Synthsis PDF

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And: No, the product is not like heroin. It is one step before heroin. Heroin is acetylated morphine (=diacetylmorphine is the chemical name for heroin).
Its very easy (much much easier than the demethylation of codeine to morphine) to make heroine from morphine, when you get acetic anhydride. This
are the common ways to get H:
opium - codeine - morphine - heroin

opium - morphine ± heroin

1. Organomagnesium halides react with morphine derivatives of the
pseudocodeine type, ie., those having an unsaturated linkage in the 6,7
position, with scission of the ether ring, and introduction of an organic
group into the nucleus. This reaction can likewise be applied to the enol
esters of the dihydroketones of the morphine group.
2. The preparation of methyl, ethyl, isopropyl, n-amyl, benzyl, and

phenyl derivatives of dihydrothebaynone is described. In the methyl,
ethyl, and phenyl series, pairs of isomeric substituted dihydrothebainones
are formed, in the isopropyl, n-amyl, and benzyl series, no isomers have
been found.
3. By closure of the 4,5-oxide ring, the alkyl, aralkyl, and aryl dihydrothebainones
can be transformed to the corresponding dihydroco
deinone derivatives, and demethylation of these leads to organic substituted
dihydromorphinones.
4. The nuclear methylated dihydrocodeinone isomers can be converted

to the enol acetates, and these derivatives brought into reaction with
methylmagnesium iodide, whereby a second methyl group is introduced.
The same dimethyldihydrothebainone is formed from both isomers. The
significance of this fact for speculations concerning the structure of the
alkyl dihydrothebainones is discussed.
5. The action of isopropyl- or phenylmagnesium bromide on dihydrothebainone

results to some extent in demethylation at the phenolic ether
group, whereby dihydromorphinone methyl enolate is formed. This
compound can also be prepared by demethylation of dihydrothebaine
under alkaline conditions.
6, Pseudocodeine methyl ether reacts with methylmagnesium iodide to

give a phenolic product containing a new methyl group. Analysis shows
that methylpseudocodehe methyl ether must contain an alicyclic unsaturated
linkage but the compound shows the same extraordinary resistance
to hydrogenation exhibited by phenyldihydrothebaine and the methyldihydrothebaines.

c

10g Opium
500ml Demineralized Water
60 g Calcium Chloride
200ml Concentrated Ammonia (anhydrous is not necessary)
4 Coffee Filters
1. Heat Opium to around 180º in Demineralized Water stir until latex dissolves
2. Remove from heat
3. Stir & pour through coffee filter
4. Discard filter and return liquid to heat( around 180º) stirring it
5. When it begins to steam add ammonia until crystals stop forming
6. Pour through coffee filter you should have white crystals
7. Allow Crystals*** <3 to dry overnight
Remember it may contain impurities so its best not to inject
i

!
10g morphineH CI:

15 grams of acetic acid
50 grams sodium carbonate
200 ml water
50 gramsa ctivatedc arbon
200 ml chloroform
200 ml ethyl alcohol
200 ml muriatic acid
200 ml ethyl ether
4 coffee filters
"
#
Add equal amounts of morphine and acetic anhydride
and bring the tenperature to 185' F. Use caution if you
don't live in a rural area, as acetic acid is what gives the
"smell" to vinegar,a nd is closet o unbearableif the chemist
is not cooking in a barn or other well-ventilated area.
One keepst he temperaturec onstanta nd stirs periodically
for a period of no less than six hours. At this point, the
chemist has bonded the acid to the opiate to form a crude
heroin (diacetyl morPhine). "
$
The product is mixed vigorously with water and chloroform
(l:l rvater:chloroform) and drained off. This extracts
any unreacted products or impurities. Pour off the waterchloroform
mixture and add sodium carbonate to the heroin
solution. This will cause heroin crystals to form and
fall out of the solution.
"
%
Filter the solution through a couple of coffee filters to
collect the heroin crystals. Dry the crystals overnight and
then add them to a portion of alcohol and activated charcoal
chips. Shake vigorously for a couple of minutes and
filter chips through coffee filter. Evaporate alcohol off
with a low heat. The product remaining is known as Nunr
ber 3 Heroin. It can be used in this form or further purified
to 99Vo in step number 4.
"
&
This step takes the heroin and turns it into super-potent,
super-pure crystals. The purity will vary, but even an average
chemist can realize a product that is 75Vo pure! The
dangers of acetic anhydride are mild compared to the precipitator
in this case: ether.
Dissolve heroin crystals in a portion of alcohol and add
simultaneously: muriatic (HCl) acid and ethyl ether. This
will precipitate the Number 4 Heroin. Filter the crystals as
in the previous step and spread them on a glass plate. position
a standard 40-watt light bulb 16 inches above the
plate and allow to dry overnight. When the crystals are dry
and crunchy, they can be used accordingly.


been found.
dihydromorphinones.



This simple procedure converts oxycodone to oxymorphone with a yield of 97%. HBr (hydrobromic acid) is widely used in related methods, but the use
of a rate-accelerant such as H3BO3 (boric acid) allows the use of less concentrated acid meaning a lower temperature reflux (so less side-products) &
a much faster conversion (1 hour versus 24 hours+) as well as a higher yield (97%).
I've also added a Youtube link to making hydrobromic acid from KBr (potassium bromide) which is non-suspicious to order & freely available as a
specialist photographic chemical. Hardware store H2SO4 (sulfuric acid) is also required. In the example the chemist makes 100ml+ of 48% HBr which
is enough to convert 50g of oxycodone. In this case, scaling down is simply a matter of dividing the mass or volume of chemicals (for example 120g KI
in 200ml of H2O and so on).
http://www.youtube.com/watch?v=JmS4roFTr08
I appreciate that is some states of the US, glassware is hard to obtain but for most people acquiring the appropriate pieces is simply a matter of
searching eBay & using some common-sense (for example a hotplate can be replaced with an oil-bath... a deep-fryer on a low setting using peanut oil,
for example).
For those looking for the very cheapest method, the patent also gives an example using HBr (hydrobromic acid) & MgCl2 (magnesium chloride). The
former is brick cleaner (try Home Depot) while the latter is Nagari (Japanese cooking item), a food supplement & a common aquarium chemical - it's
very cheap on eBay. The downside is a yield of only (!) 95% & a reflux time of 26 hours. Anyway, it's all in the patent.
H3BO3 (Boric acid) is one of the two highest yielding accelerants giving a yield of 97%. Simply adding borax to the solution at the beginning of the
reflux produces H3BO3 thus:
Na2B4O7·10H2O + 2 HBr ĺ 4 B(OH)3 [or H3BO3] + 2 NaBr + 5 H2O
'&())*(+%*,-.

CLAIMS
What is claimed is:
1. In the process of dealkylating an opioid ether by contacting the ether with an aqueous acid selected from HBr or HCl, the improvement comprising:
contacting the ether with the aqueous acid containing at least one equivalent weight, based on the ether, of boric acid or a bromide or chloride salt of a
metal selected from Li, Na, K, Al, Mg, and Ca.
2. The process of claim 1 wherein the contacting is conducted at the reflux temperature of the resulting mixture.
3. The process of claim 2 wherein the aqueous acid is hydrobromic acid.
4. The process of claim 3 wherein the hydrobromic acid contains at least one equivalent weight of boric acid or a halide salt of Li, Na, K, Mg, or Ca.
5. The process of claim 3 wherein the hydrobromic acid contains at least one equivalent weight of MgBr2.
6. The process of claim 1 wherein the ether is a methyl ether of an opioid.
7. The process of claim 1 wherein the ether is an N-substituted 14-hydroxydihydronorcodeine.
8. The process of claim 5 wherein the ether is a methyl ether of an opioid.
9. The process of claim 5 wherein the ether is an N-substituted 14-hydroxydihydronorcodeine.
10. The process of claim 9 wherein the N-substituent is cyclobutylmethyl.
BACKGROUND OF THE INVENTION
1. Field of Invention:
This invention relates to processes for the dealkylation of alkyl aryl ethers to aryl phenols and more particularly to such processes using inorganic acids
containing selected accelerators.
2. Prior Art:
A variety of reagents have been used to dealkylate alkyl aryl ethers. Commonly used reagents include hydrobromic acid, boron tribromide, organic
mercaptides, and trimethylsilyl halides. The cleavage of ethers has recently been reviewed [M. V. Bhatt and S. U. Kulkarni, Synthesis, 249 (1983)].
While these standard methods of dealkylation have proven acceptable for a variety of simple ethers, the rate of dealkylation of more complicated
ethers is often sufficiently slow that rather harsh reaction conditions or long reaction times are necessary to effect complete dealkylation, resulting in
extensive decomposition and hence lower yield of the desired dealkylated product.
Canadian Pat. No. 913077 issued on Oct. 24, 1972 to Endo Laboratories, Inc., discloses the preparation of a variety of N-substituted 14-
hydroxydihydronormorphines by dealkylation of the corresponding 3-methyl ethers. This dealkylation is exemplified by reaction with pyridine
hydrochloride at 190°-195° C. for 75 minutes. No yield is given for this dealkylation. Other dealkylation reagents include hydrogen chloride, hydrogen
chloride in acetic acid, hydrogen chloride in the presence of zinc chloride, ferric chloride, or antimony trichloride, hydrogen bromide, hydrogen bromide
in acetic acid, hydrogen iodide, etc.
The need exists for a method of accelerating the cleavage of alkyl aryl ethers which react only sluggishly under simple acidic conditions without
increasing the temperature or time of the reaction sufficiently to result in extensive decomposition.
SUMMARY OF THE INVENTION
According to the present invention there is provided in the process of dealkylating an alkyl aryl ether by contacting the ether with an aqueous acid
selected from HBr, HCl, or HI, the improvement comprising: contacting an alkyl aryl ether with the aqueous acid containing at least one equivalent
weight, based on the ether, of boric acid or an inorganic salt of a metal selected from Li, Na, K, Mg, Al, Ca, Mn and Ni.
In a preferred process, addition of an equivalent or more of a halide salt of lithium, magnesium, sodium, potassium, or calcium to the acidic dealkylation
medium results in a rate enhancement of four to five times the rate in the absence of the salt. Aluminum results in the same level of rate enhancement;
however, aluminum is not preferred due to the toxicity of any residual aluminum which may be present in the product.
DETAILED DESCRIPTION OF THE INVENTION
The process of the present invention surprisingly provides a convenient means to greatly accelerate the acidic dealkylation of alkyl aryl ethers which
otherwise are only slowly dealkylated under normal acidic conditions. The alkyl group is usually lower alkyl, i.e., 1-4 carbon atoms, and is generally a
methyl group. In general, the aryl moiety of the ethers will also contain a basic nitrogen which contributes to the decrease in the rate of the dealkylation.
In particular, this process is especially effective for the dealkylation of opioid ethers, specifically N-substituted 14-hydroxydihydronorcodeines. The N-
substituent is preferably cyclobutylmethyl.
The ethers are all readily available commercially or using literature methods to prepare them.
The acidic conditions used to dealkylate the ethers are aqueous solutions of hydrogen halides, specifically, hydrochloric acid, hydrobromic acid, or
hydroiodic acid. Hydrobromic acid is preferred at an HBr concentration up to about 48% by weight, preferably in the range of about 28%-48% by
weight.
In general, the inorganic salt which is added will be a halide salt where the halide is the same as that in the hydrogen halide being used, although
hybrid systems such as hydrogen chloride/magnesium bromide or hydrogen chloride/lithium bromide can be used. In addition to the inorganic halide
salts, the addition of boric acid is found to result in a five-fold rate enhancement. At least one equivalent weight of boric acid or the salt is used based
on the weight of the ether. The useful inorganic salts are those of lithium, sodium, magnesium, aluminum, potassium, calcium, manganese, and nickel.
The preferred salts are the bromide salts of lithium, sodium, magnesium, potassium or calcium. Magnesium bromide is most preferred.
The dealkylation reaction is conducted at the reflux temperature of the mixture, and this temperature will of course be dependent upon the exact
composition of the particular mixture, but will generally be beween 100° and 130° C.
Constant boiling 48% aqueous hydrogen bromide is a classic demethylating agent for alkaloids. When 48% by weight hydrogen bromide at reflux is
used in an attempt to demethylate N-cyclobutylmethyl-14-hydroxydihydronorcodeine, extensive decomposition is observed. To avoid this
decomposition, it is necessary to use more dilute solutions of hydrogen bromide (about 28% by weight aqueous hydrogen bromide). The more dilute
conditions result in a lowering of the reflux temperature of the mixture from about 125° C. for constant boiling 48% hydrogen bromide to about 110° C.
for 28% aqueous hydrogen bromide. The lower reaction temperature in combination with the lower concentration of hydrogen bromide results in
extended reaction times requiring 20 to 24 hours for the demethylation to go to 97% completion.
The addition of one equivalent of magnesium bromide is found to result in a dramatic increase in the rate of this demethylation. After six hours at reflux
(110° C.), the demethylation reaction is complete without giving rise to the decomposition observed with 48% aqueous hydrogen bromide. The
demethylation reaction is thus about four times faster in the presence of the magnesium bromide.
The effect of addition of a variety of inorganic bromides to the aqueous hydrogen bromide demethylation of N-cyclobutylmethyl-14-
hydroxydihydronorcodeine was determined. Table I illustrates the effect of these additions on the rate of the demethylation.
Rate enhancement can also be achieved by the addition of boric acid. The addition of one equivalent of boric acid to the hydrogen bromide
demethylation medium resulted in about a five-fold increase in the rate of the reaction, equivalent to that observed when lithium bromide is added.
A similar acceleration was observed when salts were added to the demethylation reaction conducted in aqueous hydrogen chloride. When N-
cyclobutylmethyl-14-hydroxydihydronorcodeine was treated with constant boiling hydrochloric acid (ö20% by weight hydrogen chloride) at reflux ö90%
demethylation was observed after 68 hours. Since the reaction was shown to be first order in N-cyclobutylmethyl-14-hydroxydihydronorcodeine,
extrapolation to 97% conversion results in a reaction time of ö100 hours. Addition of three equivalents of magnesium chloride resulted in optimal rate
enhancement with reaction now requiring 26 hours to go to 95% completion. The addition of magnesium chloride to the hydrogen chloride
demethylation thus also resulted in a four-fold increase in the rate.
Several hybrid systems were also examined. Addition of magnesium bromide to the aqueous hydrogen chloride demethylation medium resulted in
about a five-fold rate enhancement, the reaction now requiring 20 hours to go to 98% completion. Addition of lithium bromide to the aqueous hydrogen
chloride demethylation resulted in a similar rate enhancement. Even greater rate enhancement was observed when both magnesium chloride and
ammonium iodide were added to the aqueous hydrogen chloride demethylation with 97% of the starting material being consumed in 8 hours, however,
the presence of the iodide resulted in additional by-products being formed and consequently unacceptably low product purity.
As is readily apparent, the choice of the accelerator used to accelerate a particular dealkylation will be dependent upon a number of considerations.
Included among these considerations will be the cost of the inorganic additive, the potential consequences of trace amounts of residual inorganic in the
final product, the amount of rate enhancement necessary to make the dealkylation commercially feasible, and the ease of handling the particular
reaction mixture. Several inorganic accelerators which are generally preferred are magnesium bromide, boric acid, lithium bromide, and sodium
bromide.
The details of this invention can be further understood by the following examples in which percentages are by weight and temperatures are in degrees
centigrade. The examples illustrate the procedure used to establish the rate enhancements of various inorganic salts and boric acid.
CONTROL EXAMPLE
Rate Accelerator Not Addded
To a 100 ml round bottom flask equipped with a condenser and a nitrogen purge was charged N-cyclobutylmethyl-14-hydroxydihydronorcodeine (6.3 g,
17 mmoles), 48% aqueous hydrobromic acid, (19.7 g 13.2 ml) and 8.9 ml of deionized water. With good agitation, the reaction was heated to 109° and
refluxed gently at 109 1° for 22-24 hours to yield a tan slurry, at which point then layer chromatography indicated 97-98% conversion. The reaction
mixture was added to 200 ml of boiling water and the mixture was refluxed for 1 hour until a homogeneous yellow solution was obtained. Activated
charcoal (1.0 g) was added and the mixture was heated at reflux for 10 minutes. The charcoal was removed by hot filtration to give a colorless solution.
The solution was cooled to 90 2° and the pH was adjusted to 9 with 28% NH 4 OH. The mixture was then stirred at 0°-5° for 1 hour. The precipitate
was filtered off, washed with cold water (3×10 ml), dried overnight in a vacuum oven to yield N-cyclobutylmethyl-14-hydroxydihydronormorphine free
base (4.6 g, 75.9%).
The free base was dissolved in 53 ml of tetrahydrofuran containing 4% water in a 100 ml round bottom flask equipped with a condenser and a nitrogen
purge. The solution was heated to 50°, and then the pH was adjusted to 3 by the addition of 36% aqueous hydrochloric acid (3.0 ml) over a ten minute
period. The mixture was cooled to 0°-5° and then was stirred for 1-2 hours. The resulting precipitate was filtered off and washed with tetrahydrofuran
(2×10 ml, containing 4% water). The product was dried overnight in a vacuum oven at 90°-100° to give 4.5 g (67.4%) of N-cyclobutylmethyl-14-hydroxy
dihydronormorphine hydrochloride, m.p. 274°-275°.
EXAMPLE 1
MgBr 2 as Demethylation Rate Enhancer
To 144 ml of deionized water in a 5 liter round-bottomed flask equipped with a condenser and a nitrogen purge was added 1079 g of 48% aqueous
hydrogen bromide. Magnesium bromide hexahydrate (468 g; 1.6 moles) was added over 30 minutes and the mixture was stirred until all the
magnesium bromide had dissolved. N-cyclobutylmethyl-4-hydroxydihydronorcodeine (606 g; 1.6 moles) was added over 30 minutes. The resulting
slurry was heated to reflux (108°) over a 30 to 60 minute period during which time the starting material dissolved. The mixture was stirred at reflux for 6
hours, during which time the product began to separate. Thin layer chromatography indicated approximately 97-98% conversion. The resulting slurry
was cooled to 25° to 30° over a 2 to 3 hour period and the product was collected by filtration.
The product was worked-up as follows: The filter cake was dispersed in methanol (4.0 liters) and the mixture was heated to reflux to dissolve the
product. Activated charcoal (8 g) was added and the reflux was continued 15 minutes. The charcoal was removed by hot filtration. The pH of the warm
(50° to 60°) filtrate was adjusted to 9 by addition of 28% aqueous ammonia (236 ml) and 2.0 liters of water was added. The resulting slurry was cooled
to 5° over a 2 hour period and the product was collected by filtration and washed with 4.0 liters of ice water. This product was added to 3200 ml of
tetrahydrofuran under nitrogen and 320 ml of water was added to completely dissolve the product. Activated charcoal (8 g) was added and the mixture
was heated to reflux and stirred at reflux for 30 minutes. The charcoal was removed by hot filtration and the temperature of the filtrate was adjusted to
ö50°. The pH of the filtrate was adjusted to 3 by addition of 37% aqueous hydrogen chloride (141 ml) over a 45 minute period. The resulting slurry was
cooled to 5° over a 2 hour period and then was stirred at 5° for one hour. The product was collected by filtration and washed with 1600 ml of
tetrahydrofuran. The product was dried in a vacuum oven at 110° for 24 hours to give 484.6 g (76.5%) N-cyclobutylmethyl-14-
hydroxydihydronormorphine hydrochloride, m.p. 277°-278°.
EXAMPLE 2
Lithium Bromide As Demethylation Rate Enhancer
To a 100 ml round bottom flask equipped with a condenser and nitrogen purge was charged N-cyclobutylmethyl-14-hydroxydihydronorcodeine (7.6 g,
20 mmoles), lithium bromide (1.8 g, 20 mmoles), 48% aqueous hydrobromic acid (16.6 g, 100 mmoles) and 3.7 g of deionized water. The resulting
mixture was heated to 103° and refluxed at 103 2° for 5 hours, during which time a lavender slurry resulted. Thin layer chromatography indicated
approximately 97-98% conversion. The resulting slurry was cooled to 25° and was allowed to stand overnight.
To the slurry was added 10 ml of water and the product was collected by filtration and dried overnight in a drying oven to give 7.5 g (83.6%) of N-
cyclobutylmethyl-14-hydroxydihydronormorphine hydrobromide, m.p. 275°-276°.
EXAMPLE 3
Sodium Bromide As Demethylation Rate Enhancer
20 mmoles), sodium bromide (2.1 g, 20 mmoles). 48% aqueous hydrobromic acid (16.6 g, 100 mmoles) and 3.4 g of deionized water. The resulting
mixture was heated to 103° and refluxed at 103 2° for 6 hours, during which time the initial tan solution turned to a lavender slurry. Thin layer
chromatography indicated approximately 97-98% conversion. The resulting slurry was cooled to 25° and was allowed to stand overnight.
EXAMPLE 4
Potassium Bromide As Demethylation Rate Enhancer
20 mmoles), potassium bromide (2.4 g, 20 mmoles), 48% aqueous hydrobromic acid (16.6 g, 100 mmoles) and 3.1 of deionized water.
The resulting mixture was heated to 103° and then refluxed at 1032° for 6 hours, during which time the tan solution became a lavender slurry. Thin
layer chromatography indicated approximately 97-98% conversion. The resulting slurry was cooled to 25° and was allowed to stand overnight.
Following the procedures of Examples 1-4, rate enhancements for the demethylation of N-cyclobutylmethyl-14-hydroxydihydronorcodeine in aqueous
hydrobromic acid were established for a variety of inorganic bromides and boric acid as set forth in the following Table I.

Leafing through the MoDA (misuse of drugs act) I noted that noroxymorphone is NOT a controlled compound. This makes sense because it's the
precursor for almost every opioid antagonist. Now, it's easy to see what a simple matter synthesis of oxymorphone would be; but it's specifically
controlled. I would suggest that reacting it with phenylacetyl chloride & then reducing the amide would make N-phenylethyl noroxymorphone. This stuff
is x134 morphine; more potent than fentanyl.

!-#
To do this, you will need some chloroform or other solvent in which codeine base will dissolve, APAP won't. Merck says that chloroform works best,
although I suspect that methylene chloride will work just as well. Ether will work, but it's just too dangerous for my taste. You will also need some dry
sodium carbonate. (bicarb might work here, although I haven't tried it.) DO NOT USE SODIUM HYDROXIDE, IT REACTS WITH THE APAP TO FORM
SOME SORT OF EVIL LOOKING BLUE GOOP. Na(CO3)2 WILL RAISE THE pH JUST FINE. Lastly, you will need a large pyrex lasagna pan in which
to evaporate your product to dryness.
First, place uncrushed T3's or other APAP/codeine product in a small glass or beaker and cover with enough distilled water so that the pills will break
down into a thin paste. For 30 T3's, I use about 30-35 ml of H20. Let the pills soak until completely broken down into paste. Next add about 5-8 grams
of dry sodium carbonate to reduce the codeine phosphate to codeine base. The paste will thicken somewhat and bubbles of CO2 will form in the paste
as the codeine phosphate is reduced. Add enough distilled water so that the mixture is about the consistency of thin pancake batter and stir the mixture
thoroughly with a wooden or glass rod. The pH of the mixture should be about 11 or greater. If it isn't, add more Na(CO3)2 until it is.
Next, pour the mixture into the pyrex pan and rinse the beaker with a few ml of distilled water and add the rinse water to the mix in the pan. Use the stir
rod to spread the grayish mixture around the pan so that the layer is as thin as possible. Let the mix dry overnight. You can pop the pan into an oven
set to warm, (no hotter), if you want to speed things up.
After the mixture has completely dried, use a single-edge razor blade to scrape the mixture from the pan. It should just flake off in slabs. Now, wrap the
dried material in a coffee filter and crush it so that the pieces are about the size of grains of rice. It isn't necessary to grind the stuff any finer, since it
would probably clog the filter in the last step anyhow. Pour the dry crushed mixture into a glass bottle with a screw-on top and pour in enough
chloroform to completely cover the "gravel" in the bottle. Seal the bottle and shake for a few minutes. Let the contents settle for a minute or two while
you set up a gravity filtering apparatus. This can be a coffee filter in a metal strainer, or if you have it, a piece of filter paper in a glass filter funnel. You
can't use plastic because the chloroform will attack it and ruin your product. Clean and dry the pyrex pan and set it under the filter to catch the filtered
chloroform. Shake the chloroform/"gravel" mixture and pour it into the filter, letting the chloroform/codeine mixture run into the glass pan. Let the
chloroform evaporate while you put the wet gravel back into the bottle and shake with a fresh portion of chloroform. It isn't necessary to use as much as
you did the first time. Again pour the chloroform/gravel mix into the filter paper.
After the second portion of chloroform has run through the filter, you can drip a few ml of clean chloroform onto the filter paper and wet gravel to get the
last bit of codeine from the APAP and chalk. You should set the glass pan with the chloroform outside to evaporate to dryness. Do not place it into an
oven to force dry it. While chloroform is not very flamable, I found out the hard way that chloroform vapor is broken down on contact with the heating
elements of the stove to form deadly phosgene gas.
Be patient, soon enough you will have nearly pure codeine base in the bottom of the glass pan. After the codeine has evaporated, you might notice that
the codeine is sticky. This is because evaporating chloroform gets very cold and room humidity will condense into the mixture. If this happens, you can
oven warm the codeine, but only after you can no longer smell the chloroform in it. You can now use the razor blade to scrape up the crude product.
The codeine base will not weigh as much as an equivalent amount of codeine phosphate, because you have stripped the phosphate ions and left
behind the pure alkaloid. Fear not, it is still potent orally, just remember to adjust your dose downward. codeine base weighs only 75.3% as much as an
equimolar amount of codeine phosphate. If you want to re-salt it, you can use the following proces:
Into 20 ml of acetone add 2 ml of phosphoric acid and set this mixture aside. Dissolve your crude codeine base into enough acetone so that it just
dissolves. You might have to warm up the acetone to get it to dissolve completely. If you want to clean up any insoluble contaminants at this point, take
a pasteur pipet and pack a small wad of cotton into the point where the pipet narrows. Using another pipet, drip the codeine/acetone mixture through
the cotton. Follow this with a ml or two of clean acetone to get all the codeine from the pipet filter. Next, mix the acetone/phosphoric acid solution into
the acetone/codeine base solution in a 50/50 ratio. As you stir the resultant misture, you will see the codeine phosphate quickly precipitate from the
acetone as a sticky gummy mass. As you stir the solution, the final product should form a bolus on the stirring rod and look like a wad of chewing gum.
Rinse the bolus in a small amount of fresh acetone and then smear it on a glass plate to dry. As the acetone evaporates, the codeine phosphate (CP)
will appear to melt. This is because the CP is highly hygroscopic and is absorbing water from the air. Gently warm the CP in an oven to drive off the
last of the acetone and then use a pipet or syringe to first drip water onto the CP, and then suck up the CP solution. You may now drink your product,
or you can again reduce it to codeine base and extract it with chloroform if you prefer a much purer, powdered product.
Even after two acid-base extractions, I have gotten up to 93% of the available codeine from T3's with absolutely zero APAP in the finished product. If
you choose codeine base as your final product, you can now easily turn it into even yummier alkaloids, but that is for another posting.
Sorry about the long cross-posting, but I believe in sharing information which will result in a purer (read: safer) final product. B.B. Welch
,,/

Here is a better method for the same O-demethylation of codeine --> morphine, Only this one is alot more efficient (50-90% yield!) using BBr3 as the
cleaving agent. It leaves a cleaner product and is easy to preform given the right equiptment. The draw back would be BBr3 is highly volatile and HBr
gas is incredibly rotten shit so you would need to either use a fume hood , glove box, outdoors with a mask on etc etc. I personally have not tried this
method yet But when I do I'll post a write up about what some of the problems are so on and so forth. I'll also annotate this procedure with any usefull
info I may find.
Procedure:
1. Dissolve 2.99 g of anhydrous codeine in 25 ml of CHCL3 (Chloroform).
2. Create a solution of 15 g of BBR3 (Boron Tribromide) in 175 ml of

CHCL3. Be sure that this solution is kept well stirred for step 3.
3. Add solution 1 to solution 2 over a 2 minute period, maintained in

the range of 23-26 degrees C.
4. The reaction mixture will consist of a suspension of white solid in

the chloroform. This should then be poured into a well-stirred mixture of
80 g of ice and 20 ml of concentrated (28-30%) NH4OH. The two-phase
system should be kept at -5 to 0 degrees C for 30 minutes with
continuous stirring, then filtered. (Yes, by vacuum.)
5. The resulting crystals should be washed thoroughly with small

amounts of cold chloroform and H2O, and dried. This should yield about 2.67 g
(88.1%) of tan crystals. Now for those that are happy with a bird in the hand, voila, that's
it. For those high achievers who want to go the extra step, read on.
6. To gain additional yield, take the aqueous phase from the filtrate,
and saturate with NACL. Extract with 4 X 50 ml of CHCL3-EtOH (3:1).
7. Evaporate this, which will leave a remaining residue (approximately

151 mg).
8. Dissolve this residue in 2 ml of H2O containing 1 drop of 37% HCL.

After addition of .5 ml of chloroform, the pH should be adjusted to 9.0
with concentrated NH4OH while stirring. The crystalline material which

separates should be filtered, washed with cold H2O and chloroform, and
then dried. This will produce an additional 86 mg, giving a total yield
of 2.76 g, which is 91%. Additional product could be produced by
additional extractions of the aqueous phase. (Although I doubt more than one
additional extraction would be worth the effort.)
ummary

been found.
dihydromorphinones.



0
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'
.

,/dihydrocodeinone
It is well known that morphine and its ethers, through treatment with hydrogen gas in the presence of large amounts of noble metal catalysts through
heating the acid solution, can be transformed to the dihydrated keto derivatives.
Surprisingly, it was now found that for this transformation to take place, hydrogen is completely unnecessary, and that just heating the acidified alkaloid
solution with a larger amount of finely divided platinum row metals, will suffice to affect the simultaneous dehydrogenation/hydrogenation in good
yields.
This success is particularly unexpected because it was not to be foreseen that platinum metal not saturated with hydrogen is capable to use the
hydrogen originating from the dehydrogenation U

almost quantitatively for the hydrogenation of the double bond U

of morphine or its analogs without in addition of excess hydrogen from an external source.
01
300 grams of codeine free base was dissolved in 2000ml dilute HCl, and after the addition of 150 grams finely divided palladium, the mixture was
heated under reflux for one hour. After the palladium was filtered off, the acid filtrate was basified with NaOH solution. The base which separated was
recrystallized from alcohol. Yield of dihydrocodeinone 75-85%, mp 195°C.
$1
5 grams of codeine hydrochloride was dissolved in 30 ml water, and acidified with a little HCl, and after the addition of 4 grams platina black, the
solution was refluxed for 5 hours. After workup as in 0, the yield was 65-75% of theory.
%1
5 g of morphine HCl was dissolved in 50ml water, slightly acidified with HCl, and 5 grams of platina black was added and the solution refluxed for 4
hours. Workup as in 0. Yield 2.5 grams dihydromorpinone.
&1
To a solution of codeine hydrochloride, slightly acidified with HCl, 50 ml of a 10% solution of colloidal platinum was added, and the solution was
refluxed for 3 hours. Workup as in example 1. Yield 3 g dihydrocodeinone.
21
6 grams codeine freebase was dissolved in a solution of 4 grams of tartaric acid in 50 ml of water, and 6 grams palladium black was added. The
solution was refluxed for 1 hour and worked up as in 0. Yield 75% of theory.
Example 6:
6 g codeine phosphate was dissolved in 30 ml water, and acidified with 5ml dilute phosphoric acid. 4g of finely divided palladium was added, and the
solution was refluxed for one hour. Workup as in 0. Yield 60-70%.
*1
6 grams of codeine free base was dissolved in dilute acetic acid, and was refluxed for two hours after the addition of 5 grams palladium black. After
workup as in 0, the yield was 40% of theory.
31
21 grams of codeine free base was dissolved in an excess of dilute sulfuric acid, mixed with 16 grams palladium black and refluxed for one hour. After
workup as in 0, the yield was 80-85% of theory.
41
10 grams of ethylmorphine was mixed with 50 ml water and acidified with HCl. 10 grams of platinum black was added and the mixture was refluxed.
The yield of ethyldihydromorphinone was 65-75% of theory.
$
'

.
'
.

As in German Patent 607,931, a method is decribed below for the production of dihydromorphinones by rearrangement without the use of hydrogen,
but simply by heating the alkaloid in an acidic solution together with a platinum catalyst.
While relatively large amounts of platinum catalyst is used in German Patent 607,931, we have found that only a fraction of that amount is needed, and
sometimes with even better yields.
01
300g codeine freebase was dissolved in 2000ml dilute HCl, and was heated with 25g of finely powdered palladium, and boiled under reflux for an hour.
The palladium was filtered off, and the filtrate basified with NaOH solution. The precipitated base was recrystallized from alcohol. Yield 85-95% of
dihydrocodeinone, mp 195°C.
$1
5 grams of codeine hydrochloride was dissolved in 30ml water, and acifified with a small amount of HCl, and after the addition of 0.5g of palladium
black, the mixture was refluxed for five hours, and worked up as in example 1. The yield was 70% of theoretical.
%1
5 grams of morphine hydrochloride was dissolved in a slightly acid HCl solution, and after the addition of 0.5g palladium black, the mixture was refluxed
for three hours and worked up as in 0. The yield was 3g.
&1
6 grams of codeine freebase was dissolved in 30ml water together with 4g of tartaric acid, and 0.5g of palladium black was added. The mixture was
refluxed for one hour and worked up as in 0. The yield was 75% of theory.
21
6 grams of codeine phosphate was dissolved in 30ml water, and acidified with 5ml dilute phosphoric acid, and after the addition of 0.5g of palladium
black, the solution was refluxed for an hour. After workup as in 0, 60-70% yield of dihydrocodeinone was isolated.
)1
21 grams of codeine freebase was dissolved in an excess of dilute sulfuric acid, and two grams of palladium black was added and the solution refluxed
for one hour. The yield was 90% of theory.
*1
10 grams of ethylmorphine freebase was added to 50ml water, and HCl was added until the solution was slightly acidic and all ethylmorphine had
dissolved. 1 gram palladium black was added, and the solution was boiled under reflux. The mixture was worked up as in 0. The yield of
ethyldihydromorphinone was 75% of theory.
%
'

.
'
.

,/ dihydromorphinone
As in German Patent 617,238, a method is decribed below for the production of dihydromorphinones without the addition of hydrogen gas.
While the rearrangement in German Patent 617,238 is affected by the presence of acids, we have now found that the reaction with morphine and its
ethers is taking place in an alcoholic solution in good yields without the addition of any acid.
01
5 grams morphine was dissolved in 50 ml of alcohol and after the addition of 0.5g of palladium black, the mixture was refluxed for 4 hours. After the
catalyst wass filtered off and the solution concentrated, dihydromorphinone crystallized. Yield 3 grams.
$1
10 grams of codeine was dissolved in 100ml alcohol, and after the addition of 0.5 grams palladium black the solution was refluxed for 4 hours. Workup
as in 0. Yield 7 grams of dihydrocodeinone.
%1
5 g ethylmorphine and 0.3g of palladium black was dissolved in alcohol and the solution was refluxed. Yield 3g of ethyldihydromorphinone.

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It makes about 5 doses for morning glories and 10 from hawaiian baby wood rose seeds. You kinda have to eyeball it.
8 8i
1)Seeds - I recommend a bulk order (500+ seeds) of Hawaiian baby woodrose seeds as it requires alot less
2)Pure lemon juice (not the concentrate stuff) - This will preserve the alkaloid
3)Peppermint Oil - This will turn the LSA into LSH by lower its pH level and changing its chemical structure.
4)A Non-Polar solvent - You can use alot of things but I suggest using a 5x butane as it dries quickly and clean
5)A Polar solvent - I suggest a VERY strong alcohol. Everclear grain alcohol (190 proof) will work perfectly. This will extract the LSA/LSH
6)A coffee bean grinder - This will make your life easier.
7)A freezer - So your butane wont evaporate quickly.
A *pill* (optional) bottles and some scissors
9)Coffee filters and aluminum foil
10)Alot of time - This will take a few days
-Once you have and can do all these things, your ready to go.
Lets Do It!
1)Gring up your seeds in your coffee grinder. YOUR NOT LOOKING FOR A FINE POWDER. YOU WANT THE SEEDS TO BE BROKEN DOWN BUT
NOT LIKE A POWDER.
2)Put your ground up seeds in a bottle and add just enough lemon juice to cover them. You want to soak them NOT drown them so just place enough
to barely cover the top.
3)Let this site for about 10 minutes and filter out the lemon juice and let the seeds dry on aluminum foil. This drying may take about an hour of air
drying or 30 minutes of fan drying.
4)Here comes the hard part. Here you will use your non-polar solvent. If you've ever made hash with a butane blast tube, this will be pretty easy. Your
basically going to transfer over your seeds to a tube, cut a hole just big enough for the butant nozzle to fit and blast the butane inside the bottle. A mini
2oz bottle will do you good here. Just use the entire bottle inside.
5)After that is done, your going to want the material soak in the butane for a few hours. Place the bottle in the freezer for 1-3 hours.
6)Once done, remove the bottle from the freezer and let it dry on the aluminum foil for another 1-3 hours .
*6.5* You can repeat process 5 and 6 for a cleaner final product. The yield will be smaller but alot more potent. Just make sure your in a well vintilated
area because the butane will be all around you.
7)Now your going to want to use a bottle that will hold all the seeds and be 1/2 full. This is pretty ideal but not really required.
Add your everclear until the seeds become covered and then add 1/2 - 1 inch more of everclear so that there is more everclear then seed.
9)When thats ready, add 5 to 10 drops of peppermint oil to it.
10)This will need to site for at least 1 day. I recommend letting it sit for 2 or 3 days though. Just make sure you stir it up every now and then. Like when
you walk pass it or think about. MAKE SURE YOU KEEP THIS OUT OF THE LIGHT! Light isnt that bad but it can weaken the LSA and produce a
small yield. I recommend placing it in your frigde as the material must remain cold or the peppermint oil will dissolve and you will end up with LSA.
11)You know it will be ready when it becomes a yellow/green color.
12)Strain the material. The seeds are useless now and you want to make sure you get all the everclear out (as it contains your LSH)
*12.5* You can repeat steps 8-12 just to make sure you get out all the alkaloid. I dont recommend it as it takes a long time and its really not wirth it.
13)You can allow the everclear to evaporate (this will form LSA instead of LSH) but normally you just take the yellow.green liquid (cold) take about 5ml,
swish it in your mouth and then swallow or mix it with something and drink.
:
This recipe makes about 2-2.5 grams (roughly enough for 100-125 20mg doses) of DMT. It takes up to four days. You will spend around 9 hours the
first day then it sits for 3 days, after that you don¶t have much work but you must dry the crystals twice which can take a few hours. Do not try to speed
up this process and let them dry completely.

1 quart white vinegar
Water
5Tbs Sodium Hydroxide
250ml M&P Naptha
Distilled water
Non soapy Clear Ammonium Hydroxide
1lb Mimosa Hostilis
Gallon plastic jug
3 liter crock pot
Wide mouth glass
1 gallon container
1 gallon glass jug with lid
Glass turkey baster
2 Pint mason jars
Quart mason jar
Freezer
Funnel
Coffee filter
Blender

'

1) Break up the root bark then grind it up in the blender
2) In your 1 gallon jug mix 1quart white vinegar and 3 quarts water (this is liquid 1)
3) Add the root bark ground and most of liquid 1 to the crock pot stir well then turn on high for two hours( the liquid in pot is liquid 2)
4) Pour most of liquid 2 into the wide mouth glass
5) Pour the remainder of liquid 1 into the crock pot stir and turn on high for two hours (this is also liquid 2)
6) Pour liquid two into the wide mouth glass (now liquid 3) and throw out root bark grinds
7) Save liquid 3 in the 1 gallon glass jug do not get any sludge in it and throw out the sludge
8) Mix 5Tbs Sodium Hydroxide with one pint warm water and stir(liquid 4)
9) Combine liquids 3 and 4 in glass jug and cap the jug
10) Tilt the jug gently for one minute to mix the liquids
11) Add 250ml of M&P Naptha to the jug
12) Add warm water until the liquid is about 1 inch below the top
13) Mix the contents for 5 minutes by gently tilting the jug
14) Let it sit for 4 hours
15) There should now be a large dark layer topped by a small clear one carefully suck the clear up with the turkey baster making sure you don¶t get any
of the dark layer in it
16) Add the clear layer to the pint mason jar make sure its sealed
17) Put the jar in the freezer for 3 days
18) Put the funnel into the quart mason jar and a coffee filter onto the funnel to make a filter
19) Thoroughly shake the pint mason jar then pour the contents into the filter
20) You should have yellow/white crystals on the coffee filter let them dry completely in the filter
21) Mix equal parts distilled water and Ammonium Hydroxide in a pint mason jar then pour 100ml of it over the crystals
22) Remove coffee filter lay flat and let the crystals dry completely the crystals should end up white.

.; 1
Ketamine is more difficult to synthesize than the previously considered PCP derivatives. Although it is currently a popular and common drug on the
illicit market, it is obtained exclusively by diversion of commercial sources rather than synthesis. This route has an overall yield of ~60%, with a difficulty
rating of 2-3 out of 10 and a hazard rating of 1-2 out of 10 (ref. 64). The general necessity of producing anhydrous methylamine in a clandestine
setting, rather than purchasing it, increases the difficulty. Use of propylamine rather than methylamine would simplify this reaction, as its boiling point is
above room temperature vs. methylamine, which is a gas at room temperature.
The syntheis starts with the reaction of cyclopentyl Grignard and o-chlorobenzonitrile to give o-chlorophenyl-cyclopentyl ketone, followed by alpha
bromination of the ketone, and then reaction with methylamine to form an alpha-hydroxy imine (1-Hydroxycyclopentyl-(o-chlorophenyl)-ketone-N-
methylimine). Heating this imine results in Ketamine via a novel alpha-hydroxyimine rearangement (refs. 20, 21, 22, 23, 24 ). Overall yields are ~60%.
Tiletamine is synthesized by an analogous process in industry, substituting 2-thiophenyl magnesium bromide for the phenyl grignard and ethylamine
for methylamine. Two other ketamine analogs have been found on the black market: the compound missing the 2-chloro group on the phenyl ring, and
its N-ethyl analog. Both of these compounds are most likely more potent and longer lasting than ketamine. Synthetic procedure for ketamine synthesis:
Step 1: (o-chlorophenyl)-cyclopentyl ketone
119.0 g of cyclopentyl bromide and 19.4 g of magnesium are reacted in ether or THF to give a cyclopentyl Grignard reagent. The best yields are
obtained if the ether solvent is distilled from the Grignard under vacuum and replaced with hydrocarbon solvent, such as benzene. 55.2 g of o-
chlorobenzonitrile is then added to the reaction mixture and stirred for three days. The reaction is then hydrolyzed by pouring it onto a mixture of
crushed ice and ammonium chloride, containing some ammonium hydroxide. Extracion of the mixture with organic solvent gives o-
chlorophenylcyclopentylketone, bp 96-97 C (0.3 mm Hg) (CAS# 6740-85-8).
Step 2: alpha-bromo (o-chlorophenyl)-cyclopentyl ketone
To 21.0 g of the above ketone is added 10.0 g of bromine in 80 ml of carbon tetrachloride dropwise at 0 deg. C. After all of the Br2 has been added, an
orange suspension forms. This is washed with a dilute aqueous solution of sodium bisulfite and evaporated to give 1-bromocyclopentyl-(o-
chlorophenyl)-ketone, bp 111-114 C (0.1 mm Hg). Yield is ~66%. This bromoketone is unstable and must be used immediately. Also attempts to distill
it at 0.1 mm Hg lead to some decomposition, so it should be used without further purification.
The bromination may also be carried out with N-bromosuccinimide in somewhat higher yields (~77%).
Step 3: 1-hydroxycyclopentyl-(o-chlorophenyl)-ketone-N-methylimine
29.0g of above bromoketone is dissolved in 50 ml of liquid methylamine freebase. Benzene may also be used as solvent. After one hour, the excess
liquid methylamine is allowed to evaporate, although increasing the reaction time to 4-5 days may increase yield. The residue is then dissolved in
pentane and filtered. The solvent is evaporated to yield 1-hydroxy-cyclopentyl-(o-chlorophenyl)-ketone N-methylimine, mp 62 C (yield ~84%).
Step 4: 2-Methylamino-2-(o-chlorophenyl)-cyclohexanone (Ketamine)
The final step is a thermal rearrangement, and gives almost quantitative yield after 180 C for 30 min. An alternative to the use of decalin as solvent in
this step is to use a pressure bomb.
2.0 g of the preceeding N-methylimine is dissolved in 15 ml of decalin and refluxed for 2.5 h. After evaporation of the solvent under reduced pressure,
the residue is extracted with dilute hydrochloric acid, the solution treated with decolorizing charcoal, and the resulting acidic solution is made basic. The
liberated product, 2-methylamino-2-(o-chlorophenyl)-cyclohexanone (Ketamine), after recrystallization from pentane-ether, has a mp of 92-93C. The
hydrochloride has a mp of 262-263 C.
As with PCE, the freebase is too caustic to be smoked, and must be converted into the HCl salt in order to be consumed in this manner.
; $
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Anthranilic acid 13,7g

HCl (conc., d=1,19)
NaNO2 8g
CuCl 10g
13,7g anthranilic acid is stirred in a glass beaker in 40mls water, 28mls HCl and 20g ice. With constant stirring and cooling there's added 8g NaNO2 in
40mls water. Thus obtained clear solution of diazonium salt is very slowly added with stirring into a soln. of 10g CuCl in 25g HCl conc. A vigorous
evolution of nitrogen is observed.
When the rxn ends, the ppt is filtered, washed with cold water and reprecipitated from aq. Na2CO3. The product represents fine crystals and melts at
140-141°C.
o-Bromobenzoic acid can bee obtained in an analogous manner, substituting CuCl for CuBr.
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(RCOO)2Zn + Pb(SCN)2 = 2 RCN + ZnS + PbS + 2 CO2
The best results are obtained when a zinc salt is employed instead of free acid. This rxn is unsuitable for amino-, nitro- and oxy- acids, but can bee
used for bromo- and chlorobenzoic acids.
To a hot soln of 50g NaOH in 400mls water there's added 195g o-chlorobenzoic acid. Carefully neutralize with NH3 or NaHCO3 and add with heating
105g (~5% excess) ZnSO4 in 400mls water. The precipitated salt is dried for prolonged time at 200°C and mixed intimately with 205g Pb(SCN)2. The
mixture is coffeeground and dried at 120-140°C for a prolonged time, then heated on open flame - the mixture melts and gases are evolved.
Distilled nitrile is treated with NH4OH, steam-distilled and salted out. Yield 137g (80%), mp 43-46°C, bp 232°C. The rxn usually takes place within 30-
60 mins, but the duration of dryings makes the method quite time-consuming.
'

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This one doesn't require a prolonged drying. Sulfaminic acid is dirt cheap and can bee acquired without causing any suspicion.
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50g o-Bromobenzamide and 35g (25g=theory) sulfaminic (sulfamic) acid is thoroughly mixed and heated in a Wurtz flask. At 250-255°C distillation
begins, which is over at 285-295°C (takes approx. 1.5-2 hrs). The collected product is redistilled, yield 36g (80% of theory).
mp 53-57°C, bp 251-253°C
V

%
100g adipic acid and 10g Ba(OH)2 is intimately mixed and placed into a flask with a thermometer. The rxn is heated to 280°C, the mixture initially melts
and then the distillation takes place, which lasts about 1-2 hrs. The hot distillate is saturated with NaCl, the upper layer is decanted and distilled,
collecting the fraction boiling at 128-130°C. Dry with MgSO4.
Yield: 51g (89% of theory).

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Al(i-PrO)3 - Bp 130-140°C at 7mmHg; mp 118°C.
Into a 250ml RBF equipped with an efficient reflux condenser there's added 6g Al foil, 70mls (51mls in theory) abs. IPA (commercial reagent grade IPA
was used without any drying) and 0,1g HgSO4. The mixture is heated.
In the beginning of boiling 0,5mls CCl4 968>

> and heating continued until H2 evolution starts, when it is stopped, sometimes
even cooling's needed. After the rxn subsides, heating is continued until almost full dissolution of Al (5-7 hrs). The obtained solution is immediately
used as is in the following preparation.
2
Into a 250ml RBF equipped with a 15cm Vigreux column and distilling condenser there's added 53mls (50g) cyclopentanone in 50mls IPA and the soln
from the previous prep'n, which contains about 40g Al isopropoxide. The rxn is gently heated, which causes acetone with some water to distill off. The
distillation is ended when the temp of the vapors rises to ~85°C.
The ppt inside the flask is carefully decomposed with 50% H2SO4 until acidic and saturated with NaCl. The upper layer is decanted and distilled,
collecting the fraction boiling at 137-140°C. Drying with MgSO4.
Yield: 47g (94%)
)

In a flask there¶s mixed 47mls (45g) cyclopentanol and 60mls (90g) 48% aq. HBr. 10g Na2SO4 is added. The rxn is left for 24hrs with vigorous stirring.
After that it¶s diluted with 200mls water and the lower organic phase is separated and washed with water twice. Distill, collecting the fraction between
137-138°C. Dryed with MgSO4.
Yield = 58g (74%)
*

Into a 250mls three-necked flask equipped with a reflux condenser, addition funnel and inert gas inlet there¶s placed 50mls THF (kept over KOH, prior
to the rxn 150mls refluxed over 30g CaO for 6hrs and distilled). 9g of fine Mg turnings is added followed by some iodine crystals. The apparatus is
flushed with argon and a gentle stream of gas is left flowing in. Magnetic stirring is commenced. The mixture instantly beecomes cloudy from MgI.
From the addition funnel there¶s dripped 55g (40mls) cyclopentyl bromide in 100mls THF so that the soln boils smoothly. The rxn is usually over in an
hour, it is accompanied by precipitation of a white jelly-like mass, and at the bottom there maybee left some unreacted Mg as a dark-grey powder.
Usage of THF instead of ether is preferred since the rxn in it proceeds better and faster (THF is a more specific solvent for Grignards) , the yield is
better as well. Beesides, THF can bee dried with CaO, while for ether,sodium metal is usually employed.
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To the thus obtained Grignard soln there¶s added 48g o-chlorobenzonitrile and the mixture is stirred for 3 days at RT. It is then poured into a mixture of
ice/NH4Cl, with addition of some conc. aq. NH3 and left at ambient temp until all ice melts. The ketone partially floats, partially goes to the bottom. It¶s
extracted with benzene.
The yields fluctuate, but rarely drop beelow 55%.
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40g ketone is dissolved in 70mls CCl4 and with cooling in snow it is added into a soln of 48g dioxane dibromide in 50mls dioxane, and stirred at RT for
30mins. Then 30mls water are added and the soln is washed with Na2CO3 aq. until neutral. This may lead to some preciptation of the bromoketone,
which stays in CCl4. The solvent is removed, giving 47g (85%) of the bromoketone.
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45g of the above bromoketone is dissolved in 50mls benzene, add therein 50mls triethylamine (17g/23mL is required for neutralization of HBr, but a 2x
excess is used). The soln is then saturated with 5g methylamine, obtained by dripping a saturated soln of 15g MeNH2·HCl onto 10g NaOH, dried thru
NaOH. The rxn is left for 1 day and the solvents are removed under aspirator vacuum, giving 30g (80%) of methylketimine.
00;
10g of methylketimine is dissolved in 100mls undecane and boiled at 195°C for 3-4hrs. Ketamine is extracted with 20% HCl. Acidic extract is basified
and extracted with DCM. Solvent is removed giving the product as an oil that quickly crystallizes. It can bee purified by recrystallization from
pentane/ether or hexane/ether.
The yields are close to quantitative.
?

Form a solution of sodium hydroxide (NaOH) by placing one tablespoon (15ml) of solid sodium hydroxide in one cup (about 236ml) of distilled water in
the sodium hydroxide solution container. Stir until dissolved. If you are using lye (I don't recommend it), wait awhile to let any impurities settle out to the
bottom. Note that dissolving the NaOH will generate some heat.
Empty your cough syrup or formula into the two-liter, rinsing the last of the cough syrup out of the syrup bottles with distilled water. If using gelcaps,
break them open and rinse out the inside of the capsules.
The following steps in italics are suggested for removing some of the gunk that can make it through the extraction and leave you with a sticky residue
instead of crystalline DXM.
Add in enough lighter fluid to the two-liter bottle to make a roughly 1/4 inch (or roughly 5mm) deep layer of lighter fluid per 4oz of syrup.
Cap the two-liter bottle and shake the living hell out of it for at least five minutes. Let it sit undisturbed until the two layers separate again.
Pour the entire contents of the two-liter bottle into a sealable plastic baggie, and seal it shut. Hold it by one of the top corners so that a bottom corner is
facing down. Let the layers separate again if necessary.
Holding the baggie's corner over a CLEAN two-liter bottle, snip off the very tip of the corner. Let the cough syrup layer drain into the clean two-liter
bottle, but pinch it shut right before any of the lighter fluid drains out.
Discard the lighter fluid by placing it into an empty container and letting it evaporate outdoors. Do not put it down the drain or set it on fire.
That's it ... now you should have cough syrup that has had a great deal of the flavorings and other gunk removed from it. You can repeat the italicized
steps if you want to remove even more.
Add one tablespoon (15ml) of sodium hydroxide solution to the two-liter bottle. You should see a rapid formation of a milky precipitate. Swirl the bottle
gently to mix the syrup evenly, and the precipitate should redissolve (because there's not enough base yet).
Repeat the above step, until the precipitate doesn't redissolve with swirling. The entire solution should be cloudy (stir well to make sure the base is
evenly distributed).
Add one more tablespoon (15ml) of sodium hydroxide solution to the bottle.
Add enough lighter fluid to make a 1/8" (0.3mm) deep layer per 4oz bottle of syrup.
Cap the bottle, shake the hell out of it for five minutes, and let it stand until the layers separate again. If the layers don't want to separate, try adding
table salt.
Carefully pour the contents of the bottle into the sealable plastic bag, and close it shut ("yellow and blue make green-it's sealed!"). Hold the bag by one
of the top corners so that one of the bottom corners points down.
Let the two layers separate again (this should only take a few seconds).
Cut off the tip of the bottom corner and allow the water layer (the bottom layer) to drain out of the bag. When the water layer has drained out, pinch the
bag shut.
Hold the bag over the baking dish, and allow the nonpolar solvent layer to drain out into the baking dish.
Take the baking dish outdoors. At this point, if you don't have a gas mask and a way to heat the baking dish, you'll have to let the solvent evaporate
(which may take a day or so), so skip the next 4 steps.
Put on your gas mask and take the baking dish, hair dryer, and electric heat source outdoors.
Place the baking dish into the container of water (electric wok, electric skillet, hot plate with pan of water, whatever), and set it to simmer. If you can't
set the temperature low enough, you'll have to turn the heater on and off manually to maintain a near-boiling temperature.
Plug in the hair dryer and gently blow hot air into the baking dish. Take care not to splash solvent over the sides of the dish. Incidentally, make sure
you don't overload your circuit; it might be a good idea to alternate heating with the hot plate/wok/skillet and heating with the hair dryer.
Continue heating until all the solvent evaporates. At this point you may see a thin layer of crystalline material; you might see a shiny layer of goo that
looks a lot like the glass itself (which can be confusing); or you might see a layer of brown gunk. Whatever. Anyway, make sure all the solvent has
evaporated.
If your baking dish is covered with an oily substance (goo, gunk, whatever), you in all likelihood managed to extract some propylene glycol (or
something else) along with the DXM. Blow hot air from the hair dryer onto the surface of the dish until the material dries completely (this may take 5 to
10 minutes). This should evaporate the propylene glycol, leaving behind only DXM.
Scrape the DXM off the baking dish with a razor blade or other convenient sharp edge. You now have DXM free base.

Overview:
1 of Natural Oil to obtain pure Safrole
91 Formaldehyde + Ammonium Chloride -> MethylAmine.HCl (MeAm.HCl)
91 Safrole -(Wacker Oxidation(PdCl2+Benzoquinone))-> MDP2P
1 of Reaction contents to yield pure MDP2P
91 MDP2P -(Al/Hg Amalgam (MeAm.HCl) -> MDMA oil

<1 (MDMA oil + HCl in IPA/Xylene) (anhydrous conditions)
What you need:
This list is the basics. Do not even start this without 88 the Chemicals and Apparatus.
Apparatus and Glass:
@:c
8
@ by /' *. (A must, throughout this text, pages from this book will be mentioned. ~32$) (and
very handy pictures of glass set-ups)

(1x500mL and 1x1000mL Round Bottom Flask, 1x250mL Round Bottom Flask, condenser, distillation adapter, vacuum
adapter, thermometer adapter) (Get Ground Glass Joints. These are the best. 19/22 or 24/40 - my first set was 19/22 - and is still used to this day.)
:

(0°C to ~300°C)
(Home Depot - (2x10in., flange, 2 ft. of ½in pipe))
(Buy it. Trust me its worth it) (for holding the glassware to the stand - these support several hundred dollars in glass - buy a nice one!)
i A

(got to have it, its worth it) (www.labx.com - spend $200)

(look on the Web) (teflon coated)
B

(or a good vacuum source. But aspirators are cheap <$20)
= (for distillations. Small shards from a broken coffee mug)
: (about 10ft. total (3 meters) - hardware store - vacuum tubing is better than dialysis tubing - but both will work)
C (not much - for coating of the ground glass joints)

(Prefably pyrex, and in milliliters (mL))
0+
<
A (250mL, 500mL, 1L, 2L etc)
(a three beam analytical balance are great - and can be found for less than $100 - www.balances.com - they can weigh as much as a kilo and as
little as 0.1g - perfect!)
i
(chemical supply) (just one roll will do - ~10$) (nothing specific, just need to tell the difference between an acid and a basic solution)
Chemicals:
.
(160g)(sassafras oil, yellow camphor oil) (Natural/Essential Oil distributor)
.
(DMF) (350mL) (Diethylformamide or Formamide will work)
,=<7 (Quinone, Benzoquinone) (120g) (Photo Shop, or Chem supply)
'
(PdCl2) (2g) (Photo Shop, or chem supply)

(DiChloroMethane, DCM) (this can be distilled from automotive solvents (just go into Nationwise, PepBoys, Sears, AutoZone And
read the labels) Or a Liter can be bought from a Chem supplier.)(Zip-Strip furniture polish remover)
i (1 gram of: HgCl2, Hg(NO3)2, Hg(OAc)2, HgCl, It can be anything, and 1g should last you a long time.)
#
(IPA, Pharmacies 91% Isopropyl Alcohol will be available)(get +3L)(don't get the 70% stuff) (or you can get pure stuff from a chem
supplier)
(Magnesium Sulphate) (MgSO4) (grocery store/pharmacy) (Spread out on a cookie sheet, and bake in the oven at 200°C for 3hr to dry
them - pretty useless if you don't dry it)
:- . (heavy duty, or pie pans from the Grocery store)

(31.45% HCl)(Pool pH down, Driveway cleaner, ~3$/gallon)
i
(NaOH) (Drain Cleaner Crystals) (Read these labels, Get the stuff that is JUST NaOH.) (Red Devil Lye, Lye - Hardware Store)

(NH4Cl) (Photo Store or Chem Supplier)
'
.
(Hardware store) (called Mildewcyde or DiGas - made by the same people who brought you Damp-Rid - hint-hint)
' (this is a high boiling oil that we will use as an oil bath on the hotplate/stirring plate combo)
(for cleaning your glass and crystal work-up) (Paint Section of Hardware Stores)
? (for crystallization) (paint section - thinner - get it specifically)

Step 1. (4 hours)
1. Distillation: of Natural Oil to obtain pure Safrole.
A Comprehensive Description of This Step by Chromic
Set up for a vacuum distillation like on page 53 of Zubrick. Always put a little Vaseline on the ground glass joints - this way they won't stick when you
try to take them apart. Put as much Natural oil (Sassy, Camphor, ect) as you have, but not more than 300mL, into the 500mL Round Bottom Flask
(RBF) with several Boiling Stones. Put one of your 250mL RB flasks as the receiving flask. Set up your Water Aspirator Vacuum, in the sink (this may
require setting this up a day before - parts, trips to the plumbing store, etc.) and attach the vacuum hose to the aspirator and then to the vacuum
adapter on the distillation set up. Start turning up the heat slowly! SLOWLY! The slower you do it, the better/purer your safrole will be. At normal
pressure safrole boils at 232°C - but under your vacuum, it may boil at anywhere from 110-160°C. Whatever temp it starts to come over at - make a
note of it. And if the temp is higher than 160°C - check your seals on the tubing and glassware - More than likely there is a little leak. Remember that
Vaseline! At the end of the distillation, you should have a water white oil that really refracts light - And has a lovely smell - a little like potpourri.
Distillation set-up: Set up the distillation set-up on your bed, before you try to put it together on the stand. You will get a good idea about how the
pieces go together, and become familiar with the fragility of the whole thing. Read Zubrick for advise about where to place the clamp.
The Peanut Oil: A bowl with a flat bottom rests on the Hotplate. It is filled with Peanut Oil. The distillation flask sits in the bowl but not touching the
bottom, so that the Hotplate heats the bowl, the bowl heats the Peanut Oil, the Peanut Oil heats the distillation flask. This is VERY effective. And will be
perfect for all your distillation needs - especially if you do it under vacuum.
Step 2. (2 hour work + 4 hours wait + 4 hours work)
2. Rxn: Formaldehyde + Ammonium Chloride -> MethylAmine.HCl
In your 500mL RBFlask: Set up for distillation (not vacuum). In the distillation flask (your 500mL RBFlask) put: 108g of NH4Cl, 120g Paraformaldehyde
(molecular ratio 1:2, remember this when scaling up!) and 320ml of water and several boiling stones. Start heating very SLOWLY. Remember to turn
on the water in the condenser!
At 80°C a clear solution was obtained. Heating continued - The temperature was maintained for four hours at 104°C (this temp is VERY important - if
you over shoot it - don't worry - bring it back down and try to stabilize it at 104°C) Once you've got it at 104°C start the stop watch and do it for 4 hours.
At 104°C, a small amount of distillate will come over - very slowly - this is good. We are removing methylal, and methylformate from the reaction
contents and therefore driving the reaction to the right - or getting more of what we want.
After four hours and while the solution is still hot, set up to vacuum distill (IE its already set-up - now just add the vacuum hose!) - but don't turn on the
vacuum yet. Turn up the heat. Within 30 minutes or so - liquid should start coming over - the internal temp of the mixture should not go over 200°C -
Keep distilling off the liquid until ½ of the solution remains - (IE distill off half of the solution.) Then, take your flask off the Hotplate and let it sit in an
ice/water bath. Crystals should start to form in several minutes. Filter off these Ammonium Chloride Crystals. Now set up for distillation of the remaining
liquid again - Add a couple more boiling stones. Distill off half of the remaining liquid. When half remains (or a ¼ of the original solution), turn the
vacuum on SLOWLY! VERY SLOWLY! - you don't want the whole mess of liquid jumping out at you. At some point the whole mass will crystallize into
a yellow-white solid. This is ~95% MethylAmine.HCl, ~2% Ammonium Chloride, and 3% DiMethylAmine.HCl. This is fine for the next step. It may be a
little wet, but if you let it crystallize hot (spontaneously in the flask with heat) it should be fairly dry. Seal it in a wide mouth jar until needed.
As a way to check your product - if you live in a relatively humid area, you can put a crystal of your product on the table - walk away - and when you
come back a small puddle of water will be on the table where your product was. MethylAmine.HCl is said to be HYGROSCOPIC. Another way is to put
20mL of water in a cup then add 5g of the NaOH to it. Stir to dissolve. Now, drop several crystals of your product into it - it should smell like rotting fish
+ ammonia. If you do the same with Ammonium Chloride, it will just smell like ammonia.
You'll recover about 1/3 of the ammonium chloride for recycling and after a lot of evaporating. You'll get ~80g of pure (95%) MethylAmine.HCl, which
corresponds to ~80% yield. Congrats. This can be stored at room temperature, forever. I've heard of people using 40+ year old MethylAmine.HCl with
excellent results.
Paraformaldehyde is the polymerized form of formaldehyde - but unlike most polymerization processes - this one is reversible - so Paraformaldehyde
and formaldehyde can be interchanged at will. If all you can get is formaldehyde solution - remember that if its 37% formaldehyde then 100g of the
solution contains 37g of formaldehyde - or just go ahead and change your amounts in the flask to - 324g of 37% Formaldehyde Solution, 108g NH4Cl,
205mL water.
Step 3. (2 hours work + 7 hours wait + 1 hour work)
3. Rxn: Safrole -(Wacker Oxidation (PdCl2+Benzoquinone))-> MDP2P
This step has been called the Wacker Oxidation. It uses PdCl2 as a catalyst to put and oxygen across a double bond. This step has been worked over
many times so do not change the amounts for the fabled 'scale-up'. If you do this correctly, you will have more MDMA.HCl than you know what to do
with. (Thanks Strike!)
Procedure:
Put the following into your CLEAN 1000mL RBFlask:
300mL of dimethylformamide (DMF), 50mL of tap water, 120g of p-Benzoquinone 2g of Palladium Chloride (PdCl2), Magnetic Stirbar. 134
5
*
6#
Start the stir bar on 'slow stir'. Mix 160g of Safrole and 50mL DMF in a cup/jar. Drip the Safrole/DMF Mix into the solution at room temp (30°C) over
30min time. After the addition, the solution was dark reddish orange. Almost black. Make sure the stir bar is spinning - Now - Walk away. Go to bed. Go
somewhere else. Set your watch alarm to wake/remind you 7 hours later. "1 This reaction requires NO additional heating! Just stir!
Strikes comment: "After 4.5 h the solution will progress on its own to 45°C. Obvious exothermic reaction. After 7 h solution will be back to ~30°C."
The reaction mix was flooded with slightly acidic water (~50mL of Muriatic Acid (HCl) in 1.5L of water). The oil fell out of solution to the bottom. It was
black/blood red in color. This is when its nice to have a Big Sep Funnel.
Now we need to define several things. The upper layer (in this case!) Is the aqueous layer - IE it's the layer that contains the WATER - the bottom layer
is the organic layer (in this case!). IE it contains oil and other ORGANIC type molecules (IE the stuff you want!).
After you flood the reaction contents shake the container to mix the solution, give it about 10 minutes to settle - two layers will form. The upper aqueous
layer was a lighter blood red/pink. The upper aqueous layer was decanted from the oil (IE it was poured off). The aqueous Layer washed with 2x100mL
DCM (Methylene Chloride / DiChloroMethane). If you can't see the layers, hold the container up to the light, so that the light shines through the
container. Keep the DCM washes - They contain the goods.
You now should have about 200mL total of DCM washes. You should also have about ~100mL of the 'Organic Layer' that you separated from the
reaction contents. Pour the DCM washes and the Organic layer together. Now wash the DCM/Organic layer with 2x150mL 10% NaOH (30g NaOH in
270mL water). This will remove the other reaction by-product - hydroquinone. If you don't do this step the hydroquinone will clog your condenser when
you try to distill. Keep the DCM/Organic layer. The NaOH layer (Aqueous: is still on top) can be tossed. (Thanks Osmium!)
You can stop here and wait for another day - put the DCM/Organic Layer into the freezer.
Define Washes - 100mL of DCM was poured into the aqueous layer and then the aqueous layer+DCM was shaken so the two would mix - then it was
put down to let it settle out again. When it was settled (notice that the layer now is a different color) the aqueous layer was poured off again into
another jar where it was washed again with another 100mL portion of fresh DCM = 2x100mL washes.
Step 4. (4 hours work)
4. Distillation: of Reaction contents to yield pure MDP2P
Pour the DCM/Organic layer into your CLEAN 500mL RBFlask. Put several boiling stones in too. Set up for vacuum distillation.
This time we are going to collect a particular fraction in the flask - there is DCM (BP 40°C), water (BP 100°C), DMF (153°C), safrole (232°C), ketone
(BP ~290°C), and polymerized crap (BP ~300°C+)
Now remember when we distilled the safrole? What temp did it come over for you? Well - that temp plus approximately 25°C is the temp that the
ketone will come over under vacuum. For example, if your safrole comes over at 150°C, then the ketone will come over at 175°C. If your safrole comes
over at 130°C then your ketone will come over at 155°C. Get it?
WEIGH the receiving flask! Write the weight on a piece of tape and tape it to the flask!
Start your vacuum distillation by first turning on your vacuum - if you remembered your boiling stones, then it will begin to boil immediately. This is the
DCM coming off first. The boiling may be very vigorous, So watch it, and be prepared to vary the pressure so it won't fly into your receiving flask. Turn
on the heat (Hotplate) SLOWLY! and let the temp climb to just over the temp at which safrole came over (SLOWLY: it should take at least 2 hours to
reach that temperature - if you do it in under 2 hours you are going WAY to fast). You are going to have to change the flask, when the temp gets to
above the safrole temp. This is a bit tricky, because you are going to have to release the vacuum. Release the vacuum at the pump/aspirator and
change the flask quickly - you may just dump it out, rinse it once with acetone, or IPA (IsoPropylAlcohol) - and put it back. Start the vacuum
immediately, but be careful here, because the Organic layer that you are distilling might jump out of the flask and into the receiving flask - so if you can
- vary the vacuum so that the vacuum comes on GRADUALLY! (IE with an aspirator, turn on the water slowly.) The ketone oil is a clear white/yellow
hint of green oil. Re-weigh the flask for your yield calculation - you should have over 100g of ketone.
With an aspirator you can vary the vacuum when you are turning it on. You simply turn on the water slowly. IE Increase water pressure slowly. By
turning it off, you can make water jump into the receiving flask because there is a 'vacuum' in the distillation apparatus and it will suck water out of the
aspirator - SO - when you turn off the vacuum, do so by removing the hose from the aspirator - while the aspirator is going. You can also vary the
vacuum by removing the hose PARTIALLY - This will take some practice so play and have fun.
Strike's excellent post read: "With high vacuum at 100-140°C ~18g safrole came over. At 166°C came over ~125g ketone." When she did this
method...
Keep the ketone. Smell it. Look at it. Look at how it refracts light. For the brave: taste it. Note all of these 'properties' and remember - After you have
judged its properties, put it in the freezer. Note: it won't freeze. It will become a very viscous liquid.
If you try to distill the ketone at atmospheric pressure (no vacuum), you will get to about 220°C and then the whole flask will polymerize. Total waste of
effort, time, and precursors. So don't mess around and get a vacuum source.
The ketone is unstable. It won't explode or anything, but if left to its own devises, it will rearrange. And then it will be useless. At room temp, it will
rearrange in about a week - depending on where you live - if you keep it in the freezer - it can last months - FREEZER! After its in the freezer you can
stop for today.
Step 5.
5. Rxn: MDP2P -(Al/Hg Amalgam (MeAm.HCl) -> MDMA oil
-
*) ! 3
6#
This is called the Al/Hg Amalgam. This process utilizes the electronegative properties of the Aluminum. Now, something that most people don't realize,
is that all aluminum is actually coated with Al2O3. This is the oxidized form of Aluminum. We will remove this part of the foil so that the aluminum can
reduce the imine with elemental Al.
This reaction actually has two parts. First, there is the ketone ĺ imine condensation. This reaction reacts the ketone with methyl-amine to form an
imine - water is produced as a product. Second, the imine is reduced (Hydrogen is added across the double bond) to the amine. The condensation
really needs anhydrous (no water) conditions, and the reduction actually needs water - so there is a fine balance here - IE don't mess with the
procedure.
B

. 1
CLEAN 500mL RBFlask.
20g of thick aluminum foil cut into ~1cm squares.

0.1g of Hg(salt) (any mercury salt will do, not Hg Metal)
(Note: Hg=Mercury)
Disposal Jug (milk jug)
1L of Clean water
25mL of 25% NaOH solution (dissolve 25g NaOH in 75g of water, then 25mL of it)
50g of MethylAmine.HCl dissolved in 300mL of 91% Isopropyl Alcohol
40g of 'ketone' dissolved in 50mL of 91% Isopropyl Alcohol
Cool water bath. (A milk jug with the top cut off)
Ice (don't screw around, buy a bag) (or have at least several kilo's handy)
Set up your stand and clamp so that, when the flask is clamped to the stand the bottom of the flask is about 4 inches (10cm) from the table top. This is
so that you can put the heating plate and stirbar combo under it. Have your thermometer already in its thermometer adapter so you can throw it in the
flask at any second.
'

.!( D

1
50g MethylAmine.HCl dissolved in 300mL 91% Isopropyl Alcohol
40g 'ketone' in 50mL of 91% Isopropyl Alcohol
It is very important that these are ready before you start! =.

>
20g of Al squares are put into the 500mL RBFlask. They are covered with ~350mL of H2O (water). 0.1g of Hg(salt) (or just a very small spatula) is
placed in with the Al squares, and given a good stir. Amalgamation was allowed to proceed until there was the evolution of fine bubbles the formation
of a light grey precipitate, and the appearance of occasional silvery spots on the surface of the aluminum. (Thanks Dr. Shulgin!)
Basically here the Al2O3 is being destroyed, the water is reacting with the Al2O3 to form Al(OH)3 and H2. This should take between 15 and 30
minutes. Just be patient.
When amalgamation is complete, pour out the water into the milk jug. Pour in another ~350mL of water and carefully shake the flask to stir up the
contents. Pour it out into the jug. Do it again with another ~350mL of water. So basically, you wash the Al pieces with 2x350mL of water. Dump out as
much of the water as you can in 10 seconds or so - then immediately go to the next step - leave the Al foil in.
This will remove most of the Hg from the solution. Don't worry, the Hg will be completely removed in the successive washes during the work up. If you
let the Al squares sit in between washes, they will heat up and re-form the Al2O3 in a matter of seconds. So be quick and have the ingredients ready
for the procedure.
"!( (:i#

1
50g MethylAmine.HCl dissolved in 300mL 91% Isopropyl Alcohol
40g 'ketone' in 50mL of 91% Isopropyl Alcohol, then drop in a Magnetic Stirbar. Try to get the stirbar going - it might take several minutes.
Now drip this in 25mL of 25% NaOH solution over several minutes. Put the thermometer in the solution. Start being very paranoid about the
temperature. The temperature of the reaction flask must not climb above 60°C. Its best if the temp is kept around 50°C. Stirring is necessary so, with
the heat off, stirbar on, flask sitting in the cool water bath. When the temp gets to about 50°C, put several chunks of ice in the bath. If the temp falls
below 40°C, take some of the ice out. But whatever you do, make sure the temp remains below 60°C. The whole time you are doing this the contents
are a grey sludge. Remember to keep the stirbar going! If the stirbar is difficult to start going. Don't worry, trying to get it started seems to work just
enough.
At some point you'll notice that the temperature is not rising like it had been (in about 4 hours or so). You have reached the end of the ketone -> imine
condensation - Look inside the reaction flask and see if you still see any pieces of Al foil - if you do - continue stirring until the Al foil has been depleted.
This reaction should go no less than 6 hours.
Now, after you are convinced that the reaction has stopped (6 hours later) - IE the temp of the solution is room temperature, and there is no more foil
chips in the mix. Pour in 25mL of the 25% NaOH solution. Stir the contents some more, and then let the stirbar stop and then let the solution rest for at
least 30 minutes. The NaOH solution will make that grey sludge into a filterable consistency. If you can't tell there has been a change in the
consistency - put in another 25mL of 25% NaOH solution. The grey sludge should abruptly change from a uniform grey to a chunky white/grey blob.
Then in a matter of minutes the whole thing will be resting on the bottom of your flask.
The reaction contents will settle out. The grey sludge will settle to the bottom, and a clear yellow liquid will rise to the top. Pour off the clear yellow
liquid. Save it. Put 200mL of 91% Isopropyl Alcohol into the reaction contents, stir the solution, so that the whole thing is disturbed and swirling in the
flask and again wait. Pour off the 2nd clear yellow liquid once it settles. Add the 2nd clear yellow liquid to the first. Do this several times, or until the
clear liquid is no longer yellow.
This is an extraction out of the reaction contents. The more you do this process, the higher your yield. So don't do it once and get excited and try to
complete it with just the first extraction because you will just waste half of your product. You've gone this far - don't fuck it up now.
After you have gotten as much of the yellow liquid out as you could. Put the grey sludge in the same milk jug waste container. Dispose of it properly -
the milk jug contains elemental Hg - Not a lot - less than 0.1g. But you should dispose of it properly. Not down the sink. Take it to a High School or A
University, To the Chemistry department - tell them you broke a thermometer, and then couldn't figure out what to clean it up with.
Set up for vacuum distillation (Boiling Stones!) but we're not going to distill. We are going to evaporate the Isopropyl Alcohol (IPA) from the reaction
contents. Under an aspirator vacuum, the IPA should come over around 35°C. Make sure you get the alcohol out. When the alcohol is close to being
gone - the solution might spontaneously separate in your distillation flask. Not to worry - the top layer is probably your product, and the bottom is water.
Don't try to separate it, just dump the whole thing into the next procedure.
The next two paragraphs out line a procedure known as an Acid/Base extraction. This works very well for our target molecule, and any molecule that
contains an amino group. If the next two paragraphs are not done, then plan on not having any crystals when you're done.
After the alcohol has all gone, Take the brown oil that is left and put it into 500mL of ~0.5M HCl solution (470mL water + 30mL of Muriatic Acid). Stir or
shake it up. A lot of the brown oil should go into the acid solution. Now pour into this solution 30mL of DCM. Shake again and let it settle. You will
notice two layers formed - The top layer is the Aqueous layer - which your product, and the bottom layer contains the DCM, polymerized
crap, and non Nitrogen containing molecules. Pour off the top layer (That your product) and discard the DCM layer. Wash the Aqueous layer
again with 30mL of DCM, and repeat the process. " that the 7

-
7
! You can
discard the DCM washes, because they contain nothing useful what-so-ever. Discard!
Now, slowly add 50mL of 25% NaOH solution to the aqueous layer. When you do this the Aqueous layer will turn a milky white and may heat up just a
little bit. Not to worry. A light brown oil will fall out of the solution. This is your product (in the freebase form). Before collecting it, wash the 'now basic'
Aqueous layer with ~50mL of DCM. Shake and let it settle out. Pour off the top Aqueous layer, and - ! The DCM washes
! Wash the aqueous layer twice more with 50mL of DCM. Combine those DCM washes that contain your product, and continue.
Set up for vacuum distillation, and once again, just boil off the DCM (Boiling Stones!). There might be a little water in it, so this time when you are
boiling off the DCM, let the temp of the distillation flask reach ~50°C for several minutes. That should be good enough. You should have a light brown
oil in the flask - it kind of looks like thick Newcastle Beer.
Step 6 (2 hours work)
6. Crystallization (MDMA oil + HCl in IPA/Xylene)
This must be done in anhydrous conditions. If its not, then you will not get crystals. Anhydrous means 'no-water'. If water is present, then you can
expect to get crapola.
Procedure:
This first step can be done ahead of time. Like, during a distillation or reaction: Get a fresh bottle of 91% Isopropyl Alcohol, and pour out approximately
100mL. Now get some of your DRY Magnesium Sulphate (Epsom Salts) (about 100mL worth) and dump it into the 91% IPA. There might be a little
heat evolution, but not to worry .... Shake it up and then let it sit till the MgSO4 settles out. Pour off the IPA, and then put more fresh MgSO4 into it
(about 100mL worth). Now shake the bottle and let it sit for 15 minutes. You must do this at least three times - It really is much better to do it four times
- Why fuck it up now right? After three times you will have 'Dry' IPA. You can actually do this while you are distilling or waiting for a reaction to proceed.
Make a mixture of 100mL 'Dry' IPA and 150mL Xylene. Pour it into the flask that contains the MDMA oil, and drop the stirbar in too. Stir so that the
whole thing is mixed up real well - Now drip in Muriatic Acid slowly. Test with pH paper every 5 drops or so - keep adding the Muriatic Acid until the pH
of the solution is 5-6 - or just barely acidic.
Set up for vacuum distillation, and distill the solution, distill this with the stirbar in instead of the boiling stones - IE When the solution has reached a pH
of 5-6 - Start distilling. Be careful not to let the solution get above 120°C - When a lot of the solution has boiled away, crystals will spring to life in the
flask. Under vacuum, the solution should never get above 70°C.
Filter these with a coffee filter, suspended over a jar - This gets the excess IPA/Xylene out. Scrape the crystals on to a plate and let the crystals dry, by
letting the IPA/Xylene (mostly Xylene at this point) evaporate - this might take several hours - a 60 Watt lamp 6 inches (20cm) away from the crystals
shining brightly helps. Stir the crystals to promote even heating.
The crystals will be a brown-yellow color. Now scrape the crystals into a jar, and pour ~20mL of acetone onto them. Swirl the mixture. The crystals
won't dissolve - but a lot of the brown will. The brown-acetone is poured off, and the acetone wash is repeated.
After the acetone wash, dry the crystals. You should have around 15g of dry crystals. That's 150 hits. The now 'almost white' crystals have melting
point values over the range from 145-153 ° C, depending on how much water was in there during crystallization. And these crystals are ready for
consumption. 60mg is not enough. 80mg is great for my wife. 100mg is a great dose. 125mg is balls-to-the-wall. 150mg is too much. For me at least.
Fun for me is actually 80mg MDMA+70mg MDA in one pill. WHOH. But I guess you'll have to do another synth - right?
[

p
Ok, this is an amalgamation of many peoples methods! I beleive this to be the best, simplest, fastest, and cleanest method for producing meth-
amphetamine, in the highest yeilds possible for RP/I2/E reaction! Remember, each and every step gives small losses, and this method has the least
steps! It is a culmination of efforts by, Worlock, CHEMMAN, and maybe a few tiny touches by me! I re-iterate, I don't want any congratulations except
for the write-up itself!
You will need these things, and no substitutions allowed! If you can't get this shit, you aint ready to make the best Go-Go in town! This is a refinement
of all methods, and the next step up from Push Pull, But nobody should be dicouraged from attempting this, as you will probably find it easier! PH
paper, isn't even necessary!
This post is one method from Go to Whoah! This post has to be followed from GO to Whoah! Otherwise you can run into trouble, as povidone is not
removed in this extraction! It will be removed at the end! Each step was chosen to compliment the next! Understand?
Equipment
Various jars
2L pyrex vessel
2L 2 neck round flat bottom flask
1 condenser, I reccomend a coil condenser but a liebig will suffice!
1 sloping splashhead or better still, a steam distillation sloping splashhead!
A steam pressure cooker, that has releif valve at top
Hotplate, electric of course!
Filter paper, Bucner and vacuum would be nice too!
thermometer
1 glass stopper
lengths of clear pvc tubing
Pot with vegetable oil, that can fit your reaction vessel
Reagents (All must be clean and anhydrous!)
Iodine crystals
Red Phosphorous
Pseudo-ephedrine, or ephedrine
Methanol
Toluene
Acetone
NaOH
Ice
Extraction of pfed
Ok, this method will deal with the Hcl salt of pfed, and a streamlined version of "the cure"! All pills are dumped into a large jar and double the volume of
methanol poured on top! This is stirred vigourously and let to settle, in the fridge seems to speed it up! After top methanol layer has cleared it is
carefully decanted off. This procedure is repeated 3 times. All methanol pulls are put together and reduced on a hotplate. As methanol gets down to
last little bit, it is taken off heat Then a portion of acetone, twice your remaing liquid is dropped in. This forces the pfed crystals to crash out. Then
remaining liquid is carefully evaped off.
Now you have your crude/dirty pfed Hcl. Next we will be doing successive toluene washes So put your pfed crystals in a pyrex (heat proof glass) Now
add toluene to a safe level that can be lightly boiled on hotplate After about 5 mins boiling with stirring. Take off heat and let settle a minute. Now
carefully pour off toluene into a filter to catch any remnants of pfed that may follow. Now if you get the toluene that has our contaminents in it and add
some water You will see the crap crash from the toluene into the water This is the crap that came thru with the methanol pull!
So as we continue to do multiple toluene washes, We will continue to test the toluene after pouring it off, To see how we are progressing with the
cleanup! When we have reached a point where no crap comes out of the toluene, With the addition of water, then we are ready to try acetone! Usually
about 3 boils in toluene, but of course it depends how much your using! So, as before we will add a portion of acetone and boil lightly! Now when we
pour off the acetone, we will add a tiny amount of water and some NaOH This is our final test, when you do this and no crap falls out of acetone you
are ready!
This will be the cleanest pfed you have ever seen, guarenteed! AND, yeilds should be >90% if your careful! 95% is good.
Reaction
Smallest reaction to be attempted, especially by newbees, is 1oz of pfed! So that even taking into account sloppiness, lack of experience and losses
along the way You should get some product!
Ratios of reagents are, 3:3:1 or 1:1:1/3 ie.E:I:RP aka, equal amounts of Iodine and pfed, and a third as much RP! Comprenda!
Ok first prepare yourself an icebath! Yes icecubes and water in a sink or bucket! Now, many will say you should add this first or that first! Well after
much reading of different peoples methods, I say.... Chuck the whole shebang in together, while your flask is on ice, Lift and swirl ingredients together,
while maintaing on ice! Put your condenser on top and start water running thru, from bottom to top! Now, the idea is to get the reaction going in the
most controlled way possible. Now you want to let reagents react in the icebath, if at all, Then move vessel from icebath to room temp, If things look
like they're going too fast, put back in ice bath, You want to keep the reaction going but only at a nice slow, controlled pace! This is also necessary to
control vapour in the condenser! Thick and or dis-colored smoke is bad! and plumes of smoke will escape from condenser As things progress at a nice
slow pace, as things slow too much you can start applying heat! So prepare an oilbath and bring to about 50c, now if there is no more action in your
vessel You can move it to the oilbath, and same as before, when things slow down, Adjust heat up, to say 100c then 150c for one hour, to make sure
reaction has completed The whole time you should be watching to keep a nice reflux going, and not too much vapour is escaping from condenser!
Now remove from heat and disconnect condenser, Now add ice water to quench reaction, reason for ice water is to calm the reaction down when
NaOH is added Now its up to you if you want to filter out RP or leave till the end I would leave it, it will be washed nicely by next process and be easier
to filter! Now add lots of NaOH to bring reaction mix to positive 14PH You cannot over-basify as meth won't be destroyed, its a tough MF!
Steam Distillation
Now you need to set up your glassware for steam distillation! So attach steam distillation sloping splashhead to top hole of flask! Now attach plastic
hose to steam inlet and other end, on release valve of pressure cooker that is full of water! Now attach condenser on end of splashhead, and rig up
some kind of prop for it to stay up! Now place a jar at the end of condenser to catch our distillate! Now you want to heat both the pressure cooker, and
the reaction flask! Now sit back and get ready for one of the most beautiful sites and smells! The meth freebase that is sitting on the top of your
aqueous layer in flask will vapourise and be carried across and be condensed in the condenser and trickle down into your jar It will sit atop a bottom
layer of water! After the last of the oil has come across, change jars and leave the setup to run for another hour Just to make sure you got it all! Any
povidone from the pills will be stuck behind in the reaction vessel It has been noted that some polymer that may have been left from extraction, may
follow the steam!
Crystallisation
So, now we have a jar of water, with this sweet clear oil sitting on top! Now options are to add Hcl acid slowly with stirring until oil layer disappears and
then evap the whole lot to get crystals! Or, as I found, you may have some polymer that has come over with the steam and is now sitting in the water
layer, and it looks cloudy! So I don't want to evap all that, it will just concentrate the shit in there (plus its very time consuming evapping water, plus you
risk losing some meth as the water evaps) So, I think you should just throw a little toluene into jar, and then seperate! Now your absolutly pure meth
freebase is in your toluene! Now you can either gas, for instant clean meth, or Add minimal DH2O and then acidify to PH7, shake, seperate and evap
water for crystals! repeat this step if you do it this way, as some more may come in second go!
Now with this process from start to finish, you shouldn't need to re-crystallise As your product should be the cleanest shit anybody has ever seen
anyway! But you may want to for the purpose of growing nice big crystals! In which case, add just enough hot methanol to dissolve all your meth and
then place in freezer. The secret is, the slower the evap, the bigger the crystals! So a nice slow room temp evap over several days might be fun!
Enjoy, and do not attempt anything above, before you completely understand what you are doing! You must have a sound understanding of the basics
first!

Summary
A simplified total synthesis of the single enantiomers of cocaine and racemic cocaine is outlined. The synthesis employs common laboratory
glassware, reagents, and methods which can be performed in most forensic laboratories. The procedure for the isolation and purification of the
dextrorotatory enantiomer of cocaine is presented.
Introduction
In many jurisdictions cocaine is listed as a controlled substance under statutes covering coca leaves and their extracts. Therefore only the levorotatory
isomer of cocaine would be controlled. These laws do not include optical isomers and diastereoisomers. The question of enantiomeric composition has
recently become popular with defense attorneys. (-)-Cocaine is the naturally occurring alkaloid extracted from coca leaves. Racemic and (+)-cocaine
can only be obtained through a chemical synthesis.
The molecular structure of cocaine was first described by Willstätter and Muller1 in 1898. It was not until the early 1950's that the, principles and
methodologies of stereochemistry were applied to cocaine's tropane ring skeleton. Findlay2, Fodor3,4, and others established the stereochemistry of
the tropane alcohols and their esters. Once this groundwork was laid, the three-dimensional structures of cocaine and its diastereoisomers
(pseudococaine, allococaine, and allopseudococaine) were elucidated by Findlay5-7 and Hardegger 8 Findlay's three-dimensional structures
were confirmed in 1968 by Sinnema 9using NMR spectral analysis. Electron impact fragmentation patterns of the tropane alkaloids were later
established by Blossey 10 These workers identified the major mass spectral fragmentation patterns by deuterium and substituent labelling.
Fragmentation patterns for various tropinone analogs have also been determined by Kashman and Cherokee11.
Methods for detection of cocaine diastereoisomers have been established by Allen 12, Olieman 13, Sinnema 9, and Lewin 14
These methods incorporate IR, GC, GC-MS, NMR, and HPLC. Identification of the different enantiomeric mixtures can be done as illustrated by
Eskes15 and Allen 12 One report has been published concerning the detection of cocaine co-synthetics. This work by Cooper and Allen16 lists
and identifies the three most reoccurring substances.
60
Synthetic route to 2-CMT.
The first total synthesis of cocaine was accomplished by Willstätter 17 Cocaine is prepared following a 3-5-step synthesis which includes one
separation of epimers. This route is usually ()-2-carbomethoxytropinone (2-CMT) ĺ ()-ecgonine methylester (EME) ĺ ()-cocaine. The reduction of
2-CMT with sodium amalgam yields a mixture of ()-EME and ()-pseudoecgonine methylester (PEME). If this epimeric mixture is not separated prior
to benzoylation, a mixture of ()-cocaine and ()-pseudococaine results. Any unreacted tropinone or 2-CMT will become benzoylated to yield two co-
synthetics identified by Cooper.
It has been shown by Findlay18, Cooper and Allen16, and myself (unpublished) that direct synthesis of 2-CMT gives greater yields than the
carbomethoxylation of tropinone. Preobrashenski19 and Wallingford20 synthesized 2-CMT and other beta-keto esters from condensation of alkyl
carbonates with ketones. Findlay, Cooper, and myself found that such a route gives poor yields with resinous by-products. It is noteworthy that Carroll
et al.21 obtained 2-CMT in 80% yield through an alkyl condensation.
Methylamine, acetonedicarboxylic acid, and succindialdehyde are potential starting materials for the synthesis of 2-CMT. 2-CMT is synthesized by first
converting acetonedicarboxylic acid into its anhydride (84%) and then preparing the methyl ester from the anhydride (99%). These compounds can be
synthesized following the procedures of Adams et al.22, Kaushall23 and Findlay18, respectively. The mono-methyl ester of acetonedicarboxylic acid is
reacted with methylamine and succindialdehyde via the Mannich condensation to yield 2-CMT (86%) (Fig. 0). Thus the overall yield of 2-CMT is 71%.
Data has not been published concerning optimum conditions for 2-CMT synthesis. However an analogy can be drawn from tropinone and 2-CMT to
pseudopelletierine optimum synthetic conditions. Pseudopelletierine is a ring homolog of tropinone having an eight-membered ring as opposed to the
seven-membered ring of tropinone. Optimum conditions for its synthesis were established by Cope et al.24. Those workers found that a buffered
solution at pH 3-4 and 25°C gave highest yields. Data by Schoph and Lehmann25 show highest yields at pH 5-7. Preliminary experiments in our
laboratory to synthesize 2-CMT, via the conditions of Cope and Schoph's pseudopelletierine synthesis, indicated the optimum conditions for 2-CMT
synthesis were at pH 4-4.5 and 25°C (unpublished). I also found that a buffered reaction is critical for good yields of product. Cope stated that without
buffered reactions the pseudopelletierine condensation reaction had a pH rise of 3.5 units. Keagle and Hartung26 found that tropinone was prepared in
highest yield with 0.0225 mol succindialdehyde per liter of solution. My work has shown an 86% yield of 2-CMT from 0.053 mol succindialdehyde per
liter of solution. Mastering the ring coupling Mannich reaction is the key step in producing synthetic cocaine.
All practical routes to cocaine have used 2-CMT as the common intermediate. These routes include procedures by Findlay18, Keagle26, Kashman11,
Bazilevshaya27, Sinnema9, Schopf25, Robinson28,29, Mannich30, Preobazhenskii19, Zeigler31, Zeile32 and Willstätter17,33,34. New synthetic
methods for entry into the tropane skeleton have been reported by Tufariello35-37, Hawakawa38, Noyori39, Parker40, Peterson41, Iida42 and
Kashman11 but are novel approaches with complicated synthesis.
6$
Reduction and benzoylation of 2-CMT
(Single enantiomers are depicted for simplification,
i.e. (-)-EME, (+)-PEME, (-)-cocaine and (+)-pseudococaine).
The reported sequence of synthesis (Figs. 0 and $) combines several procedures found in the literature. Clean-up procedures are based on the
desired intermediate's solubilities in organic solvents.
2-CMT exists largely as the enol when hydrated and all three keto-enol isomers are present in solution. The keto nature allows it to be reduced by
sodium amalgam to EME and PEME. The reduction is carried out at near the freezing point of water in an acid medium to yield the equatorial 3-
hydroxy isomers of EME and PEME. The C-2 axial epimer EME is thermodynamically less stable and is easily irreversibly epimerized under basic
conditions to PEME. Clarke et al.43 attempted to influence the ratio of axial to equatorial C-2 epimers in their initial reactions but were unsuccessful.
EME is a colorless oil which is hydroscopic and any water absorbed causes slow hydrolysis to ecgonine. Aqueous alkaline solutions will also cause
slow saponification. The conversion of EME into cocaine was studied at length by DeJong44,45. Various solvents and alkaline drying agents were
used in his benzoylations. Sinnema et al.9 also reported benzoylations with high yields.
Resolution of cocaine's enantiomers is accomplished through bitartrate recrystallizations. This resolution can be performed with 2-CMT prior to
reduction and benzoylation as demonstrated by Carroll #, Clarke et al.43, and Lewin et al.46,47.
Synthesis
Acetonedicarboxylic acid anhydride
To a solution of 30 ml glacial acetic acid and 22 ml of acetic anhydride (7 ) at 10°C was slowly added 20g (0.684 mol) of 1,3-acetonedicarboxylic
acid (V ). The temperature was not allowed to rise above +12°C until the reaction was complete. For runs where precipitation of product had not
occurred within 3 h, it was induced by the addition of benzene. The product was filtered by suction filtration, washed with 100 ml of glacial acetic acid,
and next washed with 100 ml of benzene. It was allowed to dry yielding 14.8 g of white powder (84%).
Succindialdehyde
To 400 ml of 0.2 N sulfuric acid was slowly added 44.2 g (0.334 mol) of 2,5-dimethoxytetrahydrofuran (V ) and stirred for 15 min. The
succindialdehyde was allowed to stand for 4 h without further treatment.
Acetonedicarboxylic acid monomethyl ester
To a flask containing 41.0 g (0.32 mol) of acetonedicarboxylic acid anhydride was added 160 ml of cold dry methanol. The mono-methyl ester solution
was allowed to stand for one hour and filtered.
()-2-Carbomethoxytropinone
Six liters of 4.4 pH citrate buffer was made by diluting 35.3 g of citric acid and 38.8 g of sodium citrate dihydrate to volume. To the buffer was added
32.0 g (0.48 mol) of methylamine hydrochloride (7 ) and 12.8g (0.32 mol) of sodium hydroxide. The succindialdehyde solution was added dropwise
to the buffer over 10 min with stirring at room temperature. The mono-methyl ester solution was next added dropwise over 10 min with stirring. The
reaction was stirred 48 h at room temperature. The reaction was extracted in 250-ml portions by making the pH 12 with concentrated ammonium
hydroxide and extracted 4 times with 200 ml of chloroform. The extracts were dried over sodium sulfate and evaporated in vacuo. The resulting yellow
oil was dissolved in 200 ml of dry diethyl ether and filtered. The filtrate was evaporated in vacuo. The oil was next dissolved into 200 ml of petroleum
ether and filtered. The filtrate was evaporated in vacuo and the resulting oil was allowed to hydrate upon standing. The crude hydrate was 95% pure
and purified further by sublimation to yield snow white flakes, mp 96-98.5°C. Yield: 58.9 g (86%).
Resolution of ()-2-carbomethoxytropinone
To a solution of 26.60 g (0.124 mol) of sublimed racemic 2-CMT in 106 ml of absolute ethanol was added dropwise a solution of 18.57 g (0.124 mol) of
(-)-tartaric acid in 133 ml of absolute ethanol. After 48 h the mother liquor was decanted and set aside. The crystals were washed with 50 ml of
absolute ethanol and then dissolved into a minimal amount (approx. 200 ml) of hot dry methanol. The solution was filtered while hot into an Erlenmeyer
flask and covered. The solution was left undisturbed for 72 h. The solution was decanted off and combined with the first mother liquor. The crystals of
anhydrous (-)-2-CMT bitartrate were washed with 100 ml of dry acetone and dried yielding 6.8g (30%), [Į]D24 -16.9° (c=2, H2O). Findlay18 reported
[Į]D20 -16.9° (c=2, H2O). The mother liquors were evaporated to dryness and dissolved into 200 ml of water, made pH 8 with sodium carbonate, and
extracted 5 times with 200 ml of methylene chloride. The extracts were dried over sodium sulfate and evaporated in vacuo. The (+)-enriched 2-CMT
was hydrated yielding 17.5 g of powder.
To a solution of 17.2 g (0.08 mol) of (+)-enriched 2-CMT in 70 ml of absolute ethanol was added a solution of 12.0 g (0.08 mol) of (+)-tartaric acid in 86
ml of absolute ethanol. Subsequent recrystallizations yielded 6.95 g of anhydrous (+)-2-CMT bitartrate (30%), [Į]D24 +16.9° (c=2, H2O). Freebasing
the mother liquors and retreatment with (-)-tartaric acid yielded 6.0 g more anhydrous (-)-2-CMT bitartrate, [Į]D24 -17.0° (c=2, H2O). Thus the overall
yield of anhydrous (-)-2-CMT bitartrate was 12.8 g (57%).
(+)-Ecgonine methyl ester
Into a three-neck 500 ml round bottom flask was placed 7.70 g (0.036 mol) of (-)-2-CMT hydrate with 51 ml of ice cold 10% sulfuric acid. Bromophenol
blue (approx. 2 mg) indicator was added. With stirring the solution was treated with 1028 g of 1.5% sodium amalgam in small portions over 2.5 h. The
temperature was kept under +5°C. The pH was monitored via the indicator and kept between pH 3 and 4 with cold 30% sulfuric acid. Periodic addition
of water was necessary to dissolve sodium sulfate salts. The reaction was stirred an additional 45 min after the addition of amalgam was complete.
The solution was separated from the mercury, adjusted to pH 12 with sodium hydroxide and extracted three times with 200 ml of chloroform. The
extracts were dried over sodium sulfate and evaporated in vacuo to a light green oil containing a 3:1 ratio of EME to PEME. The oil was dissolved into
200 ml of petroleum ether and filtered. The filtrate was evaporated in vacuo. The resulting oil was dissolved into 500 ml of dry diethyl ether and the
hydrochloride salts were made with ethereal HCl. The salts were filtered and immediately dissolved into a minimal amount of dry methanol. The
methanol was evaporated in vacuo and 120 ml of dry chloroform was added to the crystals. The slurry of crystals was filtered and dried yielding 2.28 g
of (+)-ecgonine methyl ester hydrochloride (27%). The product was recrystallized from methanol and diethyl ether to yield 2.2 g of pure product [Į]D24
+52.3° c=1, MeOH), mp 213-214°C. Lewin et al.47 reported mp 213.5-214.5°C, [Į]D24 +52.3° (c=1, MeOH).
Racemic and (-)-EME can be synthesized by the same reduction procedure and clean-up using ()-2-CMT and (+)-2-CMT respectively.
(+)-Cocaine
In an oven-dried 100-ml round bottom flask was added 1.00g (4.25 mmol) of (+)-ecgonine methyl ester HCl with 7 ml of dry pyridine and stirred in an
ice bath. The reaction was protected from moisture with argon. Dropwise over 5 min was added a solution of 0.8 ml (6.85 mmol) of benzoyl chloride in
5 ml of pyridine. After addition was complete the ice bath was removed and the reaction was stirred 24 h under argon. Dry acetone (200 ml) was added
and the slurry was filtered by suction filtration. The crude (+)-cocaine hydrochloride was washed with an additional 100 ml of dry acetone. The product
was dried yielding 1.28 g (89%). The hydrochloride was dissolved into 20 ml of water, made pH 8 with 5% ammonium hydroxide, and extracted 4 times
with 50 ml of methylene chloride. The solvent was dried over sodium sulfate and evaporated in vacuo. The free base was recrystallized from diethyl
ether and petroleum ether yielding 1.01 g (78%) of pure (+)-cocaine base, [Į]D24 +35.8° (c=1, 50% aqueous EtOH), mp 96.0-97.5°C. The literature48
lists the (-)-enantiomer at [Į]D24 -35° (c=1, 50% aqueous EtOH), mp 98°C.
Racemic and (-)-cocaine can be synthesized using the same benzoylation procedure and clean-up using (+)-EME and (-)-EME respectively.
Experimental Procedure
Melting points were determined on a Mel-Temp capillary tube apparatus. Optical rotations were recorded at the sodium D line with a Rudolph Autopol
III Automatic Polarimeter (1 dm cell). Infrared (IR) spectra were recorded in potassium bromide disks with a Beckman Microlab 600 spectrometer. A
Finnigan Model 5100 GC-MS with Supelcos Data System was used for producing the mass spectra. A 30-m fused silica, SE 54 capillary column (i.d.
0.25 mm) (Supelco) was employed with helium (99.99% VHP) as the carrier gas. The injection port temperature was 250°C and the sample was
injected in the splitless mode. The initial column temperature was 120°C and was ramped at 10°C/min to 260°C. The quadrupole mass analyzer
operated under electron impact conditions at 70 eV.
Figures %,00 present infrared spectra of the intermediates and final products. Figures 0$,0* present mass spectra of the same compounds.
Discussion
(+)-Cocaine base was obtained overall in 8.6% of theoretical yield. Isolation and purification of intermediates and final product were performed through
their solubilities in organic solvents and recrystallizations. Liquid chromatography was not used in this procedure but could be used to increase the
yield of EME.
Extracting 2-CMT from the Mannich reaction at pH 12 restricts gummy tar-like substances from co-extracting. The extraction must be performed quickly
since the product will undergo self-condensation at this pH. Conversely a very acidic pH will cause decarboxylation to tropinone. Dissolution of 2-CMT
in diethyl ether and petroleum ether precipitates any resinous by-products. 2-CMT was found to be more stable as the hydrate. The anhydrous base
would turn dark brown within one week if it was not hydrated.
EME hydrochloride is practically insoluble in chloroform. This property allows PEME hydrochloride and other impurity hydrochlorides to be separated.
EME will slowly hydrolyze to ecgonine in water. Its extractions from aqueous alkaline solutions must be done promptly to prevent saponification.
Cocaine hydrochloride is insoluble in dry acetone. This allows cocaine to be separated from unreacted benzoyl chloride, EME, and pyridine.
(+)-Cocaine gives an identical microcrystalline precipitate to that of (-)-cocaine in gold chloride-HOAc. When the separate enantiomers are mixed they
give racemic crystals in gold chloride-HOAc as described by Allen 12 and identical crystals to a sample of racemic cocaine synthesized from this
procedure.
The infrared spectra of levo-, dextro- and racemic cocaine hydrochloride are identical. The infrared spectra of racemic cocaine base and its single
enantiomers have definite differences (Figs. 10 and 11).

It is my hope that this procedure will allow other forensic laboratories to synthesize their own (+)-cocaine and ( )-cocaine without the use of expensive
and sophisticated equipment.
'
B
Whilst messing around with codeine paracetamol tablets I tried the following: Added 96 10mg codeine 500mg+ rubbish tablets to 200ml cold tap water
and left for 10mins or so to dissolve CP. I then decided to warm the solution before filtering. So I heated the solution in a hot water bath to about 45 or
50 deg.C. I then filtered the solution and it filtered in a fraction of the time it usually does with cold water. This gives a clear solution and without
vacuum filtration you only lose about 5ml instead of 1/3 filtering cold solution. This is then placed in the freezer until it almost freezes, by which time
almost all of the paracetamol dissolved, crystalizes out in lovely large needle shaped crystals. This near frozen solution is then filtered, which is also
fast as paracetamol crystals are now large. This solution is now safe to drink containing approx. 5mg/ml,codeine phosphate or you can extract the
codeine base and convert etc. see other threads.I found with the cold extraction and cold filtration method clogged up filters as the paracetamol was so
powdery this method seems to work better and the final product was stronger than anything Ive had previously keeping everything cold?? But dont go
over 60deg.C as CP apparently degrades then! :D
c
First, the best way to do it is with a ceramic hotplate with a

magnetic stirrer. If you must use your home stove, IT MUST NOT BE A
GAS FLAME OR A TRADITIONAL BURNER. DO NOT EVEN ATTEMPT THIS UNLESS YOU
HAVE A NEWER RANGE WITH THE FLAT BURNERS or at least use your oven at
its lowest setting. Even this is very dangerous and you must watch it
constantly and were safety goggles.
First you need a beaker (300 - 600 ml ) or something pyrex that will
not break from temperature changes. Take the coating off of the pills
with a wet tissue. You do not need to get into the impressions of the
pill where the numbers are. Crush the pills with a mortar and pestle
or a coffee grinder. I recommend doing no less than 5 at a time. The
more you do the better this will work.Take the powdered pills, put them in a beaker and add a few drops of 1
N HCl to change them into Morphine HCl. You can probably skip this
step if you are using Oxy's, but I do it anyway. Then add about 50 -
100 mls of distilled water. Mix well. Now make up a mixture of 85%
mineral spirits to 15% toluene (laquer thinner). Add about twice the
volume of the mixture of the water you added. It is preferable to stir
with a magentic stirrer, but if you do not have one, stir with a glass
rod or a plastic knife. Then heat the beaker up to about 80 degrees C
while stirring at least every couple of minutes (if there is no
magnetic stirrer). Be very careful as the flash point of mineral
spirits is lower than its boiling point (have a plan of action if it
catches fire like a plate or something to smother the fire). After
about 10 -15 minutes of heating and stirring, the morphine will be in
the aqueous layer (the bottom), the wax will be in the organic layer
(the top. Use a 5 cc syringe and tilt the beaker to draw off the
bottom layer (do not try to get every last drop of water. Leave a
speck in there otherwise it is difficult to remove some of the
remaining organic solvents). Place each of the draw's into a 2nd
beaker. Leave the organic / wax layer alone unless it is oxy's. If it
is put another 50-100 mls of water in the organic layer and repeat.
Restir and redraw. Place the draw into the same beaker as the first
draw.Now heat the morphine (or Oxy) and water (there is also a few
carbohydrates in there that are placed in the oringinal pill, but
these will not hurt you. Reduce the volume to 5 cc's or less. Allow
the mixture to cool for about 2 minutes and pour it through a metal
coffee filter into another beaker. Any additonal wax will have clumped
together and will remain in the filter. Only the liquid will go
through the funnel. It is best to check the pH with pH paper and
adjust to about 6.0 -6.5 with Sodium Hydroxide. If the pH is lower
than 6, the shot will burn.
The remaining liquid after filtration will be morphine HCl, about 90+
% of what was in the pills. If you want to remove the carbohydrate so
you have pure product, add Calcium Hydroxide. This will cause
insoluble Calcium Morphenate to precipitate. Filter through a regular
paper coffee filter and reacidify to pH 6-6.5
If you want to make heroin out of it and have access to Acetic
Anhydride. Allow the morphine liquid to evaporate by leaving it on the
counter top for several hours. You will get a white powder (M HCl and
CH2O or just M HCl. If you neutralize it to pH 7 or >, you will just
have morphine freebase. Both can be converted to heroin (diacetyl
morphine). Add about 3 -5 mls of Acetic ANhydride to Morphine or
Morphine HCl powder cover the beaker with aluminum foil tightly and
bake in the oven at 80- 90 c (200 F) for about 4 hours. Then put the
exhaust fan on and uncover, raising the temperature to about 250 F
until the Last of the vinegar smell cooks off, but being careful not
to burn. It is best to cook until almost completely dry and then allow
the rest to evaporate on the counter. You can also run a lighter
underneath the beaker to make sure. Add enough water for all of your
shots. Check the pH and adjust down with HCl(or vitamin C) or or up
with NaOH(or baking soda). The ideal pH is 6 - 6.5 Remeber, about 25
- 50 mgs heroing is a great shot for most junkies. If you are not
addicted, take 25 or less. If you are on 120 mgs a day of methadone,
start off with 100 mgs.****That method was taken from the drug chemistry newsgroup and was added by mobiusdick.
Calcium morphenate (anion) is soluble in aqueous solutions and by adding the calcium hydroxide all he is doing is boosting the salt (Cation) to its
freebase which then precipitates because its insoluble. So using ammonia hydroxide rather than CaOH would be a better choice for the precipitation,
its reccomended in pretty much every patent Ive ever seen regarding morphine precipitation in different opium extraction methods etc. A pH of 9 is the
best pH for full precipitation. Its very important that it dosent go passed 11 because it will become negatively charged and become part of the solution
again, like I say 9 is the best number for ppt.****

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c 

opium - codeine - morphine - heroin

2. The preparation of methyl, ethyl, isopropyl, n-amyl, benzyl, and

4. The nuclear methylated dihydrocodeinone isomers can be converted

5. The action of isopropyl- or phenylmagnesium bromide on dihydrothebainone

6, Pseudocodeine methyl ether reacts with methylmagnesium iodide to

Remember it may contain impurities so its best not to inject

 10g morphineH CI:

2. The preparation of methyl, ethyl, isopropyl, n-amyl, benzyl, and

4. The nuclear methylated dihydrocodeinone isomers can be converted

5. The action of isopropyl- or phenylmagnesium bromide on dihydrothebainone

6, Pseudocodeine methyl ether reacts with methylmagnesium iodide to

Na2B4O7·10H2O + 2 HBr ĺ 4 B(OH)3 [or H3BO3] + 2 NaBr + 5 H2O

'&())*(+%*,- . 

What is claimed is:

3. The process of claim 2 wherein the aqueous acid is hydrobromic acid.

6. The process of claim 1 wherein the ether is a methyl ether of an opioid.

7. The process of claim 1 wherein the ether is an N-substituted 14-hydroxydihydronorcodeine.

8. The process of claim 5 wherein the ether is a methyl ether of an opioid.

9. The process of claim 5 wherein the ether is an N-substituted 14-hydroxydihydronorcodeine.

10. The process of claim 9 wherein the N-substituent is cyclobutylmethyl.

BACKGROUND OF THE INVENTION

SUMMARY OF THE INVENTION

DETAILED DESCRIPTION OF THE INVENTION

Rate Accelerator Not Addded

MgBr 2 as Demethylation Rate Enhancer

Lithium Bromide As Demethylation Rate Enhancer

Sodium Bromide As Demethylation Rate Enhancer

Potassium Bromide As Demethylation Rate Enhancer

1. Dissolve 2.99 g of anhydrous codeine in 25 ml of CHCL3 (Chloroform).

2. Create a solution of 15 g of BBR3 (Boron Tribromide) in 175 ml of

3. Add solution 1 to solution 2 over a 2 minute period, maintained in

4. The reaction mixture will consist of a suspension of white solid in

5. The resulting crystals should be washed thoroughly with small

7. Evaporate this, which will leave a remaining residue (approximately

8. Dissolve this residue in 2 ml of H2O containing 1 drop of 37% HCL.

with concentrated NH4OH while stirring. The crystalline material which

2. The preparation of methyl, ethyl, isopropyl, n-amyl, benzyl, and

4. The nuclear methylated dihydrocodeinone isomers can be converted

5. The action of isopropyl- or phenylmagnesium bromide on dihydrothebainone

6, Pseudocodeine methyl ether reacts with methylmagnesium iodide to

7)A freezer - So your butane wont evaporate quickly.

A *pill* (optional) bottles and some scissors

9)Coffee filters and aluminum foil

10)Alot of time - This will take a few days

9)When thats ready, add 5 to 10 drops of peppermint oil to it.

11)You know it will be ready when it becomes a yellow/green color.

Step 1: (o-chlorophenyl)-cyclopentyl ketone

Step 2: alpha-bromo (o-chlorophenyl)-cyclopentyl ketone

Step 4: 2-Methylamino-2-(o-chlorophenyl)-cyclohexanone (Ketamine)

 Anthranilic acid 13,7g

(RCOO)2Zn + Pb(SCN)2 = 2 RCN + ZnS + PbS + 2 CO2

%  

Yield: 51g (89% of theory).

 ÿ !"#$  % !"#$&  

&   

Al(i-PrO)3 - Bp 130-140°C at 7mmHg; mp 118°C.

In the beginning of boiling 0,5mls CCl4  968>

2  

Yield: 47g (94%)

)   

Yield = 58g (74%)

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c

10g morphineH CI:

'&())(+%,-.

A pill (optional) bottles and some scissors

Anthranilic acid 13,7g

%

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In the beginning of boiling 0,5mls CCl4 968>

2

)

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1 of Natural Oil to obtain pure Safrole

91 Formaldehyde + Ammonium Chloride -> MethylAmine.HCl (MeAm.HCl)

91 Safrole -(Wacker Oxidation(PdCl2+Benzoquinone))-> MDP2P

1 of Reaction contents to yield pure MDP2P

91 MDP2P -(Al/Hg Amalgam (MeAm.HCl) -> MDMA oil

(Home Depot - (2x10in., flange, 2 ft. of ½in pipe))

= (for distillations. Small shards from a broken coffee mug)

C (not much - for coating of the ground glass joints)

,=<7 (Quinone, Benzoquinone) (120g) (Photo Shop, or Chem supply)

? (for crystallization) (paint section - thinner - get it specifically)

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