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