-------------------------------------------------------------------------------- From: Potion Mixer 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. -------------------------------------------------------------------------------- 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. -------------------------------------------------------------------------------- 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. ------------------------------------------------------------------------------- Huge Scale Leuckart MDMA Production ------------------------------------------------------------------------------- This method is used in the past in Europe on huge scale to make MDMA: [1] 150 L MDP2P + 400 L NMF + 75 L Formic acid : heat to 190°C (at 140°C H2O + Formic acid comes over) for about 6 Hrs. until smell of Ammonia-gas is present at the collecting flask. No vacuum! Let cool and wash with 350 L water to get rid of excess NMF. Tap off 160 L oil and extract the remaining water with 2 x 30 L DCM. Cook off that DCM at 60°C and 200 mm Hg. Add the 20 L extra oil to the 160 L = 180 L. [2] Cook with HCl : Hydrolysis. 180 L oil + 100 L methanol + (250 L HCl 36% + 550 L H2O): Mix and cook. At 60-65°C MeOH distills over, after that go to 95 C and stay there for 3 Hrs. You make now the chloride salt, which dissolves in the water part. Let cool off to 40°C and extract with 40 L DCM. THROW AWAY THE DCM extract, this is full of impurities. KEEP the water-part! [3] Making Basic. 100 Kg NaOH dilute in 100 L water (90 L 100% HCl needs +/- 70 L NaOH). Use this NaOH solution to basify the remaining water portion. DO NOT exceed 40C! Bring to pH 10.3 and then +/- 100 L MDMA base oil will come. Extract with 2x30 L DCM and distill off the DCM to get raw base. [4] Distillate. At 4 mm Hg (or any other good vacuum) and 145°C you distillate the raw base to get the clean base. (first remove DCM and water). [5] Crystalls. If you know my name now, search my posts how to make them.... Use Acetone cold and HCl gas... -------------------------------------------------------------------------------- MDA using the Leuckart Reaction by Logical Add the following to 2 neck flask (with mag stirring): 1250 ml Formamide 653 ml 90% formic acid 500 g mdp2p In simple distillation setup: Heat up to 165 degrees celcius (dont let go over 170) and once reached this temp, keep it there for 5 hrs. After 5 hrs, add reaction flasks contents to 3.5 L distilled water in a sep funnel. Dark oil will fall to bottom. Wait a while for this to happen (5 mins). Drop the oil back into 2-neck flask then extract water with approx 500 ml (x2) ether. Add ehter to the oil in the flask and evaporate ether. Now add to the flask 2.5 L of 15 % potasium hydroxide in (20% water, 80% ethanol). So in other words, add 375 g KoH to 425 ml water, then add 1700 ml ethanol. Store bought denatured alcohol can be substituted for absolute ethanol. Once this solution has been added, then reflux for 1 hr. Now add 830 mls water and then strip off ethanol. Once ethanol is removed, place contents of flask in sep funnel and u will see a dark oil layer lying above the KOH/water layer. Separate the top oil layer (it is your MDA) and distil it to collect your pure free base. Then crystalize, best using dcm and gassing. Or if you want to make sulfate and dont like gassing, then add oil to ethanol and slow drip into it a 10% sulfuric acid solution (in ethanol). --------------------------------------------------------------------------------