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From: Potion Mixer <Kitchen@chef.co>
Newsgroups: alt.drugs.psychedelics
Date: Sunday, August 23, 1998 3:25 PM
Subject: mdma syntesis problem

> in "chemical abstracts 52, 11965 (1985) manufacture of extacy"
>
> "Add 23g of above ketone to 65g formamide and heat at 190° for 5 hours."
> Question - Is it 190°C or 190°F, and how would this heating practically be
> done? reflux or pipebomb?

Don't ever try anything like that, but it's 190 Centigrade, and you use a reflux
condenser.  Evolution of carbon dioxide drives the reaction forward (it's a
Leuckart condensation),  you would defeat your purpose if you used a pipe bomb.
Also 190 is probably too high.  At about 165-170 you will start to see the
formation of a lot of little tiny bubbles, like in a glass of beer.  This is
what you want, the carbon dioxide is being evolved.  You don't need to keep
raising
the temperature all the way to 190.   I would stay in the 165-175
range, just make sure you're getting the bubbles.

  Also, you say you're using formamide.  That will give you MDA
(methylenedioxyamphetamine), not MDMA (N-methyl-MDA).
Needless to say, don't ever try anything like THAT, either.  ;^)
Ecstacy is MDMA.   To get MDMA you would have to use
N-methylformamide.  The reaction with formamide is easier.

Avoid getting water in the reaction mixture -- You could prepare your formamide
FRESH by heating ammonium formate in a
distillation apparatus and driving off all the H2O that is formed.

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Cherrie Baby:

Towards the Rehabilitation of the Leuckart Reductive Amination Reaction using 
Microwave Technology. André Loupy et al, Tetr. Lett. 37(45), p 8177-80 (1996).

Abstract: The Leuckart reductive amination of carbonyl compounds was dramatically 
enhanced with respect to conventional heating by a specific microwave effect 
when the reaction was performed, under solvent-free conditions, in a monomode 
microwave reactor. Excellent isolated yields (up to 97%) were attained within 
short reaction times (typically, 30 minutes).

[This is not the actual journal article - but all details are present here - 
PS the actual article is all over the place]

Typical procedure: A mixture of formamide (0.6 mL, 15 mmol), formic acid 
(0.56 mL, 15 mmol), and the corresponding carbonyl compound (5 mmol) was 
introduced in a pyrex cylindrical tube placed in the Synthwave 402 system and 
irradiated until completion (GLC internal standard). To attain optimum results, 
three portions of formamide and formic acid were added and irradiated at 10 
minute intervals4. [the amount varies between 10 and 2 equivalents each of 
formamide and formic - depending upon the ketone]. An oven power of 60W was 
used for best effect as excessive power (120W) caused faster consumption of
carbonyl compound without concomitant transformation into the expected formamide. 
The recovery of organic products was performed by extraction with DCM, 
filtration on Florisil and solvent evaporation.

Notes:
[1]. Formamide was found to give better yields than Ammonium formate 
     (between 2% - 10% higher).
[2]. temperature range ~ 180° to 210° C. The temperature was continuously 
     measured and controlled by IR detection [Jacqualt, pat # 549495 AI (1992)]
[3]. The reaction time was 30 minutes in total.
[4]. In some cases the reaction seemed to restart when fresh formamide-formic 
     acid was added
[5]. Only tricky bit here is that special cooker they used - a "focused monomode 
     microwave reactor (due to the great efficiency of the system - needing low 
     powers and consequently high energetic yield when compared to multimode 
     domestic microwave ovens". [see Loupy et al, J. Chem. Res. (S), 1993, 
     p 36-7; Synthetic Commun. 23, 2571-7 (1993)]
[6]. No pollen was used here - so who will be the first human, in the history of 
     creation, to make honey with this? - it'll be a lot easier than it sounds.

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MDA (3,4-methylenedioxyamphetamine)

           The following synthesis is not meant to be carried out by a novice
      chemist, although it is not terribly difficult.  For descriptions of
      how to carry out the procedures, a standard lab procedures reference
      manual should be aquired by the reader (or preferably the reader 
      should take college organic chemistry).
           This is the synthesis for MDA which can be found on page 79 of
      Psychedelic Chemistry, which was first published in Chemical Abstracts
      52, 11965c (1958).  The former however has the above noted
      typographical error of 75 ml 15% HCl being written as 57ml 15% HCl.
      The original article also has a typographical error.  In the synthesis
      of MDA from the ketone it reads H2O2 where it should read H2O --
      following the former procedure would be explosive.  As a side note,
      this is the same process of making the ketone from isosafrole as
      Shulgin uses in PiHKAL, thus the synthesis of the ketone is somewhat
      more verbose than the synthesis of MDA from the ketone.

           To a well stirred, cooled mixture of 34g of 30% H202 (hydrogen
      peroxide) in 150g 80% HCO2H (formic acid) there was added, dropwise, a
      solution of 32.4g isosafrole in 120ml acetone at a rate that kept the
      reaction mixture from exceeding 40 deg C.  This required a bit over
      1 hour, and external cooling was used as necessary.  Stirring was
      continued for 16 hours, and care was taken that the slow exothermic
      reaction did not cause excess heating.  An external bath with running
      water worked well.  During this time the solution progressed from an
      orange color to a deep red.  All volatile components were removed under
      vacuum which yielded some 60g of a very deep residue.  This was 
      dissolved in 60ml of MeOH (methyl alcohol -- methanol), treated with
      360ml of 15% H2SO4 (sulfuric acid), and heated for 3 hours on the
      steam bath.  After cooling the mixture was extracted with 3x75ml
      Et2O (diethyl ether) or C6H6 (benzene).  Its recommended that, the
      pooled extracts can washed -- first with H2O and then with dilute NaOH
      (sodium hydroxide).  Then the solvent is removed under vacuum to
      afford 20.6g 3,4-methylenedioxyphenylacetone (3,4-methylenedioxybenzyl
      methyl ketone).  The final residue may be distilled at 2.0mm/108-112 deg
      C, or at about 160 deg C at the water pump.
           Add 23g 3,4-methylenedioxyphenylacetone to 65g HCONH2 (formamide)
      and heat at 190 deg for five hours.  Cool, add 100ml H20, extract with
      C6H6 (benzene) and evaporate in vacuum the extract.  Add 8ml MeOH
      (methyl alcohol -- methanol) and 75ml 15% HCl to residue, heat on
      water bath two hours and extract in vacuum (or basify with KOH and
      extract the oil with benzene and dry, evaporate in vacuum) to get
      11.7 g 3,4-methylenedioxyamphetamine (MDA).
       
      To produce MDMA substitute N-methylformamide for formamide in the
      above synthesis.

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