddSd S/cw/y. \par an equal amount of their favorite phenylasetene for the one inthe with stirring. fe e ee/utipn of ahh. Oxa/ic avid (5.40g. 60mm\'a4U in \par example while keeping everything else the same. This will not be Me0H\'bb C0mPlSlS PFS\'a4iPil\'a4W0\'a4 WGS Sfl'S\'a4lSd by adding EfzO (50 \par too big of a stretch of the old imagination with the first example S/773) te TUS TTFFXYUYS and \'a400ll\'a4Q if l0 \'b720\'b0C\'b7\ldblquote \par below. The example ketone is just phenylbutanone. One little car\par bon more than phenylacetone, but a methyl ketone nonetheless Tl1SY ST S Sclually U$ll'lQ \'a4i'VSlSlllZSll0\'a4 T0 Purlly the amine ffdm ally \par (don\rquote t ask). They react exactly the same. As it so happens this first \'a4\'b0\'a4\'b7Sml\'a4S \'800\'a4lSmll16\'a4l$\'b7 ThSY l\'a4lSl' freebeeed the \'a4FVSl6lS and \par example is also the one using ammonium acetate to make MDA. ll'SCll0\'a4Sl dlSllllS<`l TS 9Sl PUFS SmDl`iGl8ml\'a4S Willi 3 yield of 50%. \par \par Wow! That looked pretty good, huh?l The following example is \par \par ftask were combined 4.phenytbutan.g-One (7_41g' 50,11,1,0;). as the amine source. This allows one to get MDMA or Meth. The \par AcONH., [ammonium acetate] (38.54g, 500mmo/), Mg (6.08g, 8Uil\lquote l0i'S used methylamine in methanol. That means they are us\par 25Qmm00 and 70% aqugpus [l/[gQH (100 em3)_ The gaatr was ing the MeNH2 freebase, not MeNH2\lquote HCl . The authors explain

\par capped with a mercury rilled hulmler [feel tree to substitute this that they rnede their rneihyiernine/Me\'a4H eeiuiien by dripping \par aaa], to reduce escape gf NH3, and the mixture was atrrrad at 20- (Strike thinks) aq. 40% methylamine onto solid KOH and bubbling \par 25\'b0C, tar 1gh_ tr the rgggtjpn was net earrrpteta (TLC), addttrarraj the liberated MeNH2 into ice cold methanol. One can do this, or \par AcOH (6.0g, 5. 7cm\'b0', 100mmoD and Mg (2.43g, 100mm0/) were buy 6 QBS cylinder of MeNH2 gas which can be bubbled into the \par ture was poured into water (600 cm3) to which NaHCO3 (50g) was \par \par arna ofthe distillate collected. It was made alkaline (pH > 12) with glenevked flesh were combined 1.5\emdash dipheny/penfen-3-ene (7- 759, \par 50% aq_ Naot-; and extracted with cl-\{EC]; (3 X 50 emJ)_ Thg cam- 30mmo0 [<-insert said P2P herel], a solution of MeNH2 in MeOH \par - ttg - - 119 \par \par (5.4m\'a4/ dm`3. 44-5 cm; 240mm\'b0U\'bb and M9 (3\'b7?89\'b7 1? 5m\rdblquote\rquote\'b0I)\'b7 As you are about to see, the standard methods for using the \par AGOH (7449. 73-75 Cm i 240mm0U was addgd W'lh_ 6 P'F\rquote S\rdblquote 9 bg' NaBH(OAc)3 catalyst call for it to be in a dried, powder form. Strike \par \par Hlled bubblen to reduce escape of MeNH2. The mixture was sttrred laava dry aalal at But darrl uala Slrl a _ I ._ l ll_ __ - _ _ \par . ,, e. , . e ' , = . \'b7 \'b7 \'b7- \lquote = \lquote \'b7\'b7 \lquote \lquote \lquote * "* \rquote be made in situ in the DCE solvent of the reaction to come (d0n't \par (TLC), additional Mg (O. 73g, 30mrriol), MeNH2 solution (11.1 cm, ask) AW halll Jusl ao and buy tha shlll \par 60mmoI) and AcOH (3. 6g, 3.4 cm, 60mmol) were added and the \par Sfiffiflg \'a40\'a47l\'a4Ued Ulllll \'a20mPl9?l\'b0\rdblquote (3\lquote 6h\}- W\'b0"k'UP efferded the Anyway, with catalyst in hand it is time to proceed with the reduc\par monooxa/ate S8/f(6.72Q. 65%)\'b7" tive amination [56]. As far as Strike can see, this method will not \par . . . , . work well in making MDA. It will not use ammonium acetate in the \par METHOD #9: This method is not \lquote #9' because it is bad. its iust aama Way aa NaBl.l3CN_ Sa Orla la stuck Wllh maklng MDMA or

\par that it, and #8 above, are still in the experimental stage as far as malh ualag lllla rrlalrlarl Arld Wllllaul lurlhar ada] hara-S your l,ac_ \par underground chemists are concerned. So Strike placed the less lpar , \par tested methods down here so as not to confuse people too much. \par But this method has been generating more rabid attention than ra) Tha amfng rmgmyraminej and carbonyl compound [PZP] are \par any other in the underground. Feck sent Strike S0l\'a5'l\'80 8l`llG|eS Oli lt- mixed m 1'2dfch/Orcgthane and gl-gated With NaBH(gAc)3_ THE \par Ogmlum emailed Strike SOITIB of UWB Sam\'e9 l'9f\'80l`\'80m?\'80$ [56- Q/\emdash ] 2C[2, Oy- QH3QN may also bg uggd QS 30/ygnfg [but 3 lgnggr rg\par Everyone is talking about it. And for good reason. lt is essentially aallarl llma Wlll ba rlaaaaaaryl \par the second generation of reductive amination using superclean, (bl Aaallc acid (1 _ 2 rrlal aqull/) may ba usad ln raacllans ar ka_ \par gentle catalysts. Just think of it as Method #1 - except that the larlaa llha papar says that ACOH acla aa an aacalaralar ro apaad \par NaBHeCN hee been rerlleeed by el mm W\'b0l\rquote l<6b'\'80 \'b0a*a'>\rquote S*\'a5 S\'b0\lquote up the reaction with the P2i\'a4. But without it, the reaction will stint ge \par dium Ti-iaoetoxyborohydride [NaBH(OAc)a]. to completion. it will just take longer to do.] \par _ _ _ _ _ C RBECUOHS GTS DONT] -n \'b7\bullet \bullet no ne rr en c:- I \par J \lquote = = " \'b7** ' \rquote \rquote ' * \lquote ` _ `\'b7 _\'a4 l' " `\'b0 ' methylamine freebase. One can saturate the reaction solvent with \par does not suffer from the same potential toxicity that NaBH3CN - - - - _ a \par l@, \par rather eaeily in \'a4\'a4e\rquote e ewli eara\'a4e\'bb as \'a4\'a4\'a4\'a4eed l\'a4 N\'a7BH\'a4CN which etaiv [trietnyiamine] is added to the reaction mixture. The Eisiv \par will require a very complicated and dangerous cyanide generation rrlusr ba rarrravad from baallaad pradual prrarra Salt lrarmarlany \par apparatus as is shown in the Chemicals section of this book. The \par f0|l0Wl\'a49 le 6b0Ul all Strike has On lhe making Of the Catawst And here's the two representative methods one would use. Just \par N\'a4BH(OAG)a [55]? imagine the carbonyl precursor as a P2P and the amine as meth\par _ _ _ ylamine. Visualize .... man! \par "Treating a benzene suspension of sodium borohydnde (4 equiv.)

\par \par 15 min under nitrogen, after the initial rapid gas evolulten Sub- \'b7 . . - \'b7 ., .,. , \'b7 .

\par ar e aa- me 0 z ll ele e \'a4 Sm\'b0l<l\'a49ll\'bb QM 8 clgal S\'b0\rquote\rdblquote\lquote none ir>2i>i with nexametnyieneimine [MeNH2l.\lquote Hexarnetnyi\par UOM 0fN6BH(OA0)s eneamine (1.0g, 10mmol) and cylclopentanone (0.849, 10mmo0 \par were mixed in 1,2-dichloroethane (35mL) and then treated with \par - 120 \emdash - 121 \par \par Sodium irieeeiexyberehvdride ieee Mmmeii end AeOi_i ieee precursors, then that method had better have a lot of merit and \par 10mmoI). The mixture was stirred at room temperature for under a untque \'a4a*a\'a4*\'b7a*\'b7 _ \par e i d e t ne v i i Th e i ix h e y This really crazy looking method is one of them. There are a lot of \par , \'b7 III nl. I. Il..\lquote 'l .I.H " |" I \'b7 |\bullet\'b7 an \bullet \par a lng \'b7\'b7 \bullet - \bullet epro u w sex =\bullet r\'b7i=a= \rquote = ._ . U . \lquote " \par ether extract was washed with brine [NaCl solution] and dried ;t;i?Or:c\'a7\lquote i\'a7;t;ndir Z garmai YOU W\'b7\'b7\'b7raaa tn the N'tr\'b0pr\'b0pen\'b0 \par (MgSO,), The so/vent was evaporated to give the crude freebase ' aa ( n tn ra ereneee rem many etner parte at \par (1. eg 96%)- the book) that this guy has been making a lot of strangely applica\par \rquote ble advances ln catalysis, amination, and reduction of ampheta\par Method ll. The above procedure is followed without the addition rmnes add retatee \'b0\'b0'\ldblquote p$"\'b7'"eS\'b7 n '$ \ldblquote F\lquote\'b0\'b0""\'a5 "\'b0\lquote\rdblquote \'b0tt\'80\ldblquote $***9 aaa \par eeeiie acid. The reeeiien mixture remeine eieuev come across this person s work. lt is like he IS the Shulgln of basic \par throughout the reaction. This procedure is more appropriate with precnreer add ar\'a4\'a4\'a4a*am\'b7\'a4a pregreee Ga ngnret \par \lquote d/`ht'kt h\lquote hP2P .. \par \{i\rquote ;f;ej\rquote\{j"g;?jarggrgggeiggjg egefripeecie $ign;SeJ;t;iJe eminee The other attraction is the method itself: clay, a Sears microwave \par -,7 - . O 'I all I' Ill Illll l . \'b7 \lquote \'b7 ||.\bullet \'a4\emdash n ann:

\par lon 0 -pyrl lneca oxa e y e \'b7 \'b7 rr a = or - . . . \lquote i iii\lquote i t A \lquote \lquote \lquote \par piperidinecarboxyiate [MeN H2]: Ethyl 2-piperidinecarboxylate gee ee'? Stsnne tnteneetitee VF tex\'b7 bent eumbeeeeetnre e'nen\'b0t gat \par (1.57g, 10mmo0 and 4-pyridinecarboxa/dehyde (1.07g, 10mmo0 e per en dama- n Yee neww e Ven ere\'b7 re\'b7 \par were mixed in 1,2-dioh/oroethane (35mL) and then treated with _ _ _ \par Sodium irieeeiexyberehvdride (3.Oe Mmmevl The mixture Wee Anyway, there have been two very hot topics ln chemistry lately; \par stirred at room temperature under N2 atmosphere for 24-30 h. The ctey 8\lquote . tnt\'b0r\'b0weVeS\lquote Betnneve eeen en\'b0wn.t\'b0 da rernerkeete \par reaction mixture Wee quenehed by eddirig eeueeue Saturated Ne_ things ln preparative organic chemistry. And this article Strike has \par HCC and ih e preduei Wes exireeiee Wim EiOAe [ethvi eceteiei [58], has combined both to produce some stunning reductive ami\par The ECAC extract Wee dried iMeSO4i end the Seiverii Wee nations of ketones to final amine products. The procedure in\par evepereiedie giveihe erude ireebeee (2 ee 96 7%).. volves mixing naked ketone, the amine, some clay and some \par Both those methods look pretty egual to Strike. Still, Strike tends ple af mtnntee Tnete n\'b7 Tha generet preeednre te aa tenewet \par to think that the Method I looks like it\rquote s the best of the two. There __ _ P d T , \par are some dennite advantages that this method has over the \'b7 ha _ S\}\rquote ntneS\rquote S at N'Pne"Yt\lquote P' \par NeBH3CN eee Bei eil in eii they ieek ebeui even te Strike. we chlorobenzy/amine is representalve of the general procedure em\par ereet te have eptieee though' ieee ip, pioyed. A mixture of p-chiorobenza/dehyde (O. 7g, 5mmo/), aniline \par ' " (0.455g, 5mmoI) and montmorillonite K1 O clay (0.1g) contained in \par METHOD #10: You girls need to know that Strike is not just listing al 25\rdblquote\rquote L t\rquote\'b0ak\'b0' W\'e9s P\{a\'b0\'80d \rquote\rdblquote al" d\rquote d\rdblquote ?\rquote\rdblquote d ba'\rdblquote\rquote _\rquote\rdblquote S'F'a tha miam\par every method that produces a precursor or makes a tinal product. Wevereven add 'rredteted ter twe \rquote r"n\'b7 The tn Situ generated \par There are hundreds out there. Many make the product but are too Senttre W e l ad t r\'b0"9nt\'b7V 'tn r ent-V pr parad NaBH4'

\par \'b7 \'b7 \'b7 - \'b7 a \bullet I n I 2 a 2 I . I A . 2 ll \par .I OO"O' V'! O||"V'| I '.*._"- | I\'b7I I _ _ I- \'b7 \par bein. There ere special criteria inet makes e method wenny of rn- Tha raaaddd maddra Waa adam liradiafad far 30 aaa fd5\'b0Ci\'b7 dpad \par clusion in this book Often a method has been reviewed by many eentptetten at tne teeettett ntenttetee en they dia ptedeet was \par people before it makes it for consideration, When there is no one axtraatad tnte rnetn-Vtene entdrtde t3><15c\'a4Ll\'bb The rernevat at Ser' \par _ person that has actually tried a particular method on our special Vent Under r addaad pressure prevtded pure N'ler\rquote en-Vt'p\rquote \par - 122 - \'b7 123 \'b7 \par \par Chlcmbenzylamme In 90/6 \lquote w9Id' and helpful man. When asked how he would modify his method to \par This next one is a power pulse modihcation for using lower boiling ***V\'b0*V\'80 \'80*t**\'80* N*`*\'b0\'b7 *V*\'80*`**`*2\'b7 \'b0*` E**`l*'*? \'b7 hai Said *hal DMF (Dlmeth\par pointamines(readwhylateron below): '\'b0 " \lquote i ` _ T" ' \bullet \'b7' " -a ' `a "\bullet\bullet \'b7 \par be the second choice. He indicated that water may work, but that \par wi gid >c We \par (0.56g, 5mmol), n-propylamine (0.46g, 7.5mmoI) and K10 clay __ \par (0.1g) contained in a small beaker was placed in an alumina bath S\'b0 *`*\'b0*\rdblquote we *`*aV\'80 a ***\'b0F****ad ***a*h\'b0d where alla has sl\lquote flm0\'a4l8. \par rhaai Sink) arid irradiaiad far 6 min ir, a Mwavari at iis 20% pawar methylamtne or ethylamlne freebase saturated in a small amount \par using pulsed method (one min coo/ing between two successive of *3**/**:- **-**6 al****\'b0t **6** SU99aa*ad that a P\'a4W\'80l\lquote Pulse Dr\'a4t\'a4C\'a4| \par irradiation Or 2 min aachi i-ria iri Situ gariaraiad Schifies baaa was would not necessarily be needed, but that the power output from \par mixed with sodium borohydride (0,19g, 5mmo/) and K10 C/ay ***9 ****a*0WaV\'80 should be between 20-40% of full power_ A|5D_ the \par (1.53g) to which water (itat) was added andthe reaction mixture Water lll the Clay W\'a4\'a4ld stlll be needed for the reaction. \par was irradiated in MW for 45 sec at its full power Upon completion

\par \par into methylene chloride (3x15mL). The removal of solvent under P*\'b0\'b0\lquote aS$\'b7 can ** be '\'b7*\'a4Pad *0 l l**\'b0l al lhata? l'la Said he Wss Up to \par rdddmd prossuro gava the had base in 79% y,aid_ HC, Salt l50mrnol and said no decrease in yield was apparent. The time of \par iEtOAc_MaOH)_\'b7\'b7 irradiation also did not need to be any longer than the written pro\par oco s. \par Can you see what happened there? Ketone and amine react to \par give final freebase. Very nice. The authors even suggest that sim- S0 What tha hall ala all of Yau waiting f\'a4l?l Nuke lt! \par pler matrices such as alumina or silica might work in place of clay. \par But, regardless, there is one small problem. The authors did not \ldblquote\lquote \lquote\lquote\lquote\lquote \par use any of the amines that an underground chemist would. As a _ . \par \par or solid at or above room temperature. The lowest boiling amine \'b0* all tha Watts that Pgps Gah be G\'a4\'a4Vel\rquote ted t0 smphetemines or \par \'b7v I \'b7\bullet \'b7\'b7.\rquote \bullet \bullet v\'b7 J" _ *\lquote\bullet ' \'b7\'b7:\lquote 2 as ie r= \'b7:\'b7= r;\bullet\'b7 \'b7s "` *\'b7\ldblquote\rquote *7 \'b7" 'T \'bb- " -= = - -\emdash e* =. ee =! .\'b7\'b7 e e- i T. \par them to use a modified pulse method so that it would not get too **aY'***Cka* and P*a****l-l*** lh \'b0\'a4***Pl\'80X Phaaatlla aDDaVat'\'b7l$\'80s Qttlsh \par hot and osoaoo tho roaotior, matrix using injections of hydrogen gas. These ways of conversion are \par relatively clean, with good yields, but they are not what this book \par So you oar, Sao that to make MDA or MDMA Using oitttor NH3 or is about. Strike feels these ways to be too involved for those \par MeNH2 one is going to have to think of a way to keep them in the |0\'a4l<l\'a49 to make B decent profit while avoiding overly-complex set\par fray. Strike\rquote s first impulse is to dissolve the amine in a solvent. But Ups \'a4l \'80><l>sl\rdblquote lslV\'80 Gstslllsts- These Wells of Gerlversion are meant \par what solvent? And would the reaction even work in any solvent? t\'a4l\lquote thhss who are ll\rquote ltsl\rquote lt \'a4l'l sl\rquote l\'a4l'l\lquote fl\'a4Us yields. t0U|'ldll\rquote lQ an empire \par

\par work considering the clay is moistened with water anyway. ll\\\{\'80s\'b7 D\'b0l*`t Qat Stllks WF\'a4l\rquote l9\'b7 tnere'e absolutely ll\'a4thlll9 WF\'a4l\rquote l9 \par wen, when in doubt ask the guys who wrote the article. And that is and wishes to become a professional drug lord. then they would \par just what Strike did Thg coauthor gf the mgthgd was at very kind definitely want to invest in the chemicals and proper construction \par 124 of the type of apparatus necessary to do these pressure reactions. \par - 125 \par \par Apart from the academic literature, one should read the book "Se- _ \par crets of Methamphetamine Manufacture" by Uncle Fester [18]. B NITROPROPENES \par pre s met o s. tri how ver, m h i e r a i ns t . \par \par are pure y Em a The next major category of precursors, apart from the phenylace\emdash \par tones, are the \{3-Nitropropenes. One can see the two representa\par tive examples for X and meth in the little drawing below: \par /\\ O \par O \par NO2 NO2 \par / / \par \par As you can see, there is a nitrogen right in the exact place where \par one wants it. That is definitely a step in the right direction. But \par Strike was not very keen on these intermediates because there \par was really only one decent way to make them that Strike favored \par and the ways to make final product out of them were not too hot \par as well. But a lot of things have changed for Strike in a year\rquote s time \par and there are a lot of new promises for this route. \par \par found. Let\lquote s start things off with the basic recipe for this precursor. \par METHOD #1: This section is going to be as thoroughly helpful to

\par those interested in X production as it will be to those interested in \par amphetamine production. The process is known as the Knoeve\par nagel-Walter condensation which can turn a substituted benzal\par dehyde such as piperonal (X) or plain old benzaldehyde (speed) \par into an intermediate called a (3-nitropropene. This intermediate \par \par chemist. \par - 126 \emdash \emdash 127 \par \par feeling that ammonium acetate is heading towards the schedule I \par P O P O QTBV9y3I'd. \par O ts CZHSNOZ/CHQCOONW O Is NO ln a flask the chemist mixes 50g piperonal into 200mL glacial ace\par Iv CHO The solution is then refluxed 4 hours and takes on the color of \par _ _ _ _ . yellow to yellow-orange. After 4 hours and cooling, yellowish \par PlD\'80t\'a4l\rquote l\'a4| MD phenyl beta Nm\'b0pr\'b0pEn\'80 crystals of B-nitropropene will spontaneously form. lf not, the so\par lution can be diluted with 50ml of dH2O and chilled in an ice bath \par for an hour to form the crystals with some slushy glacial acetic \par C,H\'a7NO,/CH,COONH, NO2 acid and water intermixed. The mass of crystals is broken up and \par \emdash\'b7\'b7\emdash > plopped into a Buchner funnel to be vacuum filtered. The filter \par CHO cake is washed with a little extra acetic acid or water. All of the \par Bonzaidonyde Phenyl-beta-Nitropropene filtrate is saved. \par Both piperonal and benzaldehyde are List l controlled substances Thess l3\lquote l'llil\'b0PV\'b0P\'80"l\'80 crystals the chemist ll\'a4W has \'a4\'a4ll be \par just as Safrgle and ieosairoie are_ out tno Spooo maker nas tna air-dried and used as is, but that is not advisable. What they need \par advantage here because benzaldenyde makes up over 95% ofthe is a little more cleanino up. and one does this hy performing re\par quasi-leoal bitter almond oil whereas there is no natural source of crystallization. To do this the chemist is going to use a solvent that

\par piperonai Pipergnall also known as i-ieiiotropin, can bg made everything in the reaction that the crystals came from is soluble in \par from sassafras oil. lt is also a very important chemical in the fra- but that tilts \'a4l'Y$i\'a4iS are not. Get li? No? WGH. to d\'80l't`l\'a4\'a4Stl'\'a4i\'80. \par gi-ange ii1di_i5try_ But there are so many ways tg make bath it and \{TIG Ch6mlS\{ will bOii ZOOITIL of m\'80thBflOI li'! B b\'80Bk\'80l\rquote and start \par benzaldehyde inthe Build from scratch section of this book that knocking chunks of the impure B-nitropropene filter cake into the \par the Knoevenagei synthesis has e potential for resurrection from hot solvent. lf all of the crystals will not dissolve in the 200mL of \par ` \'b7*- - \rquote\'b7\'b7\bullet \'b7 * \'b7 p onl. y avy \'b7 -\'b7 \'b7 \bullet\'b7 --\'b7\'b7\'b7\'b7\'b7\'b7 \'b7-\'b7\bullet\bullet - \bullet \bullet\bullet\'b7\'b7 \lquote \par strike means that not only are ine precursors controlled but so is soon as all the crystals are added and have dissolved. then the \par the main processing chemical: nitroelnane. This substance does chemist turns off the heat and chills the mixture to 0-5 C. What is \par have a wide use in industry such that the chemist may come going to happen is that everything the chemist doesn\lquote t want will \par across some in daily life (yeah, right) or the stuff can be made as remain dlS$\'a4ll/Gd ill the \'a4\'a4W \'a4\'a4|d m\'80lh\'a4lt\'a4|, but all \'a4f the \par described in the Chemicals section. ln fact, we have quite a few B-nitropropene crystals will 'recrystallize' when cold. This solution \par more recipes for making nitroethane than before! is now vacuum filtered and the now clean crystal filter cake is \par washed with a little bit of extra, cold methanol just to make sure. \par This procedure has been performed in a variety of ways [28 p714, That extra methanol washing and the filtrate can be reduced in \par 38-42] with variations in solvent, base and time of reaction. For volume by distillation and chilled to retrieve a second crop of \par Ip \bullet '- \bullet ' \'b7. \bullet ' '\'b7 \bullet\rdblquote .\'b7' I I \bullet . \bullet E O -' i ' \bullet \bullet \'b7\'b7 V - \bullet - ov- ` ` .\bullet |\'a4 o_ \'b7 . \par acid as the solvent, ammonium acetate as the base and 4 hours thing to add is that the chemist has a choice of recrystallization \par of reflux time. Dr. Alexander Shulgin, a giant in this field, prefers solvents other than methanol. These include hexane, isopropyl \par the use of cyclohexylamine as the base. Strike would not tend to alcohol and ethanol.

\par doubt this man\lquote s choice, especially since Strike is also getting the \par -128 - \lquote 129 ` \par \par You know howiust a couple of paragraphs ago where the chemist _ \par first filtered the crude crystals from the chilled reaction mixture, pT\'b0Ced"T\'b0 is issiiY sssV shd has hi9h Yields [28 D734\'bb735]. 32g \par theh weehed them with water or eeetie acid? Weii_ dit that iiduid elemental (electrolytic) iron (Fe) and 140mL glacial acetic acid are \par \par \par 500ml dH2O and extracts it with DC|\\/|_ The DQM is washed with formation of white precipitates. One might want to do a couple of \par 100mL 5% NaOH solution then vacuum distilled to give a dark oil drv \{uns is dsisimihs the \'a2\'a4r'reGt temperature. Into the hot mix\par which is unreacted aldehyde. Hey! That's a lot of good material iuis is si\'b0\lquote\rdblquote iY dhlsbsd s $\'a4l\'a4ti<>ri \'a4f10g MD-nitropropene (that\lquote s the \par that ooh be put through rho ioroooss again_ B-nitropropene made from piperonal) and 75mL glacial acetic acid. \par The dripping is adjusted so that the reaction does not become too \par There are some slight alternatives to this process that, for educa- Visishi \'b0i i\'b0smV- The \'a4\'a4l\'a4r \'a4t the reaction will progress from or\par tional reasons only, Strike is going to lay out for you now, sings tb 9 deep red with the formation of white salt precipitates \par After addition the solution is heated for an additional 1.5 hours at \par (1) lt has been shown that by doubling the amount of nitroethane TODO "du'\rdblquote 'i'iQ Whish time the body of the reaction mixture be\par \'b7 \bullet _\'b7 ` \bullet |- \bullet |\'b7,\bullet\'b7| \bullet\'b7 g. . \bullet\bullet \bullet |-I gr Comes uitewhitewith |\lquote\bullet\bullet\bullet \bullet i ,\bullet\bullet -. a. ._ ,ss_ \lquote \par amount of ammonium acetate used can be reduced considerably Ciimbihg ihs sidss \'b0f the beaker"[28. thanks Dr. Shulginl. When \par [28 oyO3]_ cool, the reaction mix is added to 2L of dH2O, extracted 2 times \par (2) The cooled reaction mixture can be induced to crystallize its With 100ml. DCM and the DCM extract washed with 1N Nag\}-i \par i3_riitror,ror,ehe peyioed by Simply dompiho the Whoie thing ih e solution. The DCM layer is vacuum distilled to give ~8g of pale

\par ierde Volume of ioe water t4Oi_ yellow MD-P2P. Strike must say that that was a pretty easy one\par (3) Once the reaction mix has cooled after reflux, 500mL of room pm Pmcsduis using 2-3 simbie ehemieaie with an 80-90% yield. \par temperature dH2O can be added and the whole solution extracted _ \par with DCM. The DCM layer is separated and the solvent removed METHOD #2* This msV W\'b0Vi< On satmie but Strike has never tried \par by distillation to give the B-nitropropene as an oil of all things. it \'b0\ldblquote _ihs msissuis- This shbuid make Q\'a4\'a4d use of isosafrole and \par \'b7 \'b7 _, ,-, ,a ra _ \'b7 -. - ,, ,,- ,_,,\'b7 _- ,- its cis isomer 44. 76 sil er ' - \'b7 ;,t\bullet ... \'bb.. H .; \par orystaiiihe form wes [38i_ (find this at some pharmacies) are stirred in 600mL ether for 30 \par r*.~ . '\emdash r .-\emdash r.~-....-.. \lquote ,. '.- \'b7\'b7\'b7-=- \'b7\'b7\'b7%= =. =\emdash - ==-- \emdash\emdash - \lquote , ,.\'b7-, .. -_ \par no different [43]. These mothers claim that piperonal or benzal- gentle brsszs sf hiiisgsh imm a baby nitrogen tank is blown into \par dehyde will react with nitroethane by sitting in the dark at 10\'b0C ihs Q" sssss si ihs iissk\'b7 The nitrcoen displaces atmospheric \par with dhiy e eedpie dt drdpe or ethyiehediemirie Aimest 1000A oxygen from the flask so that it won't mess with the reaction mix. \par yield no less! Strike has never tried this nor does Strike fall for Ths ssiuiish is stirred at r\'a4\'a4m temperature for 4 hours, vacuum \par Russian soiohooi ootir ohyohs is ihterostodm filtered, washed with a solution of dilute NaHSO3 then washed \par with saturated sodium chloride solution. The ether is separated, \par Oriee erte has the B_Nitreprdperre_ there are two Ways dhe Cari dried through Na2SO., and removed by simple distillation to afford \par _ new be e _: _ - __ Hen _!_ :_- \'b7 g I a dark oil residue which is an iodo-nitro i e t \'b7\'b7 - - \'b7\bullet\bullet . . \par pleasure\emdash inducing product. Which you can read about in the next \'b0W\'b7 Sinks \'b0\'b0L\{id be Wis"? (end \'b0i\'b0ish is)- hui the WsV this eriisie \par - Y . _ at - . -\'b7 \'bb. i h \'b7\'b7 \'b7\'b7 \emdash n -niropropenes is o . . ` T \lquote : 'E " " '\'b0 ` \'b0` " " ` " \lquote \par turn them inte P2PS_ -i-he Chemist has to do Something with the this intermediate to the final B-nitropropene can occur in two dif-

\par stuff because if it sits around too long it's going to degrade. This feisrti WaYS\'b7 The implied \lquote\rdblquote sV is is sus 300mi- sihsi shd 300ml\par 130 pyridine to all ofthe intermediate oil sitting by itself in the flask and \par - 131 \par \par stir it at room temperature for 2 hours. The nitrogen in pyridine \par piucks the iodine crt of tne intermediate causing an elimination There is en incredible erncuni ci energy in the carbon-nitro bond. \par --. - -- - " A. -.-- .- --- - ..-- ,.. L ll sa \'b7n\'b7 A. n-- n nan; \'b7 ` an-. .\'b7 \par tane and water. The pentane layer is washed repeatedly with has reeri $tartin9 tc get the Dietllre? \par \par product at +50% yield, The other way this may be done ls listed 3 Tetl\rdblquote 8l\lquote litl'OlT1etheI\rquote le WHS used as a double bond detector and for \par couple of paragraphs up in the article in the section titled 'Prepa- the deteetien cf tl/resine in Dretein setlnenees- As Yeti een Qtlessr \par rattan ol s-Nttrd-2-cnciestene\'b7. rc tne intermediate cit is added ls\'a4sefr\'a4le's clcuble bend is the pcinl cfelieck. The problem is that \par 11g silver oxide powder and 500mL methanol and then refiuxed there is net any eeeessibie ehelnieei eempeny tedav that makes \par for 4 hours. After cooling, the solution is vacuum filtered and the this eernpetlnd enVmereSc the reve ret is 9ein9 to have lc make \par methanol removed by distillation to give product (99%'?). There is it herself. and that's where the lrcuble begins. The best methed \par also an interesting, simple zinc reducticn ofthe nitro product to fcr making letrenltrcrnelhene is in Organic Synthesis [48\} using \par kgtong Ceole trlte be another way to make pgpg from tuming nitric acid and acetic anhydride. All the glassware is \par \{3-nitropropenes instead of using Fe that is detailed in Method #1? cleenecl With seep end het Waterr rinsed _, \par Eleusis seemed to think so when asked. So here is the experi- _eretl9 Y Wi isi e we er. nnse \par mental as written in the journal article. Just imagine an equal with esetene then rinsed enee rncre with I \par amount of [3-Nitropropene in place of the *3-Nitro-2-cl\'b7iolesterie\lquote distilled Wetel\rdblquote\'b7 The 9|aSSWa_l'e le placed

\par and p2p as the product; t upside down on a sheet of foil in an oven gi . \par and baked at 425\ldblquote F for 1 hour. Baking \par reeducticn cr 3-ivitrc-2-cnciestene . - zinc dust (800mg) was destr\'b0Ys ant' rerneinine \'b0r9eni\'b0s which \par added in portions during 1 hr to a stirred warm (40\'b0C) suspension call set \'b0rr_ the tstrahltramsthahe te EX' \par of 250 mg of 3-nitro-2-cholestene in 15mL of acetic acid and 0.5 rll\'b0ds\'b7 Thls glasswars washlrlg pr\'b0ss' \par ml of water After 4 hr reflux, the mixture was filtered hot and the dure. by the way, is'the preferred way to \par zinc washed well with hot HOAc. Addition of water and extraction wash up all cr srlss glasswars eher a l: Y \par with ether gave 116`mg of product." Ollg aVs sXpsrlrhsh lrlg\'b7 ls _s sarrls ll l \par rocedure used b all the or anics labs (ti \par ivie\'b7ri-too #3:[45\emdash 47]\emdash\emdash Do nct try this method! Strike repeats, do that strike has been tired hem- \lquote \par not try this method! This is the method popularized by Dr. Shulgin _ _ a e \par and reported in some ofthe underground literature [8] which uses The snnaratl-ls ta llss ls sssh ln llgllrs is " \par the most dangerous compound in drug conversion chemistry that whlsh shrlslsls er sl htlrstts\'b7 thsl`hl\'b0rns\lquote " \par Strike is aware of: tetranitromethane. The reason this method tsrr ErlsllrrlsYsr flask and a iwchclerl \par keeps hanging around is because one can get clean, hyper yields rlll"l"sr stspnsr that hee a _slnall \par of l3-nitropropenes in less than 5 minutes. But the ultimate method V\lquote shar\rquote s\ldblquote l wsclgs cut \'b0lh cr \'b0rls slds cr \par can exact the ultimate rice death bubbal . Rave rats are ve Ll; gibgeg scglzpsr ls ;ll<;~ xlgn\'e9rgsllgls \par " " _\lquote\'b0 "\lquote 'l \'b0 \lquote \'80 l " ' l\lquote \lquote \'b0 ' i l nmrr niinc een see \'a4\'a4emr\'a4\'a4\'b7s sec\par dure in the literature or the determination of enthusiastic chemist t'\'b0nl ls r>\'a4\'a4re\'a4 lrlls the ErlshrllsVsr rlask \par to try this, no matter how much they are told not to, then Strike will aha lhs rllbbsr stsnnsr wllh lrs hllrshs [F. 131

\par at least lay down the proper way it is accomplished. allcl lhsrmalhslsr ls plassrl sh ls lhs laura \par - 132 . - 133 \par \par flask. The 1-11103 is cooled to below 10\'b0C with BH exterhst ice heth gggtgliaxillj g; $1;\'b7bG\rquote l:;n:l;a/Ei,\'b0\{;*;\lquote T\lquote 2L\lquote \lquote i'?"'S\'b7 .|l? r;\ldblquote\ldblquote\lquote\'a7T;p';\rquote P*\rquote "*\rquote \par - o - -\'b7 traton. etraecan \par \'a4 *r \'a4 t * \'a4 \'a4. \'a4 i \'a4 \'a4v 0 * * \'a4 * \'a4 \'a4* \'b7? *\'b7 - l g be extremes with ocvt sro the . ll -. . - - . .. . \par clear acrylic that the chemist buys at the home improvement store yl d ll ddlllolla \'b0l a \'b0 l la a y ald ls a ut 5ag ( )\'b7 \par ispace etweentecemtstandt eapparatustoactasa ast ` ' ' ' "' ' ' " a' "` \'b0 " ` \'b7 \par shield. The acetic anhydride is added in small little squirts or slow NOW St ,k , _ 1- t H _ \par dripping to the cold, stirred HNO;. The solution will not change was a J\'e9aausiuailngda a fy\'b0ll ill Sl\'b0ly\lquote OllCa.l\lquote lp\'b0ll a llma there \par color throughout the addition. When the addition is complete, the his infinite mlisdclllg hal; O Wa? lh agd g\'b0\'b0d Wlll bacausa G\'b0a\'b7 la \par burette is removed from the stopper but the solution continues to dance Of b al Sean rll lo lass tha, land Wllllan abll"` \par stir in the ice for another 4-6 hours then it is slowly allowed to mak ftiaslf aa H l vlgas l a llllalll \'b0f 49/\rquote af the Cmzaary ta \par come to room temperature by allowing the ice to melt. Once at gn 6 0 "ld Ta: pla. all . aaallsa ll madalllam happy Ona dev \par room temperature the flask is removed from the stirplate and the Of tag"? \'b0a lil 5 al\'b0llly Lnvlandad llla l<lrlgd\'b0lll and l\'b0\'b0k aalza \par solution should be monitored closely for at least 3-5 more hours. fa t th ee pa at"' d,\'b0:5lkSZa\'e9T a al\'b0"ty a'a nat aka aaa p\'b0"a\ldblquote\'b7 ln \par lf the temperature of the solution starts to rise above room tem- _ ' _ alo l _ _ _p ll S\'b0 u h that nat amy would \par perature urlngt is time, then the toe bath must e reapp ie . I . ' ' ' " ' \'b7 ' " \lquote " ' a \lquote a \par the temperature starts to skyrocket then mn. After monitoring, the sdiiligfkalhlzls aallag aaahpallaaras malg Thara was mach daspalr \par stopper and thermometer are removed, the flask covered with an ll t d .\'b0m all;\'b0llg gse W 9. l E aaa p\'b0llan and many la'

\par inverted beaker and stored behind the blast shield in a dry dark man E. all Own. ala Ollila alllzana bacama angry that lhasa \par place for 7 days with might would impose their will on others. So those angry citi\par ' zens took to tending bees in their cellars. lt was of great expense \par After 7 days the solution is poured into 300mL cool dH2O in a lo Callducl Such all urldarlaklllg and ll f\'b0r\'b0ad many a Cmzaa ta \par 500mL flask and slowly distilled with no vacuum. The first 20mL $l:al\'a7Aa.wiakS Wagga la \'b0bla\'e9" what they aaa \'b0ll\'b0a had l\'b0l aaa \par of distillate that comes over will be clear heavy tetranitromethane. S halcll y d$f\'b0:m t l?\'b0\'b0V\}_l?ll\'b0: that aal \'b0"ly dla many af tha alt" \par The chemist will know that all has distilled over when the last clear aaa _ ava a _ l S a a l a ew agalllsl aaa p\'b0llaa\'b7 but that many \par rops a comeoverwn ewaer a wt sa o orma ayeron h ` ` b d h " ` `\'b0` \'b0" " U A ' \par top of the tetranitromethane. The product is washed with dilute ay Wala \'b0l l an la aa s\'b0\'b7 Tala \'a4#r\'a4\'a4t angered The Ma|\'b0"'tV \par NaOH, then water and dried through a very small amount of \'b0 mac a ev a\'b0'_a \'b0 ac ua y 'mpnaan cmzans \lquote\rdblquote h\'b0 ate \par NEIZSO4 to give 169 pure t6tranm0m6than6_ bee pollen. The enormtty of such a task soon became apparent \par as millions upon millions of citizens were sent to languish in dun\par With tetrshttromethone th hand, the chemist proceeds to convert \'a7za\'b0\ldblquote $ l\'b0' agll;9 F\rquote aa.pF\rquote l'a\ldblquote\'b7 C\'b0""\'b0'G'\ldblquote '" "\lquote\'b0*' \'b0a\ldblquote $\lquote =\lquote\'b7 The M\'a4l\'b0'\'b7 \par isosafrole to B-nitropropene at an astonishing speed. 41g isosa- ly cmllalla a lllqulalll\'b0" uaabalaa \par fl.300L hd t d24 'd` llt\lquote cl .. \par tI.\'b0\'a7\rquote ttss1Elle\lquote ZZele3\ldblquote 1ZSo?E\'b0s$"rZeZ\ldblquote\'a4s sri.? \'a3ZLt\'e9TEe?l\'80e`l.ZthS1ELZ- M\'a4a\'a4wh\'b7.*\'a4\'b7 \'b7\'a4 \'a4 Stately *\'a4\'a4\'a4r\'a4*\'a2~ amp \'a4 *11**- the S\'a4\'a4\'a4\'a4\'a4 tres \'a4\'b7\emdash \par rything behind a blast shield of course). 54g of tetranitrometh;-me 6 h ml in th a n cast er sight bal/\'b0ll hal p\'b0ll\'b0l\rquote lS and up\'b0n \par tscooe \bullet\'b0 an enqutc ypoure 1no ereacton as. ` \lquote \lquote\ldblquote `\lquote `T "\'b0 ` ` ' \'b0 \'b0\'b0"\'b0"\'b0 " \'b0 \par The solution is allowed to react for exactly 2 minutes and then the spl Bak alaf ua\rquote l`l\'b0w harva la\'e9llgaa \'b0\'b0\ldblquote ;a cg\'b0m;h's\'a7 |_:;th\lquote\'a7;ghSl\ldblquote a"g \par reaction is immediatel sto ed b add'n a `xtu f 16.8 KOH .

\par in soomt drrzo. Th; tellltlersttlre wtlttghevl\'e9ll.tsQ'Z\'b0eur1nggthe s ;=\'a4\'a4**=\'b7,\'a4* \'a4\'a4\'a4,\'a71\'a4\'b7j\'a4g\'a4\'a4g\'a4\'a4\'a4;\'b7 and wm \'a4\'a4*\'a4r\'a4\'a4 lhs bee \'a4\'a4\'b7\'b7\'a4\'a4 \par minutes of reaction and the stoppage, so it is allowed to stir and awa" caam a p lll aal l al"\lquote laat\lquote\'b7\'b7aw fuakalh lll \'b7 And far \ldblquote\'b0 \par -134 - \'b7 135 \'b7 \par \par reason at all, the chemist decided to make tetranitromethane. The \par chemist made a 5X batch of the stuff and had just set the flask to AMPHETAMINES FROM \par \par house. Being the second greatest chemist in the land meant that \par \par conditions. And then, without any warning, the unattended solu\par tion decided to spontaneously get hot. The resulting explosion O d. _ \par produced a shock wave so powerful that the tiles were ripped from NP9 \'b0a"n\'b0t "ectly make _a m\'a4**~\'a4m\'a4h\'a4*\'a4m\'b7\'a4\'a4 fmm a B` \par their foundation as the blast plowed through the bathroom door, '?r\'b0p"?p\'80"e\'b7 Butwm needs em anyway when MDA am B\'80\ldblquote Z\'80' \par down hallways, around corners and shattering its way through half dn"? wil d\'b0 Very "'C?| y= thank VOL'- B\'a4l\'a4w 'S the "\'b0'bra'n\'80\rquote S\'a4h\'80\lquote \par the Windows Of the house. m8tlC fOl' HTG COHVBFSIODZ \par Strike thinks you get the picture now. Do not try this method. /\\ O \'b7 /\\ O \par How did the story end you ask? Strike doesn't remember exactly. O \par . . O \par _ .7 l l. I' t llllll l- \lquote | .I\rquote I | |" O " I |\lquote A & \par neighboring Bee Keeper Empire. .\'bb " \par MD\emdash Pheny|-beta-Nitropropene MDA \par / 4-\emdash > \par What goes on in this conversion is that the \{3-Nitropropene under\par goes a catalytic reduction whereby it loses its propene double \par bond, and the nitro's oxygens get replaced with hydrogens. All this

\par happens in one pot with, usually, just one reaction. \par When Strike wrote the first edition Strike considered there to be \par only one, decent reduction method for the B-Nitropropene. But \par since then Strike has come across quite a few new ways that \par \par make this conversion very, very easy an vane . o o e ways \par \par get to those in a minute. But Hrst Iet's start off with the basic, de\par fault recipe for the reduction of [5-Nitropropenes. \par - 136 \par \emdash 137 \par \par METHOD #1: [155, 28 p715]Using the setup in fig. 9, the chemist \par stirs sag of umn, in zoomt THF and adds dropwise to mis a METHOD #2= " . \par n o 5 g .!a 5 I ea ee\'b7\'b7\'b7 .\'b7= !!\'b7\'b7 o" " \'b7\bullet . - "IT i' \'b7 ' ' ` I V PENS yamIHSISr9pf\'80SSHt3tiV9. \par tory funnel. After addition the solution is refluxed for 24 hours A flame dried, nitro enflushed 100 ml flas ' ` \par \par minum salt precipitates and the solution will also start to darken. cvvlad tv 0\'b0C- A BHrTHF S0/Uti\'a4n (76 l77l770L 9-5 rn! vf 7-7M\} was \par The solution is cooled, 50mL dH2O is added, and the solution is injected into the reaction flask via a syn'nge, followed by the slow \par vacuum-filtered. The chemist washes the filter cake with a little addition of a solution of ,6nitrostyrene in THF (4 mmol, 0.6g in 6 \par extra THF and discards the filter cake. The filtrate is placed in a ml THF). After the addition, the ice-bath was removed and a cata\par distillation setup, the THF removed under vacuum and, if desired, Mic amount (~40 mg) of NaBH., was added to the stirred reaction \par the dark MDAlamphetamine oil in the bottom can be distilled over mixture by means of a spatula. A moderately exothermic reaction \par as well to give clear yellow freebase. An alternative cleanup ensued. The reaction was then allowed to proceed for 6 days at

\par would be to forget about removing the THF and instead adding the 25\'b0C . The reaction mixture was poured on to ice-water mixture \lquote \par solution to 200mL 0.5M HZSO4, extracting it with DCM then re- 50 ml, acidified with 10% ~ ' \par \par yields from 60-80%. was washed with ether (2x5O ml), and then the B\par phenylethylamine was liberated via the addition of aqueous so\par The following methods are all the result of one group of scientists: dium hydroxide. Solid NaCl was added and the product extracted \par Rajender S. Vanna, Laila H. M. Guindi and George W. Kabalka into ether (3x50 mh. The combined ethereal extracts were dried \par etal. They produced a series of papers in the 1980's that blew the over anhydrous MgSO4 and the solvent removed under reduced \par fuck out of nitro compound science. Their methods for reducing [3- pressure to yield 0.43 g (88%) of ,0-phenylethy/amine" \par Nitropropenes are novel and easy. And the best part is that they \par almost always used our exact precursor (Phenyl-B-nitropropene) The authors say that the 6 day reaction time at room temp can be \par as an experimental example. So there ain\rquote t onna be no uessin a \'b7 \'b7 - \'b7\'b7 \bullet ' \'a4\'b7 \'b7\'b7 \'b7 \'b7\'b7\bullet -\'b7\'b7a \'b7= \'bb \'b7= =-- ' . =\par as to whether their methods are applicable to our precursors. did not specify how much heat or how much time would be re\par \par Although Strike found most of these articles on Strike's own, our METHOD #3i The authors next stepped back and Considered the \par good friend and learned scholar Osmium emailed Strike some of cosmic imbalance caused by that 6-day reaction time. The next \par the above group's articles and quite a few more that we will get at recipe was what they came up with. \par in just a bit. The following methods can be read about in the origi- \'b7 \par nal articles in which they were published [49-51]. But there is a "Synthesis of Alkylamines. General Procedures. Method (Al. The \par nice review by the same authors in which a representative exam- synthesis of ,6phenethylamine is representative. A flame dried, \par ple of each oftheir methods is included 52. The followin were i tu-. .-\'bb u M sh un . \'b7 . -\'a2 \lquote ,

\par a en rom t at review. X and speed chemists just substitute an netic stirring bar and reflux condenser was cooled to O\'b0C. Sodium \par \'b7\bullet ||\bullet - .n\bullet a a It :.e:- .:$* eses\'b7\'b7\lquote a \'b7\'b7\'b7ao" iii *I I' . O i -if "\'b7 O- IH G BS OOWS y \par the methods below. Also, it should be obvious that these reduction sequential addition of THF (13-15 ml) and BF3-Et2O (12 mmol, 1.5 \par methods will work just fine on 2CB and other phenethylamine in- ml) at O\'b0C. After the addition, the ice bath was removed and the \par termediates. contents were stirred at room temperature for 15 min. The solution \par - [33 - - 139 \par \par . . . _ by the addition of a solution of A-methyl-,6-nitrostyrene (7mmol, 1.4 \par of ,6-mtrostyrene in THF (2 mmol, 0.3g in 5 ml THF) was then in- \'b7 - - - \'b7 \par jected dropwise into the reaction flask via a syringe and the reac- 1, ,, , Br h a dm m tha ct on IX wa \par ' ' ' ' ' ' "' ' \'b7 \'b7 ' \'b7 A O" \'b7 \'b7 \lquote S" COO"'!\} O '\'b0\'b0"\rdblquote ml) was then added and heated at 60-70\'b0C for 15 h. The mixture \par tem erature, the reaction was uenched b careful addllvn \'b7 ee.--a ' e \'b7\'b7; = a \'b7\'bb . \bullet \bullet\'b7 _ \rquote\'b7 : ixure was \par water (25 mn, the mixture acidilied (1N HCI. 25 ml), and than stirred and heated at 6065\'b0C for 2 h and then cooled to room \par h9at9d at 80-85% lvll bath\} f\'b0\rquote 2 h- Mal \'b0\'b0\'b0\rdblquote\rdblquote $Z tv VP\'b0"\rdblquote tam- temperature. The acidic water layer was washed with ether (3x30 \par perature, the product, was isolated (75%) as descnbed in method mj) to ,9,,-,0,,9 N.hyd,0Xy1HmphQ1amin9_ 1-hg PH was 11,8,, acgusted \par A [f"\'b0m \'a4b\'b0V9\'b7 wks\}- to 10 and the product extracted into ether (3x30 ml) and dried \par METHOD #4: The last one from this review [52]. The authors g/\};4S;;jV\'a7g;V;?:yE,Zg>1\'a5,;\'b7;,,;cZ;?r1-;z;d:;;,qOg1;Z,S\}?Cg(;;;; \par found that reduction occurred using soma spacey sounding Gaia- was prepared and recrystallized from an ether/ethanol (20:1) \par Iyst called lithium triethylborohydride. But something interesting miX1um_\'b7\'b7 \par occurred in the process. The catalyst reduced the nitro group and \par allto iveonl asmalIamountofthe r d'ct \lquote = ee .. a. ha, a. e- \'b7 _ - ,_,- -_, _

\par it also stuck cna its ethyls on the \'a4itr\'a4\'a4e\'a4 i\'a4 give a m\'a4l\'a4rity r>r\'a4d- least to Strike) that this reduction method on work to reduce the \par uctof N-Bihwamphaiamin\'e9i formyl intermediate made in the Leuckart reaction directly into \par MDMA instead of needing to hydrolyze to MDA with HCI (don't \par /\\O /\\O H CH ask). For this reaction one substitutes an equimolar amount of \{3\par 0 0 /C 2 \'b0 Nitropropene for the 3,4\emdash dimethoxybenzylcyahide in the repre\par NO2 E, NH sentative experimental below: \par / \'b0"= \par _ _ _ . "NaBH., (4.56g 120mmo0 was added to a solution of Me3SiCl \par MD ph\'b0""' bm N'"\'b0'\'b0'\'b0\'b0\'b0\ldblquote\'b0 ""DEA (26.04g, 240mmoi) in ri-il= (100mL) andthe mixture reriuxed for \par \par \par cousin of X). Strike hears you asking \ldblquote So if one uses lithium tri- En 3 E WG" 9 \'b0\'b0UrS9 Qf 10m'"\'b7 mg S\'b0\rquote Ut\rquote\'b0" was mflux\'e9d \par methylborohydride can one get methamphetamine out of that nitro for 8 futher 10,7* Ate \'b0\'b0\'b0h"g* _10OmL MQOH New caumusly \par group?. Geed question. Unfortunately the answer is ne. The added and the volatiles removed in vacuo. The residue was taken \par authors Say ..lm.ereSting[y\rquote Nelkyleted products were not produced up in dilute HCI and washed with ethen The aqueous solution was \par when other alkylborohydrides were used." Fair enough. Here\rquote s the treated WM SXCES? (mute NEOH and then repeatedly Qxtmcted \par recipe. CH2Cl2. The organic extracts were combined dned over Na2SO.,, \par \lquote and the solvent evaporated to afford 2-(3, 4\par "Redueiiori or iviiroaikehe with Lithium rriethyihorohydride (Su- d"\rdblquote "\rdblquote\rquote\'b0"Yp"\'b0\rdblquote >\rquote 0"\rdblquote\rquote Y\rquote a\rdblquote ""\'b0\'b7 \rdblquote\'80"" = 9-169 (90%\}\par tr ; Jgngk Begin fof\'e9 um E m uc IO". O B: The authors caution that "MeSiH is formed. lt should therefore be \par flame dried, nitrogen-flushed 100 ml flask, equipped with a sep- ` \par tum in/et, magnetic stining bar and reflux condenser was added a \par solution of LiEt3BH (10.5 mmol, , 10.5 ml) via a syringe, followed - 141 -

\par T . - 140 \par \par BROMOSAFROLE & Th b \lquote ' fo k` b 0 af Ie h b n t lx \par l=\bullet l-lElslvl.lsol=l2ol=Yl.l2\'b7la\'b70lvllola , t' " \lquote * \lquote "'_ \par That\rquote s it. The HBr does what is called a Markovnikov addition re\par \par preferentially attaches its hydrogen to the gamma carbon and its \par The third, and last, major category of X precursor is the halogen bl-emlne le lhe middle bele eelben (don\} eek) \par species. ln the world of chemistry, scientists look to add things or \par change things with a molecule by exploiting \lquote functionaI groupsi So O /\\0 \par far we have been exploring the possibilities of the ketone func- /\\ \par tional group (P2P) and the nitro group ([3\emdash Nitropropene). And al- O O Br \par though there are lots of different things that can be considered _HB" \par functional groups, the only one left that really has any broad utility \par for the underground chemist is the halogen called Bromine. When \\ \par allylbenzene (or however one can arrive at that point) one will get Satmle Bmmosafmle \par the t\'b0"\'b0Wmg specles But the key to success is getting the right fonn of HBr for the reac\par tion. A lot of people start off with the CA abstract that uses aque\par /\\ O ous 70% HBr as the reagent (this abstract is essentially a rewrite \par O B of Merck's original patent) [59]. The following is the write up: \par Br V \par "Safro/e (5.3g) added dropwise at O\'b0C to 21g. 70%HBn the mixt. \par left 14 hrs. at O\'b0C, poured on ice, extd. with Et?O, and the ext. Dis\par _ _ til/ed in vacuo yielded 97% 3, 4-CH2O2CeHeCH2CHBrMe." \par \par 0 ' D _ \par feet. the exact Precursor used bl! Merck whe Wee the tttet persen words. Nor does Strike know how any of these folks were able to l' _ s ' -

\par t\'b0 eVntt"e$tZe MDMA- Ultttt Very l'e\'b0ellttY tt Wee the defeete methdd make a supersaturated aqueous solution of HBr. All commercially \par that m\'b0$t \'a4\'a4\'a4erer\'a4\'a4\'a4\'a4 Chemists started Out with lS\'a4me\'a4\'a4e\emdash W\'a4\'a4\emdash available hydrobromic acid solutions are 48% HBr which happens \par tS\lquote N\'b0t\lquote Stttke tndtuded) because et ttfet 9te"ee\'b7 tt eeeme ee etmpte to be the constant boiling point percent for that species in water \par and uses basic chemicals and equipment. Once someone has the (please delrl eskl \par bromosafrole, all one has to do is just swap out that Br with sim\par Pte emmettte dt me'thYtemt\'a4e end the deed ie dede- Some people think that 48% aq. HBr is good enough and, until \par \par But one has to get the bromine on the safrole in the first place, \'a4 \lquote \lquote ' \par tl1\'a4\'a4\'a4bl\'b7 Net beeeuee it le nreeedurellv dlflteult. but because pee- That means mel e weter molecule lee ou) will add instead er e \par ple have been misinformed on the subject for a long time. Bl-_ \par - 142 - - 143 \par \par HBr from the tank is slowly bubbled into the acetic acid. Ever so \par The problem really isn\rquote t the concentration of the HBr, but rather is eheh the Chemist Will atpp he bubbling and reweigh the flask to \par \'b7\'b7I\bullet \'b7'Z \bullet\'b7\bullet VV.\'b7 * \bullet\bullet - \'b7\'b7 , - ' ' "' * -\bullet . \lquote I I'.V - IS \par cant amount of water present in the reaction mix with safrole,gthat \lquote\rdblquote\'b0Utd like te haVe arpdnd 1509 Ot HBr in that acetic acid which is \par water is going to compete with bromine for that juicy beta carbon how qui e \'b0"an9Y lh ep Or\par on safrole. And it's gonna win, too. The answer is to use non\par aqueous HB.- Solutions. Another way would be to generate ones own HBr gas. lf you were \par \rquote to take a look in the Crystallization section of this book one \par For the past year Strike had been ln consultation with contract Weutd eee that the apparatus used is essentially an HCI gas gen\par labs over the making of phenylisopropyl alcohols using sulfuric erater- Suhet't'-*ttn9 the epmmeretatty at/atlanta 48% aq. HBr in-

\par acid and allylbenzenes (don\rquote t ask). The lab owners would listen stead \'b0t Hel will 9lVe dne drll HBr 985 instead! That gas can be \par patiently as Strike primitively described how and why an OH ehanneled dlrsctlyinto acetic acidjust like above. \par should go on the beta carbon. And without exception, the lab _ \par owners would point out to Strike that the best way to get an OH on rhs taat_thlnQ tp remember is that the more HBr one packs into \par the beta carbon would be to put a Br there first. "But Strike don't at aeetle add- the srsatsr and qtllckerths yield will be. 70% HBr \par Wanna pm a Br there mst- Strike would say_ \'b7\'b7Smk9 Wants the OH is still the paragon and should be strived for always. So with the \par put on directly using sulfuric acid!" The lab guys had to do what prvpsr Her aetutten ln hand the evil chemist can proceed with the \par Strike said because Strike was holding all the money (...a fool and \'b0\'b0nVeral\'b0h Ot aatrdle\par her money etc.). But out of curiosity Strike asked how they would \par get that Br on the beta carbon. Every one of them said it was sim- /\\ O P O \par ply a matter of using the 48% HBr in acetic acid. They even O \par showed Strike their stock solutions (usually from Aldrich or O HB B,. \par Fisher). Q -L\'bb Q \par V 4 v 4. V ; v 4 \par Currently, there are commercially available 48% or higher HBr \par ... - -\'b7 \'b7\'b7- \'b7 . \'b7 \'b7\'b7\'b7- :\rquote\bullet - E\bullet\bullet :\bullet \par acetic acid is usually used more as a solvent than an acid. It al- r 6 \par lows the water-loving HBr and the water phobic safrole to mingle METHOD #1: To proceed, the chemist uses her concentrated \par with each other in a very positive way. lf one cannot get a ready- homemade solution that she made above or uses ~350g of any \par made solution of HBr in acetic acid then one can make one quite concentrated HBr reagent, places it in an appropriately sized flask \par easily. iam; places thi flalsk in an ice bath [60, 154]. The setup is going to \par _ _ oo exacty i et e one seen in fig. 9. In the se arato funnel is \par To make her own HBr s0tUtlQn the chemist needs to _90 d0Wn to placed 137g of safrole or 100g allylbenzene. Th; HBr/rgcetic acid

\par the local specialty gas supplier. These sorts of businesses sell gghgfgn is Syuhg -,1 the he bath fl it is bgxynean 5 mcg yy it gets \par tanks of 0X 9en to hospitals. acetylene tanks to _Weldin9 ah a too cold the acetic acid will turn to ice) then the safrole is slowly \par " ' \'a4 ' """' \'b7 \lquote "' "' \bullet\bullet\bullet\lquote | . \lquote\bullet VV \bullet\lquote .I| i\bullet 'I.\'b7\bullet Sa | W| \par of acetic acid in a small PP container or flask and then Weighs the dissolve quickly into the cold acid mix. Good, congtant stirring as\par flask with its contents. Next, the flask is stirred in an ice bath tray sums that everything Comes in Contact with everything else After \par that has lust a small amwnt \'a4t rss t\'a4 kssp the \'a4\'a4\'a4ts\'a4ts \'a4\'a4\'a4l and addition re complete the solution is a dark orange and is allowed re \par - 144 - -145 \par \par 66***6 *6 *66*** *6"*l\'b06*6****6 6*\'b0*\rdblquote *V *\rquote V *6*****9 ***6 *66 ***6** 6*\rdblquote 6V\'b7 When Strike first started the Hive web site Strike was sent a \par Then the solution IS covered with foil and stirred at room tem- newsgroup post by E Very famous underground chemist Called \par layered burgundy solution. The chemist pours this solution into a P**gS* y` ** *e d 5 ** 5** **5 ** *. * ** * 5 *5 \'b0* * \par ccn alnero nn co wa er an \bullet\bullet crus e ice ma e ea ier fu Wh . h . Stk kn .t k txk , \par gg0rpm\'a4g;gg\'e9,B;qt;qg; ;g\'b7\'b7;hg><;]5],;gg\'a4\'a4;,gg\'b7b;)g;]\'a4; gjggmgh; gggg lll;?.d'll?A\'a7a$J\'a4'\'a7\'a72\'a7\lquote ii \'a4ul'm\'b0ha2\'802l\'e9dllZ%'aid .l\'a7\'a7#\'a7\'a7a ullvii \par rated from the water and the water extracted once with 100mL 5**** *5** 5**** 5****5 *****5 0*** *****mbs ***1 \par ether or benzene which is then added to the bromo compound. M _ _ _ \par The bromosafrole/solvent is washed once with clean dl-|20, Once Subject-__ PUQ\'a7/SYS bromosafrole prep > From: no\par with 3% sodium carbonate, then dried through Na2SO4. What the body@zlh.genetlcs.utah.edu (Anonymous) > Date: 1996/06/28 > \par chemist has now is a dark red bromo-safrole compound in some Message-ld: Newsgroups: alt.drugs.chemlstly > [More Headers] \par solvent; The chemist removes the solvent by distillation then vac- \emdash _

\par uum distills the bromo compound over to get a clear, slightly or- ******6* *S ***9 9***** ***O***O$a**O*9 *0* ****0***0 pmp*****y*b*****Z********* Syn _ \par 5**95 5*\'b0m\'b0`55 *5*.5 *y*5***=55 ****1 * *5***5*** ***5 5******5 \'b0\'b0***p\'b0u**** reagents and generates no obnoxious fumes to give you away. \par *6 6*6**V 6*66** 66 *6 6**** 66**.*66 ** 6*66**6** **666 66 *6- A 6**6****6* More tha*n likely, this will spur DEA rc aclcl new watched chemicals \par :****%.*5 m**:3*;;**h\'b0*;*P'5a\'a7*i*L5ng5* \'b0*r*t2*5 i5/*\'b0nm\'a7\'e955/**\'b0*5|,xl\'b0u;d ***5**5 (like what isn't watched already- ain water; ?) To 100 ml of chilled \par t6*n *996*d 6.6 rf H 6 .t*'**\'a7*; lg 6 *6 *\'b0'***"6\lquote DMSO add 7.8m/ ccnc. llzsoi (i.e. drain cleaned. rc this add soy \par *\'b0 ***555 ***5 *5 **5 55 y 5*** 5 \'b0* 5*95 *555 *5 5\lquote of NaBn Stir well and repeatedly. Solution will turn orange as all \par If the chemist wants to know whether her final product is bromo*,*32;*35*t;1S\'80*;**;*\'a7**SZ*fT?6Nj5\'a7;g3;tg; ,*:];L@***;h,*G$V?h;W\'a7**gg 5**;;; \par safrole and notjust a bunch of unreacted safrole there is a simple DMSO is anhydrous SO W", the HBr be anhildmus Adi.] 5*mI Of \par little test she can do. Safrole is soluble (will dissolve in) cold con- Y ' - ` \par centrated sulfuric acid. But bromosafrole is insoluble in it. So the Sassqfrass 0** 0* $**5**** *****,0** ********)*******6* up *0** ***0*** $aS`*********SS' \par is can aeasogassucsraig -rom- e\emdash oe D . . . . \par H SO and lace it in the freezer until it\lquote s ice cold. Then she takes *** * *5 ** 5 *5 a n * * _ 5** 0 *** * * S * \par ** 5*** 5**** ***5***5 5 *5**** ****5**5 5* ***y5*5*y ***5****5* ****5 **\'b7 ** the 5** understand why this works so well* see Fieser and Fieser "Rea\par S\'a7\'a7\lquote ;L*:5\'a7ngh\'a7g\'e9;5\lquote\'a7;*\'e95Sfor:/*;**115;:** 55**\'a7*5\lquote ** the 5** ***555 *5 ***5 gents in Organic Synthesis" under* DMSO monograph. Note that \par * 5 g\'b0\'b0 5\lquote there are two pathways for HBr to react. Via an ionic mechanism \par _ . . . . gene rates the desirable compound. Via a free-radica/ route forms \par U\'a7L"\lquote\'a7L\'b0lZZi?e*?\'a7.\'a7EZE"\'e9slZ *\'a3Z?h\ldblquote 6\'a7S *lll?\'e93'\'b0l?i'\'a7 Ziielfll\'e9il *6"***"6* \'a4r\'a4m\'a4,\'a4\'a4m\'a4\'a4,l;~;\rquote\'b7 lgllch \'a4r,,l;S$d,9y\'a4~ gw for \par . . \lquote . . interesting ana ogue, u w o cares now a a min a ering \par E|*F*;'\'a7gn*;*; *?;*\'80g**5O*E5***cgii **5** 5555E* \'b0**5?*\'a7*5 *55*2*5 mik***E|:**5 chemicals are illegal under the Ana/oges Act, including all those in

\par i V -i . _ _ ' 5 _ 5 ****5 5 5** *\lquote * 55 \'b0 5** 5 *** - -\bullet -4- pr: - rpg - e e Je se He/mes committh felon \par l<l with S inha aca ne a a ndei wa is ma \'e9*S\'a7lT1'n6e, Sr El ll he he any belt Cells hm The M6 -=-SS-fi-SS. Oil \'a4\'a4~el~S \par in water (see the Chemicals section of this book) except these * **1 * `*\ldblquote\'b0*'** * * * U U '* ' *' ** \par . . . Thus you will get better product lf you don t purify out safrole. Also \par ;\'a7:g*O$*cg;*;*s ****5*5 **5***9 ***5 **\'b0**`5q**5\'b0u5 5\'b0*V5**** DMSO ***` keep reaction mixture away from air and UV light, both generate \par - 146 - \lquote *47 \lquote \par \par free radicals. The hnal mixture gets 500-1000ml of water added. \par The crude bromosafrole which settles to the bottom is seperated Tv 2509- Of 48 PBT Centhydfdbrdmic acid contained in a 500ml. \par \par sticky and syrupy so the water layer can be just poured off" acl in P0 l0h$ Wl S a fhg ).' Sdme hydrogen bromide may be \par \par _ _ _ _ (32.5ml.) of concentrated sulphuric acid in several portions with \par One need not inhibit oneself by using HBr. One Can USG Nel or Kl shaking, and Hnally a few chips of broken glass, Attach a ref/UX \par to make Hl which is even better than HBr inlany of these recipes. cgndgnsor to the f]aSk and renux the mlxture gently on a Wlro \par iodine adds much better and swaps out with the amines m\'a4\'a2h gauze for 2-3 hours; during this period the fomiation of sec-butyl \par better. Yield are much higher! The Other thl\'a49 tc h0Tl\'a2e IS that F6- bromide is almost complete and a layer separates above the acid. \par action carries itself out in DMSO. Seems logical to believe that ly the preparation is Carried out ln the open laboratory, nl an ab_ \par one could bubble their HBr gasses into this S0|VehlZ lhaiead of sorpticn device (compare Fig, Il,13,8 and Fig.lll 28 1) to the top of \par BCGUC aC'd\'b7 the condenseri order to absorb any hydrogen bromide and sulfur \par dioxide which may have evolved. Allow the contents of the flask to \par , ,.\bullet . _: . .__ - ._ .\bullet \'b7 ._\'b7 i ._\'b7 II l\lquote lII\lquote I' Ill'! I all \lquote I IIi|i. |

\par Strike and others have been toying with. Eleusls had been sup- ynnsgt H? Cgndsnssr \{O thO,fIOSk by "YOOOS Of O W'OO (7'8'\'b0\rdblquote\rquote Y\rquote\'b7 \par porting the idea that one could make use of the common 48% aq 'ame O; OO g/fss WOO' Dm'] the mixture unt'] "O \rquote "O\rquote O Oily \par HBr if one employed the technique of 'dehydration\rquote . We remember dmps. O. SO\'b0`OutY bmmlde tO OOSS Ol/Or (3040 m'"OtOS)\'b7_ Transfer \par that the water was competing with the Br in the nonrnal 48% solu- the O'St'//ate tO O SOpO\rquote atO\rquote Y fO"\rquote ""I and \rquote OmO\lquote\{\'80 the halide Whlch \par tion. But the literature demonstrates that in conditions such as 'KOOOS the \{OWN IOYOK Wash ll S"OOOSS'YOlY W'"' Wafer an equal \par this, a competing acid can strip away the water (dehydrate) from VOl\lquote\ {mO \'a4t,\'a4\'a4\'a4\'a4\'a4\'a4\'a2r\'a4\'a2\'a4\'b7\'a4 h\'b7VO\{OOh\rquote O"C edd (2)\'b7 Witten 5 P6" Cem\par the beta Carbon allowing the Br a Second chance to pop ln, SOC/IUH7 bIC8I\'b0bOI`l3t\'80 Of` SOdIUm C8I`bOI\lquote l3tQ SOIUNOH, and W8t\'80f`. \par Separate the water as completely as possible and dry with 2-3g. \par of anhydrous calcium chloride or anhydrous magnesium sulphate; \par -_- Q |,_ Ineg; n _ Ing! ,, gn gl _ j gjl ggllg ll l'I' I al II II' \lquote I I,II,, A I l' @lIII \'a7\lquote I a fa_ \par the idea that bubbling HCI gas into the safrole/48% aq HBr reac- 30 minutes and shaken occasionally. Filter the dried product \par \bullet " \bullet '\'b7-.\lquote \bullet\lquote \bullet - \bullet\'b7\bullet " \'a4\bullet\bullet . \bullet\bullet . \bullet III \'b7 \'bb I \lquote r||\bullet \bullet .'\bullet\'b7\bullet \'b7\bullet .|-\bullet , \par to occur. Strike does not know if that actually works. Could be. But cotton wool plug into a 200ml. distilling flask, add a few chips of \par what Strike and Eleusis draw on are the examples given b Vogel orous orcelain and distill either from an air bath Fi .ll 5 3 or on \par v p iv ( Q . , l \par [37 p277]. an asbestos-centered wire gauze. Collect the portion boiling at \par 100-1030. Th 'eld \lquote s 155 . \par When Vogel wants to brominate something using regular old 48% 9 yl I g \par aq. HBr, he has sulfuric acid already present in the pot. The fol\par lowing is a representative recipe from his book. Just read it. Strike Notee (1) tne aold rnlxtnre may be oronarod.loomoaro Soollon

\par plain Strlkeis i\'a4t\'a4\'b7\'a4rst\'a4*i\'a4\'a4 OOO\ldblquote\rdblquote OrOS\'b7 ide in a 500ml. Hask, cooling the latter in ice, and passing sulphur \par \par "lll,35. sec-Butyl Bromido (HBr-H2SOl Method) at such a rate that the gas is completely absorbed. The flask is \par shaken occasionally, and the flow of gas is- stopped immediately \par _ 148 _ the red colour due to free bromine has disappeared the mixture \par -\lquote 149 \emdash \par \par will then have a yellow colour The resulting mixture is equivalent s\'e9ffrqle he is etamng with- ll is all OH 3lC0h0|!". That\rquote s true. But in \par to 250g. or 48 par cent. hydrobromic acid to which 7sg. or can**1*5 \'b7\'a4ete\'a4ee\'a41\'a4\'a4ee net meke e difference. We know that at 48% \par eniae sup unceci ave eena e;inee no e isie ` o e eacar on \par for Qregamrion Of Sembutlil b,-Omid9_ anyway. Stiihstarting with anhalcohol will make no difference. The \par cinc er is e presence o t e H SO . lt is there not nl t t' \par Owing to the comparatively negligible difference in._the cost of off the existing OH, but to keep itinff so that brominatiogn blessing; \par bromine and the equivalent quantity of constant boiling point hy- dominant. \par drubromic acid, there is little to be gained--apart from the instruc\par tional value-- in preparing the hydrobromic acid from bromine in So if one were to replace sec-butyl alcohol in the recipe above \par the preparation of alkyl bromides. with an equimolar amount of safrole in the above reaction, Strike \par _ _ _ will wager that a positive bromination experience will occur. And \par CAUTION- Bremiee reeei ee heeelee with greet eere eee ie the eii this iieihg the very eehiiheh 48% eq. haii The ehiy iiirieiehee \par fume eepeeere Tireteeie ereeeeee eeiefel heme eee the veneer being that ONCE the reaction mix had cooled one should do either \par is unpleasant. Bromine burns should be treated immediately with of two things: (1) dist"' as described EXCG \{me bmmosafml . \par a hbelal q"'a"mLY \'b0l 9_ M\'b0'"\rquote\'b0\'b7 ll H'? \'b0_al\rquote\'b0\ldblquote ' ls \rquote ""a*\'b0_'\'b0\'b7 \{Elm ma? be the last thing to come over (not the first), or (2) flood the reac-

\par ggsieieieee er Seeking heeekerehief ie eleeeeiiheleiee it eeer the iieh mix with water to hiihe the pieetiei eei of eeitiiieh after which \par \'b7 it can be physically separated by decanting or sep funnel or some \par (2) The crude bromide contains a little unchanged alcohol and is eeeh shit \par said to contain some n-butyl ether (b.p. 141\'b0). The fomrier is re- A . . . . _ _ _ _ \par moved by washing the concentrated hydrochloric acid and this "yWay\'b7 ms 'slust ee 'dei eel '\ldblquote \'b0\rdblquote\'b0 \'b0\'a5\ldblquote\rquote f""'S '\ldblquote\'b0"\ {\ldblquote\rquote d t\'b0 We '* \par punhcation process is satisfactory for most purposes. Both the al- gr mak? Hf gas f'-\'b0m 486 aq\'b7 HBV Stijk? has p"\'b0V'd\'b0d (luna a \par Ocho, and the Ether are removed by Washing with 11_12ml. Of tew recipes orthe manufacture ofthe 48Ai in the Chemicals sec\par concentrated sulphuric acid' the butyl bromide is not affected by '\'b0n\'b7 \par You see that substrate they were using: \ldblquote sec-butyl alcohol"'? Well \par to Strike that looks just like MD-P2PoI: \par Pe \par O \par OH \par Mp-EhEn\'a5|-2-pmpaDQi \par And in the recipe above, Vogel want\rquote s to get rid of a secondary \par alcohol just like the one on MD-P2Pol and replace it with a bro\par mine. "Wait a minute!" you may say, \ldblquote That isn\rquote t a double bond like \par \lquote -150 - - 151 \emdash \par \par given here are designed to insure that this will not occur. Even \par AM PHETAMINES 8s handled carelessly the potential for harm is not as dire as it may \par seem. Nevertheless, these procedures should be done in the \par IIIIE I I II I III IIE II I IIIII IEEE hood and, if possib e, performed behind a clear pane of acrylic \par \par PHENYLISOPROPYLB ROMIDE Relax. Trust in the science and read the articles provided [62-67].

\par The setup used is the one pictured in tig. 9 except there is no ice \par bath tray. In the reaction flask is stirred a solution of 30g NaN3 in \par Wl,. mm., O, im compound in hand it is time m quit and wm 222; \'80LI\lquote ,$\lquote 5\lquote\'b0L,\'e9I\'a7\'a5f'\'b0$iBs \rdblquote\'b0iI\'a7\'a7\'a7\rquote .3-"\rquote b$Ln'12Z232'.\'a7\'b0IL$m\'a7\'e9\'a7 \par \'b0Ipl\'80S gil; \'b0VSI;lII;;hl$l0%\'b0lE\'b0lgl a$I:l$;?\'a7\'a7\'e9\ldblquote Y\'a5laIIL1;:$lI;r ere 3 few bromo-allylbenzene is dripped into the solution from the separa\par W \'b0 W \'b0\'b0" II \lquote y 9 \lquote tory funnel over a period of 20 minutes. After addition the ther\par METHOD #1; The bromine on the safrole or allylbenzene is in m m g r d p m I IIIIBI a e em v d a C IICI II BI ES \par waiscae asec i` . \bullet\rquote\'b7" ' a ` " .. I \lquote \ldblquote\'b0 ' . \par . . . . . time. The solution is refluxed for 24 hours, cooled, 100mL ether is \par II we were II? IIry_aI\lquote Id SCIGIIII QIOIIIICI WIIII lhtl IOIOITIIIIQ WIISI-6 II IS added and the entire solution slowly poured into 1000mL of dH2O. \par and replace it with something like ammonia (which would give The upper Ether layer ls Separated the bollom Water layer \'80X_ \par MDA IIQIII \'b0fI the bal) IIISII mma bed IIIIIIQF IIIQII g\'b0\'b0d w\'b0uI\'b0I \'b0\'b0` tracted once with 100mL more ether and the two ether fractions \par cur. Ammonia is a so-so nucleophile and if it tries to muscle the comblned and drlgd through Nazsca The Chemlsl HOW Vacuum \par I\'b0Ir\'b0mIIIS fI\'b0ITI IIS sP\'b0I IIIEII IIIE m.\'b0SI IIKSIYIIIIIIQ that w\'b0uId happen distills the ether/azide fraction to get what is now safrole-azide \par is that an elimination reaction will occur and the double bond will (yleld=50%) \par reform (giving safrole and isosafrole as products) or unwanted in- ` \par appI\'b0pIIaI\'b0 ?ddIII\'b0II\'80 may \'b0\'b0\'b0uI (I\'b0I\'80\'b0S\'80 CIQIII asm A? II SO IIaP` A much greater yield can be had if the chemist uses carbitol as a \par \par I I S p\'b0SI I\'b0\ldblquote qu' I \lquote a I a I I IN I I. S S pp S _ solvent and should not be breathed or placed on one's skin. The \par to be on the safrole or allylbenzene molecule is certainly a step in FE E EVER NE 55555 Ellastllr as E\'a3G,E Ellgapt that am, 2q HE lrs Bf \par the IIQIII dII`\'80\'b0II\'b0n even IIIPIIQIIII .IIapp\'b0IIs.I\'b0 have a \'b0\'b0uPI\'80 \'b0I BX` reflux and cooling the mixture is slowly poured into 1500mL ice \par tra nitrogens attached to lt. This is not going to be too big an ob- cold dl_l2O. -l-he upper solvent layer ls Separated and the aqueous

\par stack; ee Y\'b0u WIII Sea layer extracted with 200mL ether which is then combined with that \par 0 upper solvent layer. The combined solvent portions are vacuum \par /\\ /\\O /\\\'b0 distilled to afford safrole-azide (or phenylisopropyl-azide for am\par M 0 C,,,,,,,, phetamine) with the yield rising to 70%. \par \par Br\'a4\'a4\'a4\'a4e\'a4fr\'a4le Sefrele-Azide MDA (bromines or iodines) is in the use of phase transfer catalysts [68]. \par The beet ezide te eee rheee deve ie eeeium azide <NeN\'a4l\emdash ll ie i\'a4- me Ga i a Aliq a 3 6 ii i- h n e ti a is i i s la m \par \'80Xl\'b0\'80\rdblquote s'V\'80 and Unwatched- All aZ'd\'80s have the P\'b0t\'b0"t'aI te 6* used to get yields approaching 100% but an alternative catalyst of \par plode upon degradation and are toxic to breathe. The methods \par - 153 \par - 152 - V \par \par ' ' ff t' It t `th ' Id - . . \par b:;;|\'80l_Th"\'807\'a7%\'b0H\'80;i; zgueg g sia Im; izrgglf ged aah S1 lege The following two reductions are, hands down, the ways to go for \par gmmesgfmle laog phenyllSOpmpyl_bra\'bbmldal 30ml- dl_l2O and reducing azides [71, 72]. 200g safrole-azide or 160g phenyliso\par . , , I seal .- s\lquote .\'b7e !!!\'b7\'b7 \'b7\'b7'\'b7.*s .\'b7 \'b7 \lquote = \'b7 . \'b7\'b7\lquote \'b7a\'b7 \'b7a \par 599 Seem"?] amde are sinned In the reacmn as ` 9.0 buty a` ice bath with stirring. All the chemist needs now is 34g magne\par fl d K Mh f 6 h l All l. l lh _ slum g pow er or 60g calcium (Ca-), WHICH-C3D_5\'80 purchased in \par iLZ?$'.?ie $\'b0\'bbnrSei'e(ea$nn ZTner,e\'a7`ZeZrinleZ\'a7L$ne,e%.\'b0$E\'e9"\'a3eiiiiZ$ $e gg; *mlg\'a4g;a$Ltggoglh;\'a4l;\'a4l;\'a4\{y;L\'b7\'a4k;*;<;lv\'b7g;~;;L; $3%:2 gag; \par provide the azide product. The chemist should keep in mind that . . . \lquote , \par here, as with the previous two azide procedures, will be a signifi- ;: $ggl_e;\'b0\'a7C;;e;g"le1?gh;\'a3g glged |;\'a7E\'a7O:egIg\'b0mge?n\'a7:;;e;glS Tix? \par cam amwm of Salvageable Isosafrole formed as a bypm uct most immediately, heavy bubbling and heat will evolve. The bub-

\par . . - . - - ` ' d N gas which lets the chemist know that things \par One ofthe ways that this azide method is going to make it rests- b|'"9 'S release 2 , , _ _ _ \par tant to inten/ennen bylaw enrenienient is that the azide species \'a4iz*m3\'a49_\emdash lT;; S\'a4l\'a4l\'b7<;l\'a4 S\'a4*\'a4_\'b7\'a4 the wsgalh f\'a4r 15 mms? we _ \par comes in so many forms aside ot plain old sodium azide such as an e S '\'b7 e met eml 'S "em\'b0Ve by Vacuem d's\'a5'\ldblquote at'\'b0\{\lquote\'b7 \par . . . . ll l Z. e 69 ala l_law_ cooled and 500mL ice cold dH2O added to the residual oil left in \par puma ' E I I . > h ll y. gh hl ll lh- the flask. lhe solutions pFl is adjusted to hetween 9-10 with di\par ggzlevgggtbrgariilsuelgz Tgeshgc\'e9gglsaehlzelif llilg/Engr Zhcplxgglilhg lute NaOH solution and saturated with NaCl. This solution is ex\par Wheh mast underground methods lhlmduee that plaelaua hllmgeh tracted with ether, the ether washed with dilute NaCl solution then \par there ls always a ealeh Usually there ls a lermyl Ol acetyl group dried through Na2SO,, . Removal of the solvent by distillation will \par attached that has to removed in sloppy, destructive ways. Some- gwe MDA \'b0r empheiamme m y'e|de \'b0f gee! \par \lquote \lquote \lquote ' th h ' h` h- . . . . . . \par Eleiieliif eZ.E'2\'a72teg'Z`$% '2eEL'\'a7i\'b0fe`3.i\'80\lquote f,en\'a3i;\rquote ? ne\'a7.\rquote g\'b0\'b0l\lquote .Zi\'a5\'b0n,,L%l- 2 tile amen ehenle _nel_l\'b7e stannglils en\'b7ellne (lee. \par watched chemical called methylamine. The chemists using azides " 2\'b7 a\'b7 \'b7e\'b7 m \'b0 \'b0"' e) W '\'b0 'S _\'b0ne exe V as t e ee \'b0"\'b7'm \par are in a unique position because the mechanism by which those me exeept thet_eb\'b0ut 1009 \'b0f Snclz 'S used m place \'b0f the M9 \'b0' \par . h be ll-eked all and re laced Wllh h dla eh Ca and the addition occurs at room temperature and the solution \par \par are Van\'80d' easy and Successful In pmducmg almost mob we S reductions that operate almost exclusively at room temperature \par . with no pressure and give almost 100% yields are to follow. The \par rleh; t?:r$sT]LS;ir$anRLeii; cigiklenemgdssgdniiscgmzllggrres only reason Strike did not detail these methods is that some of the \par Cenil the meg 0 ulgr Wa was le use l_lAll_l [70] lla da thls chemicals involved are a little less common than Strike is used to

\par the glhemlsl mlxzspmg Ofyaalmlaazlde Wllh 300hlL anhydlaua but all are available to the public. These alternatives include: \par ether and slowly drips this solution into a stirring mix of 40g LiAlH4 eeeuyleeemne end methylenlme [73]* p'-\'b0penee'th'\'b0[ and meth` \par in 200mL anhydrous ether. After addition, the solution is refluxed ylemme [72* mpheny| pg\'b0Sph,'2e [75\} NeBH" wm" phase transfer \par for4 hours, during which time the chemist will notice profuse bub- eetelyst [7 ].\'b7h:2S av py" me l"l\'b7 lend. l\'b0e'led'\ldblquote m hVd"\'b0*' \par llh Whleh ls harmless hllm eh as lNl belh evolved. After 4 ide/carbon wit ydrazine [78], stannousc lorlde di ydrate [85]. \par h\'b0urSlandlC\'b0\'b0Img\rquote 100mLl dH. ZOl.Isl-ad deld to- d eslltlrgoyn m el Cfaatlilaysatll Recently, a nice bee named Quirks submitted an article from our \par my new, favorite patron researcher: Rajender S. Vamna. This time the \par \'b0\lquote good doctor is tackling our azide problem with another novel use \par of his clay phase transfer catalyst system. This is just going to be \par \'b7 U4 \'b7 e 155 \par \par quote from the journal article [ssl. ir you like the looks or this ex- \'a4\'a4\'a4 is 9\'a4i\'a49_f\'a4 need \'a4 seed nucleephile (like Na) to swap out at \par perimental, then go and read the entire article for more detail. Such a P\'b0$'t'\'b0hAmm\'b0hta is hat a Val\rquote Y 900d \'a4U\'a4l\'80\'a4phi|\'80. S0 in \par \ldblquote AIk]!I Azldes from Alklil Bl-OI-nides and Sodium Azlde. _- General talking a lot Ofuilil This will not only push the l'eacti0l\rquote I t0Wal'dS sub\par procedure for the synthesis of alkyl azides. ln a typical experi- $ttat_'\'b0"\'b7 but W tt tall? Ptatattt a ' ttl ta_t*\'b0h aha \'a4\'b0mP9tlhQ l'\'80a\'a4tl\'a4\'a4$ \par ment benzyl bromlde (360 mo, 21 mmol) in belrolellm elnor (3 (dont ask). The most basioammonla available to the chemist is \par ml_) end eodlum ezlde (180 mg. 2.76 mmov in Wele, (3 ml_) ere ammonium hydroxide which is ammonia (NH.,) dissolved in water. \par edn-lixed in e rOund.bOttOm9d flask To this Stir,-ed Solutionl pll_ Vllhat the chemist needs IS as C0l'lCel\rquote ltl"ated a SOluti0l`l of ammo\par lared clay (100 mg) is added and the reaction mixture is refluxed mum hVdt'\'b0Xtda as Paaatbta- eesireus tatm t\'a4l' a 900d solution \par with constant stirring at 90-100 'C until all the starting material is Watyttd be aha that has a Slaacltla 9l'aVttY ef 0-9- Ah 9)/Bn batt\'e9f

\par Consumed as obeel-ved by lnln layer onromelogrebni, using bore option would be to buy a solution of ammonia in methanol or \par hexane as solvent. The reaction is quenched with water and the athah\'b0t\'b7 A Qaad aahcahttattah ef ammahta th Such 3 $\'a4l\'a4tt0\'a4 \par product extracted into ethen The ether extracts are washed with Wautd be 18'25%\'b7 U$'h9lmathah\'b0t \'b0_t ataahat maaha that the \par Welor end lne Organic layer dned Over sodium sl_,lfele_ 1-no re_ bromo-safrole or phenylisopropyl-bromide oils can dissolve into \par moval of solvent under reduced pressure affords the pure alkyl tha ttad'uttt sa that tttall aah wma th Qtaatat \'a4\'a4hta\'a4t Wltti tha \par azidgs as oonlqnned by me Spectra] analysis? ammonia. What may prove to be the best choice for the chemist \par would be that of going down to the specialty gas cannister com\par MET**\'a4\'a4 #2= This memd is a \'a4a==*<\'a4\'a4 use fm all that i\rquote\'a7`a'1\rquote gZ2\ldblquote l\'a7E\rquote l2ZZ\'e9il"`\'a7.\lquote\'e9il?\'a7?i2l\'b0SJae? i?\'a7'a\'a4i'l?.i\'a7i'1`ZL"\'a3s\'a7Jl[.llZ,\'b0$'\'b0\rquote ZZZ \par bromo-safrole or phenylisopropyl-bromide that the chemist made. gain no more weight in ammonia All of this Work with ammonig is \par It is the simplest method in the entire book, uses the cheapest Qin to stink like Graz so ood iientiiaiion is 8 must \par most basic ingredients and happens to be the first method that g Q y g ` \par Strike ever 'studied' [59]. Strike does not have many fond remi- NOW Contrary to popular Opinions this method med not be com \par n s itc s .ab\'b0 t t t? m hcld CE E tt l d S ks t he ducted in a sealed pipe bomb. Secondary amination by substitu\par \lquote . i f i i \lquote i` .\rquote T in " ionisasmuc areaclonooppo uniyasiiso rueorcean

\par Chemist Tiheireactmn Pr9C\'b0eidiEs ias f\'b0"\'b0Ws whltth usies aimmoma heat. In fact, heating can tend to cause the reformation of safrole \par \lquote and isosafrole. So the simplest way to do this would be to use \par 500mL of ammonium hydroxide or alcoholic ammonia or, for those \par /\\ O /\\ O wishing to make MDMA or meth, 40% aqueous methylamine or \par O O alcoholic methylamine (to tell you the truth, methylamine is prefer\par Br Nl.li,,,MeNl.l2 NH2 able in this method because it is more reactive that ammonia so \par \emdash > yield will increase). This 500mL is placed ln a flask and into it is \par poured a solution of 35g bromosatrole (30g phenylisopro-

\par pyl-bromide) mixed with 50mL methanol. The flask is stoppered \par \par The chemist could also reflux the same mixture for 6-12 hours or \par All this business of swapping out bromine would be a lot easier if she could throw the whole mix into a sealed pipe bomb (see How \par that bromine were at the end of that aliphatic chain which would to Mgkg section) and cook 11 for 5 how-S ll-l 3 120-130%; Oli bam \par make it a primary bromine (don't ask). As it so happens, the bro\par mine in bromo-safrole is at a secondary position which means that \par - 156 - . - 157 \emdash \par \par When whichever reaction is complete, the excess ammonia and METHAMPHETAMINES FROM \par alcohol is distilled off. The exhaust coming from the vacuum or A|V|P|\'b7|ETAM|NE$ \par bubbled into a container of NaOH solution because all that am\par \par acidified with 500ml 10% HCI solution and extracted with 100mL METHOD #1: [26]-- gg of perfectly fine, ei.,edidn\'b7i_be_meeaed Wiih \par ether. By now you readers realize that. the MDA product will re- MDA or benzedrine freebase is mixed with 100mL methylfomiate \par main in that acid water and extracting with ether will remove valu- in a Small pipe bomb. The eeeied bomb is placad in peiiing Waiei \par able unreacted safrole, isosafrole and bromo compound. The or a 100\'b0C oven for 12 hours, cooled and the solvent removed by \par ether is separated and the water layer, which is normally brownish distillation to give approximately 8g of N-formyl intermediate. Yes, \par gray at this point, is basitied with concentrated NaOH solution and inai\'b7e ine same kind ei intermediate that one gets fmm the \par then. will appear dark brown droplets of you-know-what. Leuckart reaction, and this` recipe is going to employ the LiAlH4 \par You-know-what is extracted from the solution with ether or some Way ei stripping ine double bonded Oxygen of the formyl eide \par other solvent, dried through Na2SO4 and removed of solvent by rou to ive metham hetamine. The 8 of form in r e \lquote a \lquote

\par _ _ _ LiAlH4 in 100mL ether and refluxed 4 hours. The solution is al\par Right about now the chemist is probably screaming, "Hey, where lowed to cool, 50mL dH2O is added, the solution vacuum Tlltered \par the hell is rny big yield of you-know-what\lquote ?l"; I Sorry, Charlie- This then extracted with 3N HCI . The MDMA/meth freebase is liber\par way of aminating is easy but chemically its a crap shoot with ated from the acid with NaOH extracted with DCM and removed of \par yields anywhere from 10-50%. The theoretical odds are against solvent to give ~8g. \par the reaction but if it is done as outlined here, the chances or suc\par cess are better. Actually, Strike thinks the yields could be higher METHOD #2: [89]--1M MDA or benzedrine and 1M benzaldehyde \par because half the problem was probably caused by low bromosa\'b7 is dissolved in 95% ethanol (Everclear), stirred, the solvent re\par frole yield which we have hopefully corrected in the preceding moved b distillation then the oil vacuum distilled to ive 95% e\par that's dumped in boiling water for 5 hours giving an orangy-red \par heavy oil. The oil is taken up in methanol, 1/8 its volume of dH2O \par is added and the solution refluxed for 30 minutes. Next, an equal \par volume of water is added and the whole solution boiled openly un\par til no more odor of benzaldehyde is detected (smells like almond \par extract). The solution is aciditied with acetic acid, washed with \par ether (discard ether), the MDMA or meth freebase liberated with \par \par and 65% for MDMA. That's not a bad conversion but what's with \par another aldehyde can substitute. \par _ 158 _ l 159 \par \par METHOD #3: [90]--The folks in this article made an acetyl inter\par mediate out of an amphetamine to act as a form of protection ADVANCED SHRIMP PREPARATION \par \par anything happening to that precious aminegroup. This metho

\par acetic anhydride. This method is only for the weird. 80mL acetic \par anhydride is added to a solution of 10g MDA freebase, 50g so- . . . . \par dium acetate and 300mL dH2O, which is then shaken until the sms? hai bshepmvery q'Sapf$\'b0mt\'a7? lr tthgdlick \'b0\'e9r?Stl$"s\'80s if \par exothermic reaction ceases. The cooled solution is filtered and gar mg E .r' p reclpes \'b0m Q as "\'b0n\'b7 ny _\'b0 p\'80\'b0p\'b0 \par extracted with ether to give n_ac\'80tyI_MDA which can be Stripped contacted Strike saying they had tried them. Naturally it was the \par of its oxygen with LiA|H4 just like was done in the Leuckart basl fwd thgy had ever h? d\lquote Smke Fam understand what Wa? \par method wrong. Was it a problem with translation for the Europeans (hint. \par \lquote shrimp' in European is \lquote prawn\rquote , possibly \lquote langoustine')\rquote ? Was it \par that all of you can't afford shrimp? Can't cook'? If you can't cook \par Actually, the problem is clear. If all of you would stop taking am\par phetamines you would regain your fucking appetites! Here\rquote s the \par recipes for when you get out of detox. \par Shrimp Diablo \par Jumbo shrimp \par Jalapeno peppers (seeded and halved) \par Bacon strips (blanched 1 min in boiling water) \par \par \par against 1 shrimp, wrap with a bacon piece and secure with a \par toothpick. Place all of the shrimp \lquote brochettes' into a bowl and \par marinated at least 30 minutes covered with teriyaki sauce. Broil 5 \par minutes and serve. Yum! \par Shrimp ala Strike \par \par \par Gruyere cheese

\par -Cut the cheese into french fries-sized pieces, place one piece \par - 160 \par - 161 \par \par with a shrimp and wrap with a slice of prosciuto. Broil this for tive \par minutes and serve as is or with a dipping sauce of butter and After all the butter has been whisked in the sauce will be creamy \par \rquote IIIl .| I\lquote ,l| :'i ~\'b7$ " iii`i 'L- II \rdblquote . -*" . "I Ill ! II\par over the place the sauce has broken. You failed. Actual! , the \par \par the reward is heaven. Frenchman would like. The sauce can be kept warm over a hot \par water bath or by stirring over low heat. Anyway, at this point one \par Shrimp Acapulco stirs in the soy _sauce and pineapple into the sauce and drapes it \par over the k\emdash bob`s. Oh God is it the best flavor in the world. You \par Jumbo shrimp have been warned! \par Beef sirloin or tenderloin, cut into 1" pieces \par 1/3 cup peanut oil \par 2 tablespoons soy sauce \par the juice of 3-4 limes (or lemons) \par 1 large shallot, minced l \par 2 sticks unsalted butter, cut into tiny pieces and put in freezer \par % tablespoon vinegar \par 1-2 ounces Grande Marnier (or any orange-flavored liqueur) \par 1-2 tablespoons of crushed pineapple with juice (canned is fine) \par vi tablespoon soy sauce \par Alternate beef and shrimp on skewers. Mix the peanut oil, soy \par sauce and lime juice in a bowl to use a basting sauce. On a nice, \par \par \par keep warm.

\par In a skillet or shallow sauce pan heat 1 tablespoon butter, the \par vinegar and the orange liqueur, add the shallots and saute them \par lightly for about a minute or until soft. Now the tough part. You're \par going to make a tricky butter sauce. Luckily for you, Strike is a \par trained professional chef (true!). You're gonna take the butter \par pieces out of the freezer and grab a whisk. Now, while the pan \par \par \par pan off and on the heat source so that enough heat gets through \par to melt the butter and warm the sauce. But not so much heat as to \par cause the butter to break. \lquote \par - 162 - - 163 \par \par perature ofthe solution had dropped to 0\'b0C, an ice-cold solution of \par RHODIUM\rquote S CHAPTER 4g or NaOH in 20mi dHgO was added at such a rate that tam\par perature never rose above 10\'b0C. A white precipitate formed at the \par \par \par [-I-his is a chapter Wnuen entirely by 8 chemist named Rhodium temperature of the solution was never allowed to rise above 5\'b0C, \par (with guest speaker Osmiuml). Rhodium is, as far as Strike is con- and 3* tn? and Qi this time. 100 ml Of ice-cqld clljl2O was addedlto \par cerned, the world\rquote s leading underground scientist. Knowledgeable $I[\lquote\}eBsV$k'c:;;\ldblquote\'e9|L\lquote ?;:\lquote ;evica;e;;eI?\'80\'a7V\'a7\lquote ?O"] %';e\'a3;'ie'?(;\'a7t;*;?d\'b0g&VmV\'e9| \par in nearly every aspect of drug chemistry, this chemist has been _ _ _ \lquote _ \lquote \par the savior for many a person that was lost. Here he has contrib- mn '\ldblquote e 500m' E'le'"\ldblquote eVe' flesh "Y""eh Wes 9e"'t'V SW""ed\'b7 and \par uted some new reactions for your reading pleasure. Radical stuff there was e Shght bebbhng and nZZ'"9\'b7 wm" the eele" \'b0f the Sen" \par that you can bet will become the next wave of synthesis protocol. hen sh'f\{'"9 fmm Wmte te blue Ye Qreen te v\'a4\'a4i\'a4w in Unee" 3 "n'n\lquote

\par The rest Oftnis chapter is Rnediunfe voice] ute. Quite spectacular! When the tizzing had subsided, the \par solution was once again placed in an ice-bath with magnetic stir\par \par tion was clear with yellow granules of crude product at the bottom. \par by Rhodium 980620 The granules were filtered with suction, and recrystallized from \par IPA. After air-drying, the canary-yellow crystals amounted to a \par _ yield of 65-70% of theory. \par Preparation of 3,4-methylenedioxyphenyl-2-nitropropene \par (fl\lquote 0m PlP\'a4?\'b0n\'a4') This nitropropene should be used within a week, or stored in the \par cold, as the color fades to a slight orange over a couple of weeks \par In Pihkal, Alexander Shulgin mentions that the preparation of m r\'b0\'b0mt\'80mperatur\'b0\rquote Whlch ls 3 slgn \'b0f d\'b0\'b0\'b0mp\'b0Sm\'b0n\lquote \par more reliable, and gives higher yields than the other method ad- A\lquote |\lquote V\'b0ge|' Practlcal Orgamc Chemlsm/\rquote 5th Ed' \par \par V\'b0\'b0a 6 y G ear \'b0\'b0 \'b0r In IS \'b0\'b0 Preparation of Phenyl-2-Propanone (P2P) \par /\\ O /_\\ O In this preparation, phenyl-2-nitropropene is reduced to phenyl-2\par O O nitropropane with sodium borohydride in methanol, followed by \par \'b0=H\'a4"\'b0= NO2 hydrolysis of the nitro group with hydrogen peroxide and potas\par sium carbonate, a variety of the Nef reaction. The preparation is a \par / \par CHO _ one-pot synthesis, without isolation of the intermediate. \par \par \par in a 250ml Erlenmeyer flask. When all of the piperonal had dis\par solved, 7.1g nitroethane was added to the solution. The flask was \'b7 \par put in a ice/salt-bath with magnetic stirring, and when the tem- _165 _ \par - 164 \par

\par \par / \par

Ref: R. Ballini, Synthesis 723-726 (1994)

\par Efforts directed to prepare MDP2P via this method results in good \par yields of a ketone with properties completely dissimilar to MDP2P, lhlslhsl hlll'0sll<\'80hss 03h be l\rdblquote\'80\'a2l\'a400d l0 fh\'e9 \'a40r\lquote reSp0ndi\'a4g ketox\par and is orobabiy iiia brooioohaoooa, formed by migration of ii-ia imes by SnCl2. The second method is a modification of the first, \par riiiro group during tha bydroiyaia also allowing terminal nitroalkenes (such as nitrostyrenes) to be \par reduced to aldoximes. The oximes, in tum, can either be reduced \par _ _ _ to the corresponding amines, or cleaved to form the carbonyl \par 16.3g (0.1 mole) phenyl-2-nitropropene was dissolved in 200ml c0mp\'a4und_ \par methanol in a 250ml Erlenmeyer flask situated on a magnetic stir\par rer, and chilled to 0oC with an icelsalt bath. Then, with good stir\par ring, 7.6g (0.2 mole) of NaBH4 was added a little at the time, and rs NO is NOH \par the temperature was not allowe to rise a ove ' . VV en t e L,. wl \par generation of heat had subsided, the ice/salt-bath was removed \par and the solution was stirred at room temperature for two hours. At _ _ . _ \par the end of this period, the flask was once again placed in an phenyl 2 Nllmpmp\'e9ne Ph\'b0hyl'2'Pl\'b0pall\'b0hs Oxlms \par ice/salt bath and the solution was allowed to cool to 0\'b0C again. \par 100 ml of 30% H202 was then added, together with 30 grams of ll/leth0d \lquote l \par anhydrous potassium carbonate, and the solution was left to stir A Sodium siaririiio Solution was ra a Bd b ad -\par for TQ-24 lj0urS Bl \{00m tomp Dullljg lh\'e9 6\'80l0lll0h_0f l\ldblquote l2OglK2CO\'a4 sodium hydroxide (2.5 mol, 100;) tl; Lquecllus ggigigoiisaclqhhlgigldlg \par sl Whlls\'b7 sll\'b0kY Plsslpllsls l\'b0l'lhs\'b7 llllhlsh ssh be s hll lss lhlsk l\'b0l' s (0.25 mol, 56g). The initially formed precipitate redissolved to form \par Q|8S\'a7 \{00 \'a40Yv 600 Then \'a4FlhQl 0 llsl lW\'b0 \'b0\'a4ls\'b7 sl sl W l\'a4_ s 16.3g (0.1 mol) phenyl-2-nitropropene in THF at room tempera\par \bullet - \bullet -- . \bullet\'b7 n \bullet \bullet\bullet\'b7 an nr u- 1 \bullet BFI ma -SUE. _a t_ ,. - 2.-.. _ -_,. ,.-.__-2 _., .- -_ ,. ..

\par Ths hs\{\lquote l_<`lsV\'b7 lhs ssll-lllsh ls Sl0Wlv ssldlllsd Wllh ZM l\lquote lCl llllllh ture was stirred for 30 min, a saturated sodium chloride solution \par good Sflmng. Gale b0lh9 lsksh l'0F lhs sV\'b0l\'a4ll\'b0h \'b0l heal shd CQ- was added, and the solution was extracted with ether and the \par Ahslll 309 ml sl sslcl ls hssdsll Whsh lhs PH sl lhs sslullsll pooled extracts were evaporated under vacuum to give essentially \par tumed acid, the color became significantly more yellow, but the bura pgp oximo in 80% yiaid_ \par acidity was confirmed with pH paper. All of the precipitate was \par also be gone at this point. The solution was extracted with \par 3x100ml CH2Cl2, and the pooled organic extracts washed with Ref: G. Kabalka, Tet Lett 26(49) 6011-6014 (1985) \par 100ml 2M NaOH and 200ml H20. The organic phase was dried \par \par \par pirator vacuum, the yield was around 60-70% of phenyl-2- 16.3g (0.1 mol) Phenyl-2nitropropene and 45g (0.2 mol) of stan\par propanone (P2P) as a light yellow oil. nous chloride dihydrate (SnCI2*2H2O) was dissolved under stirring \par in 200ml ethyl acetate in a 250ml beaker, and the slightly exo\par - 166 - - 167 \par \par thermlc reaction was allowed to run its course. When the reaction \par mixture again had cooled to room temperature, it waspoured on Preparation of MDPZP from safmle \par \par with 5% NaHCO3. The product was extracted into ether, washed \par \par removed under vacuum to give almost pure P2P oxime in 90-95% phase system, using a quatemary phosphotungstlc PTC. The \par yield. formed safrole epoxlde is then isomerized to MDPZP with Lil. \par Ref: G. Kabalka, Synth Comm 18(7), 693-697 (1988) O/\\ O O/\\ O \par s O

\par Cleavage of Oximes The classic way of cleaving an oxime to the \par corresponding carbonyl compound is through acid hydrolysis, or \\ \par dl-s i -;-ol'! '. I-;l!' '\'b7 \bullet l A I '.' \bullet I||\'b7\bullet 'I \bullet " :\'a4\bullet\'b7 il. - . \par This is a crude method, and has often non-satisfactory yields. \par Below is a very good alternative method, using sodium bisulfite. preparation ofthe catalyst \par Qlgggie H2O2 \'b0an a|s\'b0 be used as m Synth C\'b0mm 1O(6)\lquote 46*468 A suspension or tungstic acid (2.50g, 10 mmol) in 7 ml or s0% \par ` aqueous H2O2 was stirred and heated to 60\'b0C until a colorless \par solution was obtained. To this solution, filtered and cooled to room \par NOH O temperature, was added 40% w/v HBPQ., (0.62mI, ca 2.5 mmol), \par and the whole was diluted to 30 ml with water. To the resultant \par soluton, 2.09g of methyltrioctylammonium chloride (97% pure, \par equiuvalent to 2.027g, 5 mmol) in DCM (40 ml) was added drop\par \par \par Oxime Cleavage with Sodium Bisumte over Na2SO.,, filtered, and gently evaporated on a rotary evapo\par 14.9 grams or P2P oxime (0.1 mol) is dissolved in 150mI 50% sl- ; 3\'a72y;'ngggergdfnmxep\'e9ggigfgarv :,2;gn?u,E,b;t;\{ Liaggdf\'e9oag \par cohol and is refluxed with grams 36.4 grams (0.35 mol) sodium almbstkolodess Syrup \par bisulfite for 6 hours, when the reaction had gone to completion. \par The ethanol was removed under vacuum, and the residue mixed \par with 25ml DCM and the mixture was treated with an excess of ZM Ref: C. Venturello, J. Org. Chem. 53, 1553-1557 (1988) \par HCI and stirred until two clear layers fOlTT'I\'80d. The layers were \par DCM, and the organic extracts were combined and the solvent OX'da\ldblquote\'b0" \'b0f Safmle t\'b0 MDPZP \par \par an orangish tinge, can be vacuum distilled to yield a light yellow chanical stirrer, thermometer and a reflux condenser, a vigorously \par oil. stin\'b7ed mixture of the above catalyst (0.7g, 0.31 mmol), safrole \par (13.24g, 80mmol), benzene (35 ml) and 40% w/v H20; (5.10ml, 60

\par - 168 - - 169 \par \par mmol) was heated to 60\'b0C and kept at this temperature for 60 min /\\ O /\\ O \par (External cooling is needed!). The mixture was cooled to room O S O \par emp, E Ol'Q8l\rquote ilC p - S "- \lquote \'b7 - \lquote\bullet - \bullet \bullet ' \lquote\bullet " `i ` 2 $ v\par Et O. ln order to remove the catal st, the o anic solution was tirst IQ A "\rquote \par stirred with a solution of Na2CO3 (0.75g) and Na2SO3 (0.75g) in ' " V V \par water (10 ml) for a few minutes, then separated, dried over MD\'b7Phenyl2\'b7Nitropropane MDA \par Na2SO.t and passed through a short column (2.5 cm diam) of silica \par gel (50g), and ~300mI anhydrous Et2O was passed through the Reduciion with NaBi_i4/Niciz \par column to ensure complete elution of the products. The solvent 3 68 _ _, _ \par was evaporated and the residue dissolved in 18ml of tetraglyme Oiiirams N'C'2 BHZO (155 mmdl) Was dlSSO|ved in 300 ml \par and treated with anhydrous Lil (0.130g, 0.97 mmol) at 13000 for C\'b0 tr \'b0?dt1.\'b77\'809 NaBH.\'b7* (46-5 m'\ldblquote\'b0') was added \'a4\'a4rti\'a4\'a4wiSe \par 5h. After cooling, the products were distilled under vacuum, re\emdash au '\'b0g\'b7 i;\'b0 h'"g\'b7) Wdh Sm"'?9 t\'b0 the Wdnddddiiy light green Solu\par covering 5.17 grams safrole (saved for the next run) and collecting xgivzz ih; ;\'b0gmt;;';\lquote 1 ';?;\lquote id\'a7&\'b0'Y :_dl'"?d bleak erid hydrogen was \par -. . --\lquote prpenewasa e aa \par once, followed by 4.1 grams NaBHt in small portions over a period \par Ref: C. Venturello, US Pat 4,731,482 of 5 minutes, care being taken for the frothing. After 15 minutes, \par \'a4~ Sims- im-iai <i99\'a4> H`.;J\'a71\lquote\'a71;\rdblquote ?t;"it;ii.\rdblquote i\'a71\'a7\'a7i$22l.2\lquote J\'b0J:ii?5if"*ill\'b06\'a7'"$ii \lquote\ldblquote f \par m e . e s \par vent was removed under vacuum, and the residue taken up (in \par Reduction of nitroalkenes to primary amines 100ml dilute H2SO., washed with 3x25 ml CHZCIZ, basified with \par 25% NaOH, and extracted with 3x5O ml CHZCIZ. The pooled ex\par tr ct w d' ci M S \lquote -

\par N\'a4BH\'b7\bullet iii m\'a4\'a41\'a4\'a4\'a4l. \'a4\'a4*\'a4*vZ\'a4\'a4 bv \'a4i\'a4*<\'a4l \'a4\'a4ri\'a4\'a4\'b7 \'a4\'a4\'a4 be \'a4S\'a4\'a4 *0 raiejiniaiudld Eseeiesidugdigfggid?t:;ti?iti;?iL`)$)n;r\'a5ia;vi);ar\lquote igi \par \lquote =..\lquote I 5.-'ii- ! .\'a4\'a4 \'a4!:\'bb:lZ. I al.! . 1. \lquote |` i _' \'bb\rquote \'bb . \rquote \par _ _ _ _ _ _ \'b7\'b7. -\bullet\bullet \bullet \'a4 ` . , \lquote \bullet I \bullet V'- " lu\'e9 Wl le y \par _ _ _ \'b7_ ciiae. ewiecstasf ht \lquote \lquote \par is general, and can be applied to many coniugated nitroalkenes. filtered DH and air drigl MD; :;.3 b;a;g\'b0ci:g\'a7r;\'b0|2\'a7;g\'a7 VE; \par Other novel promising methods are catalytic transfer hydrogena- Same fashion iusi use 6 4 grams of 3 4_meih Ignacio h V I 2 \par tion with Pd/C (Tet Lett 29(45), 5733-5734 (1988)), NaBHt in nimpiop\'e9neiiisiead Oftiie phenyi_2_niirOprOpgn\'80 ' xyp \'b0"Y' ` \par methanol, followed by AI/Hg (Tet Lett, 1317-1320 (1977)), NaBH., \lquote \par and CuSO4 (Synlett 419-420 (1990)), end finally NaBH, and tri\par iriggtsxiiyichioride in THF (Angew chem int Ed Engl 28, 218-220 Ref: Osby & Ganem, Tet Lett 26(52), 6413-6416 (1985 \par -170 - \'b7 171 \emdash \par \par Proposed Synthesis of MMDA and M\'a4S\'a4\'a4|ll'l\'a4 cold (O\'b0C), 70% methanol, and dried in vacuo at 50\'b0C overnight to \par by Rhodium and Osmium 980519 give 218.5 gtrams (95%) of 5-bromovanillin as pale yellow crystals, \par I I 5-Bromovanillin (alternative) [2] \par T\'b0 Vamuln (1529. O\'b7l m0!) In glacial acetic acid (75 m|) IS added

\par bromine (17.6g, 0.11 mol). After stirring for 1h, the reaction mix\par Mac MGQ NH2 ture is diluted with ice/water (200ml), the precipitated solid is fil\par _ tered, washed with water, and dried to give 5-bromovanillin, yield \par MMDA Mescaline 2209 (95%) \par [Rhodium's voice:] \'b7 l I OMB OMS \par I- \'a4\bullet -` \bullet IIIIIA n '\bullet .. ur \bullet l'l \'b7l0l"I \'80StBl'1dlT'IOSI \par tedious in the book. If one is going the route via myristicin, the HO HO \par Sisifos work of isolating the tiny amount of essential oil present in \'a2 ___> Q

\par nutmeg, followed by fractional distillation to purify the myristicin \par fraction is also added to the labor of the poor chemist. Therefore I Br CHO HO CHO \par propose a new route to this "essential amphetamine". \par OMG OM`! 5-Bromovanillin 5-Hydroxyvanillin \par HO HO 5-Hydroxyvanillin [3] \par G \emdash\'bb ii \par V CHO Br \'e9 CHO Sodium hydroxide, 61.2 grams (1.53 mol), was dissolved in 750 \par vanillin 5_BrOm0Van"\ldblquote n solution was added 50.0g (0.217 mol) of 5bromovanillin and 0.5 g \par of Cu powder. A white solid precipitated. The reaction mixture was \par . . refluxed vigorously under N2 and with magnetic stirring. The color \par 5'B"\'b0m\'b0va"'"'" changed gradually from yellow to green to dark green and, after \par ca 6 hours, all solid material was dissolved. After 27 hours of re\par To a stirred, cooled (0\'b0C) solution of 152.15g (1.0 mol) of vanillin fluxing, the reaction was over, and the solution was aciditied with \par in 1000ml of methanol was added during 20 min 176.0g (1.1 mol) 110ml conc HCI to pH ~2, and was .extracted*) with ether (or other \par .,.. --. .- A - .\emdash \emdash .\bullet .- - .. .\emdash\'a4 a*n. .I'I[I-I I 'I \'b7III' l\'b7\lquote |. I'! '\'b7II \par 20\'b0C. The mixture was stirred at room temperature for 1h, cooled through shaking the organic phase with an excess of saturated \par to van I-eae ur-mg m|nW| ll \bullet nd " VV.- -\'a4\'a4\'b7\bullet\'a4 \bullet\bullet \'a4 l ' ` _ \'b7.\bullet\bullet\'a4 \'b7\'b7. \'b7v. \emdash\bullet \bullet . \bullet\'b7\'b7\'b7 \par Stirring was continued for 15 min and the product was collected by cold water, and dissolved in an excess of 10% sodium carbonate \par tiltration. It was washed with water (4x500 ml), then with 500 ml of solution to release the aldehyde again. The solution was extracted \par with DCM and evaporated to yield the title compound. \par \lquote 172 \lquote - 173 \par \par 0M\'a4 ous \par *) [Osmium's voice: In the original patent a continuous, 27 hours O E 0 A \par extraction with hot toluene was used. This is very impractical. ' ' \lquote \bullet

\par \'b7 \bullet nn\'b7|\bullet |\lquote \bullet\bullet i |\bullet .I\lquote *.4- \bullet | \'b7.|\bullet \lquote ||\bullet \'b7 I l` 3. _\rquote\emdash\emdash _'_ 2 \par motion solvent, dissolve the crude product in 400 - 450 ml hot O V CHO O V7 \par toluene, put that solution in a beaker and cool it for at least 2 \par hours in an ice bath. Filter the precipitated product, wash with Myristlcinaldehyde 2-Nitroisomyrlsticin \par about 100 ml ice-cold toluene and dry at 70\'b0C or in a desiccetor to \par constant weight. Mp. 132.5-134.0\'b0C.] 2_Nm_\'b0_I8\'b0myristicin [6] \par OM OM A solution of 9.8 grams myristicinaldehyde in 35 ml glacial acetic \par E 6 acid was treated with 5.3 ml nitroethane and 3.2 grams of anhy\par ..\'b7 \bullet K ,$___....,._u_,-_\'b7 ,\'b7; -\'b7-;;a\'b7 \'b7\'b7;"\lquote :" i3` i _ _ \par It was removed, treated with H20 with good stining, to just short of \par ' turbidity. seeded with product nitropropene, and allowed to come \par H CHO O \'a4H<> i\'a7\'a5\'a7\rquote r\'e9?n\'a3$2?2\'e9$"lli\'a3?\'a33\'e9?.lf\lquote \ldblquote\lquote E 2"g*li.\rquote\'b0"\'b0\ldblquote .i\'b0"\'b0S \lquote\ldblquote F* I\'b0""\'b0" \par , was e wi a sma amoun o aque\par 5_HydrOXyVan""n Myristicinaldehyde Io;i;3;c;&i_;aag:,fand ztgckpgg ai fregtgil solvent ast pofsisibls. After \par U I i rom m oiing .gave, a er iterng and \par _ _ _ air drying, 5.1 grams of 2-nitro-isomyristicin as light yellow solids \par Myristicinaldehyde [4, 5] with a mp of 109-110\'b0C. \par \par _ \'b7\'b7e -\'b7.ee \'a4.\'b7 \'b7 \'b7 ,!!\'a4\'a4 !\'b7\'b7 cn! \'a4:-e. e\'a4\'b7:n\'b7e \bullet U\rquote \bullet li' \par up a bit. 19.1g (0.11 mol) of methylene bromide (or 9.35g methyl- O O \par ene chloride) was added to the cooled solution, and the mixture NQ2 NH2 \par was heated to 110-120\'b0C for 1.5 hours. The cooled reaction mix- L> \par ture was then separated by ether extraction followed by washing O / O \par the ethereal extracts with water to remove DMF and with cold 10% \par Na2CO,. Drying and evaporation followed by recrystallization from 2\'b7Nitroisomyristicin MMDA

\par hexane afforded myristicinaldehyde in high yields (mp 133\'b7134\'b0C). \par \par A suspension of 7.5 grams LAH in 500ml anhydrous Et2O was \par magnetically stirred, and heated in an inert atmosphere to a gentle \par reflux. The condensing Et2O leached out a total of 9.8 g 2-nitro\par - 174 - - 175 \par \par isomyristicin from a Soxhlet thimble in a shunted reflux condenser. \par This, in effect, added the nitropropene to the reaction medium as 0Me Olvle \par ..7*- .I.\lquote\bullet 2 \bullet I \bullet il'\'b7 \'b7.\bullet\bullet \bullet rr. \bullet \bullet\'b7\'b7 \par the solution were refluxed for an additional 5 hours, then the solu- H0 _& H0 Q \par tion was cooled, and the excess hydride destroyed by the addition \emdash -\emdash\'bb \par of 400 ml of 0.75M HZSO4. The phases wereseparated and sufti- I\rquote \par cient saturated aqueous Na2CO3 was added to the aqueous phase CHO Br CHO \par to bring the pH up to about 6.0. This was heated to 80\'b0C and fil- _ _ \par tered through a coarse sintered glass funnel to remove some in- Vamum 5-Btomovanillin \par soluble fines. The clear Hltrate was brought up almost to a boil, \par and treated with a solution of 10.2 grams of 90% picric acid in 110 5\emdash BromovanilIin; (another alternative) [3] \par ml of boiling EtOH. Crystals of the picrate formed immediately at \par the edges, and as the reaction flask was cooled in an ice tub, the _ _ _ _ \par \par moved by tiltration, washed sparingly with 80% EIOH, and air _ \'b7 \par dried to give 14.0 grams ofthe pieiate salt of MMDA, with a mp of (0-722 m\'b0'-074 ml) Btz\'b7 '\'a4 tha maamlpa. a Sain- \'a4f 100 9 (0.658 \par 182-184\'b0C. This salt was treated with so ml 5% NaOH, and the "\lquote\'b0'l at V\'a4\'a4*"l\'a4 *0 700 9 (470 mil pf 48/\'b7> HBr was praparad in the \par ted eetiitieit deeattted from same iiteeitibiee. Additional H20 and \lquote *'\'b000'\ldblquote 0 70000*- Wh"? F'"0 '\'b0\rquote =\lquote\'b0"\'b0\ldblquote "aslt was immatiad *0 aa \'b7\'a4a \par NaOH efleellvelv Clleeelved evervlhlng, and me resulllng beelc bath, the soln. of vanillin was dropped into the bromine with stir-

\par . ' ' 0 \par aqueous phase was extracted with 3x50mI CHZCIZ. The pooled $29 \'b0V\'b0r a p\'80\{"2d at 1 _h\{\'b7\'b7 k\'80\'80p"79_7h\'80 tamparalura at 000ut 5 C\par extracts were stripped of solvent under vacuum, and the residue 9 b'i\'b0'\ldblquote\'b0Vam"'n F\rquote 7\'80F[P'ta70d as _'l9ht Y?"0W CFYSYBIS. The slurry \par dleeelved ln 200ml H20 Saturated vvllh Hcl gee \'b7l-here was e was stirred for an additional hour in the ice bath, diluted with 940 \par heevv preclpllellen ef vvhlle crvelelel vvhleh were remevecl bv lll_ ml of water and _kept for 1 hr. 0\emdash 5\'b0C with stirring. The crystals were \par \par HI th f19-9\'b0C. \'b7 l \'b7 \par C\lquote Wl ampo O1 1 perature to constant weight. Yield: 150.9 g (99.4%), m.p. 163\par \par [Osmium's voice:] \par OMe OMe \par HO HO \par ---\emdash\emdash -> \par \par \par _ 176 _ - 177 \par \par Syringaldehyde: (3,5-dimeth\'a4xy\'b74-hydroxybenzaldehyde): [7] \par _ _ OMe 0Me \'b0 \par - romovaii \lquote \'b7 \'b7\lquote\'a4\'b7-\'b7 ii si \'b7 . \'b7 .\bullet \par uBr 1mmol in 5 M NaOMe/MeOH (10 ml) for 14 hours. Clasei\emdash \par cal work-up (addition of water and acidification followed y extras- ----\'bb \par tion of the phenol) leads to pure Syringaldehycte (95%). When Q Iv \par starting from the more soluble 5-bromovanilline dimethyl aoata|_ H CHO MBO CHQ \par reaction is achieved within 2 hours (yield 98%). Preparation of this . . _ \par acetal is probably not worth the extra work. Substituting EtONa for 5 HY\'b0'\'b0XY"a\'a4\'b7"\'b7\'a4 3\'b74\'b75\lquote T"'m9th0XVbS\'a4Za|d\'80hyde

\par MeONa seems to work, too, producing 2\emdash ethoxy-3-OH-4\par methoxybenzaldehyde, useful for ethoxy-derivatives of Mesca\'b7 3.4.5Tfimethoxybenzaldehyds [3] \{mm 5-hyd,.\'b0xyvan""n. \par line. ' \par B a DVB y . I I vg \'b7 n _ ( gg 7 n l n a 1-I round t om flask equipped with a magnetic stirrer \par easily scaled up to industrial size (French Pat. 2\{669,922,CA1\lquote 18; hYd*"\'b0><YV\'a4\'a4l||l\'a4\'b7 500 ml Bcotvno, 91 0 .(O. 1 m l) d met ylsui: \par P6734u), it is a general procedure for substituting awt-Br with - fam 100 Q (0-806 l"n\'a4|) finely ground N8gCOs.H;O 10 ml Or 10% \par OMe or -OEt, giving us the possibility to produce other com- KOH in methanol. Of course equimolar amounts of anhydrous \par pounds from already known substances, e.g bromination of MDA Na2CO;\'b7. or KZCO3 can be used. The heterogenous mixture was \par yields 6-Br-MDA. This is converted by the above procedure to stiwed under vigorous reflux for 24 hours, after which the reflux \par MMDA\emdash 2, #133, active at 25-50mg, 8-12 hrs. condenser was replaced with a descending condenser The sol\par ` vent was distilled at a bath temp. of ca. 100\'b0 until the distillation \par _ ceased. To the solid residue was dd d 400 \par Asarcnealdehyde (2,4,5-tri ethoxy-benz lde vd ) Gah 'b\'e9 PF? heterogenous mixture was stirredaVlgOROUg1;$fr;v? grhiirugsthai \par \'b0'*`\'b0":""\'b0"\'b0 :' \lquote ;: ' " " eqn ;nee\'a4e.:es\'b7\'b7ee e-:\'b7=. : Gr \'b7:\'b7ai i \'b7 \par m;0;\'a4 \'a4 9-_ \'a4 l meve lil y Y'* h '$ '**\lquote P ' N light brown ry als w re filtered by suction, washed with 3*150 ml \par and treat as described above to obtain asaronaldehyde. mg>6\'a32. - 4 . ft rrd sti aticonCg??).?nr\'a51`7L;1l(\'a70\'b0, t gr wgs gtftgi lt \par a yield of 3,4.5-trlmethoxybenzaldehyde, m.p. 73.5-75 VPC \par syringaiuenyde is easily memyieied er ethylated with ine known 5"\'b7""*i 9f_\'b73_;\rquote\'b0\'b7,(T\ldblquote 'S \'b0**5**"\'80ii\'a4\'a4 is P'\'b0b\'a4b|\'a5 unnecessary. because \par procedures in high yields forming the highly-desirable 3,4,5- eada V \'b0's ahead)! qU't\'b0 PuV\'80)\'b7 \par trimsthoxybenzaldehyde or the 3,5-di\emdash MeO-4-EtO-benzaldehyde ' \par (Escaline, #72, 40-60 mg, 8-12 hrs).

\par - 178 \emdash _ 179 _ \par \par [7] Tetrahedron Letters, Vol. 34, No. 6, pp.1007-1010, (1993) \par . [8] Pihkal, #72 Online - Pihkal can be found at \par 0Me OMG "tlli ' = \par HO EtO \par Q \emdash\'b7 U \par MeO CHO MGC) CHO \par Syringaldehyde 3\'b75\lquote Dlm\'b0*h\'b0\'a4Y\'b7 \par 4-ethoxybenzaldehyde \par 3,5-Dimethoxy-4-ethoxybenzaldehyde [8] from syringalde\par hyde: \par \par was heated to reflux in a heating mantle. There was then added a \par solution of 15 g NaOH in 60 mL H20. The heating and stirring was \par continued until the generated solids redissolved. Over a period of \par 10 min, there was added 23 g diethyl sulfate, then refluxing was \par continued for 1 h. Four additional portions each of 5 g diethyl sul\par fate and of 6 mL 20% NaOH were alternately added to the boiling \par solution over the course of 2 h. The cooled reaction mixture was \par extracted with Et2O, the extracts pooled and dried over anhydrous \par \par crude 3,5-dimethoxy-4-ethoxy-benzaldehy e weig e . g an \par \par See the same reference in Pihkal for details on how to use ethyl \par iodide instead of diethyl sulfate. \par [1] Syn Comm 20(17), 2659\'b72666 (1990) \par [2] Synthesis, 308 (1983) \par

\par \par [5] JACS 99(2), 498-504 (1977) \par [6] Pihkal, #132 (p. 787) \par - 180 - - 13] \par \par For molecules similar to safrole or allylbenzene we take the work \par PROMISING THEORETICAI- METHODS done on any terminal alkene such as 1heptene, 1 octene. An\par other term to look for is \lquote olefin\rquote which is a term for a doublebond \par \par Articles with tenmnology like \lquote methyl ketones from\rquote (P2P), \lquote ketones \par Strike and others' favorite pastime is to comb the library for new ;\'b0?r;in;T\'e9";:;;gr:; F;n\'b0e\lquote ;'f;'|:;?;r\lquote\'e9V\'a7uV;ta\'a3;:T? gggfv?/;*1;g:\lquote ;VOW\'a7gS \par methods. Even though we have so many pro,ven, high-yielding . . . r Y \par methods available (see this entire book), there is always room for am\'b0|a,ap\'b0ut k\'b0t\'b0",??NWT\'b0"\'b0 ammas ara f\'b0"m\'b0d\'b7 S\'b0u"d We SC" \par more. Relentlessness drives us to find even cheaper, higher \'b0h"\'b0\'b0 f'a)"\'b0n.t\'b0 |\}:_\'b0u\'b7 ki? h\'b0\lquote\rdblquote dj V\'b0'\'b7' thmk we came up W'th han \par yielding methods. But the biggest reason is to make a buffer zone t \'b0 r\'b0\'b0'p\'80S mt 'S b\'b0\'b0 \'b7\'b7 It W\'b0rkS\'b7 \par of so many options that governmental restriction is rendered use\par !9ss-_ That 'S \'b0\lquote\'b7" p\'b0\lquote\rdblquote\'b0r\'b7 S\'b0 ma"\lquote\'a5 \'b0\'b0mm'u\lquote\'b0`d\'b7 d?\ldblquote S&'\'b0us'V` Every article such as these may have the potential to be useful. \par intelligent people around the world with far more motivation than But it takes 8 lot Of | OOking_ 8 keen S E and a sense for what is \par \par have gone through the right channels and are contributed by the \par You're not going to find journal articles with new syntheses written ;2:S?d;':;g";?Sh;hv2 giguggggg t;'st;;;|\'b0;;:gSa?;\'b0:\'e9r;h\'a7)iBy\'a7L$ \par especially for X or speed anymore. The scientists of the world al- . . . . \par ready have recipes that work and the access to the restricted fsgsgiarigzngsel\'e9iztx fg; \'a7;S\'a7j$; \'b0:a\};r\'b0;u'e;:\'b0'?0i\'b7 ti; \lquote Z;';\'b0g% \par h`| t kth rk.Shh|dth|k .\lquote . .. . .'

\par t:ofer;t\'a7?h?n;Bri;iir\'a7?a1ryha)yn;2n<a.Tiirarggs ne$ev\'a7e\'b0\'a3$ tZYtnen$\ {e\'b0$e \'a4m\'80= \'a4\'a4s* Stvkss s\'a4\'a4\'b7*v\'b7 \'b7S mt <=><\'a4*\'a4\'b7\'a4\'b7~=\'a4 as amply as the \'a4\'a4\'b7\'a4r \par se recipes in this book. \par \par \par amphetamine science. Believe it or not, the novel applications of The dream Of every X Chemist is to get that amine function direcuy \par ]\'b0u"?a| m\'b0th\'b0ds \'b0" praaurams Such as \'b0ur?' ara \'b0n Equal par Ymh on the safrole molecule without having to go thru any intermediate \par published research work. Half of the stuff in this book is publish- Such as the ketone ef MD_P2P er the bremine Of bmmesafmle \par ab|\'b0\'b7 pmpar Saianca awa by p\'b0\'b0p|\'b0 with n\'b0 funding It is actually But Strike can tell you right now that that is very very tough (that \par a'\ldblquote aZ\lquote "9 when V\'b0\ldblquote """" ab\'b0\ldblquote t "\'b7 ae why there eln\'b7t no metnet-te ret at). About tne only article stnke \par has ever found for the actual placement of an amine dlrectly on a \par So like Strike wee saying, without any new, tnreet ntetetute synt\'a4r\'a41i\'a4\'a4l\'a4lke\'a4\'a4(\'a4.k\'b7\'a4- s\'a4fr\'a4l\'a4> iSfh\'a2f\'a4l|\'a4W\'a4\'a49[79li \par mole u le that a si ilar to ur o . n l ul s th t o e ,, A H __ . I _ _ _ _ H 2 , I _ J. t r __ _ E HHH : = U E _! \par N I \'b0 \'b0 ` 'N ' V a ' \'b0 \'b0 " ' \lquote pylene to isopropylamine and diisopmpylamine was shown to take \par place over a sodium catalyst at ca. 250\ldblquote C and 850-1000 atm \par pressure (rei 7). In contrast, we have found that these reagents \par - 182 - - 183 \par \par can react in the presence of cesium amide containing catalysts, hydmfumn is added 01 mc, Of alkene AHH Sdmng at 50 to 90cC \par under far milder reaction conditions to give mostly isopropylamine. f - t `- d _ \'b7 . ; \par \par re clsd l" s r\'a4\'a4\'a4l\'a4r Of 40 Cm Mal capacll w al"' CSN Z treated with a solution of 2 g sodium borohydride in 100 ml of 15% \par \'a7 _ Intl ; =l.QA,A-. \'a4*lIIlI | . - .\'b7;_ \'b7 _Yi' i: _i' i_ _;;v' S . . i'-l' Iv; :

\par p\rquote\'b0pYlag""\'80 (1/3 \rquote "\rdblquote ;\'b0l)\'b7 \rdblquote 'p\rquote\'b0l3\rquote ls\rquote Tl\rquote\rdblquote\'b0 l0\'b7 7 m'"\'b02 gs well las pm' extraction followed by distillation at reduced pressure. "(% yield for \par pa"; ( dTm\'b0) an "\'b0"'\'b0\'b0" \'b0"s'bl\'b0 gasses l' m'"\'b0) were the representative terminal alkenes 1-heptene and 1-octene were \par pm UGG \'b7 ~ 88% and 55% respectively) \par Man that lsclps is WEAIQ But hall Thatls 10% flnal pmduct ln That looks simple and direct don't it'il lf safrole was used as the \par one pot. Yeesh! Why bother? Don't take this tirst method seriously k Id t f I _ -d ` \par srs- ll W\'a4S1\'a4S* Strikes ww \'a4a\'b7\'a4sr\'a4l@\'a4\'a4;r\'a4\'a4= futility \'a4* my EL.\'a7'\}ZdiZ2ir\'a4\ldblquote ri\'b0\'a7Wa\'a7\rquote $nf;? li\rquote\'a7A?\lquote\'801,i\'a7kZSa.Z??\'a7$\lquote dlS\'a7L\'a7"\'a7z\'a7\rquote\'a7*,123 \par swers. All the rest ofthe stuff in this section is much, much better. pers that, with a lime Work, Wm get Safmldazidg in a totally dm,6|__ \par \par So without direct amination we are confined to \lquote semi\'b7direct' ami- l\'b7l$ln9 dlnuclaapnlllc addlllan la get an azide and a hal\'a4Q\'80n added \par nation (Strike\rquote s tenninology). In Strike\rquote s opinion, the direct addition a\lquote -Vasa a dauhla b\'b0nd- The aZ'd\'80 wvuld always 90 l\'a4 the beta \par of an azide (N3) counts. Once on the beta carbon, that azide is as $aC\'b0ndal'V Canaan and lna h\'a4l\'a4\'a4e\'a4 la tha Pnn'lal'Y carbon (JUST \par good as an amine. But can we get an azide directly onto safrole Whal ana Wanld Wanl ll salfnla was lhs Suhallalal\par without having to go thru the bromosafrole intermediate as was \par discussed earlier? Maybe we can! O \par /\\ /\\ o \par rc FO \'b0 is O \par \'b7 V - , ri N3 \par N3 V \\ @7 \'a4 \par \\ Salmla 3,4-Methylenedioxyphenyl \par serrole sarrolo-Aziue '2"*z'd\'b0`3"\'b0d\'b0p'\'b0\rdblquote a"\'b0 \par This following article was sent to Strike by Osmium and Feck (are Thi nai was fmm Egllsls l81l\lquote \\;aml\'b0uSbE:lk\'b0niS|: Zwlsgls in? \par they the same person?). It involves the direct addition of azide to a fy\'b0,\'b0a ggesrxlels me gl altE`"\'b0;,r:I ?d\'b0XTOs me \'b0 dls b \'b0 Q`

\par tem1inal alkene (you-know-who) by the in situ production of the _\'b0Wmg l l\lquote 6 .Sul\'b0p\'b0 9 Ss \'b0. a \'b0` 2 3 was ma \'b0 . y mlX` \par \par ide (please don't ask) [80]. \'b7 \par \ldblquote Gcnera/ Procedure V- To a solution or 0.3 moles of sodium azide "RG\'a4\'a4! i0\'a4 with /2 (7 .5 mmol) [cr Brzl, supported salt (1.5 mmol), \par and 0.1 mole of mencuric acetate in 200mL of 50% aqueous tetra- alkene (0-625 m\rdblquote\rquote\'b0l)\'b7 \rquote\rdblquote 5 ml Of slhsncllms CHCl\rdblquote at r\'b0\'b0m tsl"` \par ` 184 \lquote - 185 \par \par perature for 30-48 h. Work up with aq. Na2S2O3 wash, CH2Cl2 ex- thoroughly unwatched chemical called 2\emdash phenylpropanal (a.k.a. \par traction, drying (MgSO4) and solvent evaporation." methyl-phenyl-acetaIdehyde, a.k.a. hydratroplc aldehyde). Os\par \par _ _ __ __ ( it comes 87.Thefcll0win is all `-- .\'b7 - \bullet\'b7 \par right place and a halogen sticking out the end. So what?l Well, comments` \par Strike was thinking that since the easiest Grignard reagent to \par make is the one at a primary carbon (which the I or Br will be in \par this species), one could just make the Grignard reagent out of the \par intermediate then destroy it by pouring water into the solution CHO \emdash _., O \par which would immediately remove the halogen. Just a thought. \par CH3 \par The next method Strike has for semi-direct amination is really Pap \par \par this dog. But if one looks hard at the articles cited, the potential is "l/Wh H2SO4: \par there. The authors came up with this little procedure that produced g 2, l-,9,-, l r l ll d M th l_ h _ \par viginal diamines out of alkenes [83]. Later they found that W they age a5ded\}tl\ {)iri@a;grf1$gu?es toB46Vmt)cg1';c\{lilzggijiixghlystgjoizz \par dida couple of thingsdiffereni. they would alla up llillih 3 'm\'b0\'a4\'b0\'b7 to \emdash 16`\'b0C. Let react for further 15 mins at \emdash 15\'b0C. The mixture is

\par amme With the 'T'a1PmV Pmduet being at the here ea[b\'b0"'\emdash The poured on ice. An oily liquid and a gummy/rubbery/sticky mess are \par f0|l\'a4wl\'a49 IS 3 G0\'a4l0l\'a4l\'a4Q Gfthe two Papers expenmemale- evident. All is extracted with ether and distilled (91-96\'b0C/11 ton). \par Weld: 5.6g P2P (62%). \par \ldblquote The addition of N-bromosuccinimide (1.1 equiv) to a dichlo\par \par . ` t ` d t t t \par vacuo. Treatment of the bromocyanamide [intermediate] with 1% Qquimolar amount) in 45m, 75% HGH in a eealgd glass \'b0\'b0"tai"6\rquote \par palladium on charcoal in methanol (1h) led to reduction of the for- for 4`5 .h0urS\lquote Temp 100%; A .p(6c'P't8t\'80 IS mrmgdr Whmh as \par madine Addition Of base ic lhs reaction mixture (50% aqugous solves in the following steam-distillation. The oily layer resulting \par KOH i\'e9iiux 6h) foiiowed by extraction with Bihar gal/6 m0n0am_ from this steamdistil/ation is separated and fractionated. Yield \par ine." (Yield is 48-64% final amine from alkenes analogous to sa- mm; than 80% \par frole) \par They isolated theirlproducts after conversion into the solid semi\par and the fact that they distilled those tiny amounts make me be\par \par Our trusted friend Osmium has been stressing this following rec\par ipe as a breakthrough P2P synthesis for speed from a very un- _ _ \par llkely precursor. It is apparenlly a novel rearrangement of a l also found a patent dealing with phenylpropanal rearrangement: \par - 186 - - 187 \par \par . R5=R\'b0=R\rdblquote =CF andR\lquote =R'= . \'b7 \par Uspat 4,694,107 They react 2-pheny/propane! in the gee phase gf dfkgfgng ligand; R\rquote c09HR\lquote c0'g5 iggggggcg \par at 300\'b7400\'b0C with zeolilhes (silicate) to yield 86% P2P. Quite hot KOH in H2()_ Thus, 2 mmm phCH2CH2(;H_-CH2 was oxidized 2 h \par yes. UU? 0m6IVVl$6 not fee UITYIGUTT. l Think. at 7Z>" and atom O in ine presence of 20 mol% ll (R\rquote = R" = R6 =

\par E : t&d.Bii R :R : fg ml Qdga( [H to gina \par Strike found this next thing doing an all-nighter Chemical Ab- P/1CHzCH2COMe and 71% PhCH2CH2CH(OH)Me, AddnI_ 39 \par stracts search. Strike does not even want to try to explain it, Just catalysts were evaluated fer the above oxicln. And 18 other olehris \par read it. If you understand it, great! If not, don\rquote t sweat it. Hell if WWE \'b0Xld'Z\'80\lquote i` WGS- WG'? Obialngd 85 b.VPl'\'a4dU\'a4YS-" \par Strike will ever try the damn thing [88] (Note the P2Pol produc- _ _ \par tion): This next method for making P2Ps was posted anonymously on \par the a.d.c. quite awhile ago. Strike is sure most everyone knows \par who did this, but Strike doesn\rquote t to this day. So whoever you are--\par /\\ O Thanks! Although Strike has an original paper copy of this post, \par 0 O Strike had no copy on disc, So Strike snagged the text from an \par is e I '!\ldblquote .ell\bullet ' e `\bullet\bullet I:l'\bullet .Il l'll\lquote \bullet\'b7\bullet\lquote . \bullet i\'b7| \par /\\ O I"' to see more about this method go and visit the site where it rests \par / among many other chemical goodies. \par \emdash\emdash\emdash ;\emdash -> \par MD-P2P \par \\ \\ /\\ O /\\ O \par /\\ O 0 0 \par Safrole O O \par OH / \emdash *\rquote \par lsosafrole MD-P2P \par \par "113: 151836e Preparation or keienes by oxidation or orerins S\ldblquote b"?\'b0\rquote\'b7 P"\'b0`"Y\rquote a\'b06"\'b0"6$ by ""\'b0`\'b0"\'b0\rquote V"\'b0 \'b0"\rquote d8"\'b0" \par uslng cobalt diketone catalysts. Mukoyama, Mitsuaki: Isayama, Fmm-\lquote 'UUSST" <9UeST@WebShe\'a4k\'b7\'a48fe\'b7\'a40m> \par Shigeru: Kato, Koji: lnokl, Satoru: Yamada, Toru: Takai, Toshiniro Date; 1997/11/08 \par (Mitsui Petrochemical Industries, Ltd.) Jpn. Kokai Tokkyo Koho \par JP 02,121,944 [90,121,944] (Cl, C07C49/04) O9 May 1990, Ap I.

\par 88/272,450, 28 Oct 1988,- 19pp. R\rquote COCH2RZ and R1 Cl\emdash l,CORf [I Appendix - Phenyl acetones by electrolytic oxidation. Process for \par ; R' = (urdsubslifufgd (Cy;/o)s1kyr or ary/(alkyl); R2 = 1-L 3,\{4\emdash dlmethoxyphenyl-acetone preparation. European Patent Ap\par luiilsulistitiited, alkW or aryl(alkyl)] are prepd, By reaction of P17?>\'a4?l\'a4ll 02*75%. Filed U?-72-87, lv UQRK $17-6- Mliall\par R CH:CHR with O\emdash contg. Gas in the presence of a secondary alc. \par And a Co (Il) catalyst [ll; R3, R5, R6, RB = l\emdash L straight-chain, \par branched or cyclic C1-10 alkyl, (un)substituted aryl or CONH2 , EXQMPVG 7\par etc,; R" , R7 = H, alkyl halo, COZH, alkoxycarbonyl; excluding R\'b0 = \par - 189 \par - 188 \par \par 6.27 g of NaBr is dissolved in 25 ml of H O and 125 ml of CH CN, \par the mixture is then strongly stirred by means of magnetic stiraring, ieeteed et 5 heere In this wer e yield er keteee I/U ef \{36% *9/3* \par end fg it 3_76 g O; jsceugeno/_mBthy]8th9r (I) ra than addad The tively to the olehn (I) used as the starting material is obtained. \par electro chemical cell, with a constant current of 850 mA, with two \par graphite anodes with a total suh\lquote ace of about 17 cm2, and a cen- _ _ _ \par tier eieinieee-steer cathode iieviiigeeriireee of about 25 cm2 being gr;] ZN25gmil\'a4ezr>g\'a4rgz\'a4;d greljfrg ehejm\'e9egg ee/I\} 125 rrri of \par used, with a distance between electrodes of about 1 cm. 5,200 3 \'b7 m P 2 \'b7 \'b7 9 _ e C en \'b7 9 0 \rquote eeeU9e"'e\lquote \par courombs are pajased with the reeetien mixture being kept at e mettngtettrrgsg relqedrtrilrtrrrrxturzcrg eleerregreedhet e eergsgrrt \par temperature of 2 C.From the reaction mixture, d`s h d f \'b0U""e O m i W' e ' e\rdblquote\rdblquote\'b7'm e e eee e W' e \rdblquote '\rdblquote Xe U` \par the ereeimehemieer Corr two phases] ;_E._, me agnfagg\'e9phgg Ti oxide (50:50 by weight), with a total surface of about 7 cme, and \par containing Br- ions, and the organic phase, containing acetonitnle ;ee""'e\rquote ega\rquote "\rquote e;7e\lquote e\rquote ;e\rquote tee*h\'b0ie ;\rquote e"i"9 eleuffege er eeleurtij em? \par and the reaction product, are separated. From the o an`c h errra use r W' e 'S ence e Ween eeere ee ee e'\'b7' em-

\par acetonitrile is evaporated off under reduced pressure'? artd $0 iii; Through Yee ee" *000 Ceulembe ere eeeeert with the Yeeetien \par resulting reaction product 40 ml of ethyl acetate is added. The mrxtrrre berrrg kervr er the rempererure ef 20\'b0 Ollie reeerrerr rrrrx\par gas-chromatographic analyss of th o ' h h th were menpmeeseee eeeelm"9 Ye erretr rrreeeriree eererrerree "\rquote \par presence er gpgxjdg (rr) with 2, >g0% iu,-igianlc p asa S OWS 6 Example 1, until the solution of the reaction product in ethylace\par tate is obtained to such solution, 337 mg of Lil is added. The \par _ _ _ mixture is then refluxed (at ethyl acetate retluxing temperature) for \par The reaction mixture in ethyl acetate is then transferred to a 100- 5 hours, and the process is continued as described in Example 1, \par ml reactor purged under a nitrogen atmosphere, 340 mg of Lil is until 2.795g is obtained of ketone (lll), with a yield of 92.2% rela\par added, and the whole mass is then heated with mechanical stir~ tively to the olefin (I) used as the starting material. \par rrng, \'b7on an oil bath, up to ethyl acetate reflux temperature. The \par heating is continued for 5 hours, until the disappearance of the \par epoxide (ll), as evidenced by the thin-/ayer chromatography. Example 4 \par I _ I- _ l - l . _ _ . A A A H _ U I U A A _ _ or CH3CN, 25 ml ot\}-IZO, 6_40 g of NaBr and 2675 g ofisoeugenol\par - U ` ' "' ` '''' ' . ' _ ' * . V': " methylether (I) is added. The mixture, kept at v' C, is electro\par mg; 1t;Tl;rQ;i,rO(fO !hi;pLg%0SE30g;9mpV'ng mmm I0d\{dG and IS lysed with the same constant current density and the Same set or \par h y Ver ee \lquote\{' ` g IS eererrred \'b0f d'm\'b0m\'b0Xy` electrodes as of Example 1 being used through the cell 3,625 \par p. Gnxlacetoe\'e9 (I//)\rquote ee d\'e9termmed by ge$'\'b0h'\'b0met\'b0g\rquote eph\rquote e enel-V' Coulombs equalling 2 5 Faradays/mol being passed The reac\par sis with an inner standard of 4,4\'a4dimethoxybenzophenone. The don mixrura is than oaosfarrad to a rotary avaoorator for CHBCN \par W6]? gf/]Y\'80t\'b0;,rg"7(lQ) rela"`/6 t\'b0 the \'b0/em U) Used ee the Stem"? tobe stripped under vacuum. The resulting reaction preduct is then \par ma ana IS O '1A' extracted three times with 30 ml of ethyl acetate, and is then dried \par over Na2SO4. The organic extract, concentrated to a volume of 25 \par " \lquote - ,Irr 'ai ii\'a3ii\lquote i \'b7\rquote . *,1*iS "\'b7J"\'80"\lquote

\par _ _ - ___ _ _ __ . _ _ _ _ __ _ _ . _ _ _ _ __ _ _ _ fluxing temperature) for 6 hours. The process is continued as de\par . "' ' " ' ' `bedin xampe ,an .4grso aine o eone ,wi a

\par that in the isomenzatron step 250 mg of LiBr instead of 340 mg of Sqn - \'b7 \lquote \par Lil is used and that the reaction time results to be of 10 hours, gid of 865% m/am/Bly to the Glenn (I) used as the starting mate \par \emdash 190 - 191 \par \par STUFF THAT DEFIES CLASSIFICATION \par Example 5 \par To a 250-ml not-partitioned electrochemical cell, 135 ml of Iese IES\} ""ee n*e_\'b0'en\'b0eI n"e* eee neve nn *63* Kms np **7 3**ll \par __ _, _ __ !_e _ ,,5 H; we _ Q e H _ - ofthemaorcate onesor recursors.Thet1rstistheon t ls \par added. The mixture, kept at 20\'b0 C, is e/ectrolysed by using the Caeeee Stnke mere neepe*'tn_en enll \'b0*ne*\'b7 n W3$ \'b0n\'b03 3 T\'b0P Ten \par Same Glgclmdcs as Of Example ll bul Wllll 3 ccnslanl curmm recipe in the nrst edition. But it-was a reclxless gamble on Strike\rquote s \par density Of A being usedluntll the cell Cculombs pan and SI[l\rquote |kB pald TOT II. I'I\'80l'S IS what SITIKS wrote IBSI yBaF... \par have been passed. The reaction mixture is then processed as de- _ \par scribed in Example 4.2.56gis cbtained ciketcne (iii), with a yield ** v\'b0\'a4 *%*9 ***6 \'a4><\'a4\'a4**\'a4*** **99** <>\'a4**\'a4d "R\'a4$=r\'a4\'a4*\'b7\'a4l*\'a4* Drugs" by \par of 83.2%, as computed relatively to the oleiin (I) used as the Prefeeeer Buzzle] Yen n"3ll eeme 3\'b0"\'b0S$ 3 *****3 '\'b0\'a4*P9 in ***6 3m\'b7 \par Slarllng malerlal phetamtne section for something called N\emdash acetyl-phenethylamine. \par So what the hell is that? Well, actually it happens to be one step \par away from being an amphetamine but no one makes this clear to \par Examples 6-9 all the novices reading the book, Stoke means to say that asian \par -l\'b70 a 250_ml nclparllllcnsd eleclmchgmlcalrcelll 100 ml Of DMP, novices just reading for pleasure need a little help here and there. \par 50 ml of H20, 072 g Ol NaBl. and 425 0 Oli lSO8ugenOl_ lt's a lpity becattse this is a really good recipe using unwatched \par methylether (I) is charged. The mixture is then electrolysed under enen`"\'b0eIe and 'S e n"\'b0*`e dneet Well ef ennnenng Sen'\'b0*_e el 3**VI*

\par the same conditions, and by using the same set of electrodes as benzene Wnneln nnV'n9 tn ge *n*`\'b0U9n the *jn3*$'nQ Of 3n 'nte*n'*ed*\lquote \par used in Example 1. with g \{gte] Of 5,670 Cgu/gmbg being pegged em Such ZS MD\'b7P2P OI` PZP. ACTUEIIIY, SITll<8 IS Ut'ld\'80l\rquote the dlstlncl \par At reaction end, the mixture is discharged, to it 250 ml is added of *m\'a4*\'b7\lquote =S5*<>\'a4 ***3* F\rquote *\'a4*\'a4\'a7S\'a4* BUZZ e\'a4* this r\'a4\'a4\'b7\'a4e fwm the pmeenitqr \par 20% aqueous NaCl solution, and it is then extracted four times ef \'a4\'a4d\'a4r\'a4r\'a4*l\'a4\'a4 ene\{n'en'l\rquote n\'b0\'b0k$* "pellcnedenc C*'*3*n*$nV" blt M*\'b7 \par with so ml cr ethyl acetate. The extract is washed twice with so ml 9**39* V3**=\lquote ****\'a4\'a4 S*******\'b7 U***\'a4**\'a4\'a4\'a4*\'a4*v\'b7 *>\'a4*** ***\'a2S\'a4 3*****9*5 5_**'*'*P*ll \par cr 20% aquecus NaCl solution, and is then dried. The organic ax- \'b0\'b0P*\'a4:* \'a2\'b0****I*\'a4\'a4*3*'v **9*** ***9 \'a4\'a2*\'a4\'a4* S\'a2*6******\'a4 \'a4**l\'a4*\'a4 [9*1 *~\'b7***<>\'a4* \par .. ' -. -....- .. - .... na .. . .- . .. -- .- a 'e*\bullet e|I \bullet Ae! I' I- \bullet |II\lquote \par evaporated oft On three aliquots, of 20 ml each, of said extract, \par \par flux temperature. by using the same lithium salts and reaction \'b0 \par times as shown in Table 1. From the fourth aliquot of 20 ml of \'b7 O Hgms) c 62-*:*** \par above said extract, ethyl acetate is evaporated off and replaced < ,\rquote < \par with the same amount of acetonitriIe.The isomerization of the re- cn,cn \par action product is then carried out at acetonitrile refluxing tem- \'b0 \\ \'b0 "="\'b0"\'b0= \par perature, with the lithium salt and the reaction time being used as s\ldblquote "\'b0'\'b0 O \par shown in Table 1 (Table not shown)." CH \par - I , , \par Neon nn NaOH NH2 \par O QV " 0 @7 \par N-acetyl\'b7MDA MDA \par - 192 - - 193 \par \par This is almost e erle-pet predlletierl alld uses a simpler ber0t`lV\'b7 amount of heat can be applied to hasten the reaction. After 1

\par dride catalyst (NaBl-lt) than others that are out there- These cata- hour, 200ml. saturated Nacl solution is stirred in, the whole thing \par as a whole. Before this method is started, there is one bit of pre- ple distillation fg afford the intermediate \'b7l\\l-eoelyl-lvlDA\'b7 or \par pal\rquote a\rquote t0l'y W0l\rquote R that TIBBHS to be GODS by the SVII UDGSTQTOUDH \lquote N-agety|-gmphet3mlne_ Phgogyl \par chemist. The method calls for the use of anhydrous mercuric ni\par trate (Hg<N0s)s) but the only commercially available form is a This happy acetyl intermediate is just one hydrolysis away from \par |'Tl0|"l0hydl3lB (has elle \'a4\lquote l0|eGl-lie of water atteehedi bobbal)- S9 being MDA or benzedrine. By hydrolysis Strike means that by \par the chemist buys lor makes) the white. crystalline monohydrate. using simple acid or base one can chop crt that acetyl group that \par Next, if the chemist feels she is going to get really attached to this is stuck to the nitrogen and replace it with a hydrogen thus giving \par method then she's going to want to invest in a little toaster oven the chemist her final freebase. Hydrolysis is going to show up a \par that she will never. ever Put feed irl agairl- This toaster is placed lot in this book so lets discuss the two ways to do it. To that acetyl \par in the hood or lrl the baekl/ard because any l>\'a4$$ibiliiV of VaPor\'b7 oil sitting alone in the bottom of the flask is added either 500mL of \par ized Hg would be bad. ln a beaker or mom's Pyrex meatloaf dish 15% aqueous I-ICI solution (l-tcl in water, bubbal) gr 50crril_ or \par IS weighed 1009 of Flgl ilUs)z.FlzU Therl the beaker ls P aeed le the 20% aqueous NaOH with 100mL ethanol and the solution refluxed \par toaster oven which is set at approximately 220\'b0F and remains for5 hours. MDA is now in the pot. itthe chemist hydrolyzed with \par there for about an hour. The beaker is cooled and reweighed it HCI then she basities the solution with concentrated NaOH solu\par the stuff is 5% lighter (95e) then the water is cone- The mercuric tion until the prt is e and all the little droplets of rreeoase oil have \par nitrate is iherl around UP with a Spool) (spoon Thrown oWaY) and been released. She then extracts the oil with either benzene, \par used right away beeel-lee if it site around its going to goin water ether or DCM (chemists choice), dries the solvent through Na2SO.l \par from the air. and distills away the solvent to get product. lf NaOH was used to

\par hydrolyze then solution is cooled, extracted with ether, dried and \par To do the reaction the chemist places a flask in an ice bath on top distilled to give prgdugt Either way theyield is -80%_ \par of the stirplate and into it is added 100mL acetonitrile (CHaCN) \par \par that has 33g of safrole or 24g allylbenzene is placed over the flask pi lo ished report [92] in which things were produced a little differ\par so that everything looks just like that of tig. 9. The safrole is then erltly but bear description here because it has applicability as an \par slowly rlrippebl in so that the temperature stays between 20-28\'b0e alternative for those unwilling or unable to do the previous, unbe\par A yellow precipitate will form as the mercuric nitrate latches on to |i\'80Vab|y easy process Besides, irs good to seg how soierios pro\par the safrole. After the addition is finished, the ice bath is removed gresses_ \par and the solution stirred at room temperature fort hour. \par The acetonitrile and mercuric nitrate amounts remain the same \par After i hour 200ml- ot 3lVl Naolrl is SloWlY Pouiocl io followed blt except they are to be accompanied by 12.6g of fuming nitric acid \par 200ml- of 0-5Nl NaBH\'b7\bullet ii" 3M Naoini le stock solution or this is (see chemicals section) in the reaction flask. Then, with cooling, \par ol/oo l000o`il\emdash\'b7 then `l99 ol NoBl\rquote l4 is mixoo io)- Al liisi lllio9o will is immediate and takes no more than 20 minutes of stirring after \par erey then blacken slightly as elemental lnercllry is released and which 100mL ice cold dllac is slowly added. Next, with vigorous \par starts to tall to the bottom ot the flask. and the droplets ot proouot stirring, saturated sodium ehloride solution is slowly added until a \par oil Will oPPool'\'b7 The Solulioo is Sliiioo for il hou" and o Slight pronounced precipitate forms. This yellowish mass is the chloride, \par - 194 - - 195 \par \par not hydrochloride, of the acetamino-safrole intermediate (don't tO an \'a4\'a4hy\'a4r\'a4\'a4S l0l\rquote m- l\lquote la\'80l lhay USBU tha available monohydrate \par ask). The chemist wants to keep these crystals so the solution is mail W\'b0Uld haV\'80 Us\'e9fl an lhciaasad amount of the salt to compen\par

\par dl-l2O_ 40g of the filter cake is scrapped into a flask containing the arllcla just d\'a4\'a4't raad that way! Strike, nor anyone Strike has \par .\bullet \bullet - \bullet \'b7 ev \'b7-G -\'a4G =\lquote\'b7`\bullet '.\'b7a a \'b7~:~=a-\'b7\'b7 \'b7\'b7" \rquote *---' --2 \'a4\'b7\'b7\'a4- \'a4\'b7\'b7.:.\'b7s=.\'b7-\emdash\'b7 ` ' \par (a catalyst, see chemicals section) and the solution stirred for 3 trate. Does that make this method impossible? \par hours. Again, the precipitate will grey and elemental mercury will \par fall to the bottom of the flask. After 3 hours the solution is de- Sulalil \'a4l\rquote l\'80 W\'a4Uld hvpa not. What if one just used the mercuric ni\par canted into a filter (the mercury stays behind in the flask), and the trate monohydrate that is at hand. One\rquote s only real concern would \par flask with mercury is washed with 100mL ether which is also de- be if the monohydrate water would interfere with the acetonitrile in \par canted into the afore mentioned filter. The ether drips through the a competing oxymercuration reaction. But could it really consider\par filter cake then the filter is washed through once more with 100mL ing the massive excess of acetonitrile present? All Strike can say \par fresh ether. Both ether washings are combined and distilled to is that someone, somewhere is gonna try it. And Strike would \par give N-acetyl-MDA which can be hydrolyzed in the same manner really, really like to hear about it. \par \par The next weirdo method is a contribution by Ritter. This one is \par The acetyl intermediate formed by the reaction is another species Ritter\rquote s combo contribution whereby she gives all of you a novel \par that one could use l.iAlH4 on to strip the oxygen rather that hydro- synthesis for making the valuable nitroethane (this is also included \par Iyze [26, 27]. To reduce the intemwediate one can use the exact in the Chemicals section). Then Ritter gives you something to \par method as was used in the Leuckart reaction or one can substitute think about by hypothesizing how this nitromethane synthesis can \par tetrahydrofuran (THF) in place of ether as the solvent. ln using be applied in a similar manner to make a beta-Nitropropane (not \par THF the reflux goes for 24 hours instead of 4. After refluxing and propene) from bromosafrole. From there one can reduce using

\par cooling, 50mL dH2O in 100mL THF is added, then 50mL 15% methods Strike isn\rquote t even gonna get into here! \par NaOH, and finally 100mL more dH2O forming a white precipitate. \par THF and both the filtrate (the liquid stuff) and the THF washing are B` ' \par \par MDEA (~80-85%). Nitro Compounds \par Yeesh! That was what Strike wrote last year. And the sad truth is By Rm\'e9r \par that it did not work! The reason why is the way Strike proposed \par getting \lquote anhydrous\rquote mercuric nitrate. The baking of commercially Nitroethane and 1-(3,4 methylenedioxy) 2- nitropropane This \par available mercuric nitrate monohydrate was actually destroying method of producing the above mentioned nitro compounds is by \par most of the compound. Aside of that this recipe works! It really far the best Ritter has come across yet. The prob/em with stan\par =;\'b7_ e. e \'b7 ec \'b7.\'b7\'b7 ~\'b7 \'b7\'b7 " \'b7. -\emdash M9 a. -- --a. a----a\'b7\'b7 \par _ _ used is silver nitrite (al la Merck Index citing). Needless to say this \par \par authors in the original paper from which this recipe came from, able commercially but must be synthesized from cost/y silver ni\par clearly call for an amount of mercuric nitrate that is exactly aqual trate. The other methods mentioned in Vogels 5th masterpiece \par - t96 - - 197 \par \par which use DMSO and sodium nitrite produce low yields of the de- This compound is made the exact same way as above only .3 mol \par sired product because other nitrous compounds that are formed (72 grams) bromosafrole is substituted for the bromoethane. \par compete with formation of the desired product. This improvement Some extra DMSO may need to be added to facilitate stirring. Ex\par prevents those unwanted nitrous compounds from ever forming cept tor this the rea&ion proceeds as stated above. When the re\par -. an \bullet i n . H . \bullet ' h r ieldofthe desirednitro com- actionisc m l ..4 tr- -. ree . \'b7 - .... -. .; ..

\par pound. ln the case of 1-(3,4 methylenedioxy) 2- nitropropene ex- product is suitable for reduction, no vacuum distillation is needed \par isting methods for its production in the literature usually start with to purify the nitro compound. Just subject it to one of the many \par the nitropropene and reduce it to the desired nitropropane which reductions out there that will reduce an aliphatic nitro group (note \par can be easily reduced to the desired amine. There is no need to this is NOT a nitroalkene). AV(Hg) in IPA should work Hne. There \par try to make this intermediate nitropropene which uses watched are also many exotic NaBH/transition metal salt combinations \par chemicals (piperonal and nitmethane) anymore. Bromosafrole will that will easily reduce the nitro group, not to mention straight \par react in the following synthesis to yield 80% or greater of the 2- catalytic hydrogenation. One mistake not to make would be to try \par nitro compound which can be reduced a.bazillion different ways to a dissolving metal reduction such as tin/HCl. The boiling acid will \par MDA. ` destroy the methylenedioxy bridge and leave you with a frustrating \par NOW the gccdfes-_ Nitmgthan\'e9 ( ggrgistecgatggrgcpgygczmszgp Transfer Reduction detailed in Syn \par Ethyl bromide 32g, 26.0 ml (.3mol) or Ethyl iodide 46g, 24ml - . - . ._ \par mmol) is poured mm 3 Solution Of 250 ml Dimgthylsu/foxidg gg? lg/it1r$ht\'b7;p:bge;e\'e9x;\'a7;r;o be last. The Ritter Reaction [not aftili \par (DMSO) or N,N Dimethylfonriamide or N-methylpyrolidone (DMSO `\lquote `' \par preferred), 36 grams sodium nitrite (thats NaNO2 pyromaniacs, O \par not sodium nitrate) and 52 grams phloroglucinol dihydrate. This JL \par \'a5\rquote\rdblquote S $" *" % \rquote \lquote ? \rquote\'b0 " \rquote " a k A ee A H . \'b0'*= A . \rquote \'b0 r \lquote\'b0<"?

\par bath for 2 hours or until an emulsion forms. At this point dump all v \\ I, |\rquote \par into 600ml ice water and extract w? two pottions of 200ml methyl- Auylbenzem N_ace;y| _Amph;;;m;ne Amphmmins \par ene chloride. The MeCl2 extracts are washed w/water three times \par then dried w/ anhydrous magnesium sulfate then evaporated off in - - . . . \par . ,,..,.0.., drsrrioti ._.tt,,, Correcting ti. traction trogtoiot at \ {.1*;*$..i\lquote ?;."1..";a?..l\rquote\'a7\'a7'?;\lquote .\'a7i\lquote ,1.\'a7\'b0."l\'a7.\lquote $\ldblquote ,\'a7\'a7.\'a7\'a7.\'a7\'a7\'a7;".'L\lquote f,iL"\lquote 5;\rquote .'2\'a7\'b0iii;

\par 113\'b7116C 81 a1\rdblquote 1\'b0SP\rquote 19\rdblquote\'b0 F;\rquote E$S\rdblquote "\rquote as F\rquote "\rquote\'80 \rdblquote "\rquote\'b0\lquote =`\rdblquote 'a"\'b0\'b7. "t"\rquote\'b0.\ldblquote\rquote sulfuric acid and eoetohitriie iss]. This reaction works, ih theory, \par yield about 20 grams. Thats not a ton of product but this reaction in a SO_S\'a4 manner on auylbenzene but not on Safmle This \par can be scaled to any size you can dream of and yields will stay in method wm not make X for many masons. SO why does' undep \par 1119 80% range- ground literature and DEA forensic scientists keep claiming that it \par does'? Stnke Eloesnt know either. [ets see What the man who \par ,...; ,....,..-; ;, - .;;.;;_.- l \lquote |\lquote ! l U R " ne! \'a4 \{ \'b7e. | ' '" \par ` \rquote tempts to obtain amides from...safrol (sic) were fn1itless."[94]. \par What makes all these people think that this will work unless no \par one did their homework. This is another sore spot of Strike's and \par - 198 - - 199 \par \par now Strike is going to bitch for one entire paragraph and will then will rise slowly to around 50\'b0C, then start to rapidly climb towards \par rejoin you for tho rSGiPB at UWB b\'809l\'a4\'a4i\'a49 \'a4f th\'e9 $\'a4b$9\'a4\'a49\'a4t P\'a4l\rdblquote\'a4\'b7 80\'b0C. Most methods give the impression that this solution is going \par \par _ _ _ _ chemist should plunge the reaction flask back into the ice bath. lf \par will break the ether bonds of methylenedioxy ring structure on sa- super-critical and the chemist will have a horrible sulfuric acid va\par frole. This allows the resultant phenols to dimerize and polymer- por cloud in the house. The reaction color progresses from a light \par ize with other injured safrole molecules. lf one included this with orange to black after the temperature rise. The reaction mix is \par the natural protic destruction that HZSO., is going to cause on the poured into 400mL ice cold 15% NaOH solution in a PP container. \par rest of the molecule then this method becomes very untenable for lf more NaOH is needed to make the solution basic then so be it. \par X. Another contention Strike has is with the idea that cyanide pro- The N-acetylamphetamine is removed by extracting with ether

\par cedures meant as a Ritter reaction nitrile source for the conver- then removing the solvent, or by decanting the oil which will fomi a \par sion of tertiary alcohols and t-butyl primary alcohols [95] will work layer on top. The oil, dirty as it is, is hydrolyzed with 15% HCL for \par on a straight-up allylbenzene as has been suggested. This, in 10 hours just as was done above and in the Leuckart reaction. \par Let say, for example, that there was a group of 'scientists\lquote that, \par upon the suggestions from certain sources, invested in some ex- OUR FIRST EVER EPHEDRINE SECTION! \par pensive and elaborate equipment to safely perform the Ritter re\par action using cyanide (a way that supposedly produces higher Why did it take Strike so long to get with the program? Because \par yields than acetonitrile). Let\rquote s suppose that both allylbenzene and Strike does not do speed and Strike has never worked on ephed\par safrole were tried with not one active compound being produced. rine. But for some crazy reason there are a few people out there \par Next, Iet's suppose that these scientists were so pissed off that that do. Since Strike has nothing to say about it, Strike bows to the \par they had every oil fraction from the beginning of the procedure to superior knowledge of thosethat do. \par the very end analyzed by mass spectrometer and found that all \par sor. Maybe someone has a way to use these cyanide procedures pseudoephedrine and phenylpropanolamine to final product. \par \par the hassle and/or risk. to not tread on the banal work of yesterday's chemist, the ad\par vanced underground chemists associated with this book are here \par Hey, Strike is back. Anyway, the only people this procedure is to give you the next cutting edge methods for your reading pleas\par going to help are those interested in speed, and the only applica- ure. Osmium emailed Strike the journal references. She and oth\par ble version is going to be the one using acetonitrile. lt\lquote s pretty ers discovered them Strike believes. The first recipe here is a nifty \par simple though, and the chemicals needed are very basic. 59g al- little way to actually make phenylpropanolamine from the very \par lylbenzene in 200mL acetonitrile is stirred in an ice bath to a tem- safe propiophenone \{9698]. The intermediate made from propio-

\par .. . - \'a4 ... n.. - n ' .. . ..-. . . . ..-...- ' -. " . .. .. ...\'b7\'a4\bullet .\emdash ' .~. . \par the temperature remains at around 10\'b0C. An alternative to this quently reduced with palladium. Although Strike would imagine \par \par the allylbenzene in. Either way, after addition is complete, the ice \par bath is removed to allow the temperature to rise. The temperature \par - 200 - - 201 \par \par Phenyfproapanolamine. - l/Wth catalyst prepared as previously \par __ NOH NH2 described\rquote from 0. 5g of palladium chloride and 3g of charcoal, it \par was possible to reduce two portions of 9.8g of isonitrosopropio\par O O H phenone (0.06 mol), dissolved in 150 cc. of absolute alcohol con\par _ _ . _ taining 7. Og of hydrogen chloride, to phenylpropanolamine in from \par Pr\'a4\'a4i\'a4\'a4\'a4\'a4\'a4\'a4\'a4\'a4 'S\'a4\'a4\'b7**\'a45\'a4P*\'a4P*\'a4\'a4h\'b0\'a4\'b0\'a4a Ph\'b0\'a4Y'P*\'b0P\'a4\ldblquote\'b0'\'a4m*"\'b0 145 - 190 minutes with yields or the isolated chloride from 9.4g to \par _ _ . 11.0g, or 84 to 98% of the theoretical. After recrystallization from \par "l$\'a4\'a4lff\'a45\'a4\'a4f\'a4Pl\'a4\'a4h\'a4\'a4\'a4\'a4\'a4 was prepared fmm \'a4'\'b0\'a4'\'b0\'a4\rquote 2aU\'b0\rdblquote a absolute alcohol the salt melted at 191\'b0. The free base was ob\par and butt" "\rdblquote\rquote\rdblquote a\'b7 S/afar 11 usad mam'! "\rdblquote t"t8\'b7 8 988: butyl "\rquote t\rdblquote t8i 8 tained by treating an aqueous solution of the hydrochloride with \par liquid was f\'b0'\'b7"\rquote d mara \'b0\'b0"Va"ia"t\'b7 l" 8 1'ma" 8'"8\'b0k8d '\'b0\rdblquote "d' alkali' on cooling the liberated amino alcohol solidified and after \par bottomed flask, htted with stirren reflux and delivery tube for hy- mcrylstaiiizaiion \{Om Water mgiied \{\{1030 ,, \par drogen chloride, was placed a solution of 80 g. of propiophenone ' \par (0.6 mol) in 400 cc. of ether; hydrogen chloride gas was passed With ph - . _ \par through the stirred solution at the rate of 2-3 bubbles per second, ephgdrinigyyigwgjgw\'e9rx nzgegigdr\'e9gaczpilliirgqghgnigrgiiugii \par stirring and addition of acid being continued throughout the reac- group io get the finai amine Siiike understands ihai the Curigni

\par Yianf than f\rquote a$hI\'bbV distilled butyl \rdblquote\rdblquote "\rdblquote 8\'b7 b\'b7p\'b7 75*810 \'b7 was 88888 favorite methods for doing this involve lithium and amine HI and \par through the reflux condenser in 2-3 co. portions until atotal of61.8 red P or other iodine miaied proioccisi SO when you meiii heads \par 9\'b7 (0-6 mal) was addad Amar addi\rdblquote\'b0" 0f the mat P\'b0\rquote t'\'b0" the \rquote 8a\'b0\lquote ruin every aspect of those methods as well, what will you do then? \par tion mixture slowly became a yellow-brown and after several more -i-he ioiiowing are a coupig Of OH mduciion methods isiiikg \par minutes a light yellow colon alter which a second portion was ihinksiihai hav\'e9 appiicabie use [994 0Oi_ \par added\'b7 now the color change took place more rapidly, whereupon \par a third portion was added etc. The mixture gradually warmed up \par and the ether began to reflux gently. The total time required for the NH2 NH2 \par addition of the nitrite was about ninety minutes. Stirring and bub- _;_, \par bling of hydrogen chloride were continued for another hfteen min\par utes and the mixture then was allowed to stand overnight, during OH _ \par which time it became quite dark. The next day the ethereal solu- Amph\'e9tamln\'e9 \par tion was slowly stirred into dilute sodium hydroxide containing Phenylpropanolamlne ` \par pieces of ice and the ethereal layer was repeatedly extracted with \par cold alkali until no more product was obtained. The alkaline ex\par tracts were slowly stirred into concentrated hydrochloric acid con- "Direct Borohydride Reduction of Alcohols to Alkanes with \par taining sufhcient ice to keep the reaction mixture cold. ln this Phosphonium Anhydride Activation: N-Progylbenzene.: To a \par manner white crystals of isonitrosopropiophenone were obtained: solution of 5.56 g (20 mmol) of triphenylphosphine oxide in 30mL \par these were recrystallized from toluene and melted at 106.0-106.5\'b0; of dry methylene chloride at 0\'b0C was added dropwise a solution of \par Z' yield, 71 g., or 72.5% of the theoretical. When treated with hy- 1.57 mL (10 mmol) of triflio anhydride in 30mL of dry methylene \par droxylamine (hydrochloride) in alkaline solution for several hours it chloride. After 15 min when the prechnitate appeared, a solution of \par formed on acidifying, a voluminous precipitate which was recrys- 1. 36g (10 mmol) of 3phenyl-1-propanol in 10 mL of dry methylene

\par tallized from alcohol and melted at 230.5-231.0\'b0. chloride was added and the precipitate vanished in 5 min. An \par amount of 1.5g (40 mmol) of sodium borohydride was added as a \par solid all at once and the slurry was stined at room temperature for \par _ 202 _ - 203 \par \par 4.5 h. The mixture was washed twice with 1N HCI [may want to \par skip the HCI or wash with ~5% NaOH afterwards when using this BUILD FROM SCRATCH \par on an amine such as PPA etc.] and then water and bnne, dried \par over MgSO.,, and passed thru a short plug of silica to remove tri\par pheny/ph0SPhlli\'80 0Xld9- EV6RO'?C;'Q\rdblquote affvrdsd 1-079 (89%) Of The methods in this book have thus far been presented under the \par \'a4h\'a4~vl\'a4r\'a4\'a4\'a4~\'a4 as 8 Color/ESS hqw \lquote assumption that precursors such as safrole, sassafras oil, benzal\par Second method dehyde etc. are still available. We know that safrole, isosafrole, \par \lquote piperonal, ephedrine, P2P and the like are currently schedule I \par ,_Me3Sic, _ Na, _ CHJCN as an Efficient and Practical Reducing controlled substances. Strike has no doubt that natural oils such \par Agent for Benzytic Alcohols. A typical procedure for the present $;|?a?\'a7i;?;iang nutgneg sm golpg t\'b0 egimuauy bg banned as \par duction is as follows: To a mixture of Me SiCl (1.54 ml, 12 ' . . pe on 0 T C. an \'b0u \'b0\'b0m\'b01 \{Ike ls g\'b0m9 t\'b0,|aun\'b0h \par rs 1 8 12 d t ,t 7 rl O 6 I 12 I a preliminary strike against it. The following is the culmination of a \par mm\'b0l)\'b7dga(; ( \'b7 t, [$731)* he; /5;;;*2; build X and meth precursors essentially m mmrziywl lot of research on how to

\par 2/siege (g mz S`l?hLeI$nrixture vcas s\}hn\'b7ei:l for 24 h at igggm igmpera- fm"' Sclaichl\'a4 fad, there are so many ways iq dg this that a \par ture. Dilution with waten extraction with ether and subsequent `g:`?\'e9?tg;h:;\rquote BE;;l;r\'a7gt?L?1 E? `glggiulitzg (EO 2Jt?E;thgQdn\'a7:gvr;\'a7 \par \{SO/ation Pmi\'e9ss gave amy/benzene (158 mg) with Sumcient purity things down to the most direit methods-which produce the great\par in 75% yield. est yields using the least restrictive chemicals and procedures. In

\par . . . . some instances the science may be a little squirrelly, but one \par WOW! Smke Qugm to cznsldelyaklng ulp Speed as a secmd habm should keep in mind that, as far as Strike knows, all of the follow\par Th\'b0s\'80 rBdu\'b0t'\'b0ns l\'b0\'b0kE flea mg easy ing procedures are legal to perform except for those that actually \par end up making the precursor. The next drawing shows the gen\par eral pathway of synthesis that Strike is talking about. \par Speed manufacturers need only look at the molecules and imag\par ine them without those extra OHs or methylenedioxy ring struc\par tures attached to the benzene core. These particular pathways \par are, however, more uniquely suited for X precursor production be\par cause they take advantage of the hindrance that methylenedioxy \par ring structures and OHs provide on one side of the benzene core. \par This helps to better assure that mono chloromethylations or bro\par minations will occur whereas di- and tri-substitutions are possible \par on a naked benzene molecule which speed chemists are going to \par be using (please don't ask). \par It would be pretty pathetic if one had to start the synthesis of a \par complex molecule such as X from something like phenol but it can \par be done. However, since all of the intermediates listed here are \par legal, there is no excuse not to start as far up the ladder as \par - 204 - - 205 \par \par possible. This is especially true of pyrocatechol (a.k.a. catechol). \par DGH] \'a4H\'a4 One can get a ton of pyrocatechol and play with it ad nauseam. \par H H Using some of the techniques mentioned here, and others men\par \'b0\\\'a9 tioned God-knows-where-else, just about anything can be done to \par these pre-precursors. An OH or methyl group can be added here. \par e...l.mr \'bb=\'a4\'bb\'b7\'a4 s.rr.y\bullet .r\'a4\'a4\'a4y\'a4. A methoxy group can be stropped away or added there. Broml\par nations. Alkylations. Believe Strike, if you can imagine it then

\par \\` l someone has already done it or the methodology is in place for it \par to be done. \par H \par H And wouldn\rquote t you know H .... someone already has. Without a doubt \par Strike is most proud of the new testimonials that have been placed \par in this section for this edition. Strike had little faith that someone \par warm would actually apply the (legal) recipes here from the Hrst edition, \par B but one person named Merlin did! Not only is Merlin the hand\par [ \\ somest chemist around (seen a picture) but she/he has provided \par some experimentals for which every one of you ingrates will be \par C/\'b7~\'a4 thankful for years to come. Maybe not now. But someday soon. \par Br \'b7 \par 1,3-bermodiuxnln Bmm\'a4\'b7p\'bbyr\'a4cate\'a2$\bullet\'a4l \par 0 0 0 \par time ct %W \par |\'bb(2g| Br \\ \par 3.4\'b7m\bullet thyt\bullet nsdi\'a4xy- 5-Bmm0- Suirulo \par t-banzybhlorldu 1.3-lunzodloxola 4 . \par 0 \par H. \emdash\lquote M \emdash\rquote / \par sri (Ye Tie \par Prulocalodsualdmydu Pivomnnl lsoufroln I \par - 206 - _ 207 _ \par \par PYROCATECHOL, GUAIACOIW PHENOL & saiicylaldehydeiand the other has concentrated H;0; (at least \par 30 At). Both salicylaldehyde and the H;0; are dripped in simulta\par SALICYLALDEHYDE neously causing a vigorous reaction to occur and who\lquote s tempera\par ture needs to be kept at 48\'b755\'b0C with external cooling for 30

\par CHO OH minutes. After addition the solution stirs for 1 hour at 20\'b0C to give \par HO HO a yield of catechol at 95%. Looks pretty good don't it? \par ` ` \rquote e 0Me Qi-i \par . HO i-ig \par Salicylaldehyde Pyrocatechol \emdash\emdash\emdash\emdash > \par PYROCATECHOL FROM SALICYLALDEHYDE gueiacoi pyrocateohot \par METHOD #1: [101]--122g salicylaldehyde is stirred into 1L of 1N pYRO(;A\'b7rEt;i.tgt_ FRQM Gt_tAtAcOt_ \par Na0H solution at room temperature then 1420g of 3% hydrogen \par p\'a4r\'a4><id\'a4 solution (H20;. the exact % solution ppc Hncls at tha crc- Mart-too #1: [101, 103]--Before e chemist attempts trite proce\par GEVY Store) lscaddedy The $\'80\{l\'a4ll0l"* _d\'a4l'l$\'80\'a4$ and the lamp\'e9fafl-WB dure she should read both of the referenced articles to understand \par risps tp 45-50 G Ap tcp bath is applied if the lpmpptalurp Starts tp why Strike has included a hybrid apparatus like the one shown in \par rise above 50\'b0C. The mixture then stands for 15-20 hours, neu- figure \'b7t4_ \par tralized to pH 7 with acetic acid and the solution vacuum distilled ` \par of all its water so that all of the stuff that remains in the flask is into \{hg reaotion flask is added i \par completely dry. 500mL toluene is poured into the flask and slowly gtgo Crystalline guaiaoot and t \par heated to near boiling, all the while being stirred to break up the \'b7t5O0o reoutar 48% t.tBr wnioh \par crystalline mass. The pyrocatechol will dissolve into the hot tolu- is then eiowty heated to rettuX_ \par ene but all of the crap and salts will not. The hot mix is vacuum The tepid Water condenser is ar ..,\\ \par filtered and the stuff in the filter cup can be washed with a little there to attow the bro""\'b7~\\ J $\'b0\'a5,\}\'b7 \par fresh hot toluene which is combined with the original filtrate. The ntornethane that is termed to "\'b7\emdash - _, i \par toluene/pyrocatechol is allowed to cool causing the pyrocatechol teaue the reaotion ttaek but is \'a7r\par to crystallize out; which can then be separated by filtration. The etitt \'b7ootd\'b7 enough to keep the il

\par remaining toluene can be reduced in volume by distillation and other reaetante in the reaction \par allowed to cool again in order to afford a second crop of pyrocate- f|aSk_ The noxious broJg\'e9i" \par chol. lf desired the catechol crystals can be placed in fresh hot rnoethane oondeneee in the "` _ \par toluene and processed as before to give even cleaner product Cold Water oondeneer and drips Ul \par (yi\'e9ld=7\'a4%) into the chilled methanol in the \par _ collection flask. This will keep \par METHOD #2: [102]--Sodium bicarbonate and dH;0 are stirred in a this bromoethane trapped so \'b7 4T=`V Z '\'b7`l'' \par 3-neck flask with two addition funnels attached. One funnel has that the oheniiet Witt not die [Figure 14] \par - 208 - - 209 \par \par from breathing said gas. The reaction refluxes for 4 hours during nucleer winter cr bcdv parte et ine beginning cf ine erticle. Strike \par which time the temperature that registers directty above the warm ie ppl exastlli Sure. But lalei \'b0l\rdblquote l Games the pieseduie\par condenser should be about 95\'b0C. When the temperature starts to _ \par climb beyond 95-97\'b0C then it is time to stop the reaction. Some Tne appaiatl-is Y0 l-lss ls the isflux epperetue Willi dl\rquote yl\'a49 tube seep \par water and a little guaiacol will be lost during the reaction but that is in fig 7e. A tube neede tc be led frcnt the tcp ct ine apparatus tc \par ok because guaiacol is so cheap that the chemist couldn\'b7t care e Water trep beceuee l\'b7l<3l gee will be evclved- 50g ci eueieccl ie \par less. The reaction flask contents should take on a slightly pink placed ll\rdblquote l the Teastlen flask and heated sllQl'lTlY tc make ll liquid. \par color. The reaction mix is extracted hot with 2X 1L toluene and Tlieri- Willi stirring 509 ei anlivdrcue Alcle ie ereduellv edded \par both the toluene and water layers saved. The toluene layer is dis- ceuelng a Vl9\'b0T\'b0Us l'eaetl\'b0l"l tc be9ll'l\'b7 when the addltlpp is 00m\par tilled to remove any water that it may have absorbed and, upon plete ine reflux ccntigureticn ie ettecned end placed inic e 2i0\'b0G

\par ooollrigl will atitord a Crop oyrooataoliol orystalo Whlolt oar, be oil bath atop the stirplate. After two hours of reflux, the flask is \par separated by vacuum filtration. Reduction of the toluene volume all\'b0Wed tc \'b0\'b0\'b0l dcwn Whlsll Will ceuee The eateslipl tc Cl'YsTalllZs\'b7 \par by distillation Will afford a second crop OfcatechO|_ It is a good idea to dilute this solution with some 0.5M HCI and \par then stir or shake the flask so as to break up the crystalline mass. \par That aqueous layer that was saved can be removed ofrnost ofits Next. ecrne lcluene cr benzene ie pcured intc ine fleek end \par water by vacuum distillation, allowed to cool slightly then extracted neated ec that lite catecncl dieeclvee inte ine net eclvent. The \par with hot tolt_lar,o_ Whoo tho toluooo ooola_ a fgw hundred more solvent layer is separated, cooled and processed as usual to yield \par grams of cateohol will crystallize out but will be contaminated with eateehpl (70%)\par some heavy red bromo compounds. The crystals are Hltered and V \par vacuum distilled such that the pyrocatechol will distill over first, METHOD #3i [lO9]"l Part 9*-Ialacel end Z5 pafis lVl\'80c$lSNa in \par leaving the higher boiling bromo compounds behind. Yield is 1.3-dinietnyl-2-irnidezcline neeted et l85\'b00 in e eeeled pipe bcntb \par about s0% or eoog or catechol. gives 80-96% celechcl \par Technically, the chemist could avoid the complex glassware appa- METHOD #4= lll_0. i_i1l -- gueieccl end cupric percnlcrete \par ratus of this procedure for a more crude approach [104]. This re- t0utCl0t)s>\emdash eec\'a4rbic ecld ttnete vitentin C. bubbell ere mixed in \par port shows some dudes de\emdash methylating an amphetamine with an appropriate sell/epi uiidaf \'a4><Y9a\'a4 atmosphere lit allaskle 9lVe \par concentrated HCI in a pressure cooker. A similar approach with about 30% CateCh\'b0l\'b7 \par good yields was also employed in ref. 83 and should work as well \par or better on guaiacol. Hydroiodic acid or hydrobromic acid will OH \par work better than hydrochloric acid but, you know, whatever floats l.lg HO \par the chemist's boat. To do this the chemist can just plain reflux Hl \par or HBr with the guaiacol for a few hours and process as before or \par she can use Hl, HBr or HCI and place the reactants in a pipe \par bomb for a few hours.

\par phenol Pyrocatechol \par METHOD #2: [105 p725, 105-108]--This is super easy and uses \par aluminum chloride (AICIS) for which there are many uses in under\par ground chemistry. The original reference is in German but the PYROCATECHOI- FROM PHENOL \par master here has translated it for you. There's something about \par - gil) - - 211 \par \par There ele e lvl of bed ee\'a4Vel`Sl\'b0\'a4 Feelpee YOF Phe\'a4\'a4_| and 3 few should anyone else these days. These recipes are for the des\par ee\'b7e\'b0 Ones- Thle deeefll mefter because phenol le_ ebeul BS perate peoples of the future to ponder. Although by then they will \par cheap and common as dirt. This means that the chemist can ex- have starfleet replicators to do their bidding. \par periment with it at her leisure. \par Future drug user: "MDAll 100mgs" \par METHOD #1: [112]--5g phenol in dH;O is stirred 5 hours at 20\'b0C Computer voice : "AfHrmative." \par with some ferric sulfate (Fe;(SO.,)3, an additional 7mLs dH;O, \par 13mLs 6% H;O; and a \lquote pinch' of aluminum oxide (Al;O;). Yield of \par catechol is 2.5g (50%). \par METHOD #2: [113]--Phenol can be oxidized with either performic, \par formic or acetic acids to catechol. For example: phenol, formic \par acid, concentrated H;O; and polyphosphoric acid are heated 2 \par hours at 80\'b0C to give 53% catechol. Addition of phosphorus pen\par toxide (P;O5) is said to increase the yield. \par METHOD #3: [114]--Phenol and 30% H;O; in molar ratios of 10:3 \par to 10:8 is heated at 70\'b0C for 8-10 hours to give ~15% catechol. \par Addition of tert\emdash butyI alcohol increases the yield. \par METHOD #4: [115]--80% phenol in aqueous H;SO4 solution of pH \par 3 is brought to 50\'b0C. 30% H;O; is then added causing an exo-

\par thermic reaction and a temperature of 15\'b0C over 3-4 minutes time. \par 6% aqueous H;SO;? is added after 4.5 minutes, the solution \par quickly cooled and extracted with isopropyl acetone (Strike would \par think that another solvent like methyl ethyl ketone could be used) \par to give 60% catechol. \par One of the problems with all the current phenol conversions is that \par a certain amount of other phenols, such as resorcinol and hydro\par quinone, will be formed along with the catechol (don't ask). These \par species are very hard to separate from the catechol because they \par are all so similar. Aside of carefully monitored fractional distillation \par there are some vague strategies which can be found in the \par Chemical Abstract references 116-118. \par Wow! How did Strike go from such detailed articles to this load of \par crap about phenol conversion'? Well, it's probably because Strike \par has never had to stoop so low as to need these methods nor \par \lquote - 212 - - 213 \par \par METHYLENATION METHOD #1: Methylenation started out in the first part of the \par I century using a process pretty much like the following [119]. 55g \par pyrocatechol, 200mL dH2O, 40g KOH, 140g DCM and 125mL \par OH /\\ O ethanol are heated in a sealed pipe bomb at 120\'b0C for 24 hours. \par HO O The solvent is then distilled off and the 1,3-benzodioxole can be \par extracted from the remaining water solution using benzene or \par \emdash\emdash > ether and the solvent layer fractionally distilled to afford \par 1,3-benzodioxole (yield=20%). \par Pyl\lquote 0C\'a4i\'80Gh0| `l\'b73\lquote B\'80nZOdl0XO|\'80 There are other articles that have shown that this sort of reaction \par mix will work just as well under simple reflux rather than a pipe \par bomb [120]. A mixture of 220g catechol, 272g DCM (or a propor-

\par With catechol in hand there are many ways to proceed as one can tional amount of DBM or DIM), 220g potassium hydroxide and 1L \par see from the genealogy chart. Strike feels it\lquote s best just to dive ethanol is refluxed in the hood for 72 hours, cooled and the \par right in and discuss the most pivotal point of all that makes X what brown-colored solution vacuum filtered. The filter cake is washed \par it is: that little bridged ring structure stuck on the benzene core. with a little ether, which is combined with the other filtrate, and the \par When the two OH groups of catechol are brtdged, the species that solution is distilled to remove all the solvent. The residue that is \par is borne can be named either methylenedioxy benzene or, as the left will have 500mL ether, 1L dH2O and 200mL 20% aq. NaOH \par Chemical Abstracts call it, 1,3-benzodioxole. Why \lquote 1,3-\lquote ? Well, solution added to it and the whole thing stirred really well for a few \par the carbon that bridges the two oxygens is now counted as the #2 minutes, You may or may not recognize what's going on here but \par carbon. Later, when the chemist adds something to the It is the exact sort of thing that one uses to get the eugenol out of \par 1,3-benzodioxole, all the numbers change\'b7again and the #2 car- sassafras oil. Any exposed OH groups (catechols) will form those \par bon will no longer count. lsn't chemistry confusing? There is one anions with the Na from the NaOH and bring the catechol into the \par very important thing that there should be no confusion about. water as a solid. Any converted 1,3-benzodioxole or methyle\par That is that if one were to demethylate eugenol to get allylpyro- nated compound will not have any such exposed OHs because \par catechol, demethylate vanillin to protocatechualaldehyde, or ac- they will have been tied up by the successful conversion. This \par quire any species that has those two adjacent OH groups then means that such molecules will remain inthe solvent layer. This \par those molecules can be methylenated just like catechol with simi- is an excellent way to purify any of the methylenated compounds \par lar yields. One needs to remember to adjust for the weight differ- produced by any of the following methods. The ether layer is \par ences of the different species one wants to methylenate. separated, washed with water and distilled to give \par 1,3-benzodioxole in about 26-32% yields.

\par Th\'80 reaction itself works by the action of Na or K from NaOH or \par KOH which form what is called a catechoxide dianion with the two METHOD #2: Later versions of methylenation get the yield up to \par Ol-ls of the catechol species. This makes the two ripe for an at- 50% by employing the use of a catalytic metal called Tobin bronze \par tack by a methylene halide which can be either DCM (methylene [121]. The chemist can buy this or make it herself (yeah, right) by \par chloride, or dichloromethane), DBM (methylene bromide, or di- mixing or smelting or whatevering 60% Cu, 38% Zn, 1.5% Sn, \par bromomethane) or DIM (methylene iodide, or diiodomethane). 0.3% Pb, and 0.2% Fe (that all adds up to 100% by the way). \par DCM is cheap and works pretty well, but DBM and DIM work bet- 0.1M of any catechol (for pyrocatechol that's 11g), 3g of Tobin \par ter yet are more expensive. \par - 214 - - 215 \par \par bronze shavings and 10.2g DCM are placed in a pipe bomb which The found that \lquote . \par is positioned vertically in a bucket of crushed iss with the D\'80im\'a4\'b7 mix land then distilliiolgaiicirlrrign lriV\'a7tt(;c\'a7lut::uinglE(\'a3i:;Lii to lll? reactlqn \par nsnity seared end oh the bottom. The DCMrmix is allowed to get distill over with the water at the same [time as a Enzo tome Wm \par gold\} then 40mL of cold methanol is poured as Qingerly as DOSsl\'b7 aZ60tr0ps is a term for when two things are stool: iazeinmpa (an \par bis dow.-, the inner wail ofthe bomb so that as little mixing as pos- they distill over). The azeotrope will separate out lnigg an when \par sible between the two liquids occurs. Then a C\'a4ld Solution of 119 flask to give a clear upper layer of water and a clear tow cli action \par Kgi-i (or gg NaOH) in 15mL dH,O is added in the same manner Oily benzodioxole. lf one has made heavier oil s eoiegr ay? of \par as was the methanol so that as little mixing as possible occurs. piperonal or safrole using this, then it is preferablepto 'ustsgi: \rquote its \par The bomb is immediately sealed afterthe final addition. up distill the stuff without the addition of water 'llhe ieiig i \par 1,3-benzodioxole is 70%. I y O \par All of this careful addition is to keep the reaction from starting be-

\par fore the bomb is sealed. lt is also important to note that the When doin this m th \'b7 \'b7 \'b7 . \par chemist must scale upor scale down the amount of reactants s0 has l0ng bgen theogzelddbirhiaingsze\'e9irlihissatzllgfliiqezce igpilglgirigi that \par that the total amount of all the ingredients consumes no less than That is, they determined that if one tries to conven all of the cngsi \par 90 of the volume space of her particular pipe bomb. Too much chol at once like was done in the above method then it tenda ?_ \par head space with its atmospheric air will lower the yield. The bomb form a dimer side product like that shown belgw[12()] S O \par is heated in an oil bath or oven at 105-115\'b0C for 18-24 hours and ` \par the contents are then distilled with the 1,3 benzodioxole coming You see, if there is as much activ \'b7 \'b7 \par over at about 170-175\'b0C with no vacuum. Alternatively, the as there is DCM to react with it thear\'b7iF-tiltelizlisclaotiirivallrgrrglsgnilecllhqaci \par chemist can only distill off the methanol, wash with dilute NaOH the activated catechol will react with itself and form a dimer before \par solution and extract with ether, etc. the DCM has a chance at it. This accounts for about 20% of the \par I I y ' loss in yield. This was avoided by adding the NaOH and catechol \par METHOD #3: Things start to look easter and the yields higher in small batches to the al\par when the following method is employed [122]. This method uses ready hot (120\'b0C) solution of O_\emdash CH2"`O \par a solvent called DMSO (dimethylsulfoxide). Maybe you\lquote ve never DMSO and DCM. The DCM \par heard of this solvent but Strike has. It is a common solvent used was allowed to have its way \par in all fields of science; and although Strike is not 100% sure. with substrates then another O"`Cl`l2\emdash `O \par Strike believes that one can substitute DMF(dimethy|fom1aniIide) small addition was introduced, etc., until all the catechol and \par for DMSO. NaOH were added. This gradual addition strategy raised the yield \par to 91%l Strike is not about to explain the weird apparatus used to \par 11 Og catechol, 500mL DMSO, 100mL DCM and 83g NaOH are allow simultaneous addition of two dry products to a hot sealed

\par stirred in a flask with a condenser just like fig. 7a. The tempera- system. lf a chemist wants to try gradual addition then her best \par ture is brought up to 120\'b0C either by direct heat or by an oil bath. bet would be to drop the stuff down through the condenser and \par A violent reaction will start when the temperature is approached wash down anything that sticks to the inner wall of the condenser \par and will last for only 10 minutes. That\rquote s it! The solution is stirred with a few squirts of DMSO. \par for another 30 minutes and then allowed to cool. The \par 1,3-benzodioxole can be removed by methods similar to those of You do believe Strike when Strike tells you these things don\lquote t \par the previous two methylenation methods or one can do the supe- you? No? Well neither does Strike. But fortunately for us isome\par rlor method of separation employed by the scientists of this article. \rquote \par - gig - - 217 \par \par one did. And now that person, Merlin, has schooled us all. Check \par out Merlln's adaptation of #3: . \par n g\'e9chloromethane 100ml pour into the reaction flask with \par "MethyIenatlon for Beginners \par I \'b7 I On one occasion I dried the two solvents with Sodium sulphate, \par By far the best method I have tried to produce benzodloxole ln lm \rdblquote Pt sum lt uits 9'\'b0f9\'a4t9d my yields, but if it's very humid where \par tenns of yields and simplicity. ln comparison to other processes, You live than thlS would be a good idea. lt certainly wouldn't harm \par this is in fact quite fun and I'll explain it in a fashion that can be \rquote f.V\'b0\lquote\'b7' Want to UB thorough. \par followed by a complete novice, like l was when l started a while \par ago. What we do is react and reflux the ingredients nrst, then use _ _ _ _ \par 3 Simple distillation procedure to extract the plvduct with water 68 gggrcgtgii Ctcggglismellsh/Ike hospital to,/ets from Wham im Simng \par an azeotrope. Once extracted we wash until the product is clean and donltt [cpd? pljm is`? USE ? fuuust t\'b0 get this t\rdblquote t\'b0 the flask

\par and then separate, FFOITJ start to linish ilgcks to Eve,]/thing, a \par o o \lquote \'b7

take ab0Ut Six hOurS\'b7 funnel Qndrgdd

\par is added the solution will start to chang; to I; ga\rquote r:<6g?eae[n5Iu;IZ;Etgu$\'b7uIl`t \par Staga ana _ ina maanan happens in ina \{ann af a reflux with a dn, IS important that the stirrer keeps spinning, if it all stops moving in \par set-up. You will need a 2000ml reaction flask, a condenser and a there $0me bits can get left out of the reaction, and your yield will \par drying tube packed with calcium chloride or other drying agent. SUHBF \par The reaction needs to be stirred in a big way, so before we add \par the ingredients make sure you have a clean stirrer bar ready, l . . _ _ \par prefer the eggy shape bars as they tend_to be less noisy. $7;dgg?9H,\'a5C;m;(.Lq\'80 ' wg Of AR grads IS added '" the same Wal' as \par c o. \'b7 IS will slow the stirrer down loads so add slowly \par now the reaction flask will start to get warm as the magic starts. \par ingredients \par Catechol - 770g Now connect the condenser and the drying tube. An important \par DCM (AR Grada) _ mgm] point here for beginners is to make sure the drying agent is not \par DMSO (AR Grade) -500ml slurgqgheg gill? b|tI?I1\rquote t`\{ump which can MDW mtusturs to pass bY\'b7 \par Sodium Hyuroxiue (AR Grade) - sag the Qgffcn W 7 a pest/B and \rdblquote '\'b0rta" s\'b0 \rdblquote \'b0\'b0\rquote 7\rquote t""\ldblquote\lquote\'b7"V \'b0\'b0"\'b0\rquote S \par _ _ _ oo rn the drying tube. When this reaction starts in an\par gfs qui? 'liappenlng'j so if the drying tube isnt hrmly placed it \par DMSO \emdash Dimethl/Isulphoxide is a very common solvent with a n\'e9ld if Dlaggioihg? acrqss the kuchsn aud Smash Y\'b0" san \par freezing point of 20 degrees. When you buy this stuff it will be young Uslgg 8 Vacuuliwaggnftes \'b0r Clamp tu \'b0r Sven taps IL tf \par crystallised in the bottle. To melt, all you need to do is place the blocked on proper, toc p Br make S"'? tus Vacuum port ts \par bottle in a bowl orliol waterfor so minutes - simple. lryoure lucky with Shot out in fm; 0f;n\'b0"\'b0" 8 pim 0* f\'a4ll t d hlecked mine vtt \par enough to live somewhere warm it may already be liquid, where l naw I tape it in place ,V ve\rquote V ey\'e9s, and my dog nearly ate lt, so

\par live, no chance. When you open the bottle you will notice that this \lquote \par stuff smells a bit farty, don't worry too much, it doesn't get that \par bad. 500ml straight into the reaction flask and start the stirrer \par - 218 - - gig \par \par l/wth everything secured start the heating gently, The reaction will eee/d be sodium hyereXIde\rquote and veeee ee,-tee Your predeet should \par already be going so things don? normal/ytake [Ong. Amman min_ be crystal cleah slightly more viscous than waten withla very \par utes or so the reaction will start in eamest, gases fizz out of the Strong edeue S'm'Ier togeselme or benzene lpetel \rquote f You re from \par drying tube and the contents of the flask will be a lovely emerald the UK\} \par green coloun this will last for three to four minutes and then \par 9\rquote od\rdblquote o\rdblquote Y S/o"" dow"- You mall notice me Smelly DMSQ a good The best yield l\rquote ve achieved is 84g of benzodioxole from 110 or \par gPg\'a7gl;gl2;;g7ga'z:g7 gg\rquote\rdblquote\'a7`ng9o?hz;;soZ;mLSgZh igalhguhzogltogihg catechol. And to progress from here youll probably need to do this \par time and leave for half an hmm The next thing We Wih do is add reaction twice to get enough benzodioxole for the bromination. \par 500ml of distilled waten so we need it all to cool down. _ _ _ \par METHOD #4: ln this synthesis everything needs to be as dry as \par possible [123]. The potassium fluoride (KF) should be heated at \par Remove the condensen then with the aid of a funnel add the wa- 100\'b0C for an hour, all glassware baked at 425\'b0F for an hour and \par ter slowly, keep stirring. lf the solution is too hot the water will any solvents used need to be dried through NaeSO.,. 152g KF, \par evaporate and make a big mess. As the water is added you will 22g catechol and 500g DMF are stirred at room temperature for a \par notice that loads of stodgy crapp will form, this is nom1al, connect few minutes. The solution will get warm during this time and will \par the condenser for the distillation with a receiving flask at least be allowed to return to room temperature before proceeding fur\par 500ml in capacity. ther. 19g of DCM is added and the solution refluxed in a \par 110-120\'b0C oil bath for 1.5 hours. After cooling, the solution is ex-

\par . . . . . tracted with ether, the ether washed with water to remove any ab\par We new have e ele eeeeweh lets ef Weter m Ie e'/h'eh,We neee te sorbed DMF, the ether dried through Na2SOt and distilled to ive \par twat MS and me This Wil lake 3 img time andiioute lmpalenl leeeeeediexele at e yield of elidil lleilie eeeidm fluoride ilielied \par like me' ee beet te ee dewn eee expeet te Wee at least ee ` 45 KF reduces the reaction time and gives higher yields on the meth\par minutes before anything starts to happen. What we're doing here ylcnaucn Of larger molecul\'e9s \par is removing the water and our product benzodioxole together as ' \par t$St\rquote 55$5te\lquote 5S"\'a2\'ae\'a4l\rdblquote\'e9lilt\lquote 5\rquote\'bb\'a4\rquote F\'e9\lquote l$Zi\rdblquote %% r:\'b7;;i;2\'a4.:5:.;;\'b7; \'b7::\'b7*.;::i;\'a2.2:;:.:;iieitii:\'b7::.;i\'a4.::;2 \par will start to come oven as it drops into your collection Nask a blob ension if Q2 5 Sodium h md; (NEH) in 2b0mL hexameth |_ \par of oil will appear in the middle of the water The oil appears clearer sms hom; m\'e9mede (HMPTQQS added a Solution Of 28 6 Catechihl \par \rdblquote "\rquote " me wom \lquote\rdblquote "\rquote\'b0" W"' be \rquote "'\rdblquote\lquote Y i" 8pp\lquote\'b0""\rquote a"\'b0e\'b7 NOW B" We ali ioiomt HMPT over e 10 lTllI"lU(B pEl\lquote l0d A lot of buelbiing will \par need to do is wait, atyust the heat so the temperature doesnt go Occur and when it dies down 809 Of DIM or 529 DBM or 25 29 \par egg;/e me degrees end ee eewe eee Weteh TM er have e elgee DCM is added and the solution stirred for 20 minutes. After 20 \par ' minutes about 500mL cold dH2O is added and the whole thing ex\par tracted with ether. The solvent Iayer is dried through NaZSO,, and \par After a couple of hours you may notice that what's coming over distilled to give 1.3\'b7be\'a4z\'a4di\'a4><0le (vlG|d=93%). \par contains less oil, and eventually no oil at all, just water That's it, \par you've done it. The benzodioxole will form a layer undemeath the \par water. We just need to separate the oil with a sep funnel, wash \par with water twice, to remove any traces of milkiness, which I think \par - 22Q - - 221 \par

\par BROM|NAT|ON OF 1,3\'b7BENZO[)|OXO|_E 1,3-benzodioxole, and at about 30\emdash 40\'b0C higher should come the \par , mother lode of yellowish bromobenzodioxole oil (yield=91%). lf \par one has liquid bromine then one might consider pulling the vapors \par /\\ Q /\\ O that come off it into the solution using a very low vacuum pull as \par O O described in the article. The chemist may consider using acetic \par acid as the solvent instead of chloroform and drip liquid bromine \par ___, into itlhs previously described [126, 127] to give about 90% yield \par as we . \par Br \par ti3-B\'80rtZOdiOXO|\'80 5-BrOmg-1i3. The next two bromination recipes use recyclable bromine donors \par bohzodioxoio that can be used over and over again. They are called dioxane \par and succinimide and are more common than you think. No, diox\par Egyk iiqillosioweire holfway Lhere. I Qne iee tliroughomihthis im? is \'a4\'a4t the Sarnc as the notorious dioxin but it is still pretty \par oo a romlne pays a ey roe in a o o TEBCIOHS. is is oxlc. \par because it is a good nucleophile that adds well to things and helps \par in getting other things added. As usual, if the chemist wishes to Br \par use iodine instead of bromine that is perfectly okay. Since we are . i \par talking about bromine here, let's discuss what the bromine one O O \par needs is going to be like. What is needed here is bromine (Br;) \par not hydrobromic acid (HBr). Br; is just heavy enough to be an or- C D 5 \par angy red liquid at room temperature. lf one were to take the iid off O O \par a bottle of liquid bromine then lots of red, evaporated Brz smoke \par will come flying out. It isn\lquote t advisable to breathe so transfer of this Dloxana I \par stuff should be quick or in the hood. lt would be best if the liquid Br \par bromine were kept cold at all times. lf one cannot get liquid bro\par mine then they can assuredly get it from the specialty gas can\par nister supplier. The product of this bromination can be called \par 1,2-methylenedioxy-4\emdash brcmobenzene or 3,4-methylenedioxy\emdash H Bl

\par bromobenzene but Strike is lazy and is going to refer to it simply I I \par as bromobenzodioxole. O N O O N /0 \par 2 _ \par METHOD #1; [125]--143g 1,3-benzodioxole in 600mL chloroform V W \par is stirred in a flask and Br; from a little tank is slowly bubbled \par through the solution over a period of 4 hours at room temperature. Suvclnlmldo \par Ideally one wants to introduce about 190g of bromine into the flask _ _ \par so tho chemist may Wish to oioo tho ouohiiho and ohook tho These little beauties are like bromine quarterbacks in that they \par Weight gain Of the flask periodically. After 4 hours the Solution is \{SKB th\'e9 ball \'b7(Bl\rquote ) Qfld hand lt off to ThE l'\'80C\'80lV\'80l' (1,3-b8hZOdlOXO|\'80). \par vacuum distilled from the flask. The first thing to come over is the The 9**3* *****19 \'a4t>\'a4\'a4t these tw\'a4 Species is that th\'e9y are so bulky \par chloroform, thoh 3 Smaii amount of hiohor ooiiiho, uhioootod that the only place on the benzene ring that they can hand off their \par _ 222 _ Br atom with any efficiency iszgg the least hindered #5 carbon \par \par which is the exact one one wants the Br to be on. Once bromin\par ated, the Br acts as a final deterrent to the possibility of a second \par bromination. As you can surmise, multiple brominations can be a "B"\'b0mi\'a4\'a4\'a5`i\'a4\'a4 for Beginners \par problem with some methods. After releasing their bromine, both \par dioxane and succinimide are reformed and can be separated for This process will add 8 bmmmg atom Onto me b d_ \par reuse' molecule which is important for the next step of the p:>,;qs;O);'Zi; \par ulE1\'b7l~lo\'a4 #2; [128, 129]-Ja make dibramddlazana one stirs soog i\rquote yhSQ\'b0p\rquote 9 \'b0"\'b0\rquote *""'\'b0\rquote l\'b7 \'b7\rquote "" "\rdblquote =\lquote _ Ylglds are 9*681/ f\'a4 achieve. \par dioxane in a flask which is in an ice bath, all of which is in the nomengll O if`;1\'80r\'a7O7? W"S'd?\'b7tBmm/"a\rquote\'80d Chgmlca/S hal/9 8 Phe\par hood. seog or liquid larz is rapidly added, causing the solution ld Benzodioio/8% hi ; 7\rquote "fthp\'b0";/3 which in the Case of Bromo\par get hot (one can also bubble ih an appl'OXlfT18t\'80 3m0U\'a4t of b|'0* Djsyjjagjun Will Ustgcf k an 9 tgmperature at which It WI//.f\rquote y\lquote

\par mine from a gas canister). The solution is dumped into a bucket Vacuum avai/ag/9 3 jb y\'b0"r_\'b7\'b0"\'b0d\rdblquote "" unlgss YOU hal/9 8 S\'e9nvus \par containing 2L of ice water, causing the immediate formation of a It mck me aboufsig atty S\lquote 9['\'b0"S m9?"\rquote down Y0 at least 1OTTllTl. \par large mass of orange dibromodioxane crystals which are sepa- Wrong and Once I had 82150; L';\rquote ?\'a7\rquote [;;\rquote\'80fdWV;/ga? WGS QOIUQ \par . . _ _ l an eas \par ratgd by Vacuum mt"at'\'b0n and d"E\'b0d\lquote eration. lrlhth a vacuum of 2mm I distil this stuff at about 10/Ogg, \par In an ice bath a flask containing 100g 1,3-benzodioxole or cate- andlt\'e9tarts to tum black atab\'b0"t 12O\'b0C` 130% Without Vacuum \par chol or guaiacol and 200mL ether is stirred and then 200g dibro\par modioxane is slowly added so that the heat and reaction won't get For those without a fume cu bo r \par out of control. After stirring for 1 hour the solution is poured into with a fume cupboard the sgcogddbfdriligggozsnggtzlgld gcgggril\'e9 \par some water and the ether layer is separated. The aqueous layer mended. \par is extracted once with some more ether and the two ether frac\par tions combined, dlied through Na2SO,, and distilled to give bromo- _ \par benzodioxole (90%). The R8aCt\rquote O"' \par METHOD #3: 130 --This method was erfectl tailored for the - . \par bromination of 2,3-benzodioxole. The bgomosuyccinimide can be gggr\'e9ngfgi\'e9ggfggi\'a7;;\lquote iij1m'%/ta rjfgx Siiup a\{'d left for ?h'?9 \par purchased or made from succinimide in a way that is pretty much ti//Ed with vacuum WS me Sm fm mm 9 SO/\rquote d$ and then d\rquote $\'b7 \par the same as the way dibromodioxane was made (see Ziegler, ' q I pg' \par Ann., vol 551, p109 (1942)). To do this method one mixes 122g \par 1,3-benzodioxole, 188g N-bromosuccinimide and 500mL chloro- Ingredients \par form in a flask and refluxes for 3 hours. The solution is then vac\par uum filtered from the solids and the filter cake washed with a little _ \par extra chloroform. The chloroform wash is combined with the B\'80\rdblquote Z\'b0d'\'b0X\'b0/9* 1229 \par original filtrate and vacuum distilled to give about 1809 (91%) Bromosuccinimide-188g \par bromobenzodioxole. Cmomform _ 500ml

\par Now the real goods on BOTH of the reactions in #2 and #3. Again, \par courtesy of Merlin: Benzodioxole - from the previous reaction, usually you will need to \par _ 224 _ do twice to get the correct amounts. Washed and dried. \par - 225 \par \par things very thoroughly. Remove the solids f th f\lquote l \par Bmmgsugginimide - easily purchased but I could only rind OHS Wash the $0/ld$ with fV9$/7 SOIVGTIT to Q6! any p\'a53rZuctE;)ft! \par grade. /t's a very fluffy light orangy crystalline powder - use gloves and back into the solvent. Save the so/ids that you have Hltered as \par and a mask, because bromine is VERY nasty. they can be dried and reused \par Chloroform - a very common so/vent which has a rather unpleas- Place the littered solvent into a reaction flask with your vacuum \par ant smell. Try not to get too close to this stuff as it has anaesthetic distillation gear ready. If you have a vacuum pump capable of get\par properties which you don't really want to find out about. ting down to the pressure needed here it will be powerful enough \par to steel off the chloroform without adding too much heat. lf you just \par I _ _ um e vacuum on the evaporating solvent will co I the t' \par Theres no real order needed to get the stuff lnto the reaction fl k t- - . . . O mac l0ll \par \rdblquote aSk_ os,. 8 1000mltlask with 8 atirrer be and ve easter it the diisiiil \}LZ"Z\'a7Z?,\'a7,\'a7\rquote $\rquote ,\'a7\rquote ;i \{"S"";"\'a7i\rquote " S""'S\'b7 SO Whit you md to \par chloroform goes in last so you can wash down the solids if you - O ge S S\'b0IV6"t off Wlmout me l9l7l\'b7 \par . . perature getting above about 2OC. The solvent can be e d \par have any stuck ln the funnel. Set up the condenser and drying Without Vacuum ne mb] . l lll0V6 \par tube as we did with the methylenation. never eeee eee\} e 150% IBQZPGEYUTG \par . r pro uc WI urn ac . Ei\par ther way sometimes the so/vent will come off orange that Bromo\par Start the heat and wait. It will take about 20 minutes to get going Succllllllllu\'e9 96*5 everywhere and the condenser will gfgrl fg gel S0 lgngtasvflf

\par and there usually isn't much to see. The Hask will be a nice orange "\'b0a[lY dll`t.V and bl0\'a4l<6\lquote d\'b7 \par colour from the bromine and it won't change much until just before \par the end. Make sure the water is running, everything is secure and . . _ _ _ \par leave for three hours - have a sleep or something to eat maybe. HS ,ObWO.uS when the Chlomform has ulllsllud Comlllg GVBT- lf \par you re using heat with out vacuum the temperature will start to dse \par so make sure you stop before it gets too hot. lf you are using vac\par After three hours the flask will have tumed slightly darker in colour UU"' lt S umu tv STOP GNYWHY. \par and the contents will look slightly more transparent. lf so then eve\par rything is good, if not I doubt that you have anything to wony . _, _ 4 _ _ \par about- A/[OW to COO, enough for the Vacuum H/tration, usually about However well you hltered before ltsltlme to stop the distillation and \par 30 mm Ut e ee gizfgeeyejwlglnlgltup gefore yjeu dlstll your product. The condenser \par u o s le. ean a your bits and replace the flask with \par stirring and begin to heat. As I said before if you haven't \par . , got a \par Vacuum Hltering can be a bit tricky, as the hlter paper clogs up Vacuum aV8ll@bl6 thats 70mm or less don't bothep \par very quickly and stalls the process. Vwth this stuff it is particularly e \par important to get rid of as much of the solids as possible or your . . .. _ _ _ _ \par dtatillatioh be will very messy. A way rouhd that l have found (that jest \rquote "\rquote Q7"""S \'b0l dlsllllalg ls lll<<=\lquote lV l\'a4 be unleactad benzo\par isn't in any book) was to use loads of litter papers, throw them all here is"/Ve W;h \'b0?m6 Over at about 8O\'b0C\'b7 The best UWFQ to do \par into a big beaker and then rinse them with solvent, then filter the everythm I gr 6 Zmperatum to get tg about ?0\'b0C a"d then $\{0P \par solvent. Filter tiny amounts at a time, as soon as the paper blocks We k t hg' ;; ange. 88*8 and Start aga"l\'b7 _D\'b0" t a\rdblquote\'b0Y'l the l' \'b0a\'b0ll\'b0\rdblquote \par - stop and change the paper I normally run the filtrate through at bits; [fo 93 ug Wh']? yOU change fmsksq lll fact [Gt ll COO] d0Wll 6 \par least twice. Any way you can make sure that you have done two you \'b0" * you/I k"\'b0W Wh\'b7V I Sald mls-

\par - 226 \par - 227 \par \par An ice bath is needed technically but l 've never had any problems \par Vwth a new flask in place start your heating again. At around Wm hEEt9Em\rdblquote 9 \'b0U*`0f\'b00m`F\'a4/- So USS OHS anyway. \par 100oc the product will start to appear There should be loads of it, \par it will look very clean and clean and could best be described as We need\'b7 \par slightly yellowish in colour If you're lucky you'// have about 180g ` \par and it will smell similar to Benzodioxole with a hint of bmmine \par (yuck!). The bromine atom is a heavy bastard so the molecules Dioxane - 500g \par here weigh much more than the benzodioxole molecules, so ex- Broniino liquid _ 9909 \par pect a higher weight from a similar looking volume in comparison. _ _ \par Stop your disti/ling when the colour of the distillate starts to get D'\'b0XE"E ' \rquote E E "'E'Y E\'b0mm\'b0\rdblquote and \'a4h6\'a4P S0/vcrrt. \par darker in co/oun What's left in the flask is shite, and can be thrown \par EWEY\'b7 Egornrne liqiutll/7- 2 vtzry nasty red liquid with a heavy vapour that \par oo s ou o e o \'b7 e as soon as you open it, that will make our \par The receiving flask contents should contain a very pure product. Sk\rquote " E"d EYES E""79 "k\'80 YOU')/6 l7\'80V6f known. Y \par There is no need to clean up any further For the next stage how- _ \par ever they will need to be dried over sodium sulphate. This can ei- - . . \par ther be done now or later. Now is betten dry your product before g\'e9iingivigiiikjlzlzgnigtilzglggnnn the ICB bam S/OW/Y add mE \par . . . . _ _ on to get hot. The crystals will \par you weigh rt and place it in a screw capped bottle ready for the form immedlaiely and before the Wh I _ _ \par Gngnard reaction. _ U oe thing gets solid pour the \par contents of the beaker into 2 litres of cold water The who/e thing \par goes whoosh! and forms a huge lump of really nice looking orange \par Brominafion with Dibroinodioxano mass. There will be crystals all over the place including in the re-

\par lactron beaken and these should be carefully scraped into the wa\par er \par This method is by far the easiest of the two methods l describe, \par but because it uses bromine liquid as a precursor to the dibromo- I _ \par dioxono oiysials o funio cupboard lo, o fuokino good mofnod of Whats left rn the water now needs to be vacuum filtered and \par fume extraction) is absolutely essential. Surgically removing ones d"Eq\'b7 Th'? Should EE EO"'? carefully and Ufld\'e9f the fume hood. Up \par oonaus with o bluni knife would oo a muon loss painful Way of to this point the chemistry will have taken around 30 minutes, the \par harming yourself than messing with this stuff in the kitchen. d\rquote Y\rdblquote\rquote 9 m\rquote ght [ERE 6 daY OF S0- Often bfvmine liquid stays hanging \par orounlj tlte crystals whiz; makes them nasty leave in the buchner \par unne o your vacuum l er overni ht to et rid \lquote \par The procedure is similar to the reaction described above except Unless all the bromine has gone? dontggo negiiggzitvztzgge\'e9 \par that dibromodioxane crystals are used instead of Bromosuc- fume cupboard or a mask. \par cinimide and refluxing isn't necessary as the reaction is much \par easier. The dibromodioxane crystals are made quite easily and as _ _ \par for as iknow can not be purchased, The dibromodioxane crystals are now ready for the reaction. Us\par rng the same ice bath as before we have a PP beaker containing \par 100g of benzodioxole and 200ml of ethen which is being stirred. \par 228 We gently add 200g of dibromodioxane crystals and watch the \par \'b7 \'b7 - 229 \par \par solution turn a gorgeous orangy red. We leave to stir for one hour. THE B|G CHAPTER \par After an hour we pour the contents into 500mi of water. We then \par separate with a sep funnel and extract the water layer with 50ml of \par clean ether We combine these two ether layers and dry over so\par dium sulphate. Now comes the mother of all chapters. Three different controlled \par ecstasy precursors from 1 compound: bromobenzodioxole. This

\par _ _ o _ is also the point that speed makers should begin to pay more at\par The distillation is the same as rn the previous reaction. SXGSPY tention. ln the chemicals section of this book Strike has provided \par fhgrg is ne need to clean the condenser after the solvent is r\'a4\rquote\'b7 the recipe for making bromobenzene so that me speed chemist \par moved, as there are no solids left over from the reaction. No vac- ceo make an ofthe analogous oreoursma \par uum hltration is needed prior to the distillation either: However a \par vacuum of at least 10mm is still required to distil the product. \par _ 0 \\ \par Although the clean up is much easier the yield is about the same. [\lquote\'a4 /' Sum \par For those with the correct equipment this has to be the preferred \'b0 \'b0 \par method. " " < / \par Br 0 \par @5;:2:;,,.. \\ *\'b7\'a4\'b7\'b7\rquote "\'b7* \par o \par 0 \par Pip\bullet r\'a4n\bullet .I \par \par / Allylnmzana \par CLE, \emdash\'b7 (DW \par Bmmuhanzsna \\ Froponytbunmna \par 0 \par Bmuldshyda \par _ _ \'b7 \'b7 \par \par ln the three neck flask is stirred 12g Mg and 200mL THF. In the \par PREPARATION ofthe GRIGNARD REAGENT little separatory funnel is placed a mixture of either 100g anhy\par - drous bromobenzodioxole or 78g bromobenzene (for speed) in \par _ _ 200mL THF. What is not pictured is a plastic tray that the appa-

\par The preparation of the br0m0benZQdl0X0|\'a7 0F bF0m\'a4b\'80\ldblquote ZE""\'80 ls ratus will be resting in on top of the stirplate because the chemist \par going to be the same \'a4\'a4 manet which me ls usfid and "\lquote\'b0 "\lquote a"\lquote ?" may need to throw some ice water in it during the reaction, Ai\par wnien precursor th; cigemist wish? f\'a41[T1\'a7k$\{\'b7 Thggmgagri\'e9gigigz though not entirely necessary, it is probably a good idea to squirt a \par mei part needs to e one corfe\'a2 y- _ IS W5 P little nitrogen into the head space of the three neck flask before \par that Strike is talking about is the creation of e Gflgnefd FG\'a49\'80\'a4* Qul ine reaction begin; Anpiiier thing ie consider bgfgrg beginning is \par gf the bromo compound SYBVUUQA Fnaiellal [125131-1 34\} M"- Q\lquote _"'9' whether or not to place a catalyst into the reaction flask. What this \par nard earned a Nobel prize forthis in 1912 so you can bet that its a means is that it is Samagmaa difncuit to got a reaction going bg_ \par pretty good procedure. tween the magnesium and the bromo compound and chemists \par often add a little insurance policy in the form of a tiny crystal of \par iodine or, as in ref 110, exactly 2 drops of dibromoethane into the \par reaction flask liquid. Like Strike said, it is not always done but it is \par _' \rquote best that the chemist does so anyway. \par Br cMgBr \par Bromobenzene Grlgnard Reagent The reaction is started by dripping the bromo/T HF mix from the \par separatory funnel into the stirred reaction flask. A vigorous reac\par . \'b7 tion will begin to occur after a little addition. This will give off heat \par The procedure Ca"? far tge ::;;n;?;J\'a7i0Q:;;\'80 a magneslum atom so the chemist adds ice to the ice tray and/or controls the dripping \par \'b0"t_\'b0 the b'\'b0m'p|\'80 \'b0 t i 'gmgneablg to gx_ f' so that the temperature of the reaction stays below 55\'b0C. After \par Wmch makes t \'b0 \'b0\'b0mp?X t I n about in e addition, the solution is stirred for another hour, during which time \par Pha"9\'80_Wq];h y\'b0'\'b7' are ?h\'b0T?h;c?;;niSt is O_ it will take on a dark, yellow-green color and just about all the Mg \par lust a b\lquote t\'b7 'S_";1\'b0a"S a ium Owdgrggr will have dissolved into the solution. That's it. The chemist now

\par '\ldblquote 9 t\'b0 _buV Bn Fr mT1$\'b0\}$;I_ th; curl _Qs has her Grignard reagent which is the entire solution in the reac\par galagisggmOtglmazgilxyliamgefrom a Sglgun \'b7 tion flask. She needs to process this into the final product soon \par . . b ' k . \par ing pad. The procedure can be done in ei- \\ Bcausethe rEagEmW\'b0nt Gap fmever \par ther tetrahydrofuran (THF) or ether, but THF g \par is preferable. All the colmpganents neagd gooble gg \par as dry as possible, w ic means _a_ e \par solvent is dried through Na2SO., or distilled, \'b7 FROM GFUGNARD REAGENT \par the Mg is dried in an oven at 100\'b0C for an \par hw" and the Qlassware is baked in an \'b0V\'b0" ""'_"- All the glassware from the making of the Grignard reagent re\par at 425"C f\'b0'_at Ieasizq m'\ldblquote ut\'b0S\'b7 The appa` H mains exactly the same with the Grignard reagent still resting in \par rams t\'b0 use ls Seen In flgure 15' [Figure 15] the reaction flask. The only change is that the ice bath tray is re\par - 233 \par - 232 \par \par moved. into the separatory funnel is placed 50g of anhydrous al- [Tha G\rdblquote 9"a"d R\'b0a\'b0t\rquote\'b0\rdblquote \par Iylbromide (Br-CH2-CH=CH2, see chemicals section for how to \par ;t\'a4l<e> ana tms 'S tha"_S|\'b0Wt_Y dnppad '"t\'b0 the Caagnatd S\'b0t\lquote\'b7't'\'b0"\'b7 Since completing my synthesis of safrole using the methods de\par nother vigorous reaction will start and the addition IS regulated scribed here iheve ieemi rheri em the first ersen in me WO idi \par so that things do not get out of control. After addition the solution do se- There may he areas in my preeedgree that can bg ima \par is tattuxad tmt.3 h\'b0uts\lquote (fated ang than hydgjlyzad ht DOUTIQ the proved. What I am doing here is giving you my best shot as well \par ;?$r'\'a7rT iygtegttgoiggzter tca \'b0\'b0t saturate ammtmtum \'b0 \'b0"da as a fairly detailed account of my experiences. 3A|=Rg|_E Oi- ALLYLBENZENE

\par What the chemist will see is two layers: a solvent layer (THF or ;\'a3;mg;$ri;edm[5;cg%Z iisvvggg. ggcvzgreegeergaqit agtifgtrtichagiasog \par Et2O) and a Watat layer with 8 t\'b0t \'b0t suspended s\'b0ttds\'b7 The sible before attempting this reaction The apparatus required in\par ehemist can remove and discard the aqueous layer now or, pref- cludes: - 1000ml three neck flask 10d0m/ sep funnel a condenser \par erably, the chemist can vacuum filter the entire two-layered soiu- and e drying robe This eeperehie heede re be Ser en 8 me rieric \par tion to get rid of all the solids, then remove the water layer. Of srir eierer For reeeene which i Weuid prefer ner fe ge img the \par course it is always a good idea to extract that water layer once presence or env vverer during the reaerieri Wiii Severeiv Sereiiv U \par with fresh solvent before it is discarded. The solventlsafrole layer vieids so evervrhing needs ro he dried ineiudrhg the ihgredierirg \par is washed with a little dilute HCl and then with some fresh dH2O. -i-he riesr vvev re diy rhe eiesevvare is re Geek rr in your Oven fer \par "`he eehtehi *eYe' is theh dried thieudh Ne=$O\'b7= edd Veeddm die nalrarl hour at 150\'b0C (300\'b0F). The solvent (THF orether) andthe \par tilled. The tirst thing to ciistill over is, of course, the solvent. The bremebenzedioxoie need re he dried ever sedrum Snrphere and \par next thing to come overwill beafew mLs ofalow boiling oil which rhe magnesium sheuie he eeeked in ihe even eieng vviriji the \par is \'a4\'a4i\'a4\'a4 i\'a4 be i\'b73-\'a4e\'a4=\'a4\'a4i<>><\'a4ie \'a4\'a4\'a4 will he Saved i\'a4r reuse- Ai \'a4 glassware. Atmospheric mslslllia must be kept sal ofthe raaallaa \par much higher temperature comes all the safrole. The chemist will ev using rhe drying rebel \par have no trouble knowing that the procedure worked because all of \par that high-boiling oil is going to smell just like Iiconce (yield=87%). s \par Summary \par Can you believe that'? A chemist just recreated a wondrously A dm rettux S9t`\rdblquote p \rquote S used with a mms neck iieek sttdwmg s the" \par oomeiex eohsrehoe ther, before now, Wes only o grrr from God ro mometer and sep funnel to be attached to the reaction flask. The \par man via plants. Man took this gift away from her fellow man but thermometer \rquote S Ptacsd Wm] bstow the Smtsse`_ df the desk smh \par how) rhroooh rho urrholrovehlo power or chemistry, mah can ro_ tents. lf the temperaturerrlses above 55\'b0C ICG wlll need to berused

\par claim her right to self determination. Albeit illegally of course. tO @0/ tmngs down s_b't\'b7 SO the tmss "'ssk task will be s'ttl\rdblquote 9_\rdblquote " \par an lce bath on the stlr plate before we begin. lf ether IS used ln\par stead of THF the ether will boil well before 50\'b0C is reached giving \par And it would certainly be illegal if Merlin had actually done the a better indication of how hot thl'ngs are getting. \par procedure she next describes. Aside of the unsatisfactory pronoun \par use, Merlin\rquote s accounting is astonishing: _ \par The Reaction \par P/ace 12g of magnesium into the tlask along with 200ml of THF \par and stir Place 100g of bromobenzodioxole along with 200ml of \par _ _ ' ' \par \par THF into the sep funnel. lt is recommended that an iodine crystal - A . \par is placed in the reaction flask and before the condenser is atgg;gigggrggngi\'e9iuz/\'b0m;;yn;?dGdt\'b0the Gngnerd reagent- it should \par fached nitrogen should be blown into the receiving flask to re- dioxole because Whig]? .t hitgvgln [gore SO than the b"em0be'7Z\'b0\'b7 \par move any air As l didn't have any nitrogen available l skipped this Stan tO'g8t going Them ;S OS Sd t "g"ard 'eage"t_ th'\rdblquote 9S 'GGUY \par step but I did place one small crystal of iodine into the reaction particular tem Egature burr;\}. [Fit Z eip the ';Za\'b0t'\'b0\rdblquote Under ami \par flask. When the iodine is added the solvent will begin to turn boi/S 3 Sure gi n te//in O tg IS 0;], \'b0 \rquote " ere Yew Settle"? \par brown. Although this looks like the iodine is just dissolving it would was Much moregvigoroui 57877 tzeshig, $;g';\'a3mTg\'e9S/ zgzggz \par Zglplear from what l have read that this rs also caused by the reac- I-I must be Working\par . After all the allylbromide has been added, the solution is heated \par The contents of the sep funnel are now added with care to the re\par action flask. Begin by dripping small amounts of the bromobenzo- ?(;c;\};gt(;m,:g7\'a3? 8;8\rdblquote uX for three hour`; and Subsequently ISH to OOO, \par dioxole into the reaction flask and keep a close eye on the _ ' \par thermometer; remembering that the temperature should not be V

\par allowed to go above 55\'b0C. lf the temperature does begin to climb Prepare a 300ml saturated ammonium chlonde solution in a \par too fast, stop the addition and wait until r`t reduces to atleast 40\'b0C. 2000ml PP container by adding 225g of ammonr'um chloride to \par Addition of the bromobenzodioxole should take about 30 mins. 180m/ of water Carefully pour the contents of your reaction flask \par Although the reaction was described as being vigorous, in my ex- into the ammonium chloride solution. Two layers will form which \par perience there wasn\rquote t much to see except a rapid rise in tem- contain a big load of suspended so/ids - which are removed by \par perafure. Once all the bromobenzodioxole has been added the vacuum liltration. These two layers are then poured into a (clean) \par solution should be dark brown in colour The solution should now sep funnel and allowed to settle. The water layer is discarded \par be left to stir for a further 60 mins., after which it will become a leaving the organic layer which is washed once with 50ml of 5M \par dark greeny-brown with only tiny particles of magnesium that will HCL and then once with 50ml of water Any remaining water must \par be swirling around as the solution stirs. What's left in the flask is thm be f\'a2=\lquote m0l/Gd by drying Over sodium sulphate. Now all we \par the Grignard reagent. Anyone getting to this stage should feel need to do is distil, and we have safrole. \par happy in the knowledge that very few (only me up until now) have \par Seen this bromobenzodioxole - Grignard reagsm Using a standard vacuum distillation the solvent is distilled off \par This shouldn\rquote t take too long. The Nrst thing to come over after the \par Safrole from the Grignard reagent Keeping the apparatus from the solvent was the safrole, which with my vacuum (2mm) started at \par above reaction, pour 60g of allylbromide into the sep funnel. As around 90\'b0C. The safrole will be a clear liquid, slightly viscous and \par with the ingredients of the last procedure the allylbromide must be will smell of liquorice, l/Wth the above measurements one can ex\par dried over sodium sulphate. This stuff is really nasty, use a mask pecl a yield of around 85g. No further cleaning up is necessary, \par at least or a fume cupboard if you can get access to one or Hll the and the safrole can be used as is for any further reactions.\rdblquote

\par sep funnel outdoors. The fumes are invisible and pretty lethal \par Please be Wemed- You can see now why Strike is so proud of this chemists hypo\par thetical work. lt is the most professionally written and applied ex\par perimentals of this entire book. lt is made all the more remarkable \par when Strike tells you that these three contributions were the first \par ' ' _ _ \par \par chemical experiments Merlin ned ever done. Here is this reekie solution. is refluxecl for 30 minutes. The solution is hydrolyzed with \par applying some sf the most advanced, and Often difficult, Organic ammonium chlorideiust like safrole was and then isolated just the \par synlneses processes ereundl same to give an -hydroxy intermediate (please don\lquote t ask, but the \par yield is 81%). \par lGle3ll;_ ZEi?algegsfgmiglkgslhl;-li;\'a7r\{:lslb\'a7\'a7;Oifgll\'e9;% gglllgzge What the chemist has is an alcohol intermediate which is not what \par methods? Maybe. Strike likes to think that it is a testament to the She Wal"lS\'b7 ll $ll? were l\'b0 lll\'b0l$ \'b0ll lllal OH 9'\'b0uP mall 8 d\'b0ubl\'80 \par intelligence and end persistence Of one Very geed looking Chemist bond will form in its place andlisosafrole or propenylbenzene will \par (ne. Strike is not geyll 1 be borne [26]. $0 what the evil chemist does is place 60g of the \par - alcohol intermediate oil and 1g potassium bisulfate (KHSO4) into a \par PIPERONAL or BENZALDEHYDE FROM really small flask, attach the flask to a distillation apparatus and \par GRlGNARD REAGENT start heating with vacuum. As the OH group is being kicked out it \par will form water, which the chemist will see distilling over. When no \par . . more water can be seen evolving then the reaction is finished. \par l\'e9iigrgglifg g\'e9lllriillggagril laneeniggiihlglsigligulsihzln\'e9giiyis;lll; zig; However, the chemist continues to heat to distill over all of the \par nard solution is poured from the three-neck flask into the separa\'b7 ls\'b0sall\'b0l\'b0? Wlllcll Wlll Smell lllsl lllle ll\'b0\'b0ll\'b0\'b0 (yl\'80lll=9l% ll\'b0l`l`l ll"'? \par tory funnel. The three-neck flask is then cleaned and dried and llllelmelzllalel lf the cllelllllsl Wallled lo she clluld pellollll llle

\par put beck in place Ori if the chemist has s spare, swapped with e same bisulfate procedure inia beaker or flask without the glistilla\par second flask. lnto the flask is poured 30g of N-methylformanilide gm Setup ang Sggp lll\'e9eleacllml llllllgn Q Fmpelalule \'b0f lm C ll?s \par (no, that\rquote s not the same as N-methylformamide) and the ice bath gen leaclle .l p59 l` The \'b0l ls Slll gcllllg l\'b0 have l\'b0 be dls` \par tray is put back into plaoe. The chemist is going to need to cool lllled l\'b0 pullly ll lh\'b0Ugll\lquote \par the N-methylformanilide down to -20\'b0C so the chemist is going to \par have to stock the ice bath with dry ice and ethanol. The Grignard \par solution is dripped in so that the temperature of the reaction flask \par contents never rises far from -20\'b0C. After addition, the solution is \par allowed to come to room temperature and stirred at that tempera\par ture for 12 hours. From here the solution is processed exactly like \par what was done for safrole except that 300mL cold 30% HZSO4 \par solution is used for hydrolysis instead of ammonium chloride \par (yield=67%). Get it'? Good. \par ISOSAFROLE or PROPENYLBENZENE \par FROM GRIGNARD REAGENT \par To make isosafrole or propenylbenzene the chemist will do exactly \par what was done for piperonal except that the chemical in \par three-neck flask is going to be 30g of propanal chilled to -15\'b0C. \par The addition is the same except that after the solution reaches \par room temperature, the ice tray is removed, heat is applied and the \par - 238 - - 239 ~ \par \par 9 flask ofthe apparatus shown in figure 16. This whole setup looks \par THANK YOU SIR MAY I HAVE ANOTHER ' a little involved but it really isn\lquote t. The flask has all the components \par and HCI gas comes from either a gas cylinder or an HCI gas gen\par erator using HZSO4 and HCI/NaCl which happens to be the exact

\par K sth t Em? same generator that the chemist is going to have anyway so that \par Why sure you GSH- H\'80I'\'80 are an lh? a"\'b0th\'80'S t\'b0 ma E a 9 she can crystallize her freebase product (see crystallization sec\par alogy map of IOIGI PI'\'80\'a4\'a4l$\'b0l' SY"'th\'80S'S \'b0\'b0mp'\'80t\'80\'b7 tion). Either sulfuric acid is dripped into the HCI/NaCl or the valve \par on the cannister is opened so that a gentle, steady little stream of \par /\\ O /\\ O [ HCI gas starts bubbling into the reaction fluid. The temperature \par O ` needs to remain between 25-35\'b0C as the bubbling continues for \par O 3-4 hours. The solution is washed twice with cold water, twice \par , with dilute sodium carbonate solution and once again with water. \par CH Cl The solvent is dried through Na2SO., and distilled to give what is \par 2 essentially called piperonyl chloride or benzyl chloride (yield= \par _ . . 70-90%). Now, if this procedure does not work as described then \par 1.3\'b7B\'80\'a4ZOdlOXOI\'80 Plpsmnw Chlonde one should blame the Japanese, who said it would and then pro\par ceed to try it over again except this time one is going to add 30g ot \par z` c chl 'de, \par cl-ii.oRoMEri-ivLATloN [ "` \'b0" \par . PIPERONAL BENZALDEHYDE FROM \par This procedure is called chloromethylation and will not only turn CHLORONETHYL INTERMEDMTE \par 1,3-benzodioxole into a methyl chloride but will work equally well \par In \'b0\'b0"V\'b0m"9 pla"` md bengene ring? previous recipe can be The benzylchloride compound made in the

\par b\'b0"zYI \'b0h|\'b0"de\lquote B\'b0th \'a4rg1\'b7m\'a4\'a4; converted to piperonal or benzaldehyde using a chemical called \par St*\'b0pI\'b0'\ldblquote 9 Swnes t\'b0\lquote\rdblquote "'dS \lquote\'b0\rquote *\'b0'\'b0 ] [ J hexamine [137 paw, sv p700, me]. I-lexamane, also known as \par t\lquote\'b0" \'b0f X arid 'T\'b0\'b0th' E0;] Tjximp nl I \lquote . hexamethylenetetramine, is a weird looking methenamine or

\par ?\'80'HZ\'a7| \'b0I`g\'a7;?;\'e9sb;c;Ss;ituv$I| bgget \\ \'bb chemical that is easily made from fomwaldehyde but is better off \par ro e su I \lquote\'b7 \'b7

\par benzaldehyde and phenylacetonitrile I gg bemg pw-chasEd` \par (a precursor for phenylacetic acid). yy] ~ \'b7\'a4 [ /\\ O /\\ O \par The best method Strike found for this A ;] \lquote X g O \par [135] does not use ZnCl which is =\'b7 y . \lquote \par usually included in this procedure as \lquote\'b7 \lquote\lquote ` \rquote ' \par a facilitator to the addition of the chlo- I CH Cl CHO \par romethyl group [37 p539. 136]. Ctrike 2 \rquote

\par E\'b0Zs$`$JlTZLith$ giixgewfii OSLZZZ [Figure 161 =i- I F\rquote ir>\'a4r\'a4\'a4vl \'a4t\'b7l<>ri\'a4\'a4 l\'b0i\'a4\'a4*<>\'a4\'a4l \par a \par asrSlfoTma?c?gI$yde3;Dr$d1%ild0:;(EI?ol3\'a7ge are placed in the reaction In a flask with stirring is added 158g piperonyl chloride or 126g \par pa a \par - 240 - - 241 \par \par benzyl chloride, 140g hexamine and either 500mL 50% aqueous dripped from the separatory funnel into the reaction mix over a \par acetic acid or 500mL 60% aqueous ethanol. The solution is re- period of 3 hours during which time the solution will blacken and a \par fluxed for 2 hours, then 200mL 3N HCI is added and refluxing is thick brown sludge will form. After addition, the stuff is poured into \par continued for 15 minutes more. When cool, the solution is ex~ 500mL hot water, cooled and carefully acidified with concentrated \par tracted with ether, the ether washed 3 times with water, dried HZSO4 or HCI. The whole mix is vacuum filtered from the tarry \par through Na2SO4 and vacuum distilled to afford piperonal or ben- resin, extracted with ether, the ether washed with water, dried and \par zaldehyde (yieId=70%). The two products are quite fragrant which vacuum distilled to give protocatechualdehyde or vanillin \par will give the chemist an idea ofthe success of the procedure. Did (yieId=70%). \par you know that a lot of methylamine is produced as a side product \par of this reaction? How it can be salvaged Strike has no idea. When making vanillin from guaiacol the chemist can smell suc\par cess because the product will have an intense vanilla odor. One

\par PROTOCATECHUALDEHYDE FROM PYROCATECHOL can even flavor cookies with the stuff (true!). This \par Riemer-Tlemann method is also an excellent way to get salicylal\par This is a nifty little way to turn catechol or guaiacol into protocate- dehyde from phenol in yields of up to 50%. The chemist does \par chualdehyde or vanillin using what is called the Riemer-Tiemann everything the same except uses NaOH instead of KOH. \par reaction [137 pB24, 138]. It is a really ancient reaction and only \par works on benzene molecules that have an OH group. One needs ALLYLBENZENE FROM BENZENE \par to use KOH instead of NaOH because it is better at promoting \par para substitutions (don\lquote t ask). And if one is going to make vanillin This is the infamous Friedel-Crafts method and works in a manner \par from guaiacol then there needs to be a little ethanol in the reaction similar to the previously mentioned method where P2P was made \par as well. by merging benzene and chloroacetone using AICI3. This method \par is for speed makers only and is not recommended for conversion \par QH OH or 1,3-benzodioxole. However, this should work in a limited way \par HO on catechol. The conversion factor is very low but that isn't a ma\par HO jor concern of speed chemists because cheap old benzene is the \par \'b7\emdash * precursor and all of that benzene that isn't converted can be run \par CHO back through this simple little process over and over again. Be\par fore she knows it, the chemist will have amassed an enormous \par Pyrocatechol Prctocatechualdehyde am\'a4\'a4\'a4l df allylbenzene [139. 140]. \par To proceed one can merely throw all the ingredients into a reac- \emdash > \par tion flask and reflux for 5 hours or one can do the more prudent \par way as follows. Using the same apparatus in fig. 15 one places \\ \par 400g KOH and 400mL dH2O and heats it slightly with stirring to Benzene Allylbenzene \par dissolve the salt. Next, 110g of catechol or 125g guaiacol is \par added and slightly heated to dissolve. The cvndensaf and addi- Aside of benzene the chemist has a choice in which allyl she can \par tion are attached and the temperature of the reaction flask is use. Allyl alcohol, allyl bromide or allyl chloride can be used with

\par brought to 70\'b0C in an oil bath. 2409 (160mL) Ghldrdfdfm is Sl\'a4wlv equal success but allyl alcohol is a nice bonus because it is easier \par - 242 - - 243 \par \par to make than the other two. All three of these are really cheap to "educmg 8 $\'b0tUtt0n _0f CuS04 with Zinc dust). The solution is \par purchase but Slnke le oolno lo lell how all lhree are made ln the slowly heatled to a mild boil for 10 hours with the temperature kept \par chemloale Saollon below 125 C. Some ring scission will have occurred so that phe\par nolic compounds are mixed with the tar, safrole and unreacted \par Everything needs to be anhydrous and the procedure begins by b?"Z\'b0d'\'b0X\'b0te\'b7 Tneee l\'a4hen0|$ are removed by shaking the mix \par ohllllno 500g loenzana and Boo allyl aloohol to 0\'a4C ln a $ln_ vlnth 5% NaOH solution, extracting with ether and fractionally dis\par ole_neol< flash 90o ol nowdalad anhydrous Alcla ls addod which tilling under vacuum to give unreacted 1,3\emdash benzodioxoIe and Sa\par will cause a violent reaction and heat. A condenser is immedi- fidte (Y\'a4etd=3O%) \par ately attached with a tube leading to a water trap and the solution _ \par is allowed to come back down to room temperature. The reaction Them '$ \'b0ne ether benzene t0 allylbanzene method that you \par stirs for 6 more hours at room temperature, poured into ice cold enddtd take a [00k at. Osmium sent in the article in whigh that \par dilute HC! solution and the benzene layer separated. When the n'!a9!\'b0et_\'a4|eY and ether similar Catalyst add the allyl to aryl in rec\par benzene layer is distilled the first things to come over are perfectly ord taenldrt- To read more check out ref #143, \par reusable unreacted allyl alcohol and benzene and finally will come \par the high boiling allylbenzene. ISOSAFROLE FROM PIPERONAL \par There are a great many aspects to the Friedel-Crafts method that [26]\emdash This will work just as well in converting benzaldehyde to pro\par Strike does not have the space to go into. Friedel-Crafts works penylbenzene as it will in converting piperonal. This is like the \par better if chloro or bromobenzene and their X counterparts are millionth method Strike has pulled from the reference 19. This

\par used in place of plain old benzene. Also, there is a significant was the most streetapplicable article Strike has ever come \par amount of unwanted byproducts and molecular rearrangements across, but the greatest thing about this article's recipes is that \par that accompany this sort of reaction. Strike strongly suggests that THEY WORK! Strike means to say they work big time! A lot of \par people read more about this method before they attempt any such this has to do, no doubt, with the fact that the most accomplished \par reaction. almphetamine chemists co-authored the work; Drs. Shulgin and \par ichols. \par 1 3-BENZOD X LE \par SAFROLE FROM , I0 0 /\\ O /\\ O \par /` \'a4 P0 0 \'a4 \par O O \emdash > \par \emdash\'bb ci\emdash lo / \par \\ Piperonal Isosafrole \par 1 ,3-Benzodioxole Safrole \par This method is merely an application of the Grignard reaction but \par [141, 142]--This is similar to the Friedel-Crafts method but is less is a lot less troublesome because it uses really common chemi\par harsh and has been proven successful at producing safrole. ln a cals. This method can be done as it was done in the reference \par very small flask is added 7.2g of allyl chloride, 34.3g wherea phenylbutene was made using abromopropane ( bromo\par 1,3\emdash benzodioxole and 0.15g powdered Cu (which can be made by propane and bromoethane are cheap to purchase or can be made \par - 244 - - 245 \par \par from propanol or ethanol). These phenylbutenes will produce a \par perfectly respectable amphetamine that make an excellent sub- CRYSTALLIZATION \par stitute for X, but for confusion's sake Strike`is going to describe \par the isosafrole synthesis as well.

\par The apparatus to use is the same as . fig.15. 52g of Allolthe recipes in this book give ecstasy freebase oil as the final \par 1-bromopropane for the phenylbutene or 46g bromoethane for pmduet A|m\'b0egh.te'e een be esee as 'e\'b7 't 'S much mma Prem" \par isosafmle or pmpenylbenzene is placed in the scparatory f,_,m6|_ ablelto crystallize it into a distributable, usable form. To do this \par ln the flask is stirring a solution of 14g Mg turnings and 50mL an- me 'S gemg te place a_hVd'\'b0\'b0h'\'b0"'d\'80 (HQ')_\'b0"'t\'b0 the NH2 QVOUP 0* \par hydrous ether and the bromine compound is dripped into the flask lla MDA (Or empheiemme) m\'b0le\'b0U|e\lquote Tale 'S easy t\'b0 ee and dees \par over a 20 minute period of time then the solution stirred for an ex- not affect the drug In any Way' In fact- 'T me Wale t\'b0 l\'b0\'b0k at the \par tra 10 minutes Next, 3 Solution of 509 pipemnal (0,, 359 benzah active ingredients label on almost any plll bottle in the pharmacy \par dehyde) and 200mL anhydrous ether is placed in the separatory me can eee, that the drug there"` 'S referred te as 'Whab \par funnel and added drop wise to the Grignard reagent over 30 min- SYer`dmg\lquote HCI\lquote The drug eempamee eryetamze the"` freebaeas \par utes time. The reaction mix is then refluxed for 8 hours, hydro- wth HCI and so ""'" the undetgmund \'b0h\'80""iSt\'b7 \par lyzed by the addition of 75 mL ice cold saturated ammonium _ _ _ _ \par chloride solution and vacuum filtered to remove the crud. The T0 e\'b0 we- \'b0"e 'S g\'b0'\ldblquote g to ganerate 8 d"Y HCl 935 bY *15***9 the \par etherial nitrate is washed with ice cold 1.5N HCl solution, dried Setup In figure 17\lquote | _" ~ \par through NazSO., and the ether removed by distillation to afford a the rea\'b0t'\'b0\ldblquote flask 'S \lquote \par residue of 62g of crude alcohol intermediate (almost 96% yield!). placed _ abeut 1009 \'bb \par n0n\'b7iodized table salt \par The alcohol intermediate happens to be the exact kind of interme- (Nag) and 20OmL \par diate that was produced by the Grignard reagent reaction with S"a'ght`Ir\'b0m`the`b\'b0Yt| \par propanal to produce isosafrole back-a-ways in the big chapter. So 8 aO'3aA\'b0 HCl_(a9a'"\'bb *`:;_ QT; \par what the chemist does is apply the 1g of KHSO., to that crude al- Smke 'S strassmg that . a \lquote (

\par cohol intermediate and process itjust as was done before to give that $202/gal peel V `\'b7 . I \par isosafrole ,or propenylbenzene or 3,4-methylenedioxyphenyl claaner aah HCI stuff \lquote \lquote \par -1-butene or phenylbutene (yield=91%l). This is a great little pro- wmks greet!\} These l *\lquote ,. \'a4 \lquote . , .... \par Cedum amounts do not have V \'b7\lquote ~:_ 5 \'bb= Q\par to be exact. All the i \par chemist is doing is \par using enough salt to \par bind the water from \par the HCI solution. In \par the separatory funnel . \par ls placed an arbitrary [Figure 17] \par amount of concen\par trated (96-98%) HZSO., (let's say 100mLs). The l-lCl/salt mix \par d0esn't need to be stirred but a little swirling at the beginning, to \par - 246 - - 247 \par \par mix the salt and acid, and occasionally during the addition is pref- There is a very important point to stress about the above pmcE_ \par erable. dure. Strike listed ether, DCM and ethanol as crystallization sol\par _ _ _ _ vents. But the one chemists should use is DCM. That\rquote s \par ln a plastic container the chemist dissolves her golden yellow right...DCM! Strike is telling all of you right now th M is an \par freebase oil into some DCM, ether or ethanol. The chemist then absolutely superior solvent for crystallization. ln fact it is so good \par starts a steady dripping of the sulfuric acid into the HCI/salt and that one need not purify the freebases acquired from the Ends gf \par white, puffy HCI gas will start to exit the glass rod or pipette which half of the recipes in this book. \par is at the end of the hose. That tip is then plunged into the sol\'b7\'bb\'bb\emdash -\emdash

\par vent/freebase solution to bubble the gas through the solvent. Most of the final product producing recipes in this book will provide \par for the chemist to take up the final free base product in DCM. \par There's afew things to note about what happens next. If the free- Usually the freebase oil in the DCM is dark. Used to be that \par base that the chemist has is not 100% pure (which it usually isn\lquote t) SomeoneWho\emdash ls-Not-Strike (SWINS) would have to distill the \par then there is going to be a little pre-crystallization crap that will freebase to get clear yellow oil before crystallizing because when \par crystallize first. This stuff is usually orange or pink and has a SWINS used ether or ethanol as a crystallization solvent, the col\par crumbly, nugget-like appearance. If this stuff is going to come out ored crap would contaminate the final product. But not with DCM. \par it will usually occur after about 30 seconds or so of steady bub- Even with the grungiest (well...not too grungy) freebase, the crys\par bling. When the chemist sees this she stops the bubbling and tals that come out are pure snow. The DCM so strongly solvates \par vacuum filters this stuff from the solution. Every time the chemist the contaminants that none remain in the mass of crystalled final \par vacuum filters during crystallization she must always wash the fil- product. The filter cake is sooooo clean even in the darkest sol\par ter cake with a little extra solvent. Before she discards the filter vent! \par with the crap in it she washes it with a little extra ether because \par there will always be some valuable freebase oil coating the filter . The other amazing thing about DCM is that the crystals produced \par And no, that colored crap is not 'dirty X', lf one were to try it they in it are weird. Crystals produced by ether are little and powder\par would end up getting sick. puffy. Nothing wrong with that per se. But the crystals produced in \par DCM are large, crystalline and sparkly. And although there \par After the crap is removed, the bubbling is resumed and in about shouIdn't be a difference, SWINS swears the effects are more \par 30-60 seconds white, wispy crystals will start spewing from the tip powerful. \par of the pipette. Crystals will start forming everywhere and, if \par enough freebase is present, the whole solution will become a thick There are some alternatives to this HCI generator type of crystalli-

\par sludge of beautiful, white MDA.HCI crystals. lt is the most satis- zation. There are, of course, canisters of HCI gas that can be \par fying sight to behold. These crystals are removed by filtration, purchased. Also, one can crystallize with very concentrated \par washed with a little solvent and spread out to dry on a plate be- (fuming) HCI by pouring the stuff directly into the ether/freebase \par neath a warming lamp. The remaining solvent still has more free- [26]. Regular 35% HCI can do this too, but the water content may \par base and it will be bubbled as many times as necessary to dissolve the MDA.HCI or make the crystals sticky which means \par crystallize all of it out. At the end of the run, sadly, no more white that the chemist will have to dry the solution by removing the wa\par X will appear but there will be another small fomlation of colored ter. \par crap. This is also discarded. \par One idea that Strike thinks is handy would be to set up the HCI \par \'b7 generator and bubble as much HCI as possible into as much sol\par - 248 - - 249 \par \par vent as can be spared by the chemist. What the chemist now has -butyrolactone, dopamine neurotoxic lesion compounds such as \par is a reagent of super-saturated HCI/solvent. This solvent can be 6\'b7l`\'a4ydF\'a4XYd\'a4P3ml\'a4B, drugs enhancing GABA function such as \par stored indefinitely and be brought out for use when it's time to Chlormethiazole and Pentobarbitone, and excitatory amino acid \par crystallize. All the chemist has to do is dissolve her freebase in as antagonists such as Dizocilpine and Dextromethorpan. Let Strike \par little solvent as possible, then pour in some HCI/solvent reagent. tell you this: if you had a buzz you would not have it very long if \par All of the freebase will instantly go poofl into crystals. All this you were given any one of these drugs. \par means that the chemist won't have to keep setting up the genera\par tor apparatus all the time. \par ANTIDOTE \par With all that X lying around someone could conceivably OD on the

\par stuff (an average dose is 100mg). This has never been reported \par to haveihappened in more than 40 years of medical documenta\par tion. Strike knows because Strike researched this fact very thor\par oughly. About the closest the government forensic scientists \par come to attributing a death to X is by stretching the facts of a case \par so irresponsibly that it can be at times quite amusing. Usually, the \par title of a medical case reads something like "A reported case of \par death attributed to the drug ecstasy". But if one reads the case \par report it is always about how the subject had been mainlining \par speed for a week or had seventeen existing mental and physical \par abnormalities prior to taking the X. Such people are ripe for an \par adverse reaction. Attrlbuting such deaths to X is about the only \par way scientists or doctors can further whatever agenda they are \par being paid to further. \par lt is almost impossible to OD on X. A lethal dose is 70 hits for \par God\lquote s sake! Because of this, and the fact that there is rarely an \par adverse reaction to a normal dose, hospital personnel are not go\par ing to be very familiar with the proper treatment. S0, if such a \par thing occurs it should be related to the doctor what drug it is and \par how it is treated [155]. The most immediate concem for any am\par phetamine overdose is fatality caused by hyperthermia (body gets \par toc hot, bubba!). MDA and MDMA have a wide range of effects \par on the human body, but any of the following drugs, alone or in \par combination, will help: 5-HT uptake inhibitors such as Fluoxetine \par and Citalopram, 5-HT antagonists such as Ritanserin and Me\par thiothepin, dopamine antagonists such as Haloperidol and \par - 250 - - 251 \par \par CHEMICALS middle neck of the flask, a stopper in one of the side necks and in

\par the final neck attaches a simple distillation setup. 300g of sulfuric \par i acid is then dripped from the separatory funnel into the warm so\par - Iution. The heat of the reaction alone will allow for the distillation \par ofthe allyl bromide as it is formed during the addition. This should \par ALLYL ALCOHOL take no more than 30 minutes. The crude allyl bromide that is \par . . . . . collected is washed with dilute sodium carbonate solution, dried \par [37 F"t59\'b7 tee p\lquote t2]\ldblquote Tt't'e dlidliilddl ld "_\'b0t \'b0"ty useful t". F"e' through Na2SO. and simple distilled to give product which boils at \par del-Crafts reactions but IS the major stepping stone for making al- 69_72\'a4C (yi\'80| d=92_96,V) All I Chloride is mad i HCI . t d \par lyl bromide which has wide uses. The set up to use is a simple of HB', \'b0 ' y E Us ng me dd \par distillation apparatus (no vacuum,bubbal) with a tube leading \lquote \par away from the vacuum adapter to a NaOH solution trap. 400g \par glycerol and 175g 88% formic acid are placed in the reaction flask BROMOBENZENE \par and rapidly heated so that it reaches 195\'b0C in about 30-45 min- . _ _ _ _ _ _ \par utes during which time coz and a little distillate will evolve. At this Lertngggg-\rquote t"\rquote ;t\'a7\lquote ;:1f ptegett '" iltgge baihhazd tr'; lt \{S stifled 509 \par time the receiving flask is exchanged with a clean one and heating denser rsaatltacrred a pg; Qrets t? by Wade ? C emtcet)- A GO"' \par is continued until a second wave of distillation occurs between the tor is prepared so th; it hasytgicieeemzngingzgitgggtgttgtf 35132; \par - \'b0 . \'b0 ' h d h t' . . . \par ;;t`g\'a3?;a;\ldblquote ;erre\lquote\'80\'a7ig gig fc a;\lquote\'a7rit12_;29CC 1t;5Le:$O; fgwgigdjg\'e9jg (this will allow for the collection of HBr gas that will fom1 during the \par added and the solution heated again to 260\'b0C collecting all the tee\'b0t'\'b0\ldblquote )\'b7 The e'V'"9 tube \lquote\rdblquote 't't \lquote te tteee 'S "et Yet attached t\'b0 the \par distillate that comes over between 195-260\'b0C into the same re- eeneeneen t259 (item") ef liquid btemtne ld poured d\'b0W'-t tnt\'b0 the \par ceiving flask. A third formic acid addition is done to insure that as Qeggenaggitligztotjgtl/rth;\'a7\'b0;t?e"S,?t anttlthe dtytng sub; ld tttt':e' \par much allyl alcohol as possible is obtained. What the chemist has died gown th a t. g , uu ddg ren W Oeeui etgs W fg tt ee

\par collected is neutralized with a little potassium carbonate and the mm/al of the ecaebgtfgrlz itsivvse efwem up \'b0Aft `30 h bv tr? \par dlvl dlddiidl ii didilldd ddllddidd the liddidd diddd lidldli Salla. is titles upto as we \'a7\'a7d\lquote .il.ptll$;'l; is Z; 1.i.\lquote ;\lquote\'80;J.,\lquote i \par 99\'b0C. Wh tth h m\lquote t' `n to ha e now is about 210 of an . . ` \par aquasas sZiuti$a\'b0ti?at EZ %ii\'b7%\'b0L.iiLi aieaiai. This can b\'e9 magaa aa- gg glgpiygggjdhggdggglggqggg gg; 353;;%- Wjggdggdgedgadl \par hd b fl` `t `th t \'b0 b t.d't\lquote ll` d . ' \par ah\'e9illig lh\'e9elliillfn itil aa5i\'b0a2i\'a7l\ldblquote LT b\lquote i\'a7ll\'a72\'a7\lquote 34s\rquote ?dbT\ldblquote evfi."a gggdgoggczgddvgggtdgdrgldS\'b7id% tig; ggggidii bv dlSll"lll\'a4 dial Watet \par the chemist should really do is use the 70% solution directly in the 9 \'b0 E Over a l \par preeueeen ef the mere preferable envi btemiee in the next recipe The reaction solution is washed once with water three times with \par 5% NaOH and once more with water. The benzene layer is dried \par ALLYI" BROMIDE through Na2SO., and distilled with no vacuum collecting the frac\par . . . tion between 150-170\ldblquote C. This fraction is then redistilled and the \par [146 p42]--This stuff IS cheap and legal to buy. However, Strike . . _ Q . \par has a premonition about the future security of this chemical. ln a fteetlen eemmg ever at 154 157 C IS the pure bremebenzet-le` \par three-neck flask is stirred 1000g 48% HBr and 300g 98% (con\par centrated) HZSO4. After a few minutes of stirrlng 385mL of the ETHYL ETHER \par 70.% allyl alcohol made from above or 233g pure allyl alcohol is . . .. . \par added. The chemist now attaches a Separatory funnel imo the Ethyl Ether--this IS a condensed and modified version take from \par - 252 - - 253 \par \par "PracticaI Organic Chemistry" by Vogel (3rd ed., 1966 [37]). A 750g. of crushed ice is placed in a 1.5 litla round-botomted flask \par simple distillation set up is used with a magnetic heating stir plate. and a rapid stream of sulphur dioxide (from a siphon ofthe liqui\par Use of an open flame is absolutely forbidden because of the po- ded gas\} is passed into the desk, care being taken that the outlet

\par tential to ignite and explode any stray ether vapors. The distillation of the gas-delivery tube id below the surface of the bromine layer \par set up is used except that a two holed stopper is placed in the top The rate of flow of the gas is acyusted so that it is completely ad\par opening ot the three-way adapter to accommodate a thermometer sorbed. lt is advisable to cool the Hask in ice and also to shake the \par and a small separatory funnel. the collecting flask is packed in ice contents from time to time. The reduction is complete when the \par and ice cold water is coursing through the condenser. mixture assumes uniform yellowishbrown or yellowish coloun \par \'b7 which is unaffected by further introduction of sulphur dioxide; ex\par With brisk stirring 75mL Everclear (ethanol) is poured into the re- cess ofthe latter gas should be avoided as it will be evolved dur\par action flask then 75mL concentrated sulfuric acid is slowly added ing the subsequent distillation The flask is then connected with a \par until incorporated. The rest of the distillation apparatus is con- short stilll head and condensen and the mixture is distilled. The \par nected and the solution slowly heated to about 140\'b0C. Next, main product will pass over at 125-126\'b0 / 760mm., but the tem\par 150mL Everclear is dripped in slowly so as to match the approxi- perature may rise to 130\'b0; the distillation is then stopped. The \par mate distillation output that one can see condensing over into the residue is sulphuric acid. The distillate is redistil/ed from a little \par collection flask. The temperature must remain between barium bromide in order to remove traces of sulphuric acioi and \par 140-\lquote I50\'b0C. After all the ethanol has been added (which should the fraction, b.p. 125-126\'b0--constant boiling point hydrobromic acid \par have taken approximately 90 min) the distillate that has collected containing 48 per cent. HBr-- collected. The yield is about 1150g. \par is washed with 5% NaOH solution then with water (remember that or 90 per cent. of the theoretical. \par the ether will form the top layer here). The ether can then be dried \par through sodium sulfate and used or can be distilled to purify. Br; + SO2 + 2H2O = HZSO4 +2HBr \par Fuwlruc Nmzic Acro Potassium \par bromide (240g.) is dissoleved in water (400ml.) in a litre Hask, and

\par This stuff is way too expensive to buy especially since it can be the latter is cooled in ice or in a bath of cold water Concentrated \par made so easily. 500mL regular nitric acid (HNO2) and 500mL sulphuric acid (180ml.) is then slowly added. Care must be taken \par concentrated HZSO4 are mixed together in a flask and distilled with that the temperature does not rise above 75\'b0 otherwise a little \par no vacuum. A reddish haze will appear over the reaction liquid bromine may be formed. The solution is cooled to room tempera\par which will distill over to give an orangy-red fuming nitric acid dis- ture and the potassium bisulphate, which has separated is re\par tillate. This stuff needs to be stored in the dark. moved by filtration through a hardened hlter paper in a Buchner \par funnel or through a sintered glass funnel. The Hltrate is distilled \par from a litre distilling flask, and the fraction b.p 124-127\'b0 is col\par 48% aq. HYDROBROMIC ACID lecteot this contains traces of sulphate. Pure constant boiling point \par hydrobromic acid is obtained by redisti/lation from a little barium \par Recipes for making HBr (from Vogel's "Practical Organic Chemis- bromide. The yield is about 285g. or 85 per cent. of the theoreti\par try"[37]) cal. \par "Hydrobromic acid. Method 1 (from bromine and sulghur dioxide). (1). A 1-litre three necked \par A mixture of 600g. (or 188.5ml.) of bromine, 250ml. of water and Hask is charged with 27g. of flowers of sulphur and 550 ml. of \par - 254 - - 255 \par \par water The flask is equipped with a dropping funnel (with tip below phide (either form a freshly charged Kippis apparatus or from a \par the surface ofthe water), a water sealed mechanical stirrer and an cylinder of the gas) passed in as rapidly as it can be absorbed. \par Allihn reflux condenseli Ground glass joints are preferable, but After several hours the liquid assumes a yellow colour (sometimes \par used rubber stoppers are genera/ly satisfactory. The flask is im- it is almost colourless) and most of the sulphur sticks together in \par mersed in a bath of water at 60\'b0, the mixture stirred vigorously the form of a hard lump. The sulpur is removed by it/tration

\par and when the temperature inside the flask is about 50\'b0, 400g. through a funnel plugged with glass wool (or through a sintered \par (125.5ml) of bromine are introduced from the dropping funnel glass funnel), and the filtrate is boiled until the lead acetate paper \par during about 20 minutes. The temperature ofthe reaction mixture test for hydrogen sulphide is negative. The solution is Hltered \par rises rapidly as the reaction proceeds; the flask is cooled mo- again, if necessary. The hydriodic acid is then distilled from a \par mentarily in a bath of cold water if the condensed bromine vapour 500ml. Claisen Hask, and the fraction b.p. 125.5- 126.5\'b0 / 760mm. \par is near the top of the condenson When all the bromine has been is collected. This is the constant boiling point hydriodic acid and \par added, the mixture is heated on a boiling water (bath for 15 min- contains 57% of hydrogen iodide. The yield of the constant boiling \par utes. The reaction product is cooled and filtered from residual ` acid is 785g. or 90% ofthe theoretical. \par sulphur and other solid matter through a sintered glass funnel \par The H/trate is distilled and the constant b.p. hydrobromic acid col- HZS + I2 --> 2Hl + S \par lected at 125-126\'b0 / 760mm. The yield is 805g. \par Note. The hard lum of sul hur rem ` ' 'n ' \par Note. (1) The reaction between bromine and sulphur in the pres- moved by boiling wlih congentratedanitiig acizqinnilfg ;I.SIl'll;;SI2l.I;\par ence of water may be represented by the equation: board. \ldblquote \par 3BrZ + S + H20 = 6HBf + HZSO4 . LITHIUM ALUMINUM HYDRIDE (LIAIH4 , LAH) \par Scifi ?2\'a375\'e9fiZ\'b0\'a5tZ\lquote iZ7\'a7?5Z?$\'a7af'3?$52\rquote\'a3itE,Z"l\'a3Z$.t?! $iQ\'b0\'80\'a3ZZ";$ lgggg-;\'a7g;q;g\'b7gg gg;;,;q;$i 5V;t;gy;;m\'b7=\'a4 \'a4\'a4 \'bb\'a4\'a2bp\'a4\'a4;;\'a4\'a4 ev-~\emdash \par progress. By carrying out the reaction at 50-70\'b0 or above in the tus to use is the one in ny 15 I ihas Img? Eh ke appara` \par presence of a large excess of waten the inhibition observed at 3OmL Et O (Ether) and 23 HH. n 6 .rEa\'b0 Iqn as _'s pIa\'b0\'80d \par Iowertempgratures dogs not Occun _ 2 . g l lum hydride which is stirred for a \par f\'80V;l1I`S|t1LII\'80S.| ln the separatgry funnel is placed a mixture of 71.2g \par . . . . an y rous auminum chlori e (AICI,) and 300mL ether which is

\par ?5%"?i$yFti??f\'80i-%"t\'a4?ii\lquote\'bbii\'bbif-\'80?fiy\rquote t$li"\rquote\'bb\'a5\'bbt$% %\'a21" \rdblquote\rquote\ldblquote\rquote\'b0 2::z:d.2.i2;;;*;:.2*:.:;*;:;; zz::*;\'a4;.tti.:1\'a4;:i.i.\'a4.i.~i:.iits \par . . . _ . . . _ reaction gets out of control. When the reaction has visibly ceased, \par i\'a7\lquote dtiS2L\'80IZ%Sfni\ldblquote $.ZE3i$\rquote\'a5li Z\rquote ;Z?\rquote .\'a7faf,'Z7a?tlZ\rquote 7S ;*~;m==;;;g;$; mgggg igglghiie i>==\'b7;;g\'a4\'a4g\'a4\'b7\'bb$ im we $\'a4\'b7~i\'a4\'a4\'a4 by \par Htted with a stopper carrying an efhcient mechanical stirrer leading filtrate is diszued with ng Z\'e9gume \{att: S\'b0I;'t\'e9\'b0")\'b7th The \'b0Ih,\'80"\'80?I \par almost to the bottom of the flask, and the smaller apperatures re- Sym than the mst of me Em . un I egg I due a "Gma'\ldblquote $ 'S \par spectively with a lead-in tube for hydrogen Suliid\'e9 extending well P3 . th fl h . .\'80" 'S IETOVE un EI Vawum I0 9'VE \par belOw the Sattaaa ofthe liquid and with an exit tube attached to an 8 ms" UB "' E askt at 'S L'A"'*\'b7* (86 Ai)\par Im/Grted funnel just dipping Into 5% sodium hydroxide SOIUIIOII There are a few points to remember about making this catal st \par The mixture IS vigorously St/[Ted and 3 Stream Of hydrogen Sul When scientists were first synthesizing LlAIHi they found th; it \par - 256 - - 257 \par \par was neeessary te nave a tini, piece at i_iAii.i4 aiready in tne reae_ will fomt ln the hot solution as the flask is being heated. No harm \par tion vessel to facilitate the start of the reaction between the LiH hehe; Errher the eeeehd hereh Or \'a4"V$r\'a4l$ r\'a4rm 0\'a4 ih\'e9if \'a4W\'a4 or the \par and AiCie_ If the LiAiH4 was riot present then the AIC': Weuid keep ChemISt,-SHE? l'QmOVtI'\\g E third ofthe liquid, allows ThE flask to CODI \par being added and added until the solution would suddenly burst Whrch "Y'rl readily hr'r\lquote 9 \'b0Ur e $ee\'b0hd \'b0r\'a4P- This Second crop of \par into an uncontrolled reaction. It was determined later that what amm\'a4\'a4*\'a4F\'a4 Chrfmde efvslars is Sepatatad. Saved and the filtrate is \par caused this 'induction' period of no activity was the time it was ehee age'? returned to the rea\'a4h\'a4\'a4 flask to b\'e9 reduced in volume \par taking for the protective coating of lithium hydroxide to dissolve hY d'ehrrah\'b0h\'b7 \par away from the lithium hydride. Apparently all commercial lithium _ _

\par hydrlde has such a coating. Some people found that a drop of The eherhrer may heVe re de \'a4r\lquote e\'b7 Or P0$5lbrY TWQ m9re V0|Um8 \par iodine Weuid negate seen a pnenemenen ent it Was tinaiiy snewn reductions before all of the excess 8mmOHlUmtChlOfldE IS removed \par that if absolutely, 100% dry ether was used then everything went (usually ther ahe mere) N\'b0W\'b7 wher the chehlrerwrrl be l\'a4\'a4r<l\'a49 at \par smoothly. This means that the chemist needs to dry her ether arrer the rear rerh\'b0Ya' \'b0r erhm\'b0r"Um ehr0rld\'80 l$ 8 rrghr Y\'80rr\'a4W. \par tnreugn Na2SO4 and distiii itrbefere use \emdash i-he iast thine te say is slightly viscous solution that ls about 1/3 the volume of the original \par that it is probabiy 3 gccd idea to Order iirhium hydride and aiumi_ fIItI`3tS. The Ch\'80m| St QUT? lZhIS to dlSttlll ONCE ITIOTS. What OHBH \par nurn enieride separateiie happens I'iSX(iI$i that while the chemist goes off to watch T\\/ the \par solution will distill off iust a Ilttle bit of volume and poof! the hot \par ME-i-HYLAMINE solution will become an instant mass of methylamine hydrochlo\par ride. lf this doesn't happen for the chemist then she will just re\par ri44i i45i__Ne ene eheuid be ieuyiria this eiurr beeauee ii ie ex_ duce a little tblt and chill. Either way, what the chemist is going to \par rrerrieiy Watched and exirerrieiy easy ie mai<e_ ire beer ie make have IS a nice mass of methylamine hydrochloride crystals that \par this chemical in large batches. ln the reaction flask of a simple She aaparalaa bv Vawum hllrah\'b0h\'b7 \par distillation apparatus is placed 2000g of 40% formaldehyde and _ _ \par 1000g of ammonium chloride. The mixture is slowly heated to Tha Way lha Chamlal khpws lhal aha has rherhYlah\ldblquote ha aha h\'b0r \par l04\'b0c during which time all ofthe ammonium chloride will dissolve e'\ldblquote '\ldblquote\'b0r"\ldblquote "\lquote \'b0h'\'b0r\lquote\'b0'e_\lquote $ rher She \'b0\'b0"'PereS rhe '\'b0\'b0*< \'b0r rhe rw? rvpes \par and the solution will be a bright, clear golden color. Lots of er cryalala hmhaahlhm \'b0h'\'b0r'ae pryalalarhalcprhe rrprhrhle rea\'b0' \par eparkiy CO2 bubeiee Wiii be eveived and as the seiutien ap_ tion are white, tiny and fuzzy. _The methylamine hydrochloride \par proaches 100\'b0C a steady run of distillate will commence. After 4-5 crystals ara lahgah hhara aryeralhhe rh riaturs aha are a r\'b0r_ rh\'b0re \par hours of maintaining the temperature at 104\'b0C nothing more will sparkly The Chemlsl laavas .lha .mallh/lamlha Clyslals lh tha

\par distill over and the heating is stopped. If the solution is allowed to ahehher hlhhal pr tha Vacuum hhrahph apparatus aha rah\'b7'rhS_rha \par hear ever .ie4_ie5oC ineri there Wiii be preduei ieee filtrate to the dlstlllatlon set up so it ean be reduced one last time \par to afford a second crop. The combined methylamine hydrochlo\par As the solution cools a bi old mass of unreacted ammonium chlo- hda rlrrer Cake is Waahad with a llllla \'a4*~*\'a4r\'a4*\'a4mv\'b7 scraped lhla a \par ride will form. The chemast removes this by vacuum filtration and paakal pl h\'b0l.alhah\'b0l and \'b0hlllad\lquote Thamalhylamlha hydrachlahda \par eaves the eryataie ter reuse ai arieiner iin.ie_ The eeiden eeiereri that recrystalllzes lh the cold ethanol is vacuum filtered to afford \par filtrate is placed back in the flask and distilled (with vacuum now!) \'b0laah\'b7 happy prpaual (y'ala=50 A\lquote )\'b7 \par to reduce its volume by about a third. Temperature is not so much _ _ _ _ , _ \par a problem now as the chemist will let the stufr distill over at what- There ri "\'b0 Way the Se\'b0r,[\'b0\ldblquote \lquote\rdblquote\'b0\ldblquote r\lquote * Pa $\rquote\'b0'T\lquote l\'b0rere \lquote\rdblquote l*h\'b0r'r Ereuse \par ever temperature is necessary. Sometimes the reducing solution claaala Marhylamlha \'b7 ll Was. Slhka S r'r$"e"er lhlladucllah la \par is so concentrated that the remaining ammonium chloride crystals lhla paraah S Wark aha rr la ahh Slhka a ra"\'b0r're\'a5 \par - 253 - - 259 \par \par ing amine will not require purihcation, though, so it will be left up to \par \ldblquote Synthesis of Methylamine/Methylamine HCI via Hofmann Re- YOU Wh\'801h9i'OVhOHO P6\lquote ff0fl'\'a4 UYOS9 $T\'80\lquote P$\par arrangement \par To make methylamine we start with Acetamide. The general un\par There are two approaches to producing an amine from an amide balanced reaction process is mus; J \par using the Hofmann rearrangement reaction. One way is to react \par the primary amide with an alkaline-halide solution (eg - Sodium \par Hydroxide and Bromine). The other method is to use an alkaline- CHJCONHZ + Ca(OC/)z \'b7--- > (CH3CONCI)2Ca++ + /-/20 \par hypohalite solution (eg - Sodium Hydroxide and Calcium Hypo-

\par chlorite). The astute observer will notice that there is *no* chemi\par cal difference in the two processes. One produces the Hypohalite theft \par in situ, the other uses the Hypohalite itself Substitution of various \par halogens/ halides/ hypohalites/ hydroxides is acceptable, but l feel \par l have picked the best combination of maximal yield and ease of (CH:+CONC1)2C6 ++ + NaOH \'b7\'b7\'b7\'b7 > CHJVHZ + NaZCO3 \par availability. Feel free to prove me wrong ;-). Also, at least one text \par specihes that Sodium Hypochlorite produces much higher yields * \par than Sodium Hypobromite. This delicious vindication is expected CAU1-1ON* M\'80? hY\rquote 8mi\'a45\lquote is a poisonous, noxious innammab/Q \par since Chlorine is a more reactive halogen than Bromine. Now, we 988- H h?$ 5 $tl'\'a4n9 ammonia/rotting fish-like odor lt's npr as bad \par are going to USG Caicium Hypochioiiiey ii., the form Oi pcwdemd as Chlorine gas, though, which can be produced if one is careless \par pool shock, because concentrated Sodium Hypochlorite is a rare, '\rdblquote the h\'80\lquote 9'hh1h91 \par unstable creature indeed. Our yield will not suffer in the slightest \par because of this. \par One reference to keep in mind ( Thanks to J.W Smith for sending \par this one) concerns the Hrst step of the reaction. \par The main example presented will be the alkaline-hypohalite \par method as it is the easiest to acquire the necessary chemicals. lt _ \par is of interest to note that the alkaline-halide method is much easier Whlfmore and -1-h\'b0" pat J\'b7 Of the Amer Chemical S00i6\lquote !`JA V0! 63, \par to perform, process- wise, in that it is more forgiving of sloppy Ap"' 19\lquote 11\'b7 91118 \par technique. \par "lt was necessary to allow several hours for the formation ofthe N\par The general theory behind the process is that the hypohalite will chlchqamfde />ef\'a4r\'a4 h\'e9ahhg tv degradation temperature. l/Wth this \par convert me amide io 3 haioamide This then Spcriianecusiy rnodigcation was possible to prepare methylamine...consistently \par changes to the isocyanate when heated and decomposes to the \rdblquote " 78%* -V\rquote\'80`1d-

\par amine from the water present. ln effect, all that happens is that a \par Carbonyl (CO) group is stripped off the starting amide to yield the _ _ _ \par corresponding amine. Yields pre- purification are around 80%, I" mY \'80XpB\rquote 1Q"c\'80\'b7 1h'$ '\'a7` 6 *1VU\'80"' Sfaf\'e9fn\'e9nt. Please ramemberto \par post-puritication average around 65%. Certain uses of the result- kgep the reactahts We`11 'ced though- NOVM tv b\'80\lquote Qiflf \par - 260 - - 261 \par \par ln a large mixing bowl which can contain a smaller stainless steel \par mixing bowl prepare an ice bath with water and salt to bring the After the bowl has been sitting in the ice bath for a few minutes \par temperature down to -1 OC or so. Setup your glassware for simple add the Acetamide solution. Stir well until the solution has cooled \par distillation with magnetic stirring beforehand because certain steps to -1 OC. Now, *slow/y* add the Hypochlorite solution to the mixin \par need to be performed quickly. Use a vacuum adapter to connect bowl in bursts of no more than a couple mL while stirring vi og \par to the receiver flask, and attach some rubber or polypropylene ously. lf you do this perfectly there will be no lizzing or bubbling at \par tubing to the vaccum nipple to connect to a bubbler setup (a fun- all. This depends on how cold you keep the mixture and how \par nel inverted in a beaken or a plastic aquarium aerator tube). The slowly you add the pool shock! Realistically, the considerable heat \par distillrng Hask should be sitting rn a stainless steel bowl with noth- evolution of the reaction will make adding the last few ml. a trying \par ing in it (you will add pre-heated oil to the bowl). K risk! Keep ai'! additional 50g of icelon hand to throw directly into \par *NOTE* ln order to make this as painless as possible, please ob- Se\'e9yrgg ;Ii;;jidn\'a7g$; $i?sQy\lquote Th? S\'b0\rquote "t'?" may 6"\'b0"\rquote\'80 Cht\'b0'ih\'80 988 \par serve the following recommendations: 1) Keep the mixing bowl Outside) Keep Siimh Utggei gm this step wide" a fume hood QF \par temperature as close to OC or less as possible; 2) Keep the Hypo- Coioriese ic ii hi rein L, il it aj ga rgad down hm! wm\'e9d aiurhld \par chlorite solution as it is being added as close to OC or less as pos- and making Sgre gmt ii n 6 S'i \'b0r h\'b0"rSi S[\rquote\rdblquote\rquote "g Occaslohally

\par sible; 3) After half the Hypochlorite solution has been added, place EVN ga S Warmer than 5C\'b7 \par a plastic bag with 50-100g ice/salt/water mix into the bowl to help \par keep temperatures low (use this instead of directly adding ice to . . _ _ _ \par ,,,8 ,,,,G,.mS, which adds E. Ccns iderable volume of Ware making \'80,f\'a7,\'80\rquote ;\'a7\}$,,i\rquote ,,,"\'b0\'a5,$; \rquote i,,7i,\rquote ;,;\lquote , $";i,"\'80,\'a7,\'b0F""'" \'a7i\rquote ;"\'b0""\rquote 9 \ldblquote\rquote\ldblquote "\'b0" rum \par the process less volumetrically efhcient); 4) Purchase an 8lb bag White rhaiis b i i \'b0u "ttm\'e9 'E Gly fume Chalk!/I Jmlk \par Once ahead Of time! . ecause a o of Sodium Carbonate just got gener\par ated. Yori no loiiiger need be concemed over it's temperature, so \par you can eave e solution in this state overnight if perhaps the \par Next you Wm prepare ihm\'e9 solutions- gpozggihave passed by too quickly and you've suddenly realized it's \par 1 Og of Acetamide in 20ml. of distilled water. 16.4g of Calcium Hy\par pochlorite (Pool shock) in 50mL of hot distilled water 24g of So\par dium Hydrexide (we) ih 4Omi_ ei eeid disiiiied Weier Fireheiaii a water batii ori the stove (or wherever) to about BOC and \par p ace e s ain ess s ee mixing bowl in it. Once the temperature of \par the solution hits about 65C, take the bowl out and set aside while \par i-his iesi seiurieh sheuid be prepared siewiy es ii is quiie eXeiher_ stirring all the while. This r's where it rearranges, and the reaction \par mie Sei eii three eeide ir, e freezer New prepere the mixing eppe_ rs exothermr'c enough to sustain it's temperature nicely. lf you find \par ratus which will be a stainless steel "mixing bowl" suspended in tha i\'80mP6Fatl/F6 Gllmblhg past 80C, immerse the bowl into some \par the ice/salt bath made earlier We use a stainless steel bowl here Cold water h'\{6i7V\'b7 A_ft6F about 75 minutes the temperature will sion \par so that heat transfer will be maximal, while preventing any corro- th ffatir at Which Point you Should transfer the whole mess to the \par sive interaction. A glass bowl will not be sufncient for larger scale dlshlhhg flask- Before you Continue you need to choose whether \par preparations as it will not conduct heat fast enough to prevent the YOU want \{0 make the hydrochloride Salt or the aqueous solution or \par reactants from going over 10C (at which point the Haloamide will M\'e9thylamlne, though.

\par decompose and you'll have to start over). Take the Sodium Hy\par droxide solution out of the freezer once it is cool, but not cold. \par - 262 - - 263 \par \par Heat the flask using an oil bath to 1 OOC after adding this solution To clean the white residue off of your glassware, dump some mu\par to effect gentle boiling which will drive Ioff the Methylamine as a rietic acid Straight rrcrn the lug chit, them and Swirl \par gas. In my experience, misbehavlor IS likely to occur at this point. \par One particular problem to watch out for is the sucking back of \par bubbler solution (be it plain water or 6N HCI) into the receiver References: Journal of Chemical Education, v14, pg542 Organic \par flask. I don't know why the pressure in the distilling flask would go Reactions volume 3 Vogels Elementary Practical Organic Chem\par below atmospheric, and therefore cause this to happen, but it has istry, pg574 \par several times with me. Needless to say, this results in a serious \par mess and *botches* the who/e process (I have found a cure for \par this by using an automotive one-way vacuum valve, like a PCV). Methylamine/Methylamine HCI via Schmidt Rearrangement \par Continue heating the flask contents until you have collected This reaction is quite similar to the Hofmann Reanangement, but it \par ercund 1ool-nl_ of distillate in the reeeiyen reacts a Carboxylic Acid with Hydrazoic Acid to generate the de\par sired amine. Like the Hofmann, it has wide application and versa\emdash \par tility, yet also has excellent yields in many cases. It will also \par For the aqueous solution: Place 18mL of cool distilled water into preserve the chirality of the starting Acid/Anhydricle, which is not \par your bubbler setup_ The "expected*, not theoretical, yield cr lvleth. of interest to us, but an important fact to note. The restrictions on \par ylamine from this amount of reactants is 7 grams. [have used a this process are that the starting Carboxylic Acid must not ad\par plastic aquarium aerator tube as the bubbler with excellent results. versely react with either Sulfuric Acid or Hydrazoic Acid. It would

\par Sure heats using an inverted funnel be a crime if I didn\rquote t also mention that the Schmidt Rearrangement \par has much greater application than just making amines from car\par boxylics, but that is well beyond the scope of this FAQ. See Or\par For the HCI salt: Do exactly as above except use 6N Hydrochloric Qallls Rssstlslls V3 for l'll0\rquote s details\par Acid. 6N HCI may be produced by diluting 60.4mL of "Muriatic \par Acid" to 100mL with distilled water. Evaporate the bubbler solution \par to dryness then add 15ml or waten 10mL 10% NaOH soln. and Tc lhckc Mcthylamlhc cl thc hlslcclt Uclhc thc S\'b0h"llld\{ Rccc \par heat gently to e boil with constant nietien until dense white fumes rahcsrhsht vch Start ctt with glacial Acetlc Acid Ych might hc \par appear This will remove the Ammonium Chloride. Remove from sslllllg tc Ysursstf tDsm\rquote ll WW bmhs" Wlth thc Hofmsnnt" slllss \par heat while Stirling as it ccels dcWr,_ pulyerize the dry resrcluel lher, glacial Acetlc Acld IS so easy to get, but, there IS a drawback... \par reflux with absolute Ethanol for several minutes. Filter the retluxed Alld that ls /'lYdfaZ\'b0ls As'd\'b7 Whlsll ls *fl\'b0t* ssslf tc gsi Ac Ws/h \par soln. on a heated Buchner or Hirsch funnel, then distill the alcohol HYd"s\{\'b0l\'b0 Asld ls sXt"smsm\rquote Y P\'b0\rquote s\'b0"\'b0L\{s and Shchlc "'Ot hc ha'Y' \par err the nitrate until crystals just begin to form. A/low the sein. to clad wlthcht c thmc hcctl hhtlcr *chv* clrchmctchccc- Rccllx This \par ceel neturelly fg rccrn temperature\} then Cccl further lr, eh lee is coming from a guy who has no problem dlstllllng Ether solutions \par bath Filter the Solutlon eh e chllled Buchner funnel With Suellerr in his kitchen, so take It seriously. I/Ithy bothen lthenff Welt be\par The yield cf Methylemine Hydrgchfgrfde should be ereuhd 55% er cause you *can* generate the Hydrazoic Acld ln SltU using Sodium \par the tl\'b7,eOretieal_ AZId6 and conc. Sulfuric Acid. I have not personally tried this be\par cause I don't have a powder addition funnel. Anyway Sodium \par Azide is not too hard to come by through chemical supply houses \par and Sulfuric Acid is easy to acquire in the form of Instant Power \par - 264 - - 265 \par

\par Drain Openen This reaction MUST be performed in an area of . . . \par adequate upward ventilation, or at least with the air flowing away ai Preparaiioii Of Hydrazoic Acid \par from you. ` \par compound is EXTREMELY EXPLOSIVE and \par *NOTE* In the initial testing of any undesireable interaction be- Cumstances $,,,5; Z; gg,Q,i;a,\'80g;\'a7a\'a7gig;6D,%Oi:ii,Bi#,ig;:a\rquote ?ui;i6Y,gir_ \par tween Sodium Aziuu Aceiic Acid and Sulfuric Aciui i mixed 5mL 37C). Use latex gloves to handle and dis cse of small quantitigs \par of each into a small cup undemeath my "fume hood". Though I ,,8,,,9 ,),,9,.,,,, 0,,,,,3,6, ,O,,OWBdb ,:,,,,,,6 bagng Soda/,,,,8,6, \par smelled *nothing*, within seconds my head felt like it was ex- y ' \par pending, my heart started racing, and I felt more weak and con\par fused than normal. I just barely escaped and recovered in 15 Prepare a paste out of 65g sodium Azide (1m NaN;) and 65mL of \par minutes, but, Needless to say this procedure is a *tad* on the water in a beaker Add 400mL of either Chloroform or Benzene to \par dangerous side. You have been *warned*. this paste (depending on what you have available, but be consis\par tent later on) and stir well. Dump this mixture into a round bottom \par flask situated in an ice/salt bath, drop in a stirrer magnet, attach a \par Theory behind this reaction is: Claisen adapten addition funnel and thermometer Let this mix\par R-cool-r + NSN; --H2SO4-\emdash > intermediates ---r-r2o---> R-rvr-r, + i""* \'b0\'b0\'b0i i\'b0 OG \par CO2 . \par The intern-l\'e9diat\'e9s in making amines are isocyanates (Q::C::N) Place of cold COI7C8I'ItI'8f6d SUlfUf`iC into the addition fun\par just like the Hofmann Rearrangement. The isocyanates are de- net hut Only alter you make sure the stopcock is turned OFF. Ever \par composed with waten just like the Hofmann. In fact, there is a lot S0 Slowly add the aoid to the flask, dropwise, such that the flask \par of similarity between the Hofmann and the Schmidt reactions. Cnntente Stay around TC, and never go over 5C. This might take a

\par Before I detail the synthesis steps, lshould note that if you wish to Wil'i\'80\'bb be P8tient\'b7 After all is added pour the flask Contents into a \par generate the Hydrazoic Acid in the flask by adding Sodium Azide, Separately tunnel (Ventilation is absolutely required here) and \par you might need a powder addition funnel. This bit of equipment is Separate out the aqueous layer. Your HNe is diSS0lVe\'a4l in the Chlo\par quite pricey and it's likely you won't have one, so the first part of r\'b0tQ"m/Benzene layer if you wish to determine the exaot Conven\par the synthesis details howto make the Hydrazoic Acid separately. tratlfln of the aeid, you may titrate it but the reaction generally \par Z22L\'b0k2i.TlZZ\rquote QZ7,Z,\ldblquote Z\'a3L$i.\'a7"`$\'a7\rquote "\lquote\ldblquote\rquote lt 7t\'b0""\rquote 5\rquote lL"\rquote %\rquote ZS\rquote r,\rquote\'a7\rquote ;"l$\rquote ~"'Srl*\'a7,\lquote l \par W ere O yo . 3 I \par There are three variations on this process you may choose from: tlalre Qnne to the aqueous layen but mostly the resulting Sodium \par Sulfate will crowd it out. The resulting concentration, then, is the \par moles of Hydrazoic Acid over the the total moles of HN3 and your \par 1) Add Hydrazoic Acid to a Carboxylic Acid/Benzene or Chloro- Solvent (Chloroform = 177g/m, Benzene = 78g/m). \par form mixture (O.React. claims this is the preferred method). 2) \par Add Sulfuric Acid to Carboxylic Acid/Hydrazoic Acid/Benzene or \par Chloroform mixture (this is my prefered method). 3) Add Carbox- D) Making the Arnina (All Variations) \par ylic Acid/Hydrazoic Acid/Benzene or Chloroform mixture to Sulfu\par ric Acid or Sulfuric Acid/Benzene or Chlorofonn mixture. \par - 266 - - 267 \par \par Setup your glassware for simple distillation with a claisen adapten or West condenser Heat the m' t \par three Way adapter; pressure-equalized addition funnel, water mana disiiiiaia \'a40lnes oven then Itlulngeugltligiiggiaargdbggliditlhtll no \par eeeied condenser; vacuum adapter and receiver tlask to Catch any action iainparafure at 104C until once again hethih else Ceihre-

\par condensed solvent vapors. over. This should take from 4 to 5 hours. The distillgte may coir`? \par tair\'e9lnterestrng things so check out footnote 1 for details on what \par U U A \'b7 o o with rt. Next, the reaction Hask should be cooled rapidly to \par c) Specincs for Variation 2 room temperature by immersion into Hrst a warm water bath (60C) \par _ swirled, and then an ice bath. Filter the solution on the vacuum \par U U Buchner funnel to recover ~62g of Ammonium Chloride c stals \par Drop your strrrer magnet into the flask and add 250mL of Benzene Concentrate the Nitrate using moderate vacuum and entiy h \par or Chloroform (take your pick), Next add .25 moles glacial Acetic until the volume is reduced to half Filter the motherii uo? Sa \par Acid (15g) then ,5 mo/es Hydrazoi'c Acid with stirring. Warm this again aiiaf G00liHg quickly to yield a second batch Ot Agnm Dime \par solution to about 40C using a water bath. Make sure all joints are Chloride, ~19g_ Omum \par air tight. Add 20mL concentrated Sulfuric Acid very slowly. The \par reaction is mildly exothermic, so take care and watch the tem\par perature. The reaction nnishes withi'n 2 hours. The amine is in the Transfer the nitrate to a ceram' \lquote \lquote \par sulfate salt form. To convert to the hydrochloride salt form, nrst water bath until a crystalline scirsn\'e9igifnziiagrniivgltggi aggtgiliieiii li \par add an equinonnal amount of 10% NaOH solution and stir well, quickly then nlter the mess on the vacuum euenngr to ield ~9ig \par Next, extract the free amine with ether and bubble HCI gas of Methylamrne Hydrochloride. Concentrate the Nitrate oince a ag \par through it to precipitate out the crystals. Filter to recover. to obtain a second crop of crystals, \'b7\'b7\'b718g. Concentrate the Hlgaie \par g\'e9lltrrg time as far js possible using the water bath, then store the \par i a vacuum ` t I \lquote \'b7 \'b7 \'b7 \par lltlethylamine HCI from Formaldehyde and Ammonium Chlo- bottom for 24 hourssiggc? ghlgfotfgrqnrviyghtliaoijelsigul-ejiztggiindtirantgirti \par l'ld\'a2 gble to dissolve out DimethyIami'ne Hydrochloride (distill off the \par Vg\'e9zzollgoxnj tz recorver - good. stufh then nlter on the venerable old

\par This is the least desirable of all three processes [VVi\lquote lat do yan ine Hydmeisoi-E; lirggjhiiio itf\'e9dean azidlilonal ~2Og Of Memylam \par mean by that? This is really easy to do! And the yield ala ana!\} portion of Ch/oroform (~10?nl_) rysta S In me mms] with 6 Small \par The yi'eIds are lower than the two rearrangements, and it requires \lquote \par substantial labor to get a decently pure product. Not '7abor" as in \par difricult but "labor" as in a lot of it. I would suggest this only for \'b7 \'b7 - . . . \par fhO$@ who have 8 Iafg\'e9 supply of Formaldehyde available to them ;(n Orger nOM\'e9' SO transfer all \par (nqtg - Coffey found formaldehyde at Home Del30t \'b7 i00K iai absolute Ethanol (see end of FAQ rorsprgnehgdihslther 5507% Of \par "iylildgwcidg" and dissolve it in enough water t0 make 6 37% $0iU* Butyl Alcohol (see Footnote 4) Heat at regux gth IS) 07 \{ Bags n\par tlorl to depolymerize the paraformaldehyde)- ride guard tube for 30 minutes. A/low the uz/;1is;oEr;tfI:ILsrr;iids],?o \par gcetjtle lSA3rr(rm\bullet ;nium Chloride) then decent the clear solution and \par Place 250g or Ammonium cnroriue and 500g or technical Formal- the ,,gcQ,u,,\rquote ; gufgjif';j;;\'a7";n"jj*"V\rquote af"\rdblquote a HC'- Filter rapidly 0\'a4 \par dghydg \{37%, Formalin). Rig the flask for simple disfi/lati0n Sunil (see Footnote 3) Repeat th grams Sr CO/Sta\}? to 8 d\'e9sslcamr \par that a thermometer extends into the reaction mixture, and a Liebig ' 6 re uX`SEtti9'\'b0\'b0Oi"iii6\rquote Process f\'a4\'a4r \par \'b7 268 \'b7 - 269 \par \par more times if using absolute Ethanol, or two more times if using n- even need to be rec all' ` \lquote \par Butyl Alcohol. The yield of Methylamine HCI Should be 7009. with no side products)hy:lS'l1e gaf\'e9ti\'e9fh\'e9isc\'e9actlon goes to Completion \par Footnote 1 - The byproducts of the nrst Step are Dimeth- CH3COOH + NHZCONHZ ---> CHgCONH2 + 002 + zlvl-la \par oxymethane and Sodium Formate. \par C;\rquote ;\rquote ;'3;p\'80d,y zlgrggiglggt liteps Sh\'b0"\rquote d be Place 125;; Urea and 125g or Acetio Acid in a 500mL round not\par _ tom flask ln preparation for simple retluxlng with magnetic stlrrlng

\par Footnote 3 - According to the original document, centrifuging is and Without cooling Water (or use Cooling water heated to about \par the most satisfactory method of drying products because of their SOC)- Attooh oondensen claisen adapter and place thermometer \par hygrosoopic nature. lsuggest warming in an oven on a glass dish So that the bulb iS around 1cm from the bottom, fully immersed \par then transfering to a vacuum dessicator loaded with either con- Hoot on tho mantle gently to bring the temperature of the mixture \par centrated Sulfuric Acid or Sodium Hydroxide in the bottom. lt is to 750C lh 20 minutes. The mixture Should be refluxing in the con\par not normally necessary to have absolutely dry Methylamine HCI \'80lt=`\rdblquote $\'80V\'bb and PVoh6hl,V Stlbllming in it GS Well un/ess heated "cool\par anyway- lng" weter is used. Push any crystals back down as necessary. \par __ _ _ _ Hold at reflux until the temperature rises to 195-2OOC (approxi\par Footnote 4 - The solublllty of Ammonium Chloride in al-tooltlto mately 1.5 hours) Allow to cool, then rearrange the condenser for \par Ethanol iS 0.69/1009 at _15C. The Solubility in n\'b7BUtVl Alcohol is distilling (its really preferable to use 80C water in the condenser). \par negllble. even at its boiling point. lf you USG t\{\'b7BUtYl Alcohol Vol-! Heat to collect nearly pure Acetamide starting at 2OOC with most \par will only need to perform 3 reflux/nlter operations to obtain SUttl\'b7 coming over from 214-216C. lf the product smells strongly or mice \par oiontlv pure Moth\}/lamino Hydrovhloride. (as in the rodents), then recrystallization from warm methanol is in \par order To recrystallize, take 50g of Acetamide, dissolve in 40mL \par _ _ wann Methanol, add 100mL Ether to crash it out and allow to \par References to this section: Sharp &Solomon, J. Chem. Soc. 1477 Sta,,d_ rr ,-,0 C,yS;a,S have formed after an hour or SO, ggnuy \par (1931) wemen J. Chem. Soc. 850 (7917) Sommelet. Comet. scratch the inside ofthe bearer withaglass rod. lf your product is \par rend. 178, 217 (1924) Hofmann, Ann. 79, 16 (1851) only faintly odorous and is colourless to white, then it is consid\par ered pure. Melting point is 80.5C. \par Synthesis of Acetamide from Acetic Acid and Urea \par Synthesis of Acetamide from Ethyl Acetate and Ammonia

\par Urea is conveniently obtained as a constituent of many fertilizers \par and so it is easily obtained. Sources have indicated that a 50lb \par bag can be purchased for $15 in the US. lt is of less than ideal Ethyl Acetate is allowed to mix with concentrated Ammonia solu\par purity from this source, so some washing will be in order (with tion for several days to make Acetamide. This is a very attractive \par what?). Glacial Acetic Acid is easily obtained from photographic method because all the reagents involved are easy to acquire and \par supply stores in high purity and for cheap as well. This reaction cheap. \par produces Acetamide with such purity that the product does not \par - 270 - - 27] \par \par _ . . which should come over completely at 216C usin the heatin \par ;)Cil;reparatl0n of Ethyl Acetate from Ethanol and QISCIBI Acetic mantle. wgld Should be greater than 249. 9 9 \par oehyolrete atleast 100mL or gram alcohol to yield absolute latheR\'b0\'b0'\ldblquote\'b0"\'b0" \'b0\rquote \rdblquote "\rquote\'b0\rquote "\'b0\rdblquote\rquote\ldblquote "\'b0 \par nol. 74mL (58g) will be required. Add this quantity of Ethanol to a \par round bottom flask with 225g glacial Acetic Aeid ehd 3Q of s0ll\'b7 The lower nitroalkanes (sometimes refered to as nitroparam\lquote ns) \par eentrated Sulfuric Acid. Heat at reflux on an electric heating mah- arg easiiy reduoed by a rnu,,,,i,de Or Sysitamsl but by far the Gas, \par he for 12 hours then attach a Vigreaux or Hempel trestiefletmg est, and also the highest yielding, is the iron/Hydrochlorio aoid \par column to distill off the crude ester at 76-77C. Change recelver Svsrerrr The reaction iS_\'b7 \par Hasks and recover the excess of Acetic Acid, bp 118C. Wash the \par tlrst receiver contents with a half volume of saturated Sodium Bi\par carbonate solution then add 50g of anhydrous Sodium Sulfate (the ,l-ici 4 RNO2 + g i:e + 4 ,.,20 -.. ...,._ > 4 RNH2 4. 3 ,:6304 \par salt of Sulfuric Acid and Sodium Hydroxide, dried in an oven at \par >1OOC for several hours) and distill the pure dry ester once again.

\par Yield should be greater than 70g. First, your Nitromethane *may* require purihcation, especially if it \par was for "fuel" use. ln this case, it needs to be vacuum distilled at a \par _ vacuum of better than 100mm Hg. At that pressure, l't will come off \par b) Reaction of Ethyl Acetate and Ammonia to make Aeetamlde at ~4 7C. Distillation at atmospheric pressure is possible, but l do \par not recommend it due to the highly flammable nature of the com\par _ pound and because it's Hash point is 42C. lt's your choice. \par Add 44g of Ethyl Acetate and 90mL of concentrated Ammonla \par solution (~28%) to a 500mL round bottom flask with a stirrer mag- \par net. P/ug the neck with a thermometer in 3 Ulefmemetef adapter "CAUTlON* \emdash The lower nitroalkanes form shock and/or tempera\par and stir gently for 48 hvufs Of Until the mixture beeemee h\'b0m0Qe\lquote ture sensitive EXPLOSIVE compounds with amines and hydrox\par nous (stop the stirrer occasionally to check). Attach standard dIS\'b7 ideS_ 55 CAREFULI DAiviNm you have been warned \par tillation apparatus but leave off the receiver hask at llrst, \par connecting a short piece of rubber tubing to the receiver adapter \par which is submerged in a beakef of diltlte HC! ( 70\'b72O%\}- Heat ge"' Heat the reaction mixture to 1 OOC and hold for 14 hours. A tem\par tly on a mantle to drive off the exsess ammonia We the beakef- perature regulator is necessary if using a heating mantle, else use \par When no more bubbles come over then attach the receiver flask a iarge boiiing vvarer bath (ir you Wii, be doing ii overnight, so ir \par and commence distilling acetamide from 17OC up, rapldly. Run ooeenlr run our, \par BOC water though the condenser to prevent clogging. Once dIStII\'b7 \par lation slows to a crawl, remove the receiver flask and set aside in \par a hot water bath (80-90C)- Clean UP the glassware used fer the At the end of this time, allow to cool then add enough 25% So\par distillation then use the receiver flask as the distilling flask and a diunl Hydroxid\'e9 Soiuiion to to ger the pi., above 1,_ Hear on a \par Q/ess C0/ltsillef with seFeW\'b7tid TOP as a receiver- RU'? 8OC Water water bath or with gentle electric heat to drive the Methylamine off

\par through the condenser as before, and redistill the AC6t8mId6, as a gas inio ine Same beaker or Hydroeniorie acid used as a rrab \par \lquote during the reaction. \par - 272 - - 273 \par \par S32?Z22?\'b0i$*\'a7e;r$"\'a7\'a7"Z"%\lquote itLi!\'b0\lquote llZ5\rquote ,\rquote ZJ"%" "i"\'b0"2 a"\'b06 RC \par Evaporate the beaker contents tc cltyneaacn a glass plate in the errenee lubricants. One perrrenler brand regneagte\'e9tgeervliggbli \par oven to collect the crystals of Methylamine HCI (hygroscopicl). shop, was 55% ,,jtmm\'80than6_ ' \par The yield should be approximately 15g (95%). \par NOTE: Alternately you may want to try using a Tin/HCI system Johnson & D\lquote\'b0\rquote g"""g\rquote J' Am Chem SOC" V61' 1939\rquote pt)3194`3195 \par which will give an equivalent yield in a much shorter time with the \par disadvantage that Tin is a much more expensive metal. The bal- Hydmiysis of Hexamine \par anced equation for the reduction follows: \par Hexamine, more formally known as Hexamethylenetetramine, is \par 2CH3NO, + 6Sn + 12H+ ---> 2CH,NH2 + 3Sn(lV) + 4HZO easily and conveniently produced from Formaldehyde and Ammo\par nia solutions. Formaldehyde may be easily produced by depolym\par erizing, with heat, Paraformaldehyde (the only ingredient in OTC \par Cognate procedure: Setup a flask with reflux condenser in which MlldewCide). Hexamine is then reacted with Hydrochloric Acid \par .25 mol of nitromethane, .38 mol of granulated tin metal and a stir- end heeted to yield MethYtemtlle t\lquote tCt in near quantitative yield. \par rer magnet have been added. Carefully pour 115mL ,of 31.45% \par hydrochloric acid (muriatic acid) down the reflux condenser in 10\par 15mL increments, waiting for the reaction to settle down before The Petttheht equations are tt7US.' \par pouring the next aliquot. lf the reaction seems to get out of hand \par (excessive frothing, vapor escaping the reflux condenser; etc...) \par then quickly slide an ice bath in place until it slackens back down. 6 t'tCOt't "' 4 NH3 \emdash > t Cst\lquote t1ztV4 + 6 H20 7 CeH12N4 + 4 HCI + 4

\par Once all the HCI has been added, heat the mixture to reflux with H20 \lquote "> 4 Ct't2tVt\lquote ts"t\lquote tCt + 2 CO2 \par an electric mantle for 1hn At the end of this time, allow to cool, \par preferably in an ice bath, then add, carefully a chilled solution of \par 75g sodium hydroxide in 125mL of waten lf the flask contents start ai Preparation of Fehlletdehyde \par to bubble violently you will watch your yield go out the window, so \par add slowly! Since methylamine readily dissolves in wateh you will \par need to distill the reaction contents carefully to tirst liberate the P lace 3 302 Peettete of Mttdeweide into a 1L flask with an electric \par 40% constant boiling eerurien (bp; 53) ene then the gas rreerr The heating mantle and cork in the neck connected tc a gas bubbler \par product is best captured by bubbling the distillation vapor into a immersed th at least 550mt- of distilled Waten Heat the parafor\par beaker of hydrochloric acid (use a slight molar excess of HCI to metdehyde ( what is th the tVtttdeWetde) to between t8O\'b72OOC ta \par insure no loss). Proceed as above by evaporating the bubbler so- temp- tegutetet is absolutely heee$$et\}\rquote ter thte Step 0f USG 8 Sili\par lutlon to yield the crystals (take care when evaporating HCI solu- Cette Ott beth)- The Pe\rquote et0m"letdehYde Wttt depetymettze lhekthg \par tions, as the excess acid will vepenze into ine ain corroding formaldehyde gas in about 91% yield. Alternatively. the gas can \par Ovens, lungs, 9iC___)_ [Vogel;\} pg 892] be bubbled through the Ammonia solution directly (only for the \par bravelll). lf the Formaldehyde solution will not be used immedi\par - 274 - - 275 \par \par ately, 55mL of methanol should be added to it to prevent tloccula- lf h _ _ \par Hon (mpolymsrizationl ai; er gr/ysta\'e9s ire o5a;;i?g5v;hi;; and do not deliquesce quickly in \par o era e uml i o ), hey may be contaminated with \par some Hexamine. Washing 100g of the crude product with 100mL \par D) Preparation OfH6Xamm6 ;>T;\lquote aS;1l\'a2;;7o,1;rn;Sb;;;;gggg\rquote ;n allfeaker the-7 tiltering, Iilaiieated as

\par _ _ l , wi remove examine. e hy amine \par HCI is insoluble in Chloroform whereas Hexamine is at the rate of \par *CAUTION* - Formaldehyde and ammonia solutions are ex- 19 t\'b0 1OmL\'b7 \par tremely poisonous and quite noxious. Perform this step in a well\par ventilated area (outside or with direct exhaust of the fumes)! _ _ \par Synthesis, March 1979, Blazevic, \rquote l'-lexamethylenetetramine, A \par Versatile Reagent in Organic Synthesis'j pp161-176 \ldblquote \par 454mL of 40% Formaldehyde solution (Formalin) or 490mL of \par 37% technical grade solution is *sIowly* poured into a tall beaker NITRQETHANE \par containing 250mL of 28% Ammonia solution. Stir vigorously the \par entire time. The solution will get hot as the reaction occurs, take \par care that the Formaldehyde solution is not added t00 rapid/Y Oth- [148, 149]-Strike c0u| dn\rquote t End any decent nitroethane synths ex\par BFWIS6 lt will b0l/ 0VeF. i cept fo; a gouple of C\'e9hlelmicg Abstract articles. One suggestion is \par o rea . mo es o a2C 2 with 1 mole of sodium ethylsultite \par _ _ A _ _ l and 0.0645 moles of KZCO, at 125-130\'b0C. Another route would \par Allow this mixture to react, with stirring, overnight. be to use silver nitrate and ethyl iodide [8 p119]. This type of re\par actiin has been used to nitrate other paraftins and would probably \par wor , \par Evaporate off the water by heating the beaker in a hot water bath. \par (CAUTION: excess ammonia will be liberated!) \par Luckily for all of you there were a lot of people who contributed \par ' I _ some. very nice protocols for this extremely important chemical. \par The yield of Hexamine should be 140g, white crystals. The first recipe below was sent to Strike unsolicited in the mail by \par someone named Don Antoine ( a very nice person) [150] (Note: \par _ _ Strike was not given a complete citation with the article and so can \par c) Hydrolysis of Hexamine only give a partial reference for this article. Sorry):

\par 140g of Hexamine is carefully dissolved in 400mL of Muriatic Acid "lllltiel Rtlh- \'b7 Into each of Seven Stvppered bottles was placed a \par (31,45% i-ici) Wim vigorous stirring. After all is added, heat on the mixture ef ethyl Sulphate lEt<>SO2-OEU (120 g.) and sodium ni\par water bath. This will drive off the formed Carbon Dioxide and theh \{Ute [N8NOzl S0lUl`l0h (120 Q. ih 760 C.C. of wafen) The bottles \par the excess water. The yield of Methylamine HCI is 270g, colour- Were Sheheh meehehicel/y for 20 hours, the pressure being re\par igss mjus; barely whitg dgiiqnoseohtgrysteiS_ leased at intervals. The contents were then poured into a sepa\par rating funnel, and the upper layer separated, dried over calcium \par chloride and distilled at 14mm., the distillate up to 60\'b0 being col\par ` 276 _ - 277 \par \par lected (the residue, ca 230 g., consisted of ethyl sulphate and was 50***9 0f them) and others like them (which did not include) can bg \par used again). The distillate was fractionated at atmospheric pres- \'a4S\'80d tc t\'80d\'a4\'a4\'80 Species such as nitroethene to nitrgethane Thai \par sure, and the fraction of b.p. 114-116\'b0 collected. This was shaken \'a4\'a4Fi\'a4i\'a4ly Sounds reasonable. New where the hel] can me find ni_ \par with waten dried over calcium chloride, run through charcoal and \'a5l\rquote 09ih9\'a46? \par redistilled ; b.p. 114-115. 5\'b0. Yield, 124 g. (31% or allowing for re\par covered ethyl sulphate, 43. 5%). l \par SODIUM AMALGAM \par Routine Run. - A second experiment was then carried out using \par the same quantities of ethyl sulphate as above. The recovered [37 p194]--This is done in the hood because it has the potential to \par nitrite solution (lower layer) from the lirst run was concentrated by generate poisonous vaporized mercury. In a small flask is placed \par adding approximately 16 g. of sodium nitrite per 160 c.c. of solu- 15.2g of pure sodium metal with no stirbar. Sodium metal is ex\par tion. Yield, 185 g. (46%, or allowing for recovered ethyl sulphate, plosive when put in contact with water. The sodium is immedi\par 65%)." ately covered with about 100ml of toluene and slowly heated on

\par the hotplate. Near a temperature of around 50\'b0C the metal will \par l I I U I melt in the hot toluene and at this point 750g of mercury are \par This next method was included with a submission by Ritter that added drop by drop. The first few drops will cause violent bub\par appeared in the Theoretical section of this book. bling of the toluene but this will diminish as the addition continues. \par Whei1 addition is compiiiete, the chemist decants most of the tolu\par _ _ _ ene eavmg jus enoug to cover the molten catalyst so that it will \par \ldblquote Ethyl bromide 32g, 26.0 ml (.3moD or Ethyl iodide 46g, 24ml not de rade b ex osu e \lquote \lquote \lquote \par (.3moI) is poured into a solution of 250 ml Dimethylsulfoxide ene/angalgam hlix polureg gh; wire choxairxriwhgtghggfisthxisggs \par (DMSO) or N,N Dimethylformamide or N-methylpyrolidone (DMSO to store it in, the rest of the toluene is decanted and the air s ace \par preferred), 36 grams sodium nitrite (thats NBNOZ pyromaniacs, flushed with nitrogen before sealing the container The amagam \par not sodium nitrate) and 52 grams phloroglucinol dihydrate. This the chemist made is one of 2% strength. l \par stuff is expensive but it can be recycled. Stopper all this in a flask \par with a good magnetic stirring bar and stir it in a room temp. water \par bath for 2 hours oruntil an emulsion forms. At this point dump all \par into 600ml ice water and extract w/ two portions of 200ml methyl- SODIUM BOROHYDRIDE (NaBH\lquote ) \par ene chloride. The MeCl2 extracts are washed w/water three times \par than dried W/ anhydrous m6Qt'l6SlUm \'a7Ulf6t6 than QVGPOVGYW 9ff'" [151]--This catalyst should really be purchased rather than made \par a fractional distillation setup, collecting the fraction that boils at because its use in underground Chemisii is limit d d _ h d \par 113-1 16'C at atmospheric pressure as pure nitroethane. Expected Watched at ali if mi ever This ma chanye consiz fn \{S air ly \par yield about 20 grams. That's not a ton of product but this reaction Hai as 3 i, i ih N Y . 9 . , S mg 'S PO S"` \par can be scaled to any size you can dream of and yields will stay in - p ecursor O S aBH\'b0CN m Smkes #1 method Of \par the 80% range _, choice. There are a lot of ways to make this catalyst, but the least

\par \'b7 involved is the one using boron tnfluoride. What the method calls \par for is an apparatus called an autoclave. You know how using a \par The only other thing Strike has to say is that some have hinted vacuum muses the absence \'b0f press"? t\'b0 make mmgs b\'b0" at *3 \par ihai aii of those B_niimpmp\'80nE_ reduction maiiiods (Oi at iaast Iowertemperature'? Well, an autoclave is a device that causes an \par \emdash 278 - - 279 \par \par increase in pressure so that things will get to a higher temperature \par without boiling. Yeeshl This is already starting to sound compli\par cated and, yeah, Strike guesses it kind of is. But there is a little SODIUM CYANOBOROHYDRIDE (NaBl\'b7l\'a4CN) \par price to pay for total independence from government scrutiny. \par [152]--This catalyst has not been given a fair shake in under\par All biology labs and hospitals have autoclaves for sterilizing their Qtound literature and. as ef this be\'a4k's Pnntingi is still l\rquote elatlVely \par equipment sc it the chemist has access to one then all she needs sate te eurehase. A prudent chemist will meet likely steek up en \par to do is place the reactants in a flask, cover the flask with foil and this shemisal besause the eventuality ef mere intense scrutiny is \par blast them in an autoclave for a few hours. This, however, is lneVltable\'b7_ The best Way te make this Ptodnet is te Start with \par probably not feasible so about the best thing Strike can think of for NaBl`l4 Whlch is mush more safe te buy- l'loWeVeT. the way te 90 \par home use would be as follows. Still, Strike is not entirely sure if abeut meltin9 this Catalyst is net Very Safe unless strict adherence \par this apparatus is a conect one, and if the chemist also has some te safety is used. \par doubts then she would probably want to ask a professional re\par search chemist who has used autoclaving as a synthetic tool, \par Strike's idea is to use a pipe bomb with a special fitting so that The '<>yano` Pen ef syanebeiehydflde is 9\'a4ln9 te eeme frem eye\par pressure from e pump can bg jntrgducgd tmp the bOmb_ Most nide of course, and cyanide is lethal. Cyanide has no odor and

\par vacuum pumps are reversible so that they will produce pressure Will kill you instantly it a single whitt ef lt is inhaled. EVeTylhinQ \par as wel] as Veeuum_ HOW much pressure? We", that is Something must be done in a hood and study or investigation ofthe literature \par the chemist is going to have to look up because it was not pro- bevend what is published here is stl\rquote bn9ly Ul'Qed\'b7 Te aedl\'b7lll'e a \par vided, and Strike dces nct want to lcck it up either. lt is suffice to stabilized sedtee ef evanide ene is geing te need te intreeuee hy\par say that one is going to use as much pressure as is necessary to drecen Cyanide (HCN) inte tetTahydl`\'a4fUl'an (THF) s\'a4lVent\'b7 leleally \par bring an ether sptutrprr to 120-130eC without 1rppg1mg_ one would want to use a cannlster of cyanide gas and bubble it \par into the THF but Strike seriously doubts such a thing will be sold \par to a street punk. This is because such an item, in the wrong \par Tag sodium hydride (Nat-it and 100ml. of a 0.05ivi sciuticn of pc- hands- \'a4\'a4\'a4l\'a4l be a ienible tenerist weaeen. The best Way a heme \par rcn trifluoride etherate (0.4g Bi=a in 10omL ether, this usually must chemist Csnld 'sately` dtedtise HCN is by generating it herself. \par be purchased as a commercially made product)is placed in a pipe \par bomb. Pressure is applied and the bomb is placed in a 120-130\'b0 \par cii lcath tcr 2 hours. The ether is removed under vacuum and the Te make a cyanide/T HF selutien ene is geing te have te create \par NaBH4 is isolated by recrystalllzation from water. To do this the HCN frem sedium ol' eetassium cyanide. Te de this one is geino \par chemist adds water to the residue which causes the ltlaBi\emdash l4 to to need te use the apparatus seen in tie. 14. There are geins te \par crystallize out as a dihydrate precipitate. This white precipitate is be seme mlnolf ol"lanQes thoU9h\'b7 The Teaetlon llask is net 9elnQ te \par separated as a filter cake, washed with a little water and the filter be a simple sln9le\'b7neol< flask but. instead. is 90lnQ te be a sin\par cake is vacuum distilled to remove the dihydrate water molecules 9le\lquote neCk With a sldeaTm inlet tube ot a three neck tlaSl< with ene ef \par that are attached the catalyst. This dry NaBH.t is ncw suitable rcr the neeks steepered and the ether ene plugged with a rubber \par use. Although Strike is again ncl sure, Strike thinks it might be steeper that has a wide class tube extending all the way frem the

\par possible to attempt this in e plain old sealed pipe bomb without the etitside ef the flask dewn te the bettem ef the flask. At the ether \par pressure sduttgprr end of the apparatus is the vacuum adapter connected to the re\par - 280 \emdash - 281 \par \par ceiving flask. lf one were to look up into the vacuum adapter one \par will see that it has a little drip tube that extends down its neck bubbling. The solution inthe r a t\lquote fl k h \lquote \'b7 \par where liquids normally drips from into the receiving flask. Right'? ing all this so that the Na(;N Zissggesaiuostggkivggftlrgzgsgg \par Now, what one wants to do is attach an extension of tubing or gas should be evolving at this point. ' \par glass to the end of that drip tube so that it will extend all the way to \par the bottom of the receiving flask. The chemist does this because \par she wants the cyanide to bubble through the THF that she is going To release the i\emdash lcN \'b7 \'b7 - \'b7 . . \par to place in the receiving flask. The receiving flask itself must be concentrated H2SO...g$oOg\'a7 Gotti ti; sgegrssdvigin \par smmg ln 3 an me bath 30niL of HZSO4 through the inlet tube. Each addition aliqulgt will \par cause the bubbling to temporarily stop, which is normal. The pull \par ofthe vacuum will get things going again. After addition the solu\par ln professional laboratories, scientists use things called gas dis- lien is bF\'a4\'a49hi to a boil and kept there for 1 hou,-_ The chemist \par persion tubes at the ends of their \lquote drip tubes'. These kinds of 'drip Cali MW remoye the receiving flask, weigh it and hope that it has \par tubes' are commercially made pieces of glass that have a tip gaiimd aPPi'\'a4Ximete|V 609 in weight. That gain in Weight Wm be \par made out of porous ceramic. When a gas is pulled through the due *0 me absorption of HCN. \par end of a gas disperser it is busted up into a bunch of tiny. fizzy \par bubbles which greatly enhances the absorption of the HCN gas \par into the solvent. What the chemist has is a bubbling tip that is with the HCN solution in hand the B t f \par . . . . , th

\par going to produce big bubbles, This works, but not as efficiently. pretty quickly. 8Gg NaBH3 in 1L THFri; sgrredeafg\'e9zdlalfd Sitges \par The best way a chemist can approximate a phase separator is by the HCN/T HF solution is gradually added Bubblin caused b tlin \par wrapping a bunch of netting or some such shit around the tip. But release of hydrogen will occur (no smokin i) as the solut\lquote o y t` E \par one should simply buy the proper gas dispersion tube from any for 1 hour at 25\'b0C. The solution is then hi-ated at reflux Iuhlti? hg \par glassware maker. more hydrogen can be seen evolving. The solution is then vac\par uum filtered and the filtrate removed of THF by vacuum distillation \par to give NaBH CN QW . Wh l All \lquote \lquote \'b7 \par Tg make the HCN/TH; the chemist isdgoing to h?ve lhs setup as must be storead imignediately sivilhat thg?tig/jeshhnglxgq\'e9mzggseggg\rquote \par described in place, un er the hoo an the vent Fomt e vacuum sure to air and mo'st _ Th' ' \'b7 \par source must be channeled way, way outside (the vacuum is not I we ls Is Especially me for NaBH3CN\lquote \par on at this point mind you). ln the preweighed reoeiving flask is \par placed a 3ODg of THF. ln the reaction flask is placed 113g sodium \par cyanide (NaCN) and 500mL water and the stoppers are immedi\par ately put back in place. The vacuum hose, which is connected to \par the vacuum adapter is going to have a hose clamp on it so that \par vacuum flow can be regulated. With the hose pinched shut by the \par clamp, the vacuum is turned on and the flow is slowly started by \par adjusting the clamp. What the chemist wants to see is a slow \par bubbling coming from the inlet tube in the reaction flask and also \par from the bubbling tube in the receiving flask. The vacuum flow \par should not be any stronger than what is needed to cause this \par - 282 \par - 283 \par \par The following is the current list of DEA List I and List ll chemicals.

\par List I chemicals can only be bought or owned if one has a DEA or REFERENCES \par state permit. List Il chemicals can be purchased in any amount \par below the given threshold. If one requires an amount of List II \par chemical above the threshold amount, then will need the same \par DEA permit for List I chemicals. \par LIST I CHEMICALS 0. [1] CA. 37.3882 (1943) \par [2] CA, 30, 7497 (1936) \par Anthranilic Acid Piperonal Nitroethane [3] CA\'b7 24\'b7 1853 (1930) \par lsosafrole Ephedrine Safrole [4] BGL 42\'b7 P15O5 (1948) \par Phenylpropanolamlne N-Methylephedrine Ethylamlne [5] Salm\'b0lla\'b7 G-V\'b7\'b7 el al. S.VllWl\'b7 Comm. 27. P4335 (1997) \par Benzaldehyde Propionic Anhydride N-pseudoephedrine [t%5\'a7;l&l\rquote lth9l\'b7 E4 "Th\'80 E5$5\'a4fl\'a4| ONS". vol II and IV (New York, \par \lquote E ' MD-P2P \par M\'b0"\ldblquote\rquote lam'"E rg\'b0"\'b0`""E 0 [7] strike, \ldblquote seureee\'b7\'b7 (Panda lnk, sen Antonio, rx, 1998) \par Piperidine N\emdash MethyI-Pfed HI (57 A) _ _ __ _ __ _ \par _ _ _ [8] Buzz, P., Recreational Drugs , (Loompanlcs, Port Townsend, \par Benzyl Cyanide Pseudoephedrlne Phenylacetlc Acid Washlhgtcrh 1989) \par N-ACBtyIB\'a4H\lquote ll'8I\rquote IIIIC Acid EFQOTOITIIIIG [91 CAt 52, 11965 (1958) \par [10] Lukaszewski, T., J. Assoc. Anal. Chem., 61, p951 (1978) \par LIST ll CHEMICALS Thr\'a2$h\'a4ld by V\'a4l- `l'hf\'a4Sh\'a4ld bv Wl- [11] rsuji, .1., et el., "orgehie Synthesis Collective vel vllr\'b7, p137 \par [12] Clement, W.H., etal., J. Org. Chem., 29, p241 (1964) \par Acetic Anhydride 250 gal L023l<9 [13] rsuji, .1., syhiheeie, p:s59 (1984) \par ACBTCHS 50 Qal 15OkQ [14] Dal Cason, T.A., etal., J. Forensic Sci., 29, p1187 (1984) \par Behzvl Chl\'a4rld\'a4 Nlh 1l<9 [15] Clement, w.l~l., etal, J. Am Chem see., 29, p241 (1964) \par Elhvl Ether 50 cal 135\'b78l<9 [16] Lleyu, wc., etal, J. org. Chem., 34, p9949 (1969) \par l\'b7lCl (Gas) N\'a4l vet krwwh [17] lvlimeuh, H., etal, J. org. Chem., 45, psssv (1980) \par |\'a4dil\rdblquote l5 Nm Yet KNOWII [18] 'Fester, U.', "Secrets of Methamphetamine Manufacture, (4th

\par Methyl Ethyl Katohg 50 gal 145kg Ed., Loompanics, Port Townsend, Washington, 1996) \par KMhO4 [WA 55Kg [19] Rogers, H.R., etal., J. Org. Chem., 40, p3577 (1975) \par Toluene 50 gal 159kg [20] King, J.A., etal., J. Am. Chem. Soc., 73, p4911 (1951) \par [21] Cowan, D.M., et al., J. Chem. Soc., p171 (1940) \par ` [22] Johns, E.B., etal., J. Am. Chem. Soc., 60. p919 (1938) \par - 284 - - 285 \par \par [23] cA, 48, 8261, (1954) 150] V9"\ldblquote 9\'b7 R\'b7S\'b7\'b7 919-*) Svnfh Comm. 15, r>843 (1985) \par [24] Mason, J.l=\'b7., etal., J. Am. Chem. see., 62, p1622 (1940) [511V\'a4m1\'a4R\'b7S\'b7\'b7 9* =\'b7'\'b7 6Y\'a41h\'b7 Umm-. 14, r>1093 (1984) \par [25] E1kS1_1_1 913111 J1 Chem Soon p15 (19431 [52] Varma, R.S., et al, Tetrahedron, 46, p7443 (1990) \par [26] Michele, D.E.,et el., J. Med. Chem., 29, p20\'a49 (1986) )\'a7g)1\'a7'\'b0"'"'s- A-- 9* a\lquote\'b7 A9\rdblquote 9W\'b7 Chem l\'a41\'b7 Ed Eng., 28, r>218 \par [27] Braun, U., etal., J. Pharm. Sci., 69, p192 (1980) [511 Mmvic 1V 1 1 J Ch _ \par [28] Shulgin, A.T., snu1g1h,A., \'b7\'b71=\'b71hke1, A chemical Love Story", (1995) \lquote ` " 9 a" \lquote Gm S\'b0\'b0\'b7\'b7 P\'b0'""" T"\rquote "S\'b7 \rquote\'b7 1*65 \par (Transform Press, Berkley, 1995) [551 Gribble GW S1 61 J Chem S Ch \par [29] Groot-vvasslnk, B.H., et al., J. Chem. Edu., 51, p671 (1974) (1975) ' ' " ' ` ' \'b0\'b0" Gm C\'b0mm\'b7\'b7 p535 \par [30] Crossley, F.S., etal., J. Org. Chem., 9, p529 (1944) [56] Abdel-Magid, A.F,, et al, J.Org. Chem., 61, p3849 (1995) \par [31] Novell), A., J. Am. Chem. Soc., 61, p520 (1939) [57] Abdel-Magid, A.F,, el al, Tet. Lett., 31. p5585 (1990) \par [321 CA. 47. 11248 (1953) [58] verme, 12.8., etal, Tetrahedron, 54, pt-2298 (1998) \par [33] Noggle, T.F., et al., J. Assoc. Anal. Chem., 69, p681 (1986) [59] CA_ 651 14349 (1961) \par [84] Hey, DH., J- Chem. S\'a4\'a2-. r>18 (1980) ~ [80] Carter, 1-re., J. 5161. Chem., 108, p619 (1935) \par [35] CA, 37, 621 (1943) [61] Foote, P.A., J. Am. Pharm. Assn., 27, p573 (1938) \par [38] Ghbbie, e.vv., etal., Synthesis, 12, p856 (1977) [62] Lieber, E., etal., J. 0rg. Chem., 22, p238 (1956)

\par [37] Vogel, A.l., "A Textbook of Practical Organic Chemistry", (3rd 63 S 1111 A_S_ 1 [_ _)_ A C \par Ed_ Wiley & Sons, New York. 1966) :641:: Bguer .1 H it gl \rquote J Arr; Czeml goo', \ {2435 (1951) \par [38] Shulgin, A.T., et al., J. Med. Chem., 18, p1201 (1975) y ' ` " ` ' Gm OC" ' p951 (1955) \par _ [65] Levene, P.A., J. Brol. Chem., 115, p415 (1936) \par [39] Rich, P., et al., J. Med. Chem., 17, p11Cl0 (1974) 1661LGv\'8011E PA 11181 J B101 C11 120 59 9 \par [40] Standridge. R. T., etal. J.Med.Chem., 19, p1400 (1976) ' I " ' ' _ ' 9m' \rquote P7 (1 37) \par _ [67] Levene, P.A., et al., J. Blol. Chem., 140, p259 (1941) \par [41] Nichols, D.E., et al, J. Med. Chem., 22, p1264 (1979) _ \par _ [68] Reeves, WP., et al., Synthesis, p823 (1976) \par [42]Shu|g1n, A.T., J. Med. Chem., 11, p186 (1968) 1691P1akash GKS 11181 11 Org Ch 51 3215119861 \par , . . ., ., . . Gm., , p \par 4 CA, 5 ,18271 1958 \par [ 31 2 ( ) [70] Boyer, .1.H., J. Am. Chem. Soc., 73, p5B65 (1951) \par [44] Hassner, A., etal., J. Org. Chem., 34, p2628 (1969) . . \par _ [71] Marti, S.N., etal., Synth. Comm., p1201 (1988) \par [45] Shulgm, A.T., Can. J. Chem., 46, p75 (1968) . . \par _ [72] Malt], S.N., et al., Tetrahedron Lett., 27, p1423 (1986) \par [46] Shu|g1n,A.T., Nature, 201, p1120 (1964) . _ \par _ [73] Stanovnik, B., etal., Synthesis, p419 (1977) \par [47] Shulgin, A.T., J. Med. Chem., 9, p445 (1966) \par _ _ _ _ [74] Bayley, H., et al., Tetrahedron Lett., p3633 (1978) \par [48] Liang, P., "Orgaruc Synthesis Collective Vol. Ill", p803 (1955) [75]Va111t1E11 M 81 al Tetrahed n 1911 24 763 1983 \par . \'b7, \'b7, 70 ., , \par [49] Varma, R.S., et al, Synth. Comm., 14, p1099 (1984) p ( ) \par - 286 - \'b7 287 \'b7 \par

\par [76] Rolla. F., J. Org. Cl1el7l.. 47. D4327 (1982) [103] Perkin, W.H., J. Chem. Soc., 57, p586 (1890) \par [77] Becher, J., el al., Synthesis. D530 (1989) [104] Allies, G.A., J. Am. Chem. Soc., 54, p271 (1932) \par [78] Malik, AA., et al., Synthesis. 9450 (1989) [105] Thomas, c.A.. "Anhydrous Aluminum Chloride in Organic \par [79] Pez, G.P., et al, Pure 8. Appl. Chem., 57, p1917 (1985) Ch9m1910"'. (**9100919. New Y\'a4rl<, 1941) \par [atgsgueetheoek, cri., Agnew. chem. internet. Edit., 8, p134 l199lH\'a4T*\'a41\'a4\'a4\'a4. C.. ei al-. Bere 25. r>3531 (1892) \par (1 ) [107] Hartmann, C., etal., J. Chem Soc., 64, p152 (1893) \par l911 CA. 61. 4294 (19649 [108] rerhhoiz, E., etal., .1. Am. Chem. see., 90, p2402 (1938) \par [82] Ando, T., et al, J. Chem Soc. Chem. Comm., p1301 (1987) [109] CA, 113, 2114692 (1990) \par [83] Kohn, H., etal, J. Am. Chem. Soc., 105, p4106 (1983) [110] CA, 113, 78213p (1990) \par [84] Kohn, H., etal, Tet. Lett., 25, p399 (1984) [111] CA, 110, 23434y (1989) \par [85] Keana, J.F.W., et al, Synth. Comm., 23, p357 (1993) [112] CA, 80, 70534c (1974) \par [86] Varma, R.S., etal, Tet. Lett., 39, p2915 (1998) [113] CA, 74, 76134v (1971) \par [87] Ber, 60, p1050-1069 (1927) [114] CA, 78, 58024n (1973) \par [88] CA, 113, 151836e (1990) [115] CA, 83, 113953v (1975) \par [89] Woodruff, E.H., et al., J. Am. Chem. Soc., 62, p922 (1940) [116] CA, 107, 200894] (1987) \par [90] Coutts, R.T., etal., Can. J. Chem., 51, p1402 (1973) [117] CA, 90, 54658x (1979) . \par [91] Brown, H.C., etal., J. Am. Chem. Soc., 91, p5647 (1969) [118] CA, 42, 2471 (1948) \par [92] Chow, D., etal., Can. J Chem., 43, p312 (1965) [119] CA, 30, 443 (1935) \par [93] Ritter, J.J., etal., J. Am. Chem. Soc., 70, p4045 (1948) [120] Gensler, W.J., et al., J. Org. Chem., 18, p9 (1953) \par [94] Ritter, J.J., etal., J. Am. Chem. Soc., 74, p764 (1952) [121] Campbell, K.N., etal., J. Org. Chem., 16, p1736 (1951) \par [95] Ritter, J.J., "Organic Synthesis Collective Vol. l/", p471 [122] Bonthrone, W., et al., J. Chem Soc., p1202 (1969) \par [96] Hartung, W.H., etal, J. Am. Chem Soc., 51, p2262 (1929) [123] Clark, J.H., et al., J. Am. Chem. Soc., 99, p498 (1977)

\par [97] Ide, W.S., etal, J. Am. Chem. Soc., 70, p1084 (1948) [124] Castillo, J.C., et al., Synthesis, p839 (1986) \par [98] Nichols, D.E., et al, J. Med. Chem., 34, p1662 (1991) [125] Weinstein, B., et al., J. Org. Chem., 41, p875 (1976) \par [991 Hendrickson, JB., et al. J. Org. Chem. 59. 9991311993) [126] Keck, ee., etal., J. Am. Chem. see., 103, p3173 (1981) \par [100] Sakai, T., etal, Tet. Lett., 28, 03817 (1987). [127] Jones, T.G., et al., J. Chem. Soc., 111, p903 (1917) \par E*]1g;]1)Dakin, i~i.D., "Organic Synthesis Collective Vol. I", r\'a4149 [128] CA, 4;-_ 8032 (1953) \par [102] cA, 75, 48687e (1971) [429] C4 44* 835411959) \par _ 288 - [130] Gensler, W.J., etal., J. Org. Chem., 23, [3908 (1957) \par - 289 \par \par [131] Fuegas, C., Bull. Soc. Chem. Fra., p1892 (1964) EP||_QGUE \par [132] CA, 68, 16001 (1964) \par [133] Benkeser, RA., et al., J. Org. Chem., 33, p2203 (1968) \par [134] Backvall, J.E., etal., J. Org. Chem., 56, p2988 (1991) \par [135] CA, 111, 140241q (1999) We|l,_there\rquote s the second edition for ya. Bigger and more comme\par [136] CA, 33, 3777 (1939) h\'80\'a4Si\\/S that`) Ever. Strike thinks the idea of including guggt chem-. \par ten eee. tr. nee. M-. \'b7\'b7A\'b7~ ance \'a4 \'a4r\'a4a\'a4\'a4\'a4 \'a4\'a4\'a4me~\'b7\'b7E\'e9il,'\'a7?llte\rdblquote\'a32i i22g?AESi2C)\'b0\'a7;SSli\lquote hZ.$E\rquote b\'e92.\lquote $l\'b0li.L2.\'b0';L\'a7\lquote\'a7Oil.; \par (R\'80mh\'b0Id\'b7 New Y\'b0rk\'b7 1961) way. Who wants to listen to just one idiot (Strike) rant and rave'?! \par [138] Tiemann, F., et al., Ber, 14, p2015 (1881) \par i1391"'\'a45*\'b0"\'b7 R\'b7C\'b7\'b7 BML- J\'b7 Am Chem S\'b0\'b0\'b7\'b7 48\'b7 V'1955 (1926) lf you would like to learn more, ask questions, or talk to other \par [140] Patrick, T.M., et al., J. Am. Chem. Soc., 68, p1009 (1946) chemists then visit us on the internet at any of the following sites: \par [141] CA, 56, 14139 (1962) \par [142] CA, 56, 4677 (1962) The Hive (Strike\lquote s site); http;//hive.1yoaeum.ot\'b7g

\par [143] Smith, K., et al, J. Chem Soc., Perkin Trans., p3519 (1994) (or try www.lycaemn.org/~striko) \par [144] Jones, H.I., et al., J. Am. Chem. Soc., 40, p1411 (1918) \par [1;5] Marvel, C.S., et al., "Organic Synthesis Collective Vol I", Rh\'a4diUm\'b7S Sita: WWW],,Cacum_Org)~rhOdium \par p 47 \par [146] Kamm, O., et al., "Organic Synthesis Collective Vol l", \par p25_43 The Lycaeum: the world\lquote s largest entheogenic community: \par [147] Finholt, A.E., etal., J. Am. Chem. Soc., 69, p1199 (1947) \par [148] CA, 49, 836 (1955) \par [149] CA, 38, 2006 (1944) \par [150] McCombie, H., et al, J. Chem. Soc., p24 (19440 \par [151] CA, 46, 6025 (1952) \par [152] Lane, C.F., Synthesis, p135 (1975) \par [153] Jones, E.RH., et al., J. Chem. Soc., p2555 (1953) \par [154] Riegel, B., et al., J. Am. Chem. Soc., 68, p1805 (1946) \par [155] Green, R., etal., Pharmacology, 119, p247 (1995) \par - 290 - \'b7 291 \'b7 \par \par \par }