MDMA Synthesis: Bromosafrole method
Scanned fom _Secrets of Mthamphetamine Maufacture_
A good alternative to the Ritter reaction is a two step procedure
first reacting safrole with hydrobromic acid to give 3,4-methylenedi-
oxyphenyl-2-bromopropane, and then taking this material and reacting
it with either ammonia or methylamine to yield MDA or MDMA
respectively. This procedure has the advantages of not being at all
sensitive to batch size, nor is it likely to "run away" and produce a
tarry mess. It shares with the Ritter reaction the advantage of using
cheap, simple, and easily available chemicals.
The sole disadvantage of this method is the need to do the final
reaction with ammonia or methylamine inside a sealed pipe. This is
because the reaction must be done in the temperature range of 120-
140 C, and the only way to reach this temperature is to seal the
reactants up inside of a bomb. This is not particularly dangerous, and
is quite safe if some simple precautions are taken.
The first stage of the conversion, the reaction with hydrobromic
acid, is quite simple, and produces almost a 100% yield of the bromi-
nated product. See the Journal of Biological Chemistry, Volume 108
page 619. The author is H.E. Carter. Also see Chemical Abstracts
1961, column 14350. The following reaction takes place:
[ Structural diagrams deleted]
To do the reaction, 200 ml of glacial acetic acid is poured into a
champagne bottle nestled in ice. Once the acetic acid has cooled
down, 300 grams (200 ml) of 48% hydrobromic acid is slowly added
with swirling. Once this mixture has cooled down, 100 grarns of
safrole is slowly added with swirling. Once the safrole is added, the
cheap plastic stopper of the champagne bottle is wired back into
place, and the mixture is slowly allowed to come to room temperature
with occasional shaking. After about 12 hours the original two layers
will merge into a clear red solution. In 24 hours, the reaction is done.
The chemist carefully removes the stopper from the bottle, wearing
eye protection. Some acid mist may escape from around the stopper.
The reaction mixture is now poured onto about 500 grams of
crushed ice in a 1000 or 2000 ml beaker. Once the ice has melted, the
red layer of product is separated, and the water is extracted with about
l00 ml of petroleum ether or regular ethyl ether. The ether extract is
added to the product, and the combined product is washed first with
water, and then with a solution of sodium carbonate in water. The
purpose of these washings is to remove HBr from the product. One
can be sure that all the acid is removed from the product when some
fresh carbonate solution does not fizz in contact with the product.
Once all the acid in the product is removed, the ether must be
removed from it. This is important because if the ether were allowed
to remain in it, too much pressure would be generated in the next
stage inside of the bomb. Also, it would interfere with the formation
of a solution between the product and methylamine or ammonia. It is
not necessary to distill the product because with a yield of over 90%,
the crude product is pure enough to feed into the next stage. To
remove the ether from the product, the crude product is poured into a
flask, and a vacuum is applied to it. This causes the ether to boil off.
Some gentle heating with hot water is quite helpful to this process.
The yield of crude product is in the neighborhood of 200 grams.
With the bromo compound in hand, it is time to move onto the
next step which gives MDA or MDMA. See Chemical Abstracts
1961, column 14350. Also see Journal of the American Chemical
Society, Volume 68, page 1805 and Journal of the Chemistry Society,
part 2 1938, page 2005. The bromo compound reacts with ammonia
or methylamine to give MDA or MDMA:
[ Sructural diagram deleted ]
To do the reaction, 50 grams of the bromo compound is poured
into a beaker, and 200 ml of concentrated ammonium hydroxide (28%
NH3) or 40% methylamine is added. Next, isopropyl alcohol is added
with stirring until a nice smooth solution is formed. It is not good to
add too much alcohol because a more dilute solution reacts slower.
Now the mixture is poured into a pipe "bomb." This pipe should be
made of stainless steel, and have fine threads on both ends. Stainless
steel is preferred because the HBr given off in the reaction will rust
regular steel. Both ends of the pipe are securely tightened down. The
bottom may even be welded into place. Then the pipe is placed into
cooking oil heated to around 130 C. This temperature is maintained
for about 3 hours or so, then it is allowed to cool. Once the pipe is
merely warm, it is cooled down some more in ice, and the cap
unscrewed.
The reaction mixture is poured into a distilling flask, the glass-
ware rigged for simple distillation, and the isopropyl alcohol and
excess ammonia or methylamine is distilled off. When this is done,
the residue inside the flask is made acid with hydrochloric acid. If
indicating pH paper is available, a pH of about 3 should be aimed for.
This converts the MDA to the hydrochloride which is water soluble.
Good strong shaking of the mixture ensures that this conversion is
complete. The first stage of the purification is to recover unreacted
bromo compound. To do this, 200 to 300 ml of ether is added. After
some shaking, the ether layer is separated. It contains close to 20
grams of bromo compound which may be used again in later batches.
Now the acid solution containing the MDA is made strongly basic
with lye solution. The mixture is shaken for a few minutes to ensure
that the MDA is converted to the free base. Upon sitting for a few
minutes, the MDA floats on top of the water as a dark colored oily
layer. This layer is separated and placed into a distilling flask. Next,
the water layer is extracted with some toluene to get out the remaining
MDA free base. The toluene is combined with the free base layer, and
the toluene is distilled off. Then a vacuum is applied, and the mixture
is fractionally distilled. A good aspirator with cold water will bring
the MDA off at a temperature of 150 to 160 C. The free base should
be clear to pale yellow, and give a yield of about 20 ml. This free base
is made into the crystalline hydrochloride by dissolving it in ether and
bubbling dry HCl gas through it.
According to J-Forensic-Sci 35(3):675-697 this isn't the best method of
making methoxylated amphetamine derivatives. The author claims that
yields are low, synthing the intermediate is time consuming (although
so is synthing MD-P2P), and potentially hazardous -- I don't know why
its hazardous, but the author references ANALOG 9(3):1-10 which
is an article by Hansson, R.C. entitled "Clandestine Laboratories Production
of MDMA."
It is suggested that the synths using cyanoborohydride, aluminum amalgam,
borohydride or Raney Ni catalysis from MD-P2P would be more likely to be used.
The two former ones are preferred as the borohydride method has a lower yield
and the catalysis requires the construction or purchase of a hydrogenation
unit.
