Mdma

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This file is a part of the 1999 Hyperreal Drug Archives Snapshot.

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Name Post
sunlight posted 05-28-98 11:00 AM CT (US)
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In these spring nights, I often dream with the Japanese patent,
Process for producing phenylacetones (alkyl nitrite in
corresponding alcohol + safrol + PdCl2 [+ CuCl2 or amine ] =
MDP2P). I've dreamed always with methyl nitrite maden from a
solution of NaNO2 in methanol and water and dropping dilute
H2SO4. A lot of dreams with CuCl2 cocatalyst and some with
trimethylamine, and never yield was the claimed in patent.
Then I realised desired cocatalyst effect of CuCl2 or
trimethylamine never was. Why ? I don't know. Always Pd Turnover
( mols of product/ mols of PdCl2 ) was between 15 to 20, never
166 as patent claims. So I satarted to dream using
Some days ago I had a powerful dream :
1'75 liters of drugstore methanol and 6 grams of PdCl2 was
bubbled with MeONO produced with a solution of 110 cc of
methanol, 225 grams of NaNO2 and 300 cc of water (110 cc of
H2SO4 and 200 of water, chilled was added to the NaNO2 in 2'5
hours ). With stiring, of course, and with a homemade bubbler
made with a piece of glass sponge (for feet) welded to a glass
tube. After the adition of about 200 grams of NaNO2, 100 grams
of safrol (100 cc of single distilled safrol) was added.
Catalyst was not dissolved, but the reaction went to 35-40
degrees, with a great bubbling of NO and after a while all
catalyst dissapear. In 30 minutes or so reaction was done, I
think, and palladium appear again, but all MeONO was bubbled,
and reaction was kept 2 hours from the safrol addition. Then
was added 135 cc of water (water is not good before because
MeONO is less soluble in methanol-water mix, so you need more
solvent) and was stired two hours more. Methanol was evaporated
at low pressure, the result , with no safrol smell at all (all
safrol reacted) was basified, what produced a lot of brown tar
wich was filtered, and extracted with 100, 100 and 70 cc of
toluene. Toluene was distilled and the ugly deep brown product
was distilled at 158-165 C with a water pump and all joints
sealed with silicone products to give ... 81 grams of MDP2P.
Great !!! It is a 73 % yield, and I'm sure yield is more,
because my dream procedures are not exactly academic. Also
distilling flask was 500 cc to distill 100 cc, so at the end,
with good temperature, it was impossible to distill some residue.
No safrol or isosafrol in the product, only MDP2P and more heavy
products, I think these are something like pyperonyl acetic acid,
acetaldehyde and others.
Advantages, no O2 cylinders, easy to done, NaNO2 is OTC or no
suspicious product, methanol is from drugstore... Problems,
don' forget re-direct MeONO and NO fumes out through the window
with a plastic or rubber tube. Really toxic, but well done, no
problem at all. After basic wash a lot of brow tar was formed
(may be help an acid wash first). Also I did a an error, because
most palladium was precipited in the flask, so it's time to
filter and recover this product, may be is reusable (palladium or
palladium complex ?) but, I prefered evaporate before, and later
there was not palladium free, all is in the organic layer.
Finally, this the rest of this strange palladium tar is now in
the distilling flask. I think is necessary to boil NaOH strong
solution to clean it. But is a good dream. 100 cc of safrol
single distilled -----> 81 grams of MDP2P. It's my best one.
Do you like it for your book Strike ? It's my first one of
this non-cocatalyst serie.
Good dreams dear bees.
Strike posted 05-28-98 11:45 PM CT (US)
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Bra, Strike loves it! Consider your post in the book. And a
fat copy of the book to you.
But if anyone else reads this please know that Strike cannot
come across all these posts. If you have something you want
printed, please email or mail Strike the document.
All you bees with something to add REALLY have to submit very
soon or you will miss the publishing deadline!
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Ok, may be in a week I can give simplified and better
directions to do this expierence.
quirks posted 05-29-98 06:41 AM CT (US)
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Great post....
NaNO2 is available OTC as meat perservative no? and did I
hear "stump remover" from someone before??
<<
was added
>>
So after the pallidium appeared, you stirred for two more
hours. Then you added water and stirred for two more hours
again. At the end of the rxn, is the PdCl in or out of
solution?? When is the best time to recover the PdCl??
-------------------------------------------------------------
Not exactly. In my dream first I added to NaNO2 solution
almost all the H2SO4 solution. It's important the bubbles to
maximize absortion of MeONO in methanol. I think the limit is
8-10 grams per 100 cc of methanol. Then the solution has all
the MeONO needed, I suppossed, what took about 1 and half
hour, and safrol was added. Started a slightly exotermic
reaction and the rest of MeONO was bubbled. After the
addition of safrol the reaction was kept two hours, I think
one hour and half is enaugh. Then water was added and stired
two hours more. It's good to warm reaction a bit, if
possible, but not necessary, it helps hydrolisis.
Sometimes precipites palladium, normally when water is added
if there is not a lot of methanol. This time, may be the most
part of MeONO reacted in the first half hour, and palladium
precipited. I don't know why, but I think is because there is
no MeONO to react and recover palladium, some strange complex
are there. Even in the patent is said that the function of
nitrites is not clear.
I precipitate occurs, it's time to filter. I think is not Pd
metal, but Pd organic complexes.
I don't know if it can be reused. May be.
If you filter now, sure you avoid a great part of the tar.
All safrol was reacted, and no smell of isosafrol, only
ketone and other little byproduts.
Sure some night I'll have a simplified dream, you will know
it.
BTW, in #3, i think things are similar, the extracted phase
will be deep red-brown, after basic wash a lot of precipitate
will be formed, and when distilling a lot of ugly brow tar
will make the falsk really difficult to clean, or not ?
-------------------------------------------------------------
The bubbler is important. It's important to get a lot of
little bubbles to maximize absortion of gas.
Other one. Filter after hydrolisis and before evaporation.
After evaporation, with the temperature, all palladium goes
back to organic phase.
Sorry
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Ok, please forgive my stoopid questions, but
do you think it would be possible to use slightly less Pd
with a longer reaction time?? Say 4g/100g safrole??
And, me being likely to f*ck up several times before getting
things right, can I add the PdCl2 to the MeOH/MeONO after the
MeOH is saturated?? ie instead of bubbling the
PdCl2/MeOH soln and possibly screwing up
and losing precious PdCl2.
TaRa posted 05-29-98 02:11 PM CT (US)
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Sunlight: Great variation to process #3. Could you write a
more simplified step by step procedure of this. I think it
has great potential, just needs a little more explanation for
those of us that are a little slow at grasping chemical
concepts (We're chemically challenged so to speak) ;o)..
Thanks in advance
Osmium posted 05-29-98 02:26 PM CT (US)
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US Pat. 4638094 : Process for producing phenylacetones
For all of you who don't know what he's talking about.
quirks posted 05-29-98 06:48 PM CT (US)
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http://www.lycaeum.org/~rhodium/chemistry/mdp2p.abstracts.txt
Mr X posted 05-30-98 11:50 AM CT (US)
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Great one Sunlight!
You haven't mentioned temperatures. Did you keep the reaction
at room temp? Did you cool the flask down when bubbling MeONO
in, to maximize absorption?
You how fast does the MeONO evaporate away, do you need to
keep bubbling all the way through the reaction or at
intervals?
I would think this could be done in a pipe bomb , this way
you wouldn't have to keep bubbling in MeONO.
MeONO is bubbled into chilled methanol to maximize
absorbtion, add your catalyst and safrole, then let react
(under pressure from the bomb) at room temp. or maybe with a
bit of heat (or would you get more polymerisation with heat?)
Some shaking is also needed. After a few hours add water to
hydrolyize and work up. Could give you a better yield.
BTW, I like the sponge idea ;)
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The alkyl nitrites can be prepared by bubbling N2O3 gas
through them, ala pugsley can't they?? ie use stump remover
instead of NaNO2. Stop when the weight reaches the desired
concentration.
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Well, a lot of questions.
This procedure is in the japanese patent in the Osmium post.
All examples will cocatalysts doesn't run (?), give yields as
only PdCl2 were present in reaction. So I've tried with 6 %
molar PdCl2 and no catalyst, is also in the patent. What I've
done is to reduce the amount of solvent, in the patent uses
0'5 l. of methanol to 16 grams of safrol.
I think this reaction done as Uncle Fester SOMM with plenty
catalyst will give similar yields, but make the basic wash
after evaporation, becuse palladium is not in water, but in
organic phase. Other difference is that I prefered to add
water later, also is a variation present in patent, because
I've found MeONO is more soluble if there is'n water, and
yields are better.
I think there's no problem with bubbling MeONO in methanol
with the PdCl2, but it can be added later if you want. Also
safrol and PdCl2 can be added before adding MeONO, I've added
safrol later because then is a excess of MeONO and probably
the reaction works better, quick and safe. but may be works
the same. With a small quantitie I've tried this variation
also, then I didn't distill, but the product smell nothing
similat to safrol (MDP2P), what means reaction is also ok.
Methanol can be chilled and so absortion is great. The
problem in the absrtion question is to know when are is the
flask the 2 or more mols of MeONO needed for each mol of
safrol. With small quantities I weighed the flask each 15
minutes or so till the weight was the desired. So I observed
absortion at room temperature, about 20 C is about 8-10 grams
of MeONO per 100 cc of methanol. Also is needed some bubbler,
if not, you must increase the amount of MeONO bubbled in
reaction, cause absortion is slower.
There are a lot of combinations. I'll try the singlest one
and you will know it in a few days. I think may be is not
important safrol is before or later MeONO, what is important
is enough PdCl2 and enough MeONO.
Also I think PdCl2 can be reduced a bit. In other reactions
I've foun Pd Turnover of abut 20-25, wich means may be 4 or 5
% could be enough. I'll try. Just a few days.
I'll post a complete recipe, quantitites, temps, time, etc...
After 8 months, I'm starting to enjoy.
Osmium posted 06-02-98 05:35 AM CT (US)
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I'd use EtONO. Boiling point around room temperature, and
better absorption.
Keep the water content low, reaction will be faster. And
dissolve the Pd cat. properly, it takes quite some time to
dissolve completely.
Use the bisulfite for purification. O. had a powerful
explosion when O. tried to distill it.
-------------------------------------------------------------
Well Osmium, I know you are a great Bee, and I've learned
with you . Like me, you can learn with my experience.
I have dreamt with this rxn 20 times more or less, with all
the possible variations I've found.
EtONO, yes I tried with Eleusis and UF recipe. Boiling point
is 17 C, so when you have finished rxn, separating layers,
you have a mixture of sodium sulphate crystals in chilled
water and in the top the nitrite, but the crystals don't pass
through the hole in the sep funnel. So EtONO starts to boil
in a few minutes. I got stoned and intoxicated. MeONO runs
OK, and is done in situ, less time, less work.
No water, it increases solubility of MeONO in methanol. After
water to hydrolize.
6 grms of PdCl2 couldn't be dissolved in 1'75 liters of
methanol in about 2 hours, but this is not a problem,
catalyst don't need to be dissolved to react, I've seen how
it react and dissolves during rxn.
You are the second person that reports an explosion
distilling product with this rxn. I've distill it six or
seven times with no problem. Only that when PdCl2 was 0'5 %
or 1 % or 2 %, most part of distillate was safrol and others,
with 6 % all is ketone, but always the flask needed a hard
work to clean.
Otherwise, bisulphite is a good alternative. You can help me
now, once I dreamt with bisulphite addition and it yielded 7
grams. I put it in 10 % NaOH and shaked it, but there wasn't
two layers, but a strange emulsion, like ketone didn't want
to go out.
How do you do it ? May be is better adding HCl and don't
breath fumes?
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NaOH is much better than HCl. Extract it.
Labrat posted 06-02-98 10:07 AM CT (US)
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Sunlight: have you ever heard of Uncle Fester's SECRETS OF
METHAMPHETAMINE MANUFACTURE. Your so-called new method was
long ago described by Uncle Fester, so actually you're sort
of stealing it from this guy, aren't you? Sure, it is the
best way to convert safrole into MDP2P, but Uncle Fester has
given instructions following the patent. The only new thing
he came up with was bubbling methylnitrite into the reaction
mix instead of making the nitrite first and adding it in
liquid form. That's why your yields are low! That
methylnitrite is so freaking volatile, you'll lose most of it
before it reacts so you have to use a 2-3 molar excess.
Substiting isopropanol for methanol gives a nitrite that is
easier to handle and gives higher yields at 30 dg C. Well, if
that's what it takes to get in Strike's book, I have a good
"NEW" method which embraces electrochemical epoxidation of
isosafrole and then isomerisation to the ketone with LiI...
interested? Lr/
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Labrat: I'm sure he's heard of it, but not nessacarly all
people have access to places selling SOMM or the language
skills to read it. As much of a utopia as I'm sure it would
be, the whole world is not the US.
fudd posted 06-02-98 12:30 PM CT (US)
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Has anybody tried this with isopropyl nitrite? It would seem
that this would be even easier to work with than EtONO, since
you'd think it would have an even higher boiling point.
However, what would happen with steric hindrance, etc.? Any
ideas?
-fudd
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IPA seems, theoretically at least, to be the alcohol of
choice. The nitrite produced had a boiling point around 40
deg C, so it could easily be distilled. The distillate could
then be simply poured into the reaction flask. Less solvent
would be needed, so larger batches wouldn't be as limited by
the avaiability of oversized reaction vessels. On top of all
of this, due to its ease in transportation, it would make a
great substitute for poppers!
Does anybody have any feelings about this?
-------------------------------------------------------------
Say, what if you used IPA to make the nitrate, then poured it
in like Labrat said, then bubbled the exhaust from the
reaction flask into a bucket of NaOH or something. Would this
be a clean enough process to be done in a bathroom or
kitchen?
r2d3 posted 06-02-98 08:46 PM CT (US)
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WHAT IS THE MATTER WITH YOU PEOPLE?
Sunlight clearly stated in his first post that his was
posting results from a Japanese patent, not trying to post as
his own work. He has done his best ( in obviously a second
language ), to inform you of what happened. With all the
garbage posted here, so easy to flame, it surprises the hell
out of me why there are people who want to start a pissing
contest over this valuable information.
Q10 posted 06-02-98 10:19 PM CT (US)
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r2d3: I couldn't agree with you more. I hope more people feel
the same as we don't want to discourage positive and
intelligent input.
Sunlight: Thanks for the input.
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When using ethyl nitrite, it can be generated in a external
gas generator and distilled into the reaction by placing the
generator in a warm water bath. It will dissolve in the
alcoholic solution very well.
Using IPA-ONO doesn't avoid problems, at least when the
reaction solvent is MeOH. In alcoholic/MeOH solutions both
nitites, that of MeOH and that of IPA, will be present.
-------------------------------------------------------------
Labrat, I think I haven't said this is a new method. And you
can read in one of my posts :
yields are better.
I started with SOMM, of course, but with the prefered method
as UF say, what means a 0,5 % PdCl2 and a 2,5 % CuCl2.
Well, this method yields about 3 % MDP2P.
Also trimethylamine was tried, and a lot of variations since
I understood may be the problem is in PdCl2 amount.
I have read never a post with good yields in this method, so
I posted my dream. Just because I want all the bees to know
what really runs, and what doesn't run. As a contribution,
not as if I were a great chemist, what obviosly I'm not.
What about methyl nitrite ? I buy methanol OTC, and is one
step reaction. Yields in patent are 91 % but analyzed before
any extraction. I said I have losed some materials with my
poor methods. For me 81 grams from 100 cc of safrol is the
best I have done never. May be it's usual for you, but not
for me.
What we need is real reports, what I want is to share what I
have found with Japanese _ SOMM method.
May be you like to compete, but I prefer to learn what is
single and easy. And safer.
Don't compete, but collaborate. We all are one.
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Labrat, I want to explain you somethings about SOMM. As I've
said, I started with the cheaper method in the book, wich
definitively don't run. Fester say is the best. I asked
Fester about this, but he couldn't say anything, because he
hadn't done. I know also some people who have tried it, and
after some attempts, they abandon.
Fester is wrong in this point.
Well, I had then a lot of questions about why is the reason
rxn didn't run ok. I thought about absrtion of methyl
nitrite, so I started to dream with small quantities. To be
sure, I decided to put first nitrite , weighing the exact
amount of nitrite before adding safrol. But rxn didn't run.
Now, with a quantittie I can't weight, it's the same to make
this in one way or in the other, both are good, and I must
say you in the rxn I've dreamt, all safrol reacted, 100 %,
yield is not low for this reason. Also I'm sure yield was
higher, but evaporation, washings, filtration and
distillation in a too much large flask, obviously means less
product.
I thought sometimes this rxn is wrong and never yield
nothing. I know other people who have tried with no results
and they abandon as I've said.
I finally realised that rxn runs, but depends only of PdCl2
amount. Cocatalysts effects don't run, unfortunately. If you,
or other bee can discover how to do it, it would be
fantastic. 1 gram of PdCl2 and 4'25 of CuCl2 for 1 mol of
safrol.
So I tried with 6 %l catalyst, first with a test. I bubbled
then nitirte into safrol - methanol .Yields were good. Fester
is right now.
After this, I dreamt with 100 cc of safrol. Then I decided to
put first nitrite. Why ? Because was the only way to know all
nitirite is in the flask, and I have reasons to doubt about
Fester's procedure.
To simplify, next try will be bubbling into safrol -
methanol.
So, what I'm saying is that rxn with plenty catalyst runs,
what was very doubtable for me and for others.
I have never heard this rxn runs, only people said rxn
doesn't run. It's easy, and I think what I say it's
interesting.
Fester's procedure is intelligent, so I use it. But Fester
don't know exactly the reaction. For example, palladium is in
the organic phase. If you don't wash it with dilute NaOH you
will have a lot of palladium in the distilling flask, two
person have reported an explosion in distillation, may be for
this reason. Fester procedure is partially ok, not
completely. There are many errors in SOMM, so it's
interesting to clear up things.
May be all people know this rxn, may be this report is
unnecessary, then excuse me.
BTW. Mr X, yes chilled methanol increase (of course)
absortion of MeONO, Ive done it. Working with small
quantities it's possible to weight absortion. But I want to
try a general method. As Fester, but tested. If you don't
have enough NaNO2, chilled methanol reduce the amount needed
to 2/3 parts more or less.
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OK Sunlight, it's a good thing you tried the patent procedure
and found out things didn't run as was stated. That's always
a good thing. Practical experience is about as valuable as a
new theoretical procedure. But what really pissed me off
yesterday was that you practically copied Fester's method out
of PRACTICAL LSD MANUFACTURE! It was even more distressing to
me, cuz I wanted to post some more on this reaction too.
Fester presented this reaction as was it something new. It's
not new and known for a long time: it's called the
Wacker-process. This process is used to make acetaldehyde
from ethylene. The patent is new in the aspect that it covers
an alcoholic Wacker process, with an alkylnitrite as a
reoxidant for the palladium salt. I have some pretty good
refs on Wacker oxidation wherein a lot of good theory is
worked out in detail. But since you posted on this subject
first, you get the credit for it and I will not elaborate
further. Damn shame for all the work I put into it. Now you
gettit why I was a bit cranky? Good. Lr/
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sunlight: in your many dreams have you tried using straight
sassafrass oil?
sunlight posted 06-04-98 12:16 PM CT (US)
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No, never. safrol is single distilled, wich is a single
procedure if you can distill. May be it will run.
Otherwise, if you can't distill (with a water pump in this
case), you will have a problem with the ketone because is
plenty of Pd byproducts. When this brown product is in
aluminium, impurities can stop rxn and you must add then a
bit of NaOH. It runs, but you must purify your brown honey
recrystallizing a few times. (Hot acetone or hot IPA and then
acetone)
Of course distillation is better, or as Osmium say,
bisulphite recovery. This might do skip both distillations...
-------------------------------------------------------------
Sunlight : Could you please clarify a few basic points;
In setting up this rxn, you added the Methyl alcohol + PdCl2
to a 3-4 liter flat bottom flask and started stirring? Best
to use 2 neck flask; one for addition of safrol the other for
gas dispersion tube (bubbler)? Does temp need to be
monitored?
Then set up a gas generator to make the MeONO gas in? The
PdCl2+MeOH is stirred and to this solution you bubbled in the
MeONO gas?
The Methyl alcohol (chilled)+NaNO2 was dissolved and was
added dropwise to the dilute H2SO4 at the medium rate (to
create the MeONO gas)??. How did you tell when 200 grams of
NaNO2 was added? Since it's in solution with the MeOH? In any
respect the gas generated was bubbled into the alcoholic
PdCl2 solution. When approximately 4/5 of the alcoholic NaNO2
was used up (added to the H2SO4), you add the safrole?
How long did it take to bubble that much MeONO gas into the
solution?
After the safrol you stir for an additional 2 hours (then
hydrolyze with H2O)?
Great post - thanks in advance..
-------------------------------------------------------------
Please wait till next week. I've had another dream, but this
time bubbling MeONO directly in safrol+PdCl2+methanol, as the
patent say, and Fester. It also works and is easier, I put
safrol after nitrite because I wanted to be sure all nitrite
is in rxn when safrol is added.
In this new rxn, 150 cc of safrol are in 1'75 liters of
methanol and 8'5 grams of PdCl2. Then was bubbled MeONO
produced with 280 grams of NaNO2. 2 1/2 hours, (no safrol in
rxn, smell different , funny !!! ) then 200 cc of water was
added. I must distill now, but I'm sure I have more than 120
grams of ketone. Also I've realised when 5 or 6 % catalyst is
present in rxn ( is my third attempt, first one with 16 cc of
safrol )
MeONO reacts very quick, solvent and NaNO2 can be reduced
more. But it will be
my fourth dream.
Till next week. May be I can find a translator to express me
better. It's a hard work.
Piglet posted 06-05-98 04:34 AM CT (US)
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Sunlight: Nice one man. That is a very attractive route. I
notice that you use more water & less methanol than Fester.
Is there a reason for that ?
As Osmium alluded to, can the ketone be seperated with
bisulphite ? If you arn't bothered about recycling the
catalyst and just want the product...
I wondered about cooling & filtering the product mixture,
adding water & bisulphite then filtering again, throwing out
the junk...
All the best,
Piglet :)
-------------------------------------------------------------
> I notice that you use more water & less methanol than
Fester. Is there a reason for that ?
1) I've observed that water decrease MeONO solubility, so if
you put only methanol, you can work with less solvent, wich
means less time evaporating it.
After rxn with nitrite is done, we must add water to
hydrolize dimethoxy derivative of safrol to the ketone. Then
is nice to add water. But still is less than in SOMM, because
a lot of water can make a separation of phases, dificulting
hydrolisis.
2) If you done the reaction as Fester, with methanol and
water in the flask all time, yields in the patent are 83 %,
but if only methanol is present and after water is added,
patent claims 91 %
>As Osmium alluded to, can the ketone be seperated with
the junk...
I've made bisulphite addition when product is isolated, with
no distillation. Of course it runs. I've also thought as you
about to add
directly saturated bisulphite solution to the reaction, but I
haven't done, Two reasons, first is I don't know what is
solubility of bisulphite in methanol, the other is I think
that when Na in solution, as bisulphite is a weak acid, this
will make hydroxydes precipitate as tar (just as basic wash)
but I don't know. As you see, there are a lot of ways to
investigate.
I don't like distill at low pressure, but seeing these brown
products I am surrended.
Let's go on
-------------------------------------------------------------
I have just done some reading and have a few suggestions for
you all to throw around...
1. Sunlight adds his water after all the safrole has formed
an intermediate. I suggest that this may lead to more
polymerization since there will still be some nitrites &
nitrogen oxides in the brew and these are quite reactive
compounds. This leads me to...
2. I have read that you must distill off the methanol under
reduced pressure because of the nitrites & nitrogen oxides
which screw around with the product. Can these compounds be
destroyed in some simple fashion ? These are most likely the
compounds that explode.
3. I am guessing that sunlight is from europe. If so, AMYL
nitrite (pentyl nitrite) can be purchaced from head/rave/sex
shops. If you buy in bulk, it is quite cheap.
This has a B.P. high enough to prevent fumes being a problem.
No need for the gas generator. Less can be added as none will
be lost.
4. This is a crazy idea but... what if you added hydrogen
peroxide instead of water ? I don't know but maybe it will
form less dimers etc.
5. If you CAN remove the dodgy nitrogen compounds, can you
just add bisulphite to the methanol (maybe add more water as
well).
These ideas are just that. My angle is 'just how simple can
this reaction be made'.
Thanks for your replys and keep up the good work, Sunlight!
All the best,
Piglet :)
-------------------------------------------------------------
Oh yes, I also thought about those nasty nitrogen oxides in
terms of N2O3... Maybee the pseudonitrosite is being formed.
This would certainly form a nasty tar. Again, maybee a little
water in the methanol/nitrite solutiion might be good ?
Check out Rhodiums site for a good overview of these
nitrosites.
Lets keep hacking...
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> Well, patent says it will give higher yields.
I haven't had never explosions. Nitrites and NO fumes goes
out easily when adding water and when adding vacuum.
Explosions have been reported distilling product. If you
don't wash you will have a lor of tar, may be it's the
reason.
be lost.
> Good observer. I'm from Europe. But I don't want to buy any
chemicals, only OTC and the minimum amount of otheres. Amyl
nitrite is a "strange chemical" for a normal citizen, and
requires amyl alcohol, wich is other chemical. And it's no
really cheap. Fumes are not a problem if you do things right.
> No idea.
well).
> May be, but I have only nightmares with bisulphite
(metabisulphite)
> See last version, I think it's the best and simple to get
more than 70 % yield, (>80 % in weight from safrol)
> Thanks for your interest and suggestions.
nitrosites.
> Yes, some tar may be this kind of products. Patent runs as
I do, and yields are enough good. I think also Pd reaction is
quicker than nitrosite one, so, equilibrium of reactions is
clearly in the side of Pd oxydation.
Good dreams for you.
-------------------------------------------------------------
S:
1. I have only seen the fragments on Rhodiums board. Could
you post the patent (or send it to rhodium to post)
2. I just made the point for people without vaccum
aspirators. (like me)
3. Amyl nitrite IS OTC. Easier to get than NaNO2 I
think...(in the U.K. anyway)
4. Pure rubbish on my part!
5. I will test out bisulphites in methanol soon...
6. N2O3 is very reactive. Relativly, who can say (not meee!)
=================================================================
=================================================================
freya posted 05-28-98 03:22 PM CT (US)
----------------------------------------------------------
Hey there Freya again with a very urgent question.
My friends friend tried the CaO method, but had some
problems with heating on his lousy hot-plate.
Then he wrapped the flasks in alufoil and things seemed
to go well, only temperature would not rise to
244C.Because of the foil he could not see inside the
flask.
Then he tried the advise Strike gave.He filled a small
alu-pot with an inch of corn-oil and placed a 250ml flask
with the desired 100 ml safrole in it.
(safrole was very pure!,it boiled at exactly 232C!)Then
he added 15grCaO and 1gr KOH and waited for the oil to
reach 244C.But it did not happen, at 242C the oil began
to boil and stayed there.Hee let it boil for more then a
half hour and then shutted everything off.He thought
something was very wrong BUT HE CANNOT FIND THE
ANSWER.The CaO used was powdery and very pure, the KOH
came in flakes wich he grounded a little.
WHAT THE HELL WENT WRONG???????
HELP
Thanx in advance for any help...........
A frustrated FREYA....................
----------------------------------------------------------
Just a shot in the dark, but maybe your CaO is not dry
enough? O. said it's not nessacary to ground the KOH.
----------------------------------------------------------
I said it's not necessary to ground the KOH in my 1%-KOH
procedure. Don't know if it is necessary here.
007 posted 05-29-98 09:55 AM CT (US)
----------------------------------------------------------
does the CaO need to be anhydous??
----------------------------------------------------------
I don't know, I just remember someone hypothesizing that
it was there as a dehydrating agent.
----------------------------------------------------------
Wet CaO doesn't exist. It's converted into Ca(OH)2, which
is useless. So your CaO must be anhydrous.
ChemHack posted 06-03-98 12:08 PM CT (US)
----------------------------------------------------------
Osmium:
Some hack tried using Ca(OH)2 with KOH dirctly on the
kitchen stove just to see what would happen. The temp
went to 240C and started smoking like a Bad-Mutha-Fuka.
It was an awful smoke that absolutely required a gas
mask. The temperature was maintained for 15 minutes
during which time a good portion of the liquid was
vaporized. The resulting black liquid had a grey mud of
Ca(OH)2 on the bottom.
From all of this the hack got the bright idea that maybe
the KOH is the only important part and the CaO is along
for the ride. The hack never tested this hypothesis.
----------------------------------------------------------
Is the agricultural lime I see in the hardware store just
technical grade CaO or is it Ca(OH2)?? Would lime
suffice?
Rhodium posted 06-03-98 04:09 PM CT (US)
----------------------------------------------------------
It is only the KOH that is doing the job as isomerizer.
One thing that is detrimental to the reaction is water.
KOH is 15% water. The CaO reacts with that water, forming
Ca(OH)2.
Both is needed for a fast, clean reaction.
----------------------------------------------------------
Yea yea, but is agricultural lime == slaked lime
(Ca(OH)2)?? I don't think it is, which is a good thing
cause CaO is very cheap at the hardware store....
----------------------------------------------------------
quirks: The Home Drug Manufacture Depot sells lime
hydrate in the concrete area. This is Ca(OH)2 so it won't
work unless you heat it to around 1000C beforehand to
turn it back into CaO. You can tell by looking at it, the
hydrate is bright white and the regular CaO is grey.
I wonder if Drierite could be used to absorb water
instead of CaO ?? Seems like any free water would be
released as steam and it isnt soluable in safr or isosafr
anyhow....maybe just skip it ?!?! I dunno. Never tried
it.
----------------------------------------------------------
Yes, but they sell "agricultural lime" too, and I don't
know if that's the hydrate or not... Guess there's only
one way to find out though.
----------------------------------------------------------
Freya, I think there's nothing wrong. The same happened
to me. The reason is there are two isomers of isosafrol,
one of them boils at 242 C and the other at 252 C or so.
This time you have got most part of this isomer, wich is
as good as the other. This happened to me also, but in
other dream I got the other isomer. I don't know reasons
for this. We said it to you in your previous post.
Well, I can be wrong, but smell your oil. It smells more
to anise than to safrol. Also a bit of safrol, Yes ? Ok,
distill your oil at > 240 C to the end , may be 255 or
248, it's the same. You will get enough pure isosafrol to
go on. It's my experience, I did it. Think a bit, if
safrol boils at 232, what do you have boiling at 242 C ?.
Take a look to a good book or encyclopedia, you can see
bp of two isosafrol isomers.
Of course, may be I'm wrong, but it seems so clear to me.
Next week you will have nitrites procedure detailed. A
bit less catalyst, less NaNO2 and less methanol. And
easier.
----------------------------------------------------------
When distilling your post-isomerization product you may
want to do this:
1. Distill the safrole off at atmospheric pressure just
so that you can be certain that you get it all. Then...
2. Recover the isosafrole under the vacuum so you don't
need such high temps.
Probably just an old wives tale...do whatever you want.
=================================================================
=================================================================
From: eleusis@netcom.com (Eleusis)
Subject: REPOST: ZWITTERION's Complete MDMA Experience
Date: 1996/02/27
Message-ID: <4gv35d$dig_003@netcom.com>#1/8
sender: eleusis@netcom.netcom.com
organization: A Lonely Laptop on the Fringe
newsgroups: alt.drugs.chemistry
The Complete ZWITTERION Observations on Making MDMA
------------------------------------------------------------------------
Data and text provided by: ZWITTERION (anonymous user)
Editing, compilation & explanatory notes by: eleusis@netcom.com
This text describes the complete process of making MDMA starting from
the essential oil extracted from Ocotea Cymabrum (Brazilian Sassafras).
ZWITTERION wished me to put his observations into a more fluid and
correct form for "reference" use, so I am obliging. He gave me free
license to edit where necessary, but I will tend to keep modifications
offset by brackets [E - ] to indicate my intrusions, with the exception
of spelling/grammar mistakes, which will not be offset. For humor
purposes I will also leave most of his rants and raves in. Also, this
is *not* a step-by-step synthesis, but the observation of following
previously published syntheses. Those syntheses are from the sources:
The Safrole Isomerization Document - eleusis@netcom.com
PiHKAL Synthesis #109, pg734-735 - Dr. Alexander and Ann Shulgin
[PiHKAL = Phenethylamines I Have Known And Loved]
Data interjected by me can be found in the sources:
The Merck Index, 11th ed.
Essential Oils, Gunther
Lange's Handbook of Chemistry, Lange
The Organic Chem Lab Survival Guide, Zubrick
***
[E - compare the structures of Safrole and Isosafrole:
Safrole - 3,4-Methylenedioxyphenyl-1-propylene
O /\\ /\ //
/ \ / \\/ \//
/ || |
\ || |
\ / \ //
O \//
bp(760): 232C; d(20): 1.096
Isosafrole - 3,4-Methylenedioxyphenyl-2-propylene
O /\\ /\\ /
/ \ / \\/ \\/
/ || |
\ || |
\ / \ //
O \//
bp(760): 253C; d(20): 1.1206]
Well, old ZWITTERION is back! Just when you thought it was safe to post
STUPIDITY, I've come to PROVIDE THE EMPIRICAL DATA you sleazy little
chemical WHORES love so much.
Today's topic is: Isomerization of Safrole
Today's victim is: Eleusis
Old ZWITTERION, feeling especially felonious this weekend, decided to
START A THREE-ALARM FIRE, and felt that there would be NO better way to
do this than to isomerize some safrole.
Now, as eleusis has posted, one heats up safrole to 244C, which
technically ain't gonna happen, with some KOH and CaO. Well, funny thing
is, it does happen, and pretty much like he says it will.
One BIG FUCKING PROBLEM, Mr. Eleusis (who is no doubt yukking it up in
some bizarre spring mystery ceremony when he writes these things) and
that is...
FIRE!
Mr. E, coy as usual, says heat the safrole to 244C. Well, he originally
didn't specify how one would do this, assuming, probably, that we all
have nice EXPENSIVE Thermowell (TM) brand heating mantles, or Dow-
Corning (TM) magnetic stirrer hotplates. Only in your WET DREAMS, E -
buddy.
[E - a glass-fiber heating mantle is ideal for this process]
Though, maybe you SHOULD if you want to do this. Alright. Good enough
point.
Still, this is what old ZWITTERION did:
First ZWITTERION used good old Discount Auto Parts 20W-50 motor oil
(because, like the Infamous Wet Dreamer sez - "today's flasks run hotter
and rev higher" - funny, funny).
Immense smoking commenced at 150C with no sign of letting up! ZWITTERION
abandoned this as a suitable heating bath fluid.
Next, ZWITTERION sees Eleusis's repost with "gulf wax paraffin" slid in
for the heating bath.
So, ZWITTERION fires up the old Buffet Burner and throws in 1.5 boxes of
Gulf Wax (TM) paraffin. Smoking starts at about 200C this time, but it
does make it to 250C. Unfortunately, the way ZWITTERION tested the
temperature at 250C was by wrapping a thermometer in Aluminum Foil so
that it would be easy to clean. BOOM!
[E - a buffet burner is a single coil burner, ~$15]
When that Aluminum foil hit the paraffin it went up like a FUCKING
FOURTH OF JULY EXTRAVAGANZA.
ZWITTERION burned up a nice chem. catalog smothering that one.
Finally, after e-mailing Eleusis, who was no doubt feverishly
masturbating to the sight of his chemical supply cabinet at the time, he
said to use DOT 5 Brake Fluid, as that is what someone else had
suggested to him.
So, feeling SAUCY, ZWITTERION fired up the buffet burner for a THIRD
time and VOI-FREAKIN'-LLA. It works.
ZWITTERION wrapped the heating pot and flask, supported on a lattice,
with aluminum foil. This was to help keep the heat constant and reduce
the smoking, which, MIGHT I ADD, the brake fluid smokes as well, and is
a nasty, eye-burning smoke TOO!
Once the brake fluid hit 250C, tested WITHOUT wrapping the thermometer
in foil, ZWITTERION then added 100g of Oil of Ocotea Cymbarum to which
had already been added the required amounts of calcium oxide and
potassium hyroxide.
[E - it is improper to add the bases before heating, but apparently
it worked]
ZWITTERION plugged the RB flask with a thermometer in a thermometer
adapter, and watched the temp climb, just as Eleusis says it should,
from 232C to 250C over a period of 15 minutes.
[E - it is dangerous to plug the flask, better to allow some means of
venting so that pressure does not build up]
At the expiration time, ZWITTERION noticed that the oil was a slightly
darker brownish red color instead of the golden piss-yellow color that
it started as. It was vacuum filtered, to little advantage, and then
OOPS washed with water first - WHICH IS NOT WHAT eleusis SAYS TO DO.
[E - it is best to let the post-isomerization mixture settle in a beaker
for several hours, then decant off as much of the liquid layer for final
distillation]
A VICIOUS emulsion formed which was only satisfactorily broken by adding
a lot of salt and 10% HCl.
ZWITTERION then drew off the aq. layer and the organic layer, and washed
the organic layer with 5% HCl one more time before distilling ISOSAFROLE
over the range 250-255C (ZWITTERION's thermometer ain't 100% accurate,
BTW). Yield was, oh, maybe 85%.
All in all, not a bad day's work.
[snip]
*Part 2 - Purification of the crude Isosafrole*
Here's the followups to the fuckups, plus some NEW data all will be sure
to LOVE.
On Isosafrole:
ZWITTERION broke down and bought a goddamn HEATING MANTLE as a result of
the brake fluid nonsense in isomerizing SAFROLE TO ISOSAFROLE.
Why didn't someone tell me it'd be the BEST $85.00 I'd ever spend?
ZWITTERION assembled a fractional distillation setup using the following
equipment:
500mL boiling and receiving flasks.
10cm Liebig condenser w/ warm water flow.
20cm Vigreaux (whatever the fuck you spell it) column.
3-way and vacuum receiver adapter (left open).
Here's a HOT TIP that eleusis snuck onto a post in a.d.c a while ago
which probably NONE of you paid attention to.
Mount a bilge pump in a 5 gallon paint bucket (TAKE THE PAINT OUT,
GODDAMNIT!) with hoses leading to your condenser. Run the pump off a
12volt power supply (can you say BATTERY CHARGER?) and VOI-FREAKIN'-LLA,
you have a self-contained cooling system without the need for a SINK!
Not to mention, you can charge the bucket with hot water for high
temperature condensations, like ISOSAFROLE, or ice water for ETHER
RECOVERY (an all-time favorite thing for ZWITTERION to do while smoking
a 6 foot water bong).
[E - need I mention that incendiary substances of any form do not mix
well with volatile solvents?]
Now, where were we?
OH YES.
So, ZWITTERION took the dark-red product which resulted from the
ISOMERIZATION of OIL of OCOTEA CYMBARUM and fractionally distilled it on
the heating mantle. There was NO FORERUN. That means NO product came over
at a temperature less than ISOSAFROLE's bp of 253C. Approximately 75ml of
the crude isosafrole was distilled, with the COLUMN WRAPPED IN ALUMINIUM
FOIL to yield 72mL of a CLEAR distillate. There remained in the boiling
flask a nasty CRUD which has THUS FAR RESISTED ALL SANE AND INSANE
ATTEMPTS AT REMOVAL.
[E - Note, the fact that no forerun came over means that all the safrole
was consumed, as it is the lowest boiling fraction in oil of ocotea
cymbarum. Furthermore, it is necessary to wrap the column with Al foil
to prevent excessive heat loss which would otherwise make distillation
impossibly long. Finally, drop the heating mantle away from the flask
while still stirring magnetically when several mL's are still left to
go so that the crud won't carbonize and then *first* rinse the cooled
flask with mineral spirits twice before washing with soap and water.]
Calculated yield, based on amount of oil of ocotea cymbarum, is 80% pure
ISOSAFROLE. There was NO decomposition of product noted as a result of
distilling at atmospheric pressure, but then again, ZWITTERION didn't
exactly run it through a GODDAMN gas chromatograph.
[E - Isosafrole is a clear, somewhat viscous liquid. If it came over
clear, as ZWITTERION implies, it likely did not suffer decomposition.
The Merck does not indicate that Isosafrole decomposes at it's bp, but
no need to take unnecessary chances.]
*Part 3 - Conversion of Isosafrole to the ketone intermediate MDP-2-P*
[E - MDP-2-P is shorthand for 3,4-MethyleneDioxyPhenyl-2-Propanone and
has the structure:
O /\\ /\ /
/ \ / \\/ \/
/ || | ||
\ || | ||
\ / \ // O
O \//
bp(2): 110C; bp(40): 160C; bp(100): 190C]
Due to the RESOUNDING SUCCESS experienced making Isosafrole, ZWITTERION
pursued the NEXT STEP, which is to form the ketone, MDP-2-P.
Now, old ZWITTERION always thought that reacting a peracid with a non-
terminal alkene would make an epoxide, and hydrolysis of said epoxide
would result in a 1,2-glycol - but then again, ZWITTERION don't know
shit.
[E - Under most circumstances, this is correct, but the term is 1,2-Diol
or just plain Glycol. It is because of the extreme difference in
carbocation character on one side of the epoxide to the other that
makes a ketone, rather than a symmetrical diol.]
So, ZWITTERION opened up PiHKAL to synthesis #109, courtesy of Dr.
Shulgin, and tried to interpret the SPARTAN DETAILS into a workable
PROCESS.
Here is what has happened SO FAR:
ZWITTERION diluted ~20mL of 50% Hydrogen Peroxide to 32mL of 30% Hydrogen
Peroxide with distilled water.
[E - rumor has it that "Wood Bleach Kits", seen at Builder's Square,
contain 27% H2O2 which should work fine.]
ZWITTERION poured 133g of 90% Formic Acid into a 500mL RB flask situated
in a cold water bath on a magnetic stirrer then added 17mL of distilled
water to make 150g of 80% Formic Acid. Is there something fishy with that
math? Probably. Fuck it.
[E - the math is fine.]
The 30% H2O2 solution was SLOWLY added to the HCOOH with stirring and
allowed to chill for 30 minutes.
32.4g of Isosafrole was dissolved in 120mL of fresh-from-home-despot(c)
Acetone (I always like to have a wild-card reagent just for fun) and this
was loaded into an addition funnel which was then placed onto the RB
flask and allowed to drip at 1 DROP PER SECOND.
All 120mL was delivered within 2 hours with temp checking every 15
minutes to make sure it wasn't getting too HOT. The temp never climbed
above 35C as long as ZWITTERION kept adding a few pieces of ice here and
there.
[E - the ice is added to the water bath, not to the reaction contents]
The color of the reaction is the KEY OBSERVATION in this process, since
these are the ONLY DETAILS Shulgin gives! Here's a list of the observed
color changes at various points in the addition:
~15mL: a slight yellow tinge.
~50mL: definitely orangish
~100mL: kind of a clear reddish
~120mL: looks like transmission fluid; deep red but clear.
The solution remained on the stirrer MUCH TO THE DIFFICULTY OF ME TRYING
TO SLEEP for an additional 14 hours. The color remained as it did after
all was added and the temperature was STABLE the entire time as noted by
my DATA LOGGING thermometer.
In other words: SO FAR, SO GOOD.
Now the setup was changed to distill on the heating mantle using a cold
water condenser and VACUUM from a VACUUM PUMP. Shulgin sez: "distill till
ya get about 60g of residue". Whatever that means, so ZWITTERION distills
under vacuum (dunno how hard a vacuum, but not out of the reach of a water
ass-pirater (c)-POPeye) until he THINKS he has 60g. The temperature
started at about 37C and climbed to 45C when I disassembled the setup to
weigh the mother liquor. It still had the noxious odor of Formic Acid and
when thin was a distinct yellow-red color. The mother liquor weighed 88g
so ZWITTERION fired up the distillation again and let the temp reach 53C
this time. Upon this second weighing, the mother liquor was much less
smelly, but still with a faint odor of HCOOH, and now weighed 44g! GREAT!
WHERE DA FUCK did that other 16g go? The distillate was still clear, so I
can only assume SOMETHING FISHY happened. Maybe Shulgin just has better
lab technique than me?
[E - there is no problem here, the final volume of the mother liquor is
not an exact target, as long as it is less than twice the starting
isosafrole]
To this was added 50mL of methanol (not 60 because I had 70% of the
expected yield) and ~250mL of 15% Sulphuric Acid (41.5g H2SO4 + 233.5mL
water). ZWITTERION placed a thermometer & therm. adapter into the flask
and heated GENTLY on the mantle to SIMULATE a steam bath, which
ZWITTERION has NO INTENTION of ever using! I was shooting for around
80-90C but the temp quickly hit 115C within minutes, so I dropped the
heating mantle down from the flask and continued stirring in the free
air. When the temp dropped back down to about 80C, the mantle was
replaced and set at a lower setting, where it slowly climbed from there
to 95C over the next two hours. In the next 15 minutes, though, the
temperature began falling, indicating, at least to this old bastard,
that the reaction was coming to a PEACEFUL close.
Less than an hour left, I'll let you know what happens in the next
edition.
*Part 4 - Continuation of making MDP-2-P*
Well kids, the ballots are in and all the votes are counted.
When we last left off, ZWITTERION was still hydrolysing the epoxide
using H2SO4 on a "simulated" steam bath. Temperature proved a bit
difficult to control, wandering between 80 and 115C. Not exactly sharp
lab technique, but THEN AGAIN, ZWIT ain't none for his flashy lab
skills. Besides, the more I FUCK up, the better chance YOU have of
doing better, right? Right.
Okay, so the temperature falls in the flask and it's been 3 hours so
what the fuck - let's dump this baby into a goddamn beaker and start
EXTRACTING. Whoa there! Better chill that shit down first... nothing
like having ether contact something that's currently TWICE IT'S BOILING
POINT. Yah - That'd be pretty spectacular.
So ZWIT sets the beaker in ice water while preparing the necessary
reagents for all the washes and extractions. After the ketone/acid mix
has cooled to about 18C, ZWIT notes the color and appearance. There are
two layers present, though not entirely immiscible. A dark, almost black
one is on the bottom - the ketone layer, and a translucent reddish-
yellow one is on top (the yellow is only apparent near the glass-liquid
interfaces, though). ZWIT does the customary three-volumes of ether
extraction and combines the extracts, keeping them in the freezer all
the while. A total of 225mL of ether is used. ZWIT sets aside the post-
extraction aqueous solution JUST IN CASE!
Next comes the water wash. ZWIT uses CHILLED distilled water in two
washes of 100mL each. The wash water looks much like the aqueous post-
extraction layer, proving the wash was a neccessary step. NOW COMES THE
TRICKY PART!
The final wash is with 10% Sodium Hydroxide solution, and this one is a
BITCH. Why? Because a lot of the black shit goes into the hydroxide
layer, MAKING IT INDISTINGUISHABLE FROM THE ORGANIC LAYER! ZWIT does a
single wash with 100mL of 10% NaOH, but notices that it would be smarter
in the future to do 2 or 3 washes of 50mL each. ZWIT solves the "can't-
tell-which" problem by REMEMBERING how much NaOH solution was added and
holding the sep funnel IN FRONT OF A WINDOW (bright light kids - works
every time).
[E - you definitely want to use a dilute NaOH wash, of larger volume and
split into multiple sections, as ZWITTERION suggests he'd do next time]
The organic layer was dumped into a distillation setup and the ether was
recovered for reuse using ice water in the condenser flow.
Now the vacuum pump is connected and the distillation system is taken
down to whatever the damn thing can manage. There is some VIOLENT
bumping for a minute and a little water jumps through to the receiver.
ZWIT ignores it because a little water never hurt MDP-2-P before. The
heating mantle was cranked way up for the projected 200C distillation
temp and a pale yellow begins to condense at around 180C. When charring
appeared imminent, the mantle was dropped down from around the flask and
the vacuum released. It charred anyway. Bastards!
The distillate is a PALE YELLOW OIL that smells JUST LIKE CARDAMON -
goddamn! That's a NICE bit of information to know, kids! And that smell
is the smell of MDP-2-P. Yes!
The yield of the distillate, and GET THIS KIDS, was 20.6g! Can you
believe that? To the goddamn tenth of a gram JUST LIKE SHULGIN. Maybe my
lab technique ain't so bad after all?
Oh, and just like most ketones, be careful with it and PLASTIC! A drop
got on the top of ZWIT's scale and started EATING A HOLE THROUGH IT!
Here's a quick review and chronology:
1) Fractionally distilled isosafrole - 1hr
2) Formed ketone - 24hr
a) prep - .5hr
b) addition of isosafrole - 2hr
c) formation of epoxide - 14hr
d) prep for hydrolysis - .5hr
e) hydrolysis of epoxide - 4hr
f) workup of ketone - 2hr
g) distillation of ketone & cleanup - 2hr
Note - THE charring is BAD from distilling the ketone. One of ZWIT's
flasks is STILL sitting in conc. HCl 6 hours later without any sign of
breakup.
Next - the MONEY QUESTION: performing the Aluminum Amalgam Reductive
Amination ala Dr. Shulgin's PiHKAL #109 - does it work for the home
chem.idiot?
*Part 5 - Reductive Amination of MDP-2-P to MDMA using Aluminum Amalgam*
Holy SHIT you've gotta be FAST with this one.

First, let's start with making the aluminum amalgam - IT SUCKS!!! I am
relaying the experience from TRY NUMBER TWO because try number one
turned into a MONUMENTAL fiasco. Charred mess, lot's of ruined product
down the drain. OH THE TRAGEDY! Other than that, though, it's a very
nice process.
Do not, I repeat, DO NOT make this until you have EVERYTHING ready to
go! Line up ALL your little beakers with all your little reagents pre-
mixed and THEN YOU CAN START MAKING THE AMALGAM!
Why? THE SHIT WILL CATCH ON FIRE! God almighty can I make it through a
week without a fire??? I've had to refill the extinguisher TWICE
already, and NO IT ISN'T HALON! What will I tell the landlord???
Anyway, so the nun says to the priest, "5 bucks, same as in town". No,
wait... Aluminum. Yes, Aluminum.
So ZWITTERION has assembled 34g of MDP-2-P, which, upon scaling
Shulgin's reaction using a nice little spreadsheet eleusis sent me,
meant 26g of Aluminum needed to be cut up into little 1 inch squares.
Scissors were considered and abandoned in favor of ripping the living
hell out of the crap. You won't BELIEVE how much Aluminum foil is
required to make 26g! God! I must have been tearing at the shit for 30
minutes!
So the Aluminum gets dumped into a plastic bowl, god forbid you
amalgamate mother's silver serving bowl, and approximately 900mL of
water was added. Next, .6g of Mercuric Chloride was dissolved in 300mL
of water... well, almost dissolved. The SHIT DOESN'T DISSOLVE. Oh well.
It was stirred BRISKLY and dumped into the plastic bowl. The whole
sloppy mess was stirred for several minutes while watching the news -
say, nice job those Serbians have done. After 5 or so minutes, the water
starts to turn gray and little fizzies are heard. Stirring is continued
for 30 more minutes, occasionally, while ZWITTERION measures out the
remaining reagents:
38.5g methylamine hcl in 39mL water
93mL 25% sodium hydroxide soln.
340mL Isopropyl alcohol
The amalgam gets toasty warm, and starts steaming.
[E - Note, next the water is drained off the Al-Hg and washed, though
ZWITTERION does not indicate that]
I pour the methylamine hcl solution onto it which does nothing. Then I
dump a hundred mL's of the IPA on it, it calms down a bit. Next comes
the MDP-2-P, a little IPA in the container for rinsing, the NaOH
solution - whoa that's a scorcher - and finally, the remaining couple
hundred mL's of IPA. I mash the Al-Hg down with a Nalgene(tm) plastic
stirrer and commence stirring. The temperature climbs up rapidly and as
it passes 50C I submerge the lower half of the plastic reaction
cylinder into cold water. The temp stabilises at 55C - whew! Just in
time.
The Al-Hg has a nasty tendency to rise up above the solution surface
forcing me to babysit the damn thing. I stir periodically, not really
sure if this is supposed to be a true phase-transfer type of reaction
or not, because, clearly, there are two phases forming when unperturbed.
Shulgin doesn't specify, so I opt for periodic stirring, figuring it
will only be half-fucked up if I'm wrong.
After an hour of this, the reaction temp falls from it's stable 55C down
to about 35C, but every time I stir it, it jumps back up to 45C. Shulgin
sez the reaction is done when it hits room temperature, but he didn't
say anything about the temperature jumping while stirring. Fuck it - I'll
let it sit all night if I have to, because god-damn, I expect to get 26g
of MDMA out of this!
4 hours later, the shit is STILL hovering at 35C, and bubbling like a
mini-volcano every few minutes or so. Very bizarre stuff, but not even
something as mindlessly fascinating as this can hold ZWITTERION's
interest for long, so I go to a bar for a couple of stiff drinks.
After 7 hours total elapsed time, the temp is at 27C, the waters are
calm with a delicate amber tint, much like apple juice. A small amount of
turbidity is present, so it isn't quite the "clear yellow overhead" that
Shulgin describes. Great, it's probably contaminated with MPTP or
something.
ZWIT decants the overhead and filters on the vacuum buchner. Next, 25 mL
of Methanol is added to the sludge and half is filtered. The paper is
changed and 25mL more MeOH is added for filtering the remaining half.
The total filtered solution is then distilled under vacuum. The
temperature rises from a start of about 37C to 53C where it stays for
SEVERAL HOURS. There is A LOT of liquid that must be removed from the
mixture, so be prepared to spend a LONG time at the vac. pump. BTW -
ZWIT estimates his pathetic pump to be pulling a GODDAMN WORTHLESS 80mm
Hg, assuming the highest boiling fraction to be stripped is water. After
a total of approximately 8 hours distilling, there remained 55g of a
reddish-yellow liquid with some water and perhaps 10g of what appeared
to be regular old table salt. I wasn't about to sprinkle any on my
dinner, if you know what I mean.
ZWIT only has 2 250mL Sep funnels, so the next part of the process was
a REAL TREAT, lemme tell ya. The reddish liquid was dumped into a half-
gallon apple juice container which contained 1.54L of distilled water.
ZWIT then did a Tag Team no-holds-barred elimination match with his two
sep funnels. The suspension was first acidified to pH 5 using 10% HCl.
It took approximately 100mL to get it there. Next it was washed by
successively treating 7 225mL portions with 2x15mL of methylene
chloride. After this strenuous TEDIUM, ZWIT had a cigarette break - to
fully enjoy the carcinogenic methylene chloride vapors that were
assuredly in the air.
Next the washed suspension was basified to pH 9 by the addition of
approximately 75mL of 10% NaOH. The suspension turned white with just a
slight tinge of pink. Also, on the bottom there was a thin layer of
PRODUCT!!! Now kids, it's time to have a little chemistry lesson as to
WHY Shulgin likely specified methylene chloride as the organic solvent
here: Because it is denser than water, and so is our product. This means
that there is no wish-washiness on whether the organic layer will go to
the top or bottom of the sep funnel depending on how much dissolved
product is in it - it will always want to go to the bottom!
[E - this is a nice explanation but not likely correct. the real reason
probably has more to do with the relative solubility of the amine in
CH2Cl2 rather than it's density]
The 7 deal thing was repeated, except using 2x20mL portions of methylene
chloride to extract into.
The MDMA-laden methylene chloride, a distinctive clear red in color, was
then distilled on the heating mantle with an ice-water condensor flow to
strip off the solvent. The temp stays dead on 40C for a little over an
hour and solvent removal is stopped after the temperature FALLS (no more
vapor coming over, kids). Yield of oil is 24g - hey! Where'd the other 2
grams go to??? Oh yes. I almost forgot - this is the BASE, not the SALT.
The salt will weigh heavier. Okay.
ZWIT always wondered why Shulgin went to the extra trouble of distilling
the MDMA oil that remains after stripping the solvent. It's just asking
for trouble in my book, especially if you don't have a good vacuum pump,
like me (poor things' been subjected to every corrosive substance on the
planet, just about). ZWIT added 100mL of IPA to the flask, swirled, then
dumped the red liquid into beaker. ZWIT is about to find out WHY you
distill the product...
Next is crystal-forming time! Are we EXCITED yet or what??? Boy this sure
beats making cyanogen bromide any day of the week.
ZWIT adds 10mL of concentrated HCl (muriatic acid - if it's good enough
for cleaning concrete, it's good enough for drugs) to the beaker while
swirling. There is quite a bit of fuming, but no crystals form!?!?
Puzzled, ZWIT adds 200mL of ether, and now there is a dilute solution
with still no crystals forming. ZWIT suspects one of two things here:
either the water content of the IPA (9%) or the water content of my well-
used ether (it's assuredly no longer anhydrous) is the culprit, or it's
because I didn't DISTILL the goddamn shit like I was supposed to.
Awwwwww jeez don't tell me I have to do an acid/base extraction on this
shit and DISTILL yet again today?
[E - ZWITTERION used too much HCl. Only enough to get the pH mildly
acidic is necessary. Also, the crude MDMA must be vacuum distilled at
a pressure of 40mm Hg (bp(40): 200C) or lower, to avoid decomposition.]
ZWIT, wanting to avoid this as much as possible, evaporates off the
solvents to leave a syrupy reddish-brown liquid that smells RIGHT, but
doesn't LOOK too healthy. This liquid was then poured onto a glass
dinner plate and set on top of a frying pan with boiling water to get it
nice and toasty warm for about an hour. The plate was removed and set to
cool on the counter, SLOWLY.
The next morning, there were CRYSTALS. Of course, they were somewhat
brownish and not at all "sellable", but some judicious washing can take
care of that problem.
Total yield of crystals, pre-purification: 28.4g!
Total yield of crystals, after Et2O wash: 27.0g!
(2x25mL Ether was used)
The crystals were a light brown and had just the right smell: a hint of
cardamon mixed with amine! Ahh the JOY of home COOKING!
Kids, if you want to try this yourself, remember, it's a GODDAMN FELONY
AND A HALF! But, please, learn from my MISTAKES and then you might REVEL
IN MY SUCCESS!
[E - The structure of MDMA follows:
O /\\ /\ /
/ \ / \\/ \/
/ || | |
\ || | N
\ / \ // / \
O \// H \
mp of the HCl salt: 150-152C]
[EOF]
*DISCLAIMER* - I have functioned only as archiver, editor & reposter.
--
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. <eleusis@netcom.com> - Finger me for my PGP Key .
. _ _ .
. /o\ Give me lava lamps or give me death... /o\ .
. \_/ \_/ .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From: anonymous <genstaff@dillons.co.uk>

Subject: Qu: MDA from MDP2P using Al/Hg
Date: 1995/10/04
Message-ID: <44tn38$eev@bsdi002.britain.eu.net>#1/1
content-type: text/plain; charset=us-ascii
organization: Dillons the Bookstore, Gower Street, London
mime-version: 1.0
x-mailer: Mozilla 1.1N (Windows; I; 16bit)
I have looked at Phikal, SOMM, Vogel, the Hyperreal archives, and Dal
Casson's JFS article.
Phikal suggests using unprepared Al foil, and allowing up to 30 mins for
amalgamation.
Fester and vogel both prepare the foil with NaOH Soln, and allow only 2
mins for amalgamation. However Fester uses 0.1%NaOH, while Vogel uses
10%. I am surprised to find that Fester's method apears better, as I'm
almost certain that 10% NaOH heated for 2 mins would dissolve most of the
foil.
Phikal suggests amalgamation with a 0.07% soln of HgCl2. Fester and
Vogel suggest 2% HgCl2.
Any Comments?
A FOAF tried Fester's method of reductive amination with NH4OH, refluxing
for 8 hours at 100 C. The result was more ploymer than psychoactive.
Looking at Phikal #109, when making MDMA Shulgin did not reflux, and kept
the temp below 60 C. However when making MDA he used NaBH4CN.
Question: Does Shulgin's use of the slow, low yeild NaBH4CN method for
MDA suggest that Al/Hg does not work as well as it does for MDMA?
NB. Dal Casson suggests that MDP2P and NH4OH will work with Al/Hg, but
seems generally unreliable as he says of the NaBH4CN synthesis that it
does not require complex glassware, when Shulgin ends this synthesis with
distillation at 0.2 torr.
If Al/Hg does work for MDA, can anyone suggest conditions?
There is such a vast difference between keeping things below 60 C, and
refluxing for 8 hours at 100 C. Also, should one add NaCL, and NaOH as
shulgin does when making MDMA (I'd guess that the NH4OH is so basic that
the NaOH is redundant).
Having created the MDA freebase, at what temp does it begin to decompose?
Shulgin gives Bp0.2 as 80 C, I fear decomposition at a relativly low temp
as he gives Bp2 and Bp20 for MDP2P, but no mid-vaccum boiling points for
MDA. I'd be curious to know its Bp at 5 torr if it would not have
decomposed before boiling ath this preassure.
Shulgin (#100) suggests forming MDA.HCl by dissolving in C3H7OH & adding
HCl (aq) and (C2H5)2O, while fester dispenses with the alcohol and uses
gaseous HCl. Which method is best?
If Fester's alcohol-free method works, would it work of one used butane
rather than ether?
Thank y'all in advance.
THE CONTENTS OF THIS E.MAIL ARE PROMPTED SOLELY BY ACADEMIC CURIOSITY.
NOTHING CONTAINED IN IT SHOULD BE CONSTRUED AS ENCOURAGEMENT TO PERFORM
THE SYNTHESES MENTIONED IN ANY JURISDICTION WHERE SUCH ACTIVITIES ARE
PROSCRIBED BY LAW.

Subject: Re: Qu: MDA from MDP2P using Al/Hg
Date: 1995/10/04
Message-ID: <44uk5o$de8_002@netcom.com>#1/2
sender: eleusis@netcom9.netcom.com
references: <44tn38$eev@bsdi002.britain.eu.net>
In article <44tn38$eev@bsdi002.britain.eu.net>,
anonymous <genstaff@dillons.co.uk> wrote:
>Phikal suggests using unprepared Al foil, and allowing up to 30 mins for
>amalgamation.
No! PiHKAL doesn't *suggest* using unprepared foil, it merely does not
MENTION the extraneous, and understood, detail of preparing the surface.
Aluminum foil should be washed with dilute alkali to remove the oxide
coating, else it takes a long time to amalgamate, and with highly variable
results at that (see my post on making Al-Hg, or request it from me).
>Fester and vogel both prepare the foil with NaOH Soln, and allow only 2
>mins for amalgamation. However Fester uses 0.1%NaOH, while Vogel uses
>10%. I am surprised to find that Fester's method apears better, as I'm
>almost certain that 10% NaOH heated for 2 mins would dissolve most of the
>foil.
10% is better. 10% NaOH will not dissolve a significant amount of the foil.
The point is to take it out once hydrogen stops evolving, whether that
takes 5 seconds or 2 minutes depends on the state of the foil to begin
with. Crinkling it while handling puts chinks in the oxide coating allow it
to be cleaned much faster. Cutting up the foil then letting it sit for a
day will cause the reverse: slower cleaning due to oxide reformation and
little intervening handling.
>Phikal suggests amalgamation with a 0.07% soln of HgCl2. Fester and

>Vogel suggest 2% HgCl2.
Whatever you like. The 2% will go faster. There is no absolute number
required here.
>A FOAF tried Fester's method of reductive amination with NH4OH, refluxing
>for 8 hours at 100 C. The result was more ploymer than psychoactive.
Typical. How were the reactants prepared? Ie - what level of purity, what
was synthesised, what was purchased, etc...
>Looking at Phikal #109, when making MDMA Shulgin did not reflux, and kept
>the temp below 60 C. However when making MDA he used NaBH4CN.
He probably was just to trying to illustrate a variety of methods.
Certainly, the Al-Hg method is hard to beat from a practicality, yield and
ease of procuring point of view. Sure, it may not be the *best* yielding,
or the *easiest* to do, but the overall makes it quite attractive.
>Question: Does Shulgin's use of the slow, low yeild NaBH4CN method for
>MDA suggest that Al/Hg does not work as well as it does for MDMA?
>NB.
Probably not. As I said above, it was likely just illustrative.
>Dal Casson suggests that MDP2P and NH4OH will work with Al/Hg, but
>seems generally unreliable as he says of the NaBH4CN synthesis that it
>does not require complex glassware, when Shulgin ends this synthesis with
>distillation at 0.2 torr.
Shulgin distilled at .2t because he *could*. Glassware should be considered
de rigeur for this type of experimentation, though. Distillation with an
aspirator is quite acceptable, IF your water supply has a high enouugh
pressure. See an upcoming post for a good trick to get around that problem.
>If Al/Hg does work for MDA, can anyone suggest conditions?
Hehe... oh, that's the *good* question. Lot's can be suggested, but if you
don't have access to some serious analytical equipment, how are you going
to know what you got and how much of it? However, it would be safe to say
that substituting ammonia for methylamine and proceeding as in #109 would
be a good start.
>There is such a vast difference between keeping things below 60 C, and
>refluxing for 8 hours at 100 C. Also, should one add NaCL, and NaOH as
>shulgin does when making MDMA (I'd guess that the NH4OH is so basic that
>the NaOH is redundant).
No, CH3CH2 (methylamine) is much more basic than ammonia, so if anything
you will want to add slighly more NaOH.
>Having created the MDA freebase, at what temp does it begin to decompose?
>Shulgin gives Bp0.2 as 80 C, I fear decomposition at a relativly low temp
>as he gives Bp2 and Bp20 for MDP2P, but no mid-vaccum boiling points for
>MDA. I'd be curious to know its Bp at 5 torr if it would not have
>decomposed before boiling ath this preassure.
5 torr should be more than adequate. As I noted above, distillation at the
water pump (40t) should be more than adequate. Decomposition probably is
not significant within 20C of it's 760t boiling point.
>Shulgin (#100) suggests forming MDA.HCl by dissolving in C3H7OH & adding

>HCl (aq) and (C2H5)2O, while fester dispenses with the alcohol and uses
>gaseous HCl. Which method is best?
Bubbling gaseous HCl makes crystal recovery much easier. You need only
filter and collect, but you also have to generate the HCl gas. There is no
real difference, yield wise, between the two, though. It's whatever you
prefer.
>If Fester's alcohol-free method works, would it work of one used butane
>rather than ether?
Why not? It's a bit of pain to handle, but as long as you keep it cold, no
problem.
*For intellectual pursuits only*

--
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. _ _ .
. \_/ \_/ .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Subject: REPOST: Tragedies & Mishaps in MDMA Production by ZWITTERION (longish)
Date: Mon, 25 Mar 1996 00:00:00 GMT
Message-ID: <4j7831$cn4_003@netcom.com>
sender: eleusis@netcom12.netcom.com
The road to MDMA is paved with good chunks of broken glass so be careful
with your feet!
Lately ZWIT has had some SERIOUS FUCKING PROBLEMS trying to scrounge
together a batch of MDMA. What was the cause of 8 consecutive failed
runs?!?! Why all the wasted methylamine, ketone and time??? What dark and
evil conspirators lurked in the shadows waiting to FUCK ME UP THE ASS
AGAIN?!?!
It was all really quite simple, but the process by which the answer was
found illustrates the PROFOUND LACK OF KNOWLEDGE an underground chemist has
about the quality of his (and they almost all are HISes) reagents as well
as what da fuck he's doing! This tale is possibly the MOST EDUCATIONAL ZWIT
WILL EVER POST.
Pay the fuck attention, damnit!
ZWIT had secured some new space to conduct his operations, and was feeling
the old urge to fire up the glassware once again. The minions were getting
fiesty, product was running low, demand was high. No better time to satisfy
the screaming lunatics among us who LOVE PURE MDMA. ZWIT's product is well
known for it's quality among those in the know, and ZWIT NEVER LET'S THE
AFFICIONADO DOWN. Or so ZWIT thought.
Two batches of isosafrole were made, simultaneously, in a fists of fury
tag-team no holds barred fight to the death match. ZWIT vacuum filtered the
hot batches and directly distilled to yield an unprecedented 190g of
"isosafrole". ZWIT, casual in doing this process, did not bother to
actually watch the temperature of the reaction vessels, and in combination
with vacuum filtering, introduced TWO VARIABLES into an otherwise solid
process. ZWIT should have known that a 95% yield was UNPRECEDENTED and
likely NOT the result of filtering, but HINDSIGHT IS 20/20, huh?
Error #1 - Two variables introduced in making isosafrole - result:
INCOMPLETE conversion of the safrole to isosafrole.
ZWIT then started up two simultaneous batches of MDP-2-P at the largest
batch size ZWIT's glassware selection could accomodate: 85g of isosafrole
processed each. ZWIT was intending on neutralizing the glycol intermediate
as per Eleusis's "Improved Method" document, so ZWIT figured a bigger batch
wouldn't be a problem (otherwise ZWIT would not be able to distill &
concentrate that much volume conveniently). Anyway, things were going
NORMALLY, the neutralization went smoothly using 40% NaOH solution, and
resulted in a large quantity of the pure glycol ester from each batch. The
separate yields of glycol ester were placed into 1L beakers with stir
magnets in place, the requisite amount of methanol was added, and as much
15% Sulfuric Acid as could be working on the premise that as it evaporated
off over the 3 hour hydrolysis time, more would be added. The beakers were
placed in a hot water bath that barely got the core reaction temp up to
75C, but it seemed fine. The smell was different, but ZWIT assumed that
this was the result of the "cleaner neutralization" process, as compared to
vacuum distillation. So far, in just this process alone, we have racked up
2 variables! Poor form on ZWIT's part!
After hydrolysis, the solutions were individually neutralized and extracted
with CH2Cl2 (2 more variables, total of 4). The solvent was stripped off,
flashed with vacuum to get the last bit out, then the vacuum cranked down
hard to 10mm Hg and the "yellow oil" distilled off. the distillation range
covered from 120-160C, which is unusually WIDE. Normally the range is
145-165C. The product was the familiar yellow oil, had the "right" smell,
etc... If I actually had kept some MDP-2-P from a previous batch, though,
it would have been obvious that something was seriously wrong!
Error #2 - 4 freakin' variables were introduced into this process! 1) the
glycol ester was neutralized with base instead of concentrated under
vacuum, 2) the glycol ester was hydrolysed on a water bath which only got
the temp up to 75C instead of refluxed in a flask with a heating mantle @
100C, 3) the post-hydrolysis mixture was neutralized with base instead of
extracted & washed and 4) the crude "ketone" was extracted with methylene
chloride instead of toluene or ether.
The result was a homogenous mixture of the alcohol & the ketone.
No surprise then that the Al-Hg reduction failed, then, huh? But the
trickies bastard part of this collection of fuckups is that all the errors
pointed to a PROBLEM WITH THE Al-Hg REDUCTION, NOT THE INITIAL SCREWUP WITH
THE ISOSAFROLE!!! To further compound the problem, a different brand of
Aluminum foil was used! The biggest mystery that faced ZWIT was why E &
me's process, which had a screaming yeild up to this point, suddenly
dropped by 50% while also making a nasty goo which was nearly impossible to
crystallize!?!?! My reasoning and deduction process is listed below,
substantially assisted by the venerable bastard himself, e.
Observations: the almagam reduction gives a 50% yield instead of 85%, the
product is oily and difficult to crystallize, a substantial part is lost in
the acetone wash, later runs where the freebase was distilled yielded the
PROPER AMOUNT OF OIL, the color of the reaction was the same, two layers
formed in the flask as usual after vacuum filtering off the oxidized
aluminum, the reduction was finished within 3 hours instead of 7, the
temperature was unusually easy to control, there weren't too many fumes
being made.
The strangest clue came at batch #6 when ZWIT vacuum distilled the crap
left over from solvent washing the post-reduction, post-concentration
mixture. What ZWIT found, not surpisingly, was the alcohol!!! E was totally
floored by this, saying that there was no way the Al-Hg reduction could
reduce the ketone back to the alcohol, but the proof was there, so we
thought! E asked about the ketone, and ZWIT told him it looked normal -
what else could E do??? He suggested ZWIT try using plain old Reynolds wrap
and see if that corrects the problem. No dice, yield was even worse. All
this time, ZWIT was prepping the isosafrole with the same carelessness, and
the MDP-2-P without modification - ZWIT didn't want to introduce any new
variables! Hah!
Finally, ZWIT started to suspect the ketone, and reverted back to the
completely normal way of making it - the result? A much more obviously
fucked up product! The ketone was definitely wrong smelling and wrong
looking, and yield was horrible. Does this mean the improvements E has made
to the process are invalid? Not necessarily, but it does mean the
improvements MASK THE PRESENCE OF SAFROLE IN THE ISOSAFROLE!!! Having
exhausted every other possibility, requiring 8 consecutive fucked up
batches to determine, ZWIT finally produced the ketone successfully by
MONITORING THE TEMPERATURE OF THE ISOMERIZATION PROCESS THE ENTIRE TIME!!!
The isosafrole was then used in the conventional ketone process (ZWIT
hasn't gotten around to actually verifying E's improvements with the
genuine isosafrole yet) and a side-by-side comparison of the fucked-up
ketone with the real ketone showed an obvious difference. The fucked up
ketone had a milder smell and was a darker yellow, compared to the
pepper-like smell of the real ketone with it's fluorescent green-yellow
transparent color. What a tiny amount of difference to detect without
side-by-side comparison, though!
The final test was doing another amalgam reduction, BUT, ZWIT had run out
of reagent grade methylamine so had to use some he made following E's
process!! ARGH! Two variables once again, but this time the ending was
HAPPY!
34g of MDP-2-P and 38g of the homemade methylamine HCl were reduced to
yield 31g of MDMA*HCl doing it completely by the book (Shulgin's book, that
is). The product was exceptionally clean, just as expected, and burst into
white crystals on the plate when disturbed by a plastic rod. Acetone
washing resulted in little improvement in cleanliness (but would have had
ZWIT used his improved process of purifying the crude MDMA, which skips the
bastard wash & extract steps).
ZWIT breaths a big sigh of relief!
In conclusion, it should now be obvious that a fuck-up in the first part of
the process has monumental effects in the final product! Pay attention!
However, it's nice to see that E finally came up with a process for making
methylamine that works AND isn't a pain in the ass! Thanks E for saving
ZWIT's ass, more than once. I owe yah.
[END OF TRANSMISSION]
*DISCLAIMER* - I have functioned only as archiver & reposter.
--
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. _ _ .
. \_/ \_/ .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From: dnaugler@sfu.ca
Date: 1 Mar 1998 04:23:00 GMT
Newsgroups: rec.drugs.chemistry,alt.drugs.chemistry
Subject: Re: Why wont my aluminum amalgamate?
> From: narcicus <narcicus@bellsouth.net>

>
>Alright, how about with triple distilled 99.999% mercury and aluminum
>foil. Ground the shit out of it with a glass mortar and pestle and
>still just got grey powder.
We could talk chemistry in this newsgroup for a change. Mechanically
combining mercury and aluminum and mercury will produce a crude
amalgam of the same quality as the dental amalgam I have in my mouth. But
that does not necessarily give the best mercury/aluminum amalgam to be
used for chemical reduction. The way to make such an amalgam is
chemically by reducing a solution of mercuric chloride with the
aluminum. That way there is a uniform thin molecular layer of mercury all
over the aluminum. Some people like to use aluminum foil for
convenience but others prefer to grind their own aluminum dust.
Aluminum tends to resist oxidation because the surface forms a layer
of aluminum oxide which resists further oxidation. It may be necessary
to react the aluminum with dilute NaOH to remove the oxide layer and
to promote the reaction with the mercuric chloride. When the reaction
has deposited a uniform layer of mercury on the aluminum, the excess
mercuric chloride can be washed away.
The purpose of the mercury layer is to make the aluminum into a
reducing agent. In the absence of this treatment it will not react
because of the oxide layer. The mercury allows the aluminum atoms to
diffuse to the surface one atom at a time where it can engage in an
organic reduction reaction. Also the mercury has the highest hydrogen
overpotential so reducing power is not wasted in the
production of hydrogen gas which occurs in most dissolving metal
reactions. Aluminum engages in dissolving metal reaction under basic
condition which makes it suitable for reductive aminations. Zinc
amalgam works under acidic conditions, on the other hand.
A while back someone posted a report on electrochemical reduction
using a clay pot with a pool of mercury at the bottom. Exactly the
same principles apply but without the necessity of aluminum.
=================================================================
=================================================================
From: "John Payne" <aj6742741309@Big.Black.Vagina.remailer.com>
Subject: Re: using sodium cyanoborohydride to synthesize meth.
Date: 1997/03/26
Message-ID: <01bc398a$a409b160$027b3a8e@nameserver.sfu.ca>#1/3
References: <01bc344f$01c85c20$LocalHost@default>
Organization: Big Black Vagina Anonynous Internet Remailer
Newsgroups: alt.drugs,alt.drugs.chemistry,rec.drugs.chemistry
Skunky <dpozo@gibnet.gi> wrote in article

<01bc344f$01c85c20$LocalHost@default>...
> I was very interested at reading Uncle Festers reductive alkylation using
> aluminum amalgam to make meth. This was quite a while back and since I
> have
> come across similar methods using sodium cyanoborohydride for the
> reduction but mainly for synthesizing MDA & MDMA.
> I am pretty sure I can work out the reaction conditions for myself
> but would not like to give it a go without someone with experience to
> advise me first. I'm not quite up to deducing my own procedure.
> So if anyone can e-mail me or post up some info on using sodium
> cyanoborohydride for synthesizing methamphetamine I'd be infinitely
> grateful.
It is interesting that you mention Uncle Fester as a preamble to discussing
the use of sodium cyanoborohydride for the reductive amination in the
synthesis of MDA & MDMA. Actually sodium cyanoborohydride is most useful
for the synthesis of MDMA and methamphetamine, less so for MDA. However,
Uncle Fester says that sodium cyanoborohydride gives him poor yields and he
dismisses its usefulness. Uncle Fester is wrong on this count and on other
points. Sodium cyanoborohydride reductive amination of phenylacetone or
3,4MDP2P can give up to 98% yield in very large batches with no side
reactions. Alexander Shulgin in PiHKAL discusses the use of sodium
cyanoborohydride reductive amination but only for very small batches. In
fairness to both authors it should be said that Fester is a good read but
is often wrong, whereas Shulgin is a difficult read but is often deficient.
Uncle Fester presents the use of activated aluminium for reductive
amination and so does Shulgin. Aluminium may be the best way to go, but
since I have not yet had the opportunity to try it, I am not in a position
to comment.
Let us start with theory. Why do reductive amination at all? Many poor
thinkers advocate the bromination of safrole with hydrobromic acid followed
by amination with methylamine. What could be simpler? What could be more
stupid? Chemists have been synthesising various amphetamines for nearly one
hundred years now using various sophisticated approaches and only now is
the simplistic route being promoted. The problems these people fail to
address are two fold. 1) Hydrobromination of saffrole is problematic. 2)
The nucleophilic potential of an amine goes up with the degree of
substitution. That means the reaction will not stop at the secondary amine
MDMA but will aminate one or two more bromosafrole molecules to give a
tertiary or quaternary amine and not the product you want.
Reductive amination using sodium cyanoborohydride address this issue
properly. Sodium borohydride is more accessible than sodium
cyanoborohydride, but it will reduce the ketone to the secondary alcohol
and so it is not used. Sodium cyanoborohydride used at neutral pH has the
property that it will reduce the imine (Schiff base) formed between the
ketone and methylamine much much faster that the imine. It is a selective
reducing agent of the first rank.
For research purposes the place to start for primary literature is the
Merck Index. The entry for will lead you to the original literature which
details the synthesis of sodium cyanoborohydride and also the typical
procedures used in reductive amination or other selective reductions.
Sodium cyanoborohydride can be made by reacting equimolar quantities of
sodium borohydride and hydrogen cyanide in THF. One gram of hydrogen
cyanide can kill one hundred men so do not attempt this unless you are a
first rank chemist like me. The hydrogen cyanide is made following a
procedure found in Organic Synthesis, Collective Edition. Work at the 50
-100 gram scale in a distillation apparatus with ground glass joints. Emil
Fischer established the practice where you must smoke cigarettes while you
do this work. Nicotine accentuates the taste of HCN to give you an early
warning of danger. In the absence of a fumehood wear scuba gear when
disassembling the glassware. Store the liquid HCN frozen in the freezer.
Combine equimolar quantities of NaBH4 and HCN in THF and allow the reaction
to go to completion with the evolution of H2. Remove the THF with a rotary
evaporator. If you do not own a rotary evaporator go out and buy one right
now. The NaCNBH3 you made fresh is better than any you can buy. If you
don't mind the heat, go out and buy the NaCNBH3 instead.
More theory: the reductive amination of the ketone can lead to higher
amines but this can be overcome with the use a five times molar excess of
methylamine. That means that for this reaction you are going to want to
make a large quantity of methylamine hydrochloride. 40% aqueous methylamine
is easy to get and work with. Take equimolar quantities of 40% MeNH2 and
concentrated HCl and make them as cold as you can in a deep freeze. Do the
next part outdoors, clandestine and at night to avoid detection. Combine
the two cold liquids quickly in a 1000 ml beaker. It will get real hot real
quick and a lot of MeNH3CL smoke will be given off but you can put a cover
on the beaker and the smoke will dissipate real quick so the neighbours
will be unaware of what you did. Take the solution inside cool it and then
remove all the water with your rotary evaporator to yield a good crop of
white methylamine hydrochloride as a cake in your flask.
So now you are all set to do your reductive amination of your ketone. You
start with either phenylacetone or with 3,4MDP2P. Organic Synthesis,
Collective Edition describes to methods for making the phenylacetone. One
involves the condensation of acetic anhydride with benzylcyanide using
sodium ethoxide, the other, the tube furnace method from phenylacetic acid.
Or you made the 3,4MDP2P from isosafrole, 30% H2O2 and formic acid
following the "Japanese Method" detailed somewhere in Chemical Abstracts.
You can also find more details of the methods by using DejaNews to wade
through the last several years of this newsgroup.
More theory: sodium cyanoborohydride is a selective reducing agent and it
evolves hydrogen at a slow rate in solution. So you do not want to want to
react at reflux. Reductive amination with sodium cyanoborohydride is best
done in methanol at room temperature. The reaction is mostly over in a day
and a half and 98% yield can be achieved in three days of waiting. Starting
with a given molar quantity of ketone use a 25-50% molar excess of NaCNBH3
based on moles of hydrogen and a five times molar quantity of MeNH3CL in
sufficient methanol to bring everything into solution. The beauty of this
reaction is that you do not need expensive glassware of fixed capacity. You
can work at humungous scale using even a plastic garbage can.
After three days neutralize any unreacted NaCNBH3 using a calculated
quantity of dilute HCl or acetic acid. Remove all of the methanol using
your rotary evaporator. Then dissolve all of the cake in H2O. Add
sufficient 5 N NaOH to cause the desired amine product to separate as a
slightly brown layer floating on top of the aqueous layer. Here is where
the work up can be slightly different depending on whether the product is
methamphetamine or MDMA. The meth cook will sample the meth and continue
his work in an energized manner for many more hours or days. Good meth
cooks tend to be fastidious about the quality of the meth he makes and
does. It is possible to just separate the top layer using a separatory
funnel and to carry on. A better approach is to steam distill the amine out
of the pot. The water in the aqueous layer is sufficient. The steam
distillate is collected. Separation is enhanced by the addition of just
sufficient 5 N NaOH. The floating amine layer is now clear. The top layer
is removed with a separatory funnel an the bottom layer is washed a couple
of times with a small quantity of ethyl ether which is combined with the
top layer. You now have liquid meth with a small quantity of ether, a
little dissolved water and perhaps some MeNH2 or unreacted ketone as a
water white oily liquid. It is traditional to dry this over anhydrous NaSO4
or equivalent. Now set up your vacuum distillation apparatus with a water
aspirator vacuum pump. If you do not own a distillation apparatus with
ground glass joints go out and buy one right now. Depending on your vacuum
the product will distill at 130 C or so and the liquid MDMA somewhat
higher.
With the pure liquid meth it is now time to create the hydrochloride. Many
people think it is possible to create crystal meth using gaseous hydrogen
chloride. I have never seen this to be true. What is obtained instead is an
amorphous product. Why bother. Instead use your HCL gas generator to
produce a quantity of anhydrous methanolic HCL in the case of MDMA or you
can use aqueous HCL for meth. Combine equimolar quantities of HCl solution
and amine product in methanol to neutrality. Use your rotary evaporator to
remove solvent to yield a white cake in your flask. This is crude though
pure methamphetamine HCl or MDMA HCL.
It is now time to recrystallize your immensely valuable product. Dissolve
the cake in the minimum quantity of hot isopropyl alcohol. Cool the IPA
solution in the fridge. Crystallization may begin. Layer the solution on
top with an equal quantity of anhydrous diethyl ether and put beaker into
freezer overnight. I am told it is also possible to use methanol and MEK as
solvent pairs. Overnight the ether layer will be seen to diffuse into the
IPA and a massive crystallization has occurred. Stir if necessary. Some
crystals will be needles upto one mm in length. You are laughing. Separate
solvent from filter mass using a buchner filter and vacuum. Air dry for a
while and then remove residual using a vacuum desiccator. You have a world
class crystalline product. You have money in the bank.
=================================================================
=================================================================
Name Post
-------------------------------------------------------------
In these spring nights, I often dream with the Japanese patent,
Process for producing phenylacetones (alkyl nitrite in
corresponding alcohol + safrol + PdCl2 [+ CuCl2 or amine ] =
MDP2P). I've dreamed always with methyl nitrite maden from a
solution of NaNO2 in methanol and water and dropping dilute
H2SO4. A lot of dreams with CuCl2 cocatalyst and some with
trimethylamine, and never yield was the claimed in patent.
Then I realised desired cocatalyst effect of CuCl2 or
trimethylamine never was. Why ? I don't know. Always Pd Turnover
( mols of product/ mols of PdCl2 ) was between 15 to 20, never
166 as patent claims. So I satarted to dream using
Some days ago I had a powerful dream :
was added 135 cc of water (water is not good before because
MeONO is less soluble in methanol-water mix, so you need more
solvent) and was stired two hours more. Methanol was evaporated
at low pressure, the result , with no safrol smell at all (all
safrol reacted) was basified, what produced a lot of brown tar
wich was filtered, and extracted with 100, 100 and 70 cc of
toluene. Toluene was distilled and the ugly deep brown product
was distilled at 158-165 C with a water pump and all joints
sealed with silicone products to give ... 81 grams of MDP2P.
Great !!! It is a 73 % yield, and I'm sure yield is more,
because my dream procedures are not exactly academic. Also
distilling flask was 500 cc to distill 100 cc, so at the end,
with good temperature, it was impossible to distill some residue.
No safrol or isosafrol in the product, only MDP2P and more heavy
products, I think these are something like pyperonyl acetic acid,
acetaldehyde and others.
Advantages, no O2 cylinders, easy to done, NaNO2 is OTC or no
suspicious product, methanol is from drugstore... Problems,
don' forget re-direct MeONO and NO fumes out through the window
with a plastic or rubber tube. Really toxic, but well done, no
problem at all. After basic wash a lot of brow tar was formed
(may be help an acid wash first). Also I did a an error, because
most palladium was precipited in the flask, so it's time to
filter and recover this product, may be is reusable (palladium or
palladium complex ?) but, I prefered evaporate before, and later
there was not palladium free, all is in the organic layer.
Finally, this the rest of this strange palladium tar is now in
the distilling flask. I think is necessary to boil NaOH strong
solution to clean it. But is a good dream. 100 cc of safrol
single distilled -----> 81 grams of MDP2P. It's my best one.
Do you like it for your book Strike ? It's my first one of
this non-cocatalyst serie.
Good dreams dear bees.
Strike posted 05-28-98 11:45 PM CT (US)
-------------------------------------------------------------
Bra, Strike loves it! Consider your post in the book. And a
fat copy of the book to you.
But if anyone else reads this please know that Strike cannot
come across all these posts. If you have something you want
printed, please email or mail Strike the document.
All you bees with something to add REALLY have to submit very
soon or you will miss the publishing deadline!
-------------------------------------------------------------
Ok, may be in a week I can give simplified and better
directions to do this expierence.
-------------------------------------------------------------
Great post....
NaNO2 is available OTC as meat perservative no? and did I
hear "stump remover" from someone before??
<<
was added
>>
So after the pallidium appeared, you stirred for two more
hours. Then you added water and stirred for two more hours
again. At the end of the rxn, is the PdCl in or out of
solution?? When is the best time to recover the PdCl??
-------------------------------------------------------------
Not exactly. In my dream first I added to NaNO2 solution
almost all the H2SO4 solution. It's important the bubbles to
maximize absortion of MeONO in methanol. I think the limit is
8-10 grams per 100 cc of methanol. Then the solution has all
the MeONO needed, I suppossed, what took about 1 and half
hour, and safrol was added. Started a slightly exotermic
reaction and the rest of MeONO was bubbled. After the
addition of safrol the reaction was kept two hours, I think
one hour and half is enaugh. Then water was added and stired
two hours more. It's good to warm reaction a bit, if
possible, but not necessary, it helps hydrolisis.
Sometimes precipites palladium, normally when water is added
if there is not a lot of methanol. This time, may be the most
part of MeONO reacted in the first half hour, and palladium
precipited. I don't know why, but I think is because there is
no MeONO to react and recover palladium, some strange complex
are there. Even in the patent is said that the function of
nitrites is not clear.
I precipitate occurs, it's time to filter. I think is not Pd
metal, but Pd organic complexes.
I don't know if it can be reused. May be.
If you filter now, sure you avoid a great part of the tar.
All safrol was reacted, and no smell of isosafrol, only
ketone and other little byproduts.
Sure some night I'll have a simplified dream, you will know
it.
BTW, in #3, i think things are similar, the extracted phase
will be deep red-brown, after basic wash a lot of precipitate
will be formed, and when distilling a lot of ugly brow tar
will make the falsk really difficult to clean, or not ?
-------------------------------------------------------------
The bubbler is important. It's important to get a lot of
little bubbles to maximize absortion of gas.
Other one. Filter after hydrolisis and before evaporation.
After evaporation, with the temperature, all palladium goes
back to organic phase.
Sorry
-------------------------------------------------------------
Ok, please forgive my stoopid questions, but
do you think it would be possible to use slightly less Pd
with a longer reaction time?? Say 4g/100g safrole??
And, me being likely to f*ck up several times before getting
things right, can I add the PdCl2 to the MeOH/MeONO after the
MeOH is saturated?? ie instead of bubbling the
PdCl2/MeOH soln and possibly screwing up
and losing precious PdCl2.
-------------------------------------------------------------
Sunlight: Great variation to process #3. Could you write a
more simplified step by step procedure of this. I think it
has great potential, just needs a little more explanation for
those of us that are a little slow at grasping chemical
concepts (We're chemically challenged so to speak) ;o)..
Thanks in advance
-------------------------------------------------------------
US Pat. 4638094 : Process for producing phenylacetones
For all of you who don't know what he's talking about.
-------------------------------------------------------------
http://www.lycaeum.org/~rhodium/chemistry/mdp2p.abstracts.txt
Mr X posted 05-30-98 11:50 AM CT (US)
-------------------------------------------------------------
Great one Sunlight!
You haven't mentioned temperatures. Did you keep the reaction
at room temp? Did you cool the flask down when bubbling MeONO
in, to maximize absorption?
You how fast does the MeONO evaporate away, do you need to
keep bubbling all the way through the reaction or at
intervals?
I would think this could be done in a pipe bomb , this way
you wouldn't have to keep bubbling in MeONO.
MeONO is bubbled into chilled methanol to maximize
absorbtion, add your catalyst and safrole, then let react
(under pressure from the bomb) at room temp. or maybe with a
bit of heat (or would you get more polymerisation with heat?)
Some shaking is also needed. After a few hours add water to
hydrolyize and work up. Could give you a better yield.
BTW, I like the sponge idea ;)
-------------------------------------------------------------
The alkyl nitrites can be prepared by bubbling N2O3 gas
through them, ala pugsley can't they?? ie use stump remover
instead of NaNO2. Stop when the weight reaches the desired
concentration.
-------------------------------------------------------------
Well, a lot of questions.
This procedure is in the japanese patent in the Osmium post.
All examples will cocatalysts doesn't run (?), give yields as
only PdCl2 were present in reaction. So I've tried with 6 %
molar PdCl2 and no catalyst, is also in the patent. What I've
done is to reduce the amount of solvent, in the patent uses
0'5 l. of methanol to 16 grams of safrol.
yields are better.
I think there's no problem with bubbling MeONO in methanol
with the PdCl2, but it can be added later if you want. Also
safrol and PdCl2 can be added before adding MeONO, I've added
safrol later because then is a excess of MeONO and probably
the reaction works better, quick and safe. but may be works
the same. With a small quantitie I've tried this variation
also, then I didn't distill, but the product smell nothing
similat to safrol (MDP2P), what means reaction is also ok.
Methanol can be chilled and so absortion is great. The
problem in the absrtion question is to know when are is the
flask the 2 or more mols of MeONO needed for each mol of
safrol. With small quantities I weighed the flask each 15
minutes or so till the weight was the desired. So I observed
absortion at room temperature, about 20 C is about 8-10 grams
of MeONO per 100 cc of methanol. Also is needed some bubbler,
if not, you must increase the amount of MeONO bubbled in
reaction, cause absortion is slower.
There are a lot of combinations. I'll try the singlest one
and you will know it in a few days. I think may be is not
important safrol is before or later MeONO, what is important
is enough PdCl2 and enough MeONO.
Also I think PdCl2 can be reduced a bit. In other reactions
I've foun Pd Turnover of abut 20-25, wich means may be 4 or 5
% could be enough. I'll try. Just a few days.
I'll post a complete recipe, quantitites, temps, time, etc...
After 8 months, I'm starting to enjoy.
-------------------------------------------------------------
I'd use EtONO. Boiling point around room temperature, and
better absorption.
Keep the water content low, reaction will be faster. And
dissolve the Pd cat. properly, it takes quite some time to
dissolve completely.
Use the bisulfite for purification. O. had a powerful
explosion when O. tried to distill it.
-------------------------------------------------------------
Well Osmium, I know you are a great Bee, and I've learned
with you . Like me, you can learn with my experience.
I have dreamt with this rxn 20 times more or less, with all
the possible variations I've found.
EtONO, yes I tried with Eleusis and UF recipe. Boiling point
is 17 C, so when you have finished rxn, separating layers,
you have a mixture of sodium sulphate crystals in chilled
water and in the top the nitrite, but the crystals don't pass
through the hole in the sep funnel. So EtONO starts to boil
in a few minutes. I got stoned and intoxicated. MeONO runs
OK, and is done in situ, less time, less work.
No water, it increases solubility of MeONO in methanol. After
water to hydrolize.
6 grms of PdCl2 couldn't be dissolved in 1'75 liters of
methanol in about 2 hours, but this is not a problem,
catalyst don't need to be dissolved to react, I've seen how
it react and dissolves during rxn.
You are the second person that reports an explosion
distilling product with this rxn. I've distill it six or
seven times with no problem. Only that when PdCl2 was 0'5 %
or 1 % or 2 %, most part of distillate was safrol and others,
with 6 % all is ketone, but always the flask needed a hard
work to clean.
Otherwise, bisulphite is a good alternative. You can help me
now, once I dreamt with bisulphite addition and it yielded 7
grams. I put it in 10 % NaOH and shaked it, but there wasn't
two layers, but a strange emulsion, like ketone didn't want
to go out.
How do you do it ? May be is better adding HCl and don't
breath fumes?
-------------------------------------------------------------
NaOH is much better than HCl. Extract it.
-------------------------------------------------------------
Sunlight: have you ever heard of Uncle Fester's SECRETS OF
METHAMPHETAMINE MANUFACTURE. Your so-called new method was
long ago described by Uncle Fester, so actually you're sort
of stealing it from this guy, aren't you? Sure, it is the
best way to convert safrole into MDP2P, but Uncle Fester has
given instructions following the patent. The only new thing
he came up with was bubbling methylnitrite into the reaction
mix instead of making the nitrite first and adding it in
liquid form. That's why your yields are low! That
methylnitrite is so freaking volatile, you'll lose most of it
before it reacts so you have to use a 2-3 molar excess.
Substiting isopropanol for methanol gives a nitrite that is
easier to handle and gives higher yields at 30 dg C. Well, if
that's what it takes to get in Strike's book, I have a good
"NEW" method which embraces electrochemical epoxidation of
isosafrole and then isomerisation to the ketone with LiI...
interested? Lr/
-------------------------------------------------------------
Labrat: I'm sure he's heard of it, but not nessacarly all
people have access to places selling SOMM or the language
skills to read it. As much of a utopia as I'm sure it would
be, the whole world is not the US.
-------------------------------------------------------------
Has anybody tried this with isopropyl nitrite? It would seem
that this would be even easier to work with than EtONO, since
you'd think it would have an even higher boiling point.
However, what would happen with steric hindrance, etc.? Any
ideas?
-fudd
-------------------------------------------------------------
IPA seems, theoretically at least, to be the alcohol of
choice. The nitrite produced had a boiling point around 40
deg C, so it could easily be distilled. The distillate could
then be simply poured into the reaction flask. Less solvent
would be needed, so larger batches wouldn't be as limited by
the avaiability of oversized reaction vessels. On top of all
of this, due to its ease in transportation, it would make a
great substitute for poppers!
Does anybody have any feelings about this?
-------------------------------------------------------------
Say, what if you used IPA to make the nitrate, then poured it
in like Labrat said, then bubbled the exhaust from the
reaction flask into a bucket of NaOH or something. Would this
be a clean enough process to be done in a bathroom or
kitchen?
r2d3 posted 06-02-98 08:46 PM CT (US)
-------------------------------------------------------------
WHAT IS THE MATTER WITH YOU PEOPLE?
Sunlight clearly stated in his first post that his was
posting results from a Japanese patent, not trying to post as
his own work. He has done his best ( in obviously a second
language ), to inform you of what happened. With all the
garbage posted here, so easy to flame, it surprises the hell
out of me why there are people who want to start a pissing
contest over this valuable information.
Q10 posted 06-02-98 10:19 PM CT (US)
-------------------------------------------------------------
r2d3: I couldn't agree with you more. I hope more people feel
the same as we don't want to discourage positive and
intelligent input.
Sunlight: Thanks for the input.
-------------------------------------------------------------
When using ethyl nitrite, it can be generated in a external
gas generator and distilled into the reaction by placing the
generator in a warm water bath. It will dissolve in the
alcoholic solution very well.
Using IPA-ONO doesn't avoid problems, at least when the
reaction solvent is MeOH. In alcoholic/MeOH solutions both
nitites, that of MeOH and that of IPA, will be present.
-------------------------------------------------------------
Labrat, I think I haven't said this is a new method. And you
can read in one of my posts :
yields are better.
I started with SOMM, of course, but with the prefered method
as UF say, what means a 0,5 % PdCl2 and a 2,5 % CuCl2.
Well, this method yields about 3 % MDP2P.
Also trimethylamine was tried, and a lot of variations since
I understood may be the problem is in PdCl2 amount.
I have read never a post with good yields in this method, so
I posted my dream. Just because I want all the bees to know
what really runs, and what doesn't run. As a contribution,
not as if I were a great chemist, what obviosly I'm not.
What about methyl nitrite ? I buy methanol OTC, and is one
step reaction. Yields in patent are 91 % but analyzed before
any extraction. I said I have losed some materials with my
poor methods. For me 81 grams from 100 cc of safrol is the
best I have done never. May be it's usual for you, but not
for me.
What we need is real reports, what I want is to share what I
have found with Japanese _ SOMM method.
May be you like to compete, but I prefer to learn what is
single and easy. And safer.
Don't compete, but collaborate. We all are one.
-------------------------------------------------------------
Labrat, I want to explain you somethings about SOMM. As I've
said, I started with the cheaper method in the book, wich
definitively don't run. Fester say is the best. I asked
Fester about this, but he couldn't say anything, because he
hadn't done. I know also some people who have tried it, and
after some attempts, they abandon.
Fester is wrong in this point.
Well, I had then a lot of questions about why is the reason
rxn didn't run ok. I thought about absrtion of methyl
nitrite, so I started to dream with small quantities. To be
sure, I decided to put first nitrite , weighing the exact
amount of nitrite before adding safrol. But rxn didn't run.
Now, with a quantittie I can't weight, it's the same to make
this in one way or in the other, both are good, and I must
say you in the rxn I've dreamt, all safrol reacted, 100 %,
yield is not low for this reason. Also I'm sure yield was
higher, but evaporation, washings, filtration and
distillation in a too much large flask, obviously means less
product.
I thought sometimes this rxn is wrong and never yield
nothing. I know other people who have tried with no results
and they abandon as I've said.
I finally realised that rxn runs, but depends only of PdCl2
amount. Cocatalysts effects don't run, unfortunately. If you,
or other bee can discover how to do it, it would be
fantastic. 1 gram of PdCl2 and 4'25 of CuCl2 for 1 mol of
safrol.
So I tried with 6 %l catalyst, first with a test. I bubbled
then nitirte into safrol - methanol .Yields were good. Fester
is right now.
After this, I dreamt with 100 cc of safrol. Then I decided to
put first nitrite. Why ? Because was the only way to know all
nitirite is in the flask, and I have reasons to doubt about
Fester's procedure.
To simplify, next try will be bubbling into safrol -
methanol.
So, what I'm saying is that rxn with plenty catalyst runs,
what was very doubtable for me and for others.
I have never heard this rxn runs, only people said rxn
doesn't run. It's easy, and I think what I say it's
interesting.
Fester's procedure is intelligent, so I use it. But Fester
don't know exactly the reaction. For example, palladium is in
the organic phase. If you don't wash it with dilute NaOH you
will have a lot of palladium in the distilling flask, two
person have reported an explosion in distillation, may be for
this reason. Fester procedure is partially ok, not
completely. There are many errors in SOMM, so it's
interesting to clear up things.
May be all people know this rxn, may be this report is
unnecessary, then excuse me.
BTW. Mr X, yes chilled methanol increase (of course)
absortion of MeONO, Ive done it. Working with small
quantities it's possible to weight absortion. But I want to
try a general method. As Fester, but tested. If you don't
have enough NaNO2, chilled methanol reduce the amount needed
to 2/3 parts more or less.
-------------------------------------------------------------
OK Sunlight, it's a good thing you tried the patent procedure
and found out things didn't run as was stated. That's always
a good thing. Practical experience is about as valuable as a
new theoretical procedure. But what really pissed me off
yesterday was that you practically copied Fester's method out
of PRACTICAL LSD MANUFACTURE! It was even more distressing to
me, cuz I wanted to post some more on this reaction too.
Fester presented this reaction as was it something new. It's
not new and known for a long time: it's called the
Wacker-process. This process is used to make acetaldehyde
from ethylene. The patent is new in the aspect that it covers
an alcoholic Wacker process, with an alkylnitrite as a
reoxidant for the palladium salt. I have some pretty good
refs on Wacker oxidation wherein a lot of good theory is
worked out in detail. But since you posted on this subject
first, you get the credit for it and I will not elaborate
further. Damn shame for all the work I put into it. Now you
gettit why I was a bit cranky? Good. Lr/
-------------------------------------------------------------
sunlight: in your many dreams have you tried using straight
sassafrass oil?
sunlight posted 06-04-98 12:16 PM CT (US)
-------------------------------------------------------------
No, never. safrol is single distilled, wich is a single
procedure if you can distill. May be it will run.
Otherwise, if you can't distill (with a water pump in this
case), you will have a problem with the ketone because is
plenty of Pd byproducts. When this brown product is in
aluminium, impurities can stop rxn and you must add then a
bit of NaOH. It runs, but you must purify your brown honey
recrystallizing a few times. (Hot acetone or hot IPA and then
acetone)
Of course distillation is better, or as Osmium say,
bisulphite recovery. This might do skip both distillations...
-------------------------------------------------------------
Sunlight : Could you please clarify a few basic points;
In setting up this rxn, you added the Methyl alcohol + PdCl2
to a 3-4 liter flat bottom flask and started stirring? Best
to use 2 neck flask; one for addition of safrol the other for
gas dispersion tube (bubbler)? Does temp need to be
monitored?
Then set up a gas generator to make the MeONO gas in? The
PdCl2+MeOH is stirred and to this solution you bubbled in the
MeONO gas?
The Methyl alcohol (chilled)+NaNO2 was dissolved and was
added dropwise to the dilute H2SO4 at the medium rate (to
create the MeONO gas)??. How did you tell when 200 grams of
NaNO2 was added? Since it's in solution with the MeOH? In any
respect the gas generated was bubbled into the alcoholic
PdCl2 solution. When approximately 4/5 of the alcoholic NaNO2
was used up (added to the H2SO4), you add the safrole?
How long did it take to bubble that much MeONO gas into the
solution?
After the safrol you stir for an additional 2 hours (then
hydrolyze with H2O)?
Great post - thanks in advance..
-------------------------------------------------------------
Please wait till next week. I've had another dream, but this
time bubbling MeONO directly in safrol+PdCl2+methanol, as the
patent say, and Fester. It also works and is easier, I put
safrol after nitrite because I wanted to be sure all nitrite
is in rxn when safrol is added.
In this new rxn, 150 cc of safrol are in 1'75 liters of
methanol and 8'5 grams of PdCl2. Then was bubbled MeONO
produced with 280 grams of NaNO2. 2 1/2 hours, (no safrol in
rxn, smell different , funny !!! ) then 200 cc of water was
added. I must distill now, but I'm sure I have more than 120
grams of ketone. Also I've realised when 5 or 6 % catalyst is
present in rxn ( is my third attempt, first one with 16 cc of
safrol )
MeONO reacts very quick, solvent and NaNO2 can be reduced
more. But it will be
my fourth dream.
Till next week. May be I can find a translator to express me
better. It's a hard work.
-------------------------------------------------------------
Sunlight: Nice one man. That is a very attractive route. I
notice that you use more water & less methanol than Fester.
Is there a reason for that ?
As Osmium alluded to, can the ketone be seperated with
the junk...
All the best,
Piglet :)
-------------------------------------------------------------
> I notice that you use more water & less methanol than
Fester. Is there a reason for that ?
1) I've observed that water decrease MeONO solubility, so if
you put only methanol, you can work with less solvent, wich
means less time evaporating it.
After rxn with nitrite is done, we must add water to
hydrolize dimethoxy derivative of safrol to the ketone. Then
is nice to add water. But still is less than in SOMM, because
a lot of water can make a separation of phases, dificulting
hydrolisis.
2) If you done the reaction as Fester, with methanol and
water in the flask all time, yields in the patent are 83 %,
but if only methanol is present and after water is added,
patent claims 91 %
>As Osmium alluded to, can the ketone be seperated with
the junk...
I've made bisulphite addition when product is isolated, with
no distillation. Of course it runs. I've also thought as you
about to add
directly saturated bisulphite solution to the reaction, but I
haven't done, Two reasons, first is I don't know what is
solubility of bisulphite in methanol, the other is I think
that when Na in solution, as bisulphite is a weak acid, this
will make hydroxydes precipitate as tar (just as basic wash)
but I don't know. As you see, there are a lot of ways to
investigate.
I don't like distill at low pressure, but seeing these brown
products I am surrended.
Let's go on
-------------------------------------------------------------
be lost.
well).
All the best,
Piglet :)
-------------------------------------------------------------
nitrosites.
Lets keep hacking...
-------------------------------------------------------------
> Well, patent says it will give higher yields.
I haven't had never explosions. Nitrites and NO fumes goes
out easily when adding water and when adding vacuum.
Explosions have been reported distilling product. If you
don't wash you will have a lor of tar, may be it's the
reason.
be lost.
> Good observer. I'm from Europe. But I don't want to buy any
chemicals, only OTC and the minimum amount of otheres. Amyl
nitrite is a "strange chemical" for a normal citizen, and
requires amyl alcohol, wich is other chemical. And it's no
really cheap. Fumes are not a problem if you do things right.
> No idea.
well).
> May be, but I have only nightmares with bisulphite
(metabisulphite)
> See last version, I think it's the best and simple to get
more than 70 % yield, (>80 % in weight from safrol)
> Thanks for your interest and suggestions.
nitrosites.
> Yes, some tar may be this kind of products. Patent runs as
I do, and yields are enough good. I think also Pd reaction is
quicker than nitrosite one, so, equilibrium of reactions is
clearly in the side of Pd oxydation.
Good dreams for you.
-------------------------------------------------------------
S:
1. I have only seen the fragments on Rhodiums board. Could
you post the patent (or send it to rhodium to post)
2. I just made the point for people without vaccum
aspirators. (like me)
3. Amyl nitrite IS OTC. Easier to get than NaNO2 I
think...(in the U.K. anyway)
4. Pure rubbish on my part!
5. I will test out bisulphites in methanol soon...
6. N2O3 is very reactive. Relativly, who can say (not meee!)
GBL----
electrolyte for batteries and capacitors and
is used as an intermediate for numerous compounds. See Merk Ed. 11,1596

Mdma

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This file is a part of the 1999 Hyperreal Drug Archives Snapshot.

Holy SHIT you've gotta be FAST with this one.

From: anonymous <genstaff@dillons.co.uk>

From: eleusis@netcom.com (Eleusis)

>Phikal suggests amalgamation with a 0.07% soln of HgCl2. Fester and

>Shulgin (#100) suggests forming MDA.HCl by dissolving in C3H7OH & adding

For intellectual pursuits only

From: eleusis@netcom.com (Eleusis)

DISCLAIMER - I have functioned only as archiver & reposter.

> From: narcicus <narcicus@bellsouth.net>

Skunky <dpozo@gibnet.gi> wrote in article

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