From: lamont@hyperreal.com (Lamont Granquist)
Newsgroups: alt.drugs
Subject: chemistry: if anyone *ever* asks for a "MDMA recipie" again...
Date: 23 May 1994 04:56:03 GMT
Message-ID: <2rpd13$sav@news.u.washington.edu>

I believe  this will eventually be in the MDMA FAQ (or at least the info
in it will be...):

INTRODUCTION:

  All information here is to be used at your own risk.  The procedures
documented in this file, if carried out by unlicensed individuals would
violate laws against controlled substances in most countries and could result
in criminal charges being filed.  If carried out by individuals unskilled
at chemistry they could result in serious bodily harm.

  MDMA ("Ecstasy") is a semi-synthetic compound which can be made relatively
easily from available precursors.  Synthesis instructions exist which can
be followed by an amateur with very little knowledge of chemistry.  However,
people with less than 2 years of college chemistry experience would probably
not be capable of sucessfully synthesizing MDMA, and would either botch it
in the best case or kill themselves in the worst case.  For those interested
in the techniques involved in synthesizing MDMA, a good book for self-
learning is the following:

  Zubrick, James W.  "The Organic Chem Lab Survival Manual: A Students Guide
  to Techniques."  ISBN #0471575046.  Wiley John&Sons Inc.  3rd ed.

It is recommended that this book should be supplemented with at *least* one
more of the 'dry' and technical O-Chem lab manuals available at any college
bookstore.  It is not recommend that the information from these books or
herein this file be used to synthesize MDMA for the previously stated
reasons.  Knowledge, however, is not (yet) illegal.

PRECURSORS:

  The following chemicals are some of the more important ones in the
synthesis of MDMA and related chemicals:

            O
            ||
    O  //\  /\       O  //\  /\       O  //\  /\\       O  //\  /\\  NO2
   / \//  \/  H     / \//  \/  \     / \//  \/  \\     / \//  \/  \\/
  /   |   ||       /   |   ||  ||   /   |   ||   |    /   |   ||   |
CH2   |   ||      CH2  |   ||  ||  CH2  |   ||   |   CH2  |   ||   |
  \   |   ||       \   |   ||  CH2  \   |   ||   CH3  \   |   ||   CH3
   \ /\\  /         \ /\\  /         \ /\\  /          \ /\\  /
    O  \\/           O  \\/           O  \\/            O  \\/

    piperonal          safrole         isosafrole     beta-nitroisosafrole

   O  //\  /\  O     O  //\  /\  Br
  / \//  \/  \//    / \//  \/  \/
 /   |   ||   |    /   |   ||   |
CH2  |   ||   |   CH2  |   ||   |
 \   |   ||   CH3  \   |   ||   CH3
  \ /\\  /          \ /\\  /
   O  \\/            O  \\/

     MDP-2-P      3,4-methylenedioxy-
                 phenyl-2-bromopropane

safrole:              3,4-methylenedioxyallylbenzene,
                      1-(3,4-methylenedioxyphenyl)-2-propene

isosafrole:           3,4-methylenedioxypropenylbenzene,
                      1-(3,4-methylenedioxyphenyl)-1-propene

MDP-2-P:              3,4-methylenedioxyphenyl-2-propanone,
                      3,4-methylenedioxyphenylacetone,
                      3,4-methylenedioxybenzyl methyl ketone,
                      piperonylacetone

piperonal:            3,4-methylenedioxybenzaldehyde,
                      heliotropin

beta-nitroisosafrole: 3,4-methylenedioxyphenyl-2-nitropropene

  safrole, isosafrole, MDP-2-P, piperonal and beta-nitroisosafrole are the
most commonly found precursors to MDMA in clandestine labs.

SYNTHETIC ROUTES:

  For an overview of MDMA synthetic routes it is suggested that the readers
familiarize themselves very thoroughly with the following reference:

  Dal Cason-TA. "An Evaluation of the Potential for Clandestine Manufacture of
  3,4-Methylenedioxyamphetamine (MDA) Analogs and Homologs." Journal of Forensic
  Sciences. Vol 35(3):675-697. May 1990.

  The most common synthetic routes for production of MDA, MDMA, MDE (MDEA),
and MDOH are from the precursor MDP-2-P.  To get MDP-2-P first a natural
source of safrole is acquired.  Safrole can be extracted from sassafras
oil, nutmeg oil, or several other sources which have been abundantly
documented in _Chemical Abstracts_ over the years.  The safrole is
then easily isomerized into isosafrole when heated with NaOH or KOH.  The
isosafrole is then oxidized into MDP-2-P.  This latter procedure has been most
clearly presented in _Phenethylamines I Have Known and Loved_ by Alexander
Shulgin under synthesis #109 (MDMA).  The synthesis of MDP-2-P from isosafrole
will require the use of a vacuum pump to evaporate the solvent from the
final product in vacuo.  An aspirator will not, unfortunately, be sufficient.

  Once the MDP-2-P is synthesized there are several synthetic routes which
can be taken:

  1. Sodium Cyanoborohydride
  2. Aluminum Amalgam
  3. Sodium Borohydride
  4. Raney Nickel Catalysis
  5. Leukart Reaction via N-formyl-MDA
  6. Leukart Reaction via N-methyl-N-formyl-MDA

The sodium cyanoborohydride method is probably the one most attractive to
clandestine chemists.  From the Dal Cason reference:

  "It requires no knowledge of chemistry, has a wide applicability, offers
  little chance of failure, produces good yields, does not require expensive
  chemical apparatus or glassware, and uses currently available (and easily
  synthesized) precursors"

The aluminum amalgam synthesis is often used but has a slightly higher risk
of failure and is not as versatile.  The Raney Ni synthesis is more dangerous
and requires special equipment to be done right (although this scheme is used
in a significant number of clandestine labs).  The sodium borohydride
requires harsher conditions for the chemicals (ie. reflux) than sodium
cyanoborohydride or aluminum amalgam and produces lower yields.  The
Leukart reaction is 2-step with lower yields and requires chemical apparatus.

  There are also two synthetic methods which proceed directly from safrole
rather than through isosafrole.  The first is the Ritter reaction which goes
through the intermediate N-acetyl-MDA.  The Ritter reaction is time-consuming,
requires a degree of laboratory skill and produces poor yields.  The other
method uses HBr to produce 3,4-methylenedioxyphenyl-2-bromopropane which is
then converted into MDA or MDMA.  This scheme produces poor yields, and
Dal Cason referenced the australian journal _ANALOG_ where a hazard had
been documented.  It is, however, attractive for its sheer simplicity.  It
requires no specialized chem equipment or reagents at all.

  Beta-nitroisosafrole is a less used precursor, but there is a large
literature on the synthesis and reduction of nitro alkenes.  This synthetic
route isn't as popular due to the easier availability of precursors for
MDP-2-P, and it also results in MDA which must then be further processed
to give MDMA or any other N-alkyl homolog of MDA.  There are numerous ways
to convert beta-nitroisosafrole to MDA:  LiAlH4, AlH3, electrolytic, Na(Hg),
BH3 - THF / NaBH4, Raney Ni catalyst, Pd / BaSO4 catalyst, Zn (Hg).
Beta-nitroisosafrole, when used, is commonly synthesized from piperonal.
Beta-nitroisosafrole can also be used as a precursor for MDP-2-P, but this
is not commonly done.

  There are other synthetic routes, such as the use of substituted
3,4-methylenedioxycinnamic acid or the construction of alkyenedioxy bridges
from dihydroxy compounds.  These, however, are typically not used for a
variety of reasons (difficulty, multiple-step, special equipment, etc).  It
is also possible to synthesize n-alkyl derivatives of MDA from MDA (e.g.
synthesizing MDMA from MDA) but this is not commonly done in clandestine labs.

METHYLAMINE

  Methylamine is a chemical which is technically not a "precursor" to MDMA,
but it is necessary in most of the syntheses.  It is also a watched
chemical.  A private citizen ordering methylamine from a chemical supply
company would get the undivided attention of the local DEA.  Methylamine
can be diverted in small quantities by individuals working in legitimate
chemical labs.  In some cases this "diversion" is simply theft.  It is
not recommended that any persons engage in this activity, but it remains a
common source of methylamine.
  Methylamine can be synthesized through hydrolyzing N-methylacetamide via
refluxing it with concentrated HCl.  This leaves water, methylamine and acetic
acid, boil of the water, and strip the acetic acid off with a vacuum pump
and what's left is the methylamine.  It can also be synthesized by doing
a large hypohalite Hofmann degradation on acetamide with bleach and lye.
Heat it up and distill off the water/methylamine from the basic mush and
catch it in HCl.  Boil off the water/acid distillate and the result is
methylamine HCl.

SUMMARY:

oil of sassafras -------> safrole ----------> isosafrole --------> MDP-2-P
               (extraction)  |  (isomerization)         (synthesis)   |
                             |                                        |
                             V                                        V
                      *1. safrole + HBr           *1. sodium cyanoborohydride
                       2. Ritter reaction         *2. aluminum amalgam
                                                   3. sodium borohydride
piperonal ------> beta-nitroisosafrole             4. Raney Ni catalyst
        (synthesis)      |                         5. Leukart reaction
                         |
                         V
               [numerous routes to MDA]

* of interest to aspiring kitchen chemists

- the sodium cyanoborohydride method is the preferred method
- the safrole + HBr route is attractive due to its sheer simplicity
- the aluminum amalgam route is as useful as cyanoborohydride, but may
  have a slightly higher risk of failure.

"POPULAR" LITERATURE:

Psychedelic Chemistry:  Contains instructions for isomerizing safrole,
  a synthesis of MDP-2-P from isosafrole, and a synthesis which uses the
  Leukart reaction.  The synthesis of MDP-2-P is better presented in 
  PiHKAL and the Leukart reaction is is not a recommended synthesis.  Also,
  please see "ROAD HAZARDS" below, on the dangerous typos in this
  synthesis.

Secrets of Methamphetamine Manufacturing:  Contains instructions for
  synthesizing MDMA via the safrole + HBr method.  This is the simple and
  dirty way to synthesize MDMA.  Pay attention to the part where it tells you
  to make sure that you've got all the ether evaporated before placing it
  in the reaction bomb...  for your own good.  References to the original
  journal articles and Chem Abstracts are included.

PiHKAL #100 (MDA): Synthesis of beta-nitroisosafrole from piperonal,
  synthesis of MDA from beta-nitroisosafrole using lithium aluminum
  hydride, synthesis of MDA from MDP-2-P using sodium cyanoborohydride.
  The latter is probably the most useful.  Although piperonal is commonly
  used to synthesize beta-nitroisosafrole.  LAH is somewhat dangerous.

PiHKAL #105 (MDDM): Synthesis of MDDM (N,N-dimethyl-MDA) from MDP-2-P
  using sodium cyanoborohydride.  This stuff isn't terribly active, its
  just another example of a sodium cyanoborohydride synthesis.

PiHKAL #106 (MDE): Synthesis of MDE from MDA via N-acetyl-MDA.  Synthesis
  of MDE from MDP-2-P using aluminum amalgam.  Synthesis of MDE from
  MDP-2-P using sodium cyanoborohydride.  The latter two are the most 
  useful.  Synthesizing MDE from MDA is not particularly useful to
  clandestine chemists.

PiHKAL #109 (MDMA): Synthesis of MDMA from MDA via N-formyl-MDA.  Synthesis
  of MDP-2-P from isosafrole.  Synthesis of MDP-2-P from beta-nitro-
  isosafrole.  Synthesis of MDMA from MDP-2-P using aluminum amalgam.
  The synthesis of MDP-2-P from isosafrole and the aluminum amalgam
  synthesis are probably the most useful.  The synthesis of MDP-2-P from
  beta-nitroisosafrole might be useful, but most often beta-nitroisosafrole
  is used to produce MDA directly.  Synthesizing MDMA from MDA is not
  particularly useful to clandestine chemists.

PiHKAL #114 (MDOH): Synthesis of MDOH from MDP-2-P using sodium 
  cyanoborohydride.  This stuff is active, and the synthesis is useful.

  Unfortunately, i haven't found an explicit synthesis for MDMA using
sodium cyanoborohydride.  Substituting the correct number of moles of
methylamine for ethylamine in the MDE synthesis *should* work okay.  Also,
substituting methylamine for ethylamine in the cyanoborohydride synthesis
produces better yields.

NET SOURCES:

ftp://ursa-major.spdcc.com/pub/pihkal
  the text of book 2 of PiHKAL with all the syntheses
http://www.hyperreal.com/~lamont/pharm/pihkal-ht/pihkal.index.html
  html version of PiHKAL
ftp://hemp.uwec.edu/pub/drugs/psychedelics/mdma/mdma.mda.syntheses
ftp.hmc.edu:/pub/drugs/mdma/mdma.mda.syntheses.Z 
  the synthesis of MDP-2-P from PiHKAL, plus the Leukart reaction from
  Psychedelic Chemistry.
ftp.hmc.edu:/pub/drugs/mdma/mdma.synth.Z
  this is the safrole + HBr method out of Secrets of Methamphetamine
  Manufacturing

ROAD HAZARDS:

Chemical Abstracts 52, 11965c (1958):  In the synthesis of MDA from MDP-2-P
  this reference has a misprint that should read "add 100ml H2O" instead
  of "add 100ml H2O2" which would cause an explosion.  Chemistry is
  dangerous, and a little ignorance can cause spectacular pyrotechnics...
Psychedelic Chemistry:  The synthesis for MDA/MDMA is the same as the
  above Chemical Abstracts reference including the explosive typo.  There
  is also another typo which should read "75 ml 15% HCl" instead of "57ml
  15% HCl."  This might simply mess your yields up.
Et20/THF: AKA diethyl ether and tetrahydrofuran.  These two chemicals form
  explosive peroxides when they are exposed to air for extended periods of
  time, and which are easily set off by refluxing (for example).  These are
  likely the cause of most explosions and fires in amphetamine labs.  Do not
  play around with these chemicals, and if you use them, know what you are
  doing.
MDP-2-P: "piperonylacetone" is an ambiguous term which might refer to the
  4-carbon analogue of MDP-2-P.  Shulgin has noted that at least one chemical
  supply house has sold this 4-carbon analogue as "piperonylacetone."  The
  correct piperonylacetone (MDP-2-P) is sassafras-smelling oil that is
  yellow colored.  The incorrect piperonylacetone has a weak terpene smell
  and is white and crystalline.  Substitution will merely result in some
  interesting 4-carbon analogues of MDMA which are probably totally
  inactive.  See PiHKAL #109 (MDMA).
LAH: Lithium Aluminum Hydride (LiAlH4), is a chemical which explodes on
  contact with water, and can be set off by moisture in the air.  It should
  only be used under an inert atmosphere, which requires special equipment.
 
-- 
Lamont Granquist (lamont@hyperreal.com)
"And then the alien anthropologists - Admitted they were still perplexed - But
on eliminating every other reason - For our sad demise - They logged the only
explanation left - This species has amused itself to death" -- Roger Waters


