============================================================================= Notes on the Synthesis of Methcathinone ============================================================================= Author: Anonymous Date: 1997/07/10 Oxidation of sec-alcohols to ketones using Sodium Hypochlorite (reprinted & edited from a former post to alt.drugs.chemistry) (I DID NOT DEVELOP THIS PROCEDURE NOR HAVE I TRIED IT. I HAVE MY OWN DOUBTS ABOUT IT, BUT DO TO SOME INTEREST I'VE DECIDED TO REPOST THE INFORMATION. TRY IT AT YOUR OWN RISK AND $$. IF YOU GET IT TO WORK, PLEASE LET THE REST OF US KNOW.) 2.62 g of (pseudo)ephedrine HCl was dissolved in 11.6 g glacial acetic acid in a 100 ml beaker equipped with a magnetic stirrer. 20 g of 5.25% sodium hypochlorite solution (Regular Chlorox) was added slowly with stirring. The mixture tested positive to starch iodide paper. Stirring was continued for 1 hour then sufficient saturated sodium sulfite solution (9.6 g) was added to produce a negative starch iodide test. 50 ml of saturated sodium chloride solution and 15.5 g of ice was added and the solution basified with 50% sodium hydroxide solution (16.7 g). At this point a white precipitate formed and a sweet odor indicative of ketone was observed. The slurry was extracted with 1x75 ml then 2x50 ml chloroform. The organic phase was dried over sodium sulfate, filtered, and evaporated to yield 2.51 g of slightly yellowish waxy crystalline solid. This was dissolved in 100 ml hot hexane and decanted from a small amount of insoluble material. [editor's note: the yellow color might be due to the hitherto discussed CAT dimer byproduct] Excess HCl gas was bubbled through the hexane solution to form a white precipitate. This was filtered, washed twice with ether and dried to yield 2.25 g (86% yield) of slighly off-white powder with a MP of 161-171 C. The crude product was recrystallized from alcohol-ether, filtered and washed with cold ether to yield a bitter white powder with a MP of 179-180 C (final yield 74%). CONCLUSION: Melting point of the final product is consistent with methcathinone HCl (lit. 182-184 C). It appears that the oxidation of sec-alcohols to ketone using sodium hypochlorite originally reported in JOC 45 (1980): 2030ff can be successfully applied to amines. This procedure is superior to the more traditional chromate & permanganate oxidations in a number of ways, including cost of reagents, no hazardous waste generation, and the easier product isolation resulting from lack of unwanted precipitates in the reaction mixture. [editor's note: My reservations about the above post come from the fact that it looks almost exactly like a combination of the permanganate method published by Zhingel et al. in J. Forensic Sci. 36 (1991): 915-20 (this is in the Methcathinone FAQ 2.2, towards the end of the FAQ.) and the hypochlorite method of oxidizing alcohols I've seen in a number of recent organic chemistry laboratory textbooks. The original poster may just have replaced the steps in the permangante method, with those from the hypochlorite method. Of course, this may be exactly how the original poster developed a synthetic protocol that maybe does work.] ============================================================================= Subject: (New) synthesis for cathinone Date: Tue, 14 Apr 1998 14:14:53 +0200 From: plop Newsgroups: alt.drugs.chemistry The synthesies for cathinone and its derivates wich were presented in these newsgroups, only uses (nor)ephedrine (I haven't read another one). But cathinone (and its N-derivates) were prepaired long before cathinone was known as a natural product. Because of the cathinones chemical instability (and the plants, wich were extracted, weren't fresh. The cathinone gave by the extaction for basic substances dimeric products, f.e. 2,5-dimethyl-3,6-diphenyl-pyrazine) it was discoverd in the second half of this century. But cathinone was prepared completely synthetic by the german chemist Schmidt 1889 (synthesis: Chemische Berichte 22 (1889),3250-3253) and nobody has discriped these way. Methcathinone con be made in the same manner. Preperation: The outgoing stuff is propiophenone. This can be bought in a standard chemical-store. It can be made by Friedel-Crafts-Acylation from benzene with propionic-acid-chloride or propione-acid-anhydride. To make standard-(unsubstituted) propiophenone, this synthesis is not interessting, but for ringsubstituted propiophenones it is very interessing, cause cathinone has nearly the same effects like amphetamine. And so, the ring-substituted cathinones could have an nearly equal effect like the ring-substituted amphetamine-derivates (f.e.: take 2,5-dimethoxy-benzene for making 2,5-dimethoxy-cathinone, the related amph. is 2,5-DMA). 1) To brominate the propiophenone, put propiophenone in glacial acetic acid and drop equimolar parts bromine in the solution and shake (better stirr) it. Now it must stand for half an hour. Hasn't the reaction taken place (you can see it, if the sol. has the typical bromine-deep-red colour) you can induce it by puting the beacer in warm water shortly. Then the solution produces slowly, then more intensive, H-Br and the colour disappears. Then drop it under good stirring in much cold water. The bromoketone sinks as a colourless, heavy oil to bottom. To free it from H-Br wash the seperated layer with water and NaCO3-solution. The bromoketone cristallizes by 0 grade (Celsius). It should be recristallized from ether. 2) Equimolar amount of Phtalimido-postasium and bromoketone were heated in an oilbath. Up to 160-170 grades (C) the pieces of the postasiumsalt are disappearing. It will be stirred by these temperature for a few more minutes (perhaps 10 or so). Then you have a heavy yellow-brown mass wich goes solid by cooling down to RT. The mass will be soluted with EtOH and the unsolutible K-Br removed. Then the EtOH is removed by heating and the resulting substance is treated with water and heated to boiling to remove unreacted phtalimide. The resulting melted product can be recritallized from alcohol (m.p. 85 Grade (C)). This is phtalimidopropiophenone 3) The phtalic acid can be removed by heating the cristalls from 2) with conc. H-Cl for 1-2h. The solution was allowed to cool to RT and the crysts were filtered (phtalic acid). Then the water was removed and the resulting solid substance will be treated with a few cold water. Then the solution os filtered to remove the rest of phtalic acid. Then the solution is evaporated to dryness. The resulting crysts are cathinone-H-Cl. (Before treating it with conc H-Cl the crysts from 2) can be treated with aq. postasiumhydroxide. The resulting substance is postasiumsalt of the phtalamin-acid. The sol. will be diluted with water and treated with diluted H-Cl. Then it crystallized as fine nedles with a m.p. 140 grade (C). The crysts can used instead of phtalimidopropiophenone on the top of point 3) To make Methcathinone, 0.1 mole of bromoketone was added dropwise to 0.25 mole of methylamine (30% solution in abs. alcohol) over a period of one hour. The reactionflask was immersed in ice water during the reaction and stirring was continued for one-half hour after the addition of the bromoketone. Then cold, conc. H-Cl was added very slowly along with some finely cracked ice until the mixture was acidic. If it became warm the product turned very dark in color and a larger propartion of tar war produced. At this point the reaction mixture was orange or red dur to the presence of some bromo ketone that hasn't reacted and to formation of certain tarry by-products. These were extracted with ether from the water layer and the bromo ketone recovered. The water layer was evaporated to dryness in vacuo, treated with a little choroform and evaporated to dryness again to assist in removing the moiture from the rather hard mass. After standing in the vaccuum execator for one day, the residue was extracted several times with fresh portions of choroform and each time the insoluble cysts of methylamine hydrochloride were filtered. The choroform solution was then evaporated until it was very concentrated, and acetone was added to cause the crystallisation of the amine ketone hydrochloride. Recrystallisation was carried out by dissolving in a small amount of alcohol, filtering, and adding about twice the vol. of acetone in small protions (from Journal of chemical society, London 50 (1928), 2290) Perhaps it could be get in higher yields, when the bromo-propiophenone was treated with the methylimine from benzaldehyde. Sorry for the bad english in the upper synthesis. ============================================================================= Ok, this has got to be the easiest drug made at home (by far). This is very similar to methamphetamine in structure, effect, and use. Typical doses start at 20mg up to 60mg. Start low, go slow. Cat can be taken orally (add 10 mg) or through mucous membranes (nasally). Ingredients: Diet pills, or bronchodilator pills (1000 ea) containing 25mg ephedrine. Potassium chromate, or dichromate (easily gotten from chem lab. orange/red) Conc. Sulfuric acid - it's up to you where you get this. Contact me if you need help locating it. Hydrochloric acid or Muriatic acid - Pool supply stores, hardware stores, it is used for cleaning concrete. Sodium Hydroxide - Hardware stores. AKA lye. Toluene - Hardware store, paint store. Lab equipment: 1 liter, 3 neck flask - get it from school or Edmund's Scientific ($20.00) 125 mL seperatory funnel - same as above glass tubing - same as above Buchner funnel - This is a hard to find item, but must schools have at least one. They are usually white porcelain or plastic. They look like a funnel with a flat disk in the bottom with lots of holes in it. If you need one, arrangements can be made. Aspirator or vacuum pump - Any labware supply catalog, about $10.00 Refrences to Edmund's Scientific Co, in NJ, are accurate. You have to go to their "Lab Surplus/Mad Scientist" room. The prices are incredible. This place is definitely a reccommended stopping sight for anybody going through New Jersey. It is locat in "Barrington", about 30 minutes from center city Philadelphia. All of the above can be purchased from "The Al-Chymist". Their number is (619)948-4150. Their address is: 17525 Alder #49 Hesperia, Ca 92345 Call and ask for a catalog. That's it. The body of this article is stolen from the third edition of "Secrets of Methamphetamine Manufacture" by Uncle Fester. This is a tried and proven method by many people. If you want a copy of this book, contact me. Good luck and keep away from the DEA, -The Professor CHAPTER 16 M E T H C A T H I N O N E K I T C H E N I M P R O V I E S E D C R A N K The latest designer variant upon the amphetamine molecule to gain popularity and publicity is methcathinone, commonly called cat. This substance is remarkably similar to the active ingredient found in the leaves of the khat tree which the loyal drug warriors on the network news blame for turning peace loving Somalis into murderous psychopaths. The active ingredient in the khat leaves is cathinone, which has the same structural relationship to methcathinone that amphetamine has to methamphetamine. It is made by oxidizing ephedrine, while meth can be made by reducing ephedrine. The high produced by methcathinone is in many ways similar to methamphetamine. For something so easily made and purified, it is actually quite enjoyable. the main differences between the meth high and the methcathinone high are length of action and body fell. With methcathinone, one can expect to still get to sleep about 8 hours after a large dose. On the down side, it definitely gives me the impression that the substance raises the blood pressure quite markedly. This drug may not be safe for people with weak hearts of blood vessels. Be warned! Cat is best made using chrome in the +6 oxidation state as the oxidizer. I recall seeing an article in the narco swine's Journal of Forensic Science bragging about how they worked out a method for making it using permanganate, but that method gives an impure product in low yields. Any of the common hexavalent chrome salts can be used as the oxidizer in this reaction. This list include chrome trioxide (CrO3), sodium or potassium chromate (Na2CrO4), and sodium or potassium dichromate (Na2Cr2O7). All of these chemicals are very common. Chrome trioxide is used in great quantities in chrome plating. The chromates are used in tanning and leather making. To make methcathinone, the chemist starts with the water extract of ephedrine pills. The concentration of the reactants in this case is not critically important, so it is most convenient to use the water extract of the pills directly after filtering without any boiling away of the water. See the section at the beginning of Chapter 15 [I included this at the end -The Professor] on extracting ephedrine form pills. Both ephedrine hydrochloride and sulfate can be used in this reaction. The water extract of 1000 ephedrine pills is placed into any convenient glass container. A large measuring cup is probably best since it has a pouring lip. Next, 75 grams of any of the above mentioned +6 chrome compounds are added. They dissolve quite easily to form a reddish or orange colored solution. Finally, concentrated sulfuric acid is added. If CrO3 is being used, 21 mL is enough for the job. If one of the chromates is being used, 42 mL is called for. These ingredients are thoroughly mixed together, and allowed to sit for several hours with occasional stirring. After several hours have passed, lye solution is added to the batch until it is strongly basic. Very strong stirring accompanies this process to ensure that the cat is converted to the free base. Next, the batch is poured into a sep funnel, and a couple hundred mLs of toluene is added. Vigorous shaking, as usual, extracts the cat into the toluene layer. It should be clear to pale yellow in color. The water layer should be orange mixed with green. The green may settle out as a heavy sludge. The water layer is thrown away, and the toluene layer containing the cat is washed once with water, then poured into a beaker. Dry HCl gas is passed through the toluene as described in Chapter 5 [I included this at the end -The Professor] to get white crystals of cat. The yield is between 15 and 20 grams. This reaction is scaled up quite easily. CHAPTER 15 (part of it anyway) P R O C E D U R E F O R O B T A I N I N G P U R E E P H E D R I N E F R O M S T I M U L A N T P I L L S In the present chemical supply environment, the best routes for making meth start with ephedrine as the raw material. To use these routes, a serious hurdle must first be overcome. This hurdle is the fact that the most easily obtained source of ephedrine, the so-called stimulant or bronchodilator pills available cheaply by mail order, are a far cry from the pure starting material a quality minded chemist craves. Luckily, there is a simple and very low profile method for separating the fillers in these pills from the desired active ingredient they contain. A superficial paging through many popular magazines[New Body is where I found it (in GNC) -The Professor] reveals them to be brim full of ads from mail order outfits offering for sale "stimulant" or "bronchodilator" pills. These are the raw materials today's clandestine operator requires to manufacture meth without detection. The crank maker can hide amongst the huge herd of people who order these pills for the irritating and nauseating high that can be had by eating them as is. I have heard of a few cases where search warrants were obtained against people who ordered very large numbers of these pills, but I would think that orders of up to a few thousand pills would pass unnoticed. If larger numbers are required, maybe one's friends could join in the effort. The first thing one notices when scanning these ads is the large variety of pills offered for sale. When one's purpose is to convert them into methamphetamine, it is very easy to eliminate most of the pills offered for sale. Colored pills are automatically rejected because one does not want the coloring to be carried into the product. Similarly, capsules are rejected because individually cutting open capsules is just too much work. Bulky pills are to be avoided because they contain too much filler. The correct choice is white cross thins, preferably containing ephedrine HCl instead of sulfate, because the HCl salt can be used in more of the reduction routes than can the sulfate. Once the desired supply of pills is in hand, the first thing which should be done is to weigh them. This will give the manufacturer an idea of how much of the pills is filler, and how much is active ingredient. Since each pill contains 25 milligrams of ephedrine HCl, a 1000 lot bottle contains 25 grams of active ingredient. A good brand of white cross thins will be around 33% to 40% active ingredient. 25 grams of ephedrine HCl may not sound like much, but if it is all recovered from these pills, it is enough to make from 1/2 to 3/4 ounce of pure meth. This is worth three or four thousand dollars, not a bad return on the twenty odd dollars a thousand lot of such pills costs. [I don't know where he got 3 or 4 thousand dollars from, but the pills go for about $35.00/1000 now. 2 months ago they were $25.00 but now they have to do more paper work because it is a DEA controlled substance -The Professor] To extract the ephedrine from the pills, the first thing which must be done is to grind them into a fine powder. This pulverization must be thorough in order to ensure complete extraction of the ephedrine form the filler matrix in which it is bound. A blender does a fine job of this procedure, as will certain brands of home coffee grinders. Next, the powder from 1000 pills is put into a glass beaker, or other similar container having a pouring lip, and about 300 mL of distilled water is added. Gentle heat is then applied to the beaker, as for example on a stove burner, and with steady stirring the contents of the beaker are slowly brought up to a gentle boil. It is necessary to stir constantly because of the fillers will settle to the bottom of the beaker and cause burning if not steadily stirred. Once the contents of the beaker have been brought to a boil, it is removed from the heat and allowed to settle. Then the water is poured out of the beaker through a piece of filter paper. The filtered water should be absolutely clear. Next, another 50 mL of water is added to the pill filler sludge, and it too is heated with stirring. Finally, the pill sludge is poured into the filter, and the water it contains is allowed to filter through. It too should be absolutely clear, and should be mixed in with the first extract. A little water may be poured over the top of the filler sludge to get the last of the ephedrine out of it. This sludge should be nearly tasteless, and gritty in texture. The water extract should taste very bitter, as it contains the ephedrine. The filtered water is now returned to the stove burner, and half of the water it contains is gently boiled away. Once this much water has been boiled off, precautions should be taken to avoid burning the ephedrine. The best alternative is to evaporate the water off under a vacuum. If this is not practical with the equipment on hand, the water may be poured into a glass baking dish. This dish is then put into the oven with the door cracked open, and the lowest heat applied. In no time at all, dry crystals of ephedrine HCl can be scraped out of the baking dish with a razor blade. The serious kitchen experimenter may wish to further dry them in a microwave. Chapter 5 (The part about the HCl gas) A source of anhydrous hydrogen chloride gas is now needed. The chemist will generate his own. The glassware is set up as in Figure 1. He will have to bend another piece of glass tubing to the shape shown. It should start out about 18 inches long. One end of it should be pushed through a one hole stopper. A 125 mL sep funnel is the best size. The stoppers and joints must be tight, since pressure must develop inside this flask to force the hydrogen chloride gas out through the tubing as it is generated. Into the 1000 mL, three-necked flask is placed 200 grams of table salt. Then 25% concentrated hydrochloric acid is added to this flask until it reaches the level shown in the figure. The hydrochloric acid must be of laboratory grade [I use regular muriatic acid for pools -The Professor]. Figure 1: \ / ÖÄ\ /ÄÄ· Ö½ Ó· <--125 mL seperatory funnel º º º º Ó· Ö½ ÓÄ· ÖĽ glass tubing Ä¿ Ó· Ö½  º º ÉÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ» stopcock->ºÛÛºÄÄ´ º ºSalt and Hydrochloric acid stopper ->ÖÄÄÄ· ÖÐ\/з ÖÄÐÄ· <-1 hole ºmixed into a paste by add- ºÄÄĺ º º ºÄÒĺ stopper ºing HCL to salt and mixing. ÖÄÄĽ ÓÄÄÄÄĽ ÓÄÄÄÄÄĽ º ÓÄÄÄ· ºThe surface should be rough Ö½ º Ó· ºand a good number of holes º º ºshould be poked into the º 1000 mL, 3 neck flask º ºpaste for long lasting º º ºgeneration of HCl gas. Ó· ÄÄÄÄÄÄacid/salt levelÄÄÄÄÄÄ Ö½ º ÓÄ· ÖĽ º ÓÄÄ· ÖÄĽ º ÓÄÄÄÄÄÄ· ÖÄÄÄÄÄĽ º ÓÄÄÄÄÄÄÄÄĽ º Some concentrated sulfuric acid (96-98%) is put into the sep funnel and the spigot turned so that 1 mL of concentrated sulfuric acid flows into the flask. It dehydrates the hydrochloric acid and produces hydrogen chloride gas. This gas is then forced by pressure through the glass tubing. One of the Erlenmeyer flasks containing methamphetamine in solvent is placed so that the glass tubing extends into the methamphetamine, almost reaching the bottom of the flask. Dripping in more sulfuric acid as needed keeps the flow of gas going to the methamphetamine. If the flow if gas is not maintained, the methamphetamine may solidify inside the glass tubing, plugging it up. Within a minute of bubbling, white crystals begin to appear in the solution, More and more of them appear as the process continues. It is an awe-inspiring sight. In a few minutes, the solution becomes as thick as watery oatmeal. It is now time to filter out the crystals, which is a two man job. The flask with the crystals in it is removed from the HCl source and temporarily set aside. The three-necked flask is swirled a little to spread around the sulfuric acid and then the other Erlenmeyer flask is subjected to a bubbling with HCl. While this flask is being bubbled, the crystals already in the other flask are filtered out. The filtering flask and Buchner funnel are set up as shown in figure 2. The drain stem of the buchner funnel extends all the way through the rubber stopper, because methamphetamine has a nasty tendency to dissolve rubber stoppers. This would color the product black. A piece of filter paper covers the flat bottom of the Buchner funnel. The vacuum is turned on and the hose attached to the vacuum nipple. Then the crystals are poured into the Buchner funnel. The solvent and uncrystallized methamphetamine pass through the filter paper and the crystals stay in the Buchner funnel as a solid cake. About 15 mL of solvent is poured into the Erlenmeyer flask. the top of the flask is covered with the palm and it is shaken to suspend the crystals left clinging to the sides. This is also poured into the Buchner funnel. Finally, another 15 mL of solvent is poured over the top of the filter cake. Figure 2: ÚÄÄÄÄÄÄÄÄÄÄÄ¿ ³ ³ <-Bchner Funnel ³___________³ \ / \ / \ / ÚÄÄÄÄÄÄ¿ ³ ³¯¯¯¯ <--To vacuum ÚÄÙ ÀÄ¿ ³ ³ ³ ³ ÚÄÙ ÀÄ¿ Filtering ³ ³ flask--> ÚÙ À¿ ³ ³ ÀÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÙ Now the vacuum hose is disconnected and the Buchner funnel, stopper and all, is pulled from the filtering flask. All of the filtered solvent is poured back into the erlenmeyer flask it came from. It is returned to the HCl source for more bubbling. The Buchner funnel is put back into the top of the filtering flask. It still contains the filter cake of methamphetamine crystals. It will now be dried out a little bit. The vacuum is turned back on, the vacuum hose is attached to the filtering flask, and the top of the Buchner funnel is covered with the palm or section of latex rubber glove. The vacuum builds and removes most of the solvent from the filter cake. This takes about 60 seconds. The filter cake can now be dumped out onto a glass or China plate (not plastic) by tipping the Buchner funnel upside-down and tapping it gently on the plate. And so, the filtering process continues, one flask being filtered while the other one is being bubbled with HCl. Solvent is added to the Erlenmeyer flask to keep their volumes at 300 mL. Eventually, after each flask has been bubbled for about seven times, no more crystal will come out and the underground chemist is finished. If ether was used as the solvent, the filter cakes on the plates will be nearly dry now. With a knife from the silverware drawer, the cakes are cut into eighths. They are allowed to dry out some more then chopped up into powder. If benzene was used, this process takes longer. Heat lamps may be used to speed up this drying, but no stronger heat source. [The above section of chapter 5 is talking about methamphetamine. You could, in most instances, substitute the word methcathinone, but I wanted to present the text to you in its exact form. -The Professor] ============================================================================= Email: nobody@REPLAY.COM Date: 1997/06/28 Despite a recent post to the contrary by Anonymous Artical, there is an easy-to-find academic article with relevant info on CAT cyclization: Berrang-BD; Lewin-AH; and Carroll-FI: "Enantiomeric alpha-aminopropiophenone (Cathinone): Preparation and investigation." J. Org. Chem. 47 (1982): 2643-2647. Since there is no academic info on methcathinone (aka CAT), it appears that other posters on the WWW/Usenet have extrapolated the info from this article on cathinone to methcathinone. This artcle contains info on the chemical conditions under which (meth)cathinone is unstable, and will racemize & dimerize(cyclize), and under what chemical conditions (meth)cathinone is stable. It also has info on the 'yellow' cyclization product, 3,6-dimethyl-2,5-diphenylpyrazine of cathinone. Presumably the cyclization product from methcathinone is 1N,3,4N,6-tetramethyl-2,5-diphenylpyrazine. For those of you who can read technical German the article: Gabriel-S. "Wandlungen der aminoketone" Chem. Ber. 41 (1908): 1127-1156. has a more detailed chemical description of the cyclization of cathinone (alpha-aminopropiophenone) (see esp. pp.1146ff). A UN literature review on the chemical composition of khat, including cathinone & the cyclization product can be found in: Szendrei-K."The chemistry of khat." Bulletin on Narcotics 32 (1980):5-35. [This is a UN publication] ============================================================================= Author: Anonymous Date: 1997/02/01 Cathinone and Methcathinone both form bright orange cyclization products when in the free base form and sometimes even in basic solution. Chloroform and 1,1,1 TCE however are notable solvents where the bases are stable over extended periods. Moreover, both drugs do not form stable acid salts with anything but mineral acids. (although ascorbic acid would be interesting experiment, since epinepherine is stable as ascorbate) Thus follows an easy way of characterizing yield without self administration or complicated testing. Simply take some of the base before final preparation of salt and put it on a white bowl in a warm place. The relative level of bright orange cyclo product shows the relative yield of the synthesis. Note that the cyclo products are not psychoactive, nor are they easily reverted back to their original amino-ketone forms. Also, the cyclo product smells sickly sweet. Have fun, Pugsley. =============================================================================