M.E.TEK revised w/pics

Discussion in 'Cacti Delecti' started by ancient powers, Apr 9, 2008.

  1. ancient powers

    ancient powers Member

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    Studies On The Production Of TMA-2

    That route has several drawbacks which make it impractical for clandestine synthesis. The first and most important problem is the availability of 2,4,5-trimethoxybenzaldehyde. This substance is not exactly a linchpin of chemical commerce. So far as I know, it has one use: making TMA-2. Those same folks who gave me the hassle over the purchase of Rochelle salts will certainly report a shipment of 2,4,5-trimethoxybenzaldehyde, and the heat will not be far behind.

    Further chemical supply problems arise from this method's use of large amounts of anhydrous ether or THF in the LiAlHj reduction. This too will be duly noted by the heat, especially in combination with buying LiAlHt. A much more low-profile synthetic route is possible using calamus oil as the raw material. A couple of patents granted in the late 80s have completely changed the field of psychedelic amphetamine manufacture from the way Dr. Shulgin knew it during his days of cooking in the 60s. Previous to the publication of these patents, the Knoevenagel condensation of benzaldehydes to yield the nitroalkene, followed by the reduction of the nitroalkene to the amphetamine, was far superior to an alternative route making use of the common essential oils.

    Many essential oils have as major components substituted allylbenzenes. For example, sassafras oil is 80-90% safrole: The alternative route was to take this substituted allylbenzene, move the double bond to the propenyl position by heating with anhydrous alcoholic KOH, yielding in the case of safrole, isosafrole. Then a messy, tedious and low-yield reaction was used to convert this propenylbenzene to the corresponding phenylacetone. All we veteran speed cooks love phenylacetones, because they offer the cleanest and best route to the amphetamines, but the old-fashioned method of converting propenylbenzenes to phenylacetones made this route impractical.

    My own experience with this reaction dates to the early 80s, when I decided to torment myself by trying it. Detailed cooking procedures using it can be found in Pikhal under MDMA. My experience with the KOH isomerization was that the conversion of safrole to isosafrole went cleanly at about 100% yield, as long as traces of moisture were excluded from the reaction. The conversion of isosafrole to methylenedioxy-phenylacetone is another matter. The yields are low, a lot of work is required because the formic acid and hydrogen peroxide must be removed from the reaction mixture under a vacuum before final treatment with sulfuric acid solution to yield the phenylacetone, and these vapors corrode the aspirator supplying the vacuum. This method stinks!

    Two patents dating to the late 80s, and to a lesser extent a journal article dating back to 1970, have turned the situation around. The first patent I will cite is US patent 4,638,094, titled "A Process for Producing Phenylacetones." This patent reveals, using many different examples over the course of 36 pages, the best general method for converting allylbenzenes to the corresponding phenylacetone in very high yields.

    This procedure reacts the allylbenzene (for example safrole, as obtained in pure form by vacuum distilling sassafras oil) with methylnitrite in methanol solution containing water and a palladium catalyst to yield the phenylacetone. The palladium catalyst can be used in a variety of forms, as detailed in the patent. The best choices for use with safrole are palladium bromide, chloride, or a mixture of palladium chloride and copper chloride. Of the three, the mixture catalyst is better for reasons which will be explained in the following cooking example:

    In a 4000 ml beaker, or one-gallon glass jug, is placed 3000 ml methyl alcohol, 150 ml safrole, 300 ml distilled water, and the chemist's choice of either 20 grams palladium bromide or ten grams of palladium chloride or a mixture of one gram palladium chloride and 4.25 grams copper chloride (CuCk). The catalyst choices have been given here in order of good to best. The reason why the last choice is best is because of the very high cost of palladium salts. Palladium chloride is preferred over the bromide because palladium chloride finds use in the electroplating field. It is used there in baths to plate palladium, and as part of the activation process to prepare plastics to be plated. The bromide is not as commonly used. Next, a methyl nitrite generator is rigged up as shown in Figure 3:

    Into the 2000 ml flask is placed one pound of sodium nitrite, 225 ml of methyl alcohol, and 260 ml of water. They should be swirled around for a while to
    mix. Then 680 ml of cold dilute sulfuric acid (made by adding 225 ml of sulfuric acid to 455 ml of distilled water, mixing and chill-ng) is put into the dropping funnel.

    Now vigorous /V.2000 ml magnetic stirring is begun in the beaker or glass jug containing the Figure3 allylbenzene-alcohol-pal-Methyl nitrite generator. In the 1-mole batch given in this example, about 6 moles of methyl nitrite are bubbled into the reaction mixture, while only 2 are required for the reaction. The reason for the excess is because methyl nitrite is not held in solution very well on account of its very low boiling point. If ethyl nitrite was used instead, then only three or four moles would be needed.

    While the reaction is being done, the mixture takes on the appearance of mud if palladium bromide is being used. A fizzing also occurs, which gives the reaction mixture the appearance of freshly poured Coke. Note above that a bit of acid is required to get hydrolysis of the intermediate dialkoxyphenylpropane to the phenylacetone.

    The best pH for this reaction is between 4-7. If palladium chloride or the mixed catalyst PdCh-CuCla is being used, the pH of the reaction mixture can be adjusted to this range by adding a small amount of HC1. If PdBr2, is used, it is best to wait until the catalyst is filtered out before adding HC1, as the HC1 could form PdCh and complicate catalyst recovery. The pH of the reaction mixture is best measured by first dampening some indicating pH paper with distilled water, then putting a drop of reaction mixture on the paper. The preferred temperature for this reaction is about 25° C throughout.

    When all the methyl nitrite has been bubbled into the reaction mixture, stirring should be continued for another hour. Then, if palladium bromide was used, it should be filtered out. Repeated filtrations will be needed to remove all of the catalyst, because it gets quite finely divided during the course of the reaction. This leaves a clear light-reddish solution. If palladium bromide was used, now adjust pH to 4-7, and allow another hour to complete the hydrolysis.

    If palladium chloride or the mixed catalyst was used, these substances are soluble in alcohol. In this case, the catalyst will be recovered later. Here, check the pH of the solution again to be sure it is in the proper range before proceeding.

    Now the alcohol solvent must be removed. This is best done by pouring the reaction mixture into a large filtering flask, stoppering the top of the flask, and removing the solvent under a vacuum. Use of a hot-water bath to speed evaporation is highly recommended for this process. It is not OK to distill off the alcohol at normal pressure, as the heat will cause the nitrite and NO in solution to do bad things to the product.

    To the residue left in the flask after removal of the alcohol, add some toluene to rinse the product out of the flask into a sep funnel. Next, put 300 ml of water into the flask to dissolve the catalyst if PdCla or the mixed catalyst was used. Add the water solution to the sep funnel to dissolve carried-over catalyst there, then drain this water solution of catalyst into a dark bottle and store in the dark until the next batch. If PdBr2 was used, this step can be skipped. Just store the filtered-out PdBra under water in the dark.

    Now the toluene-phenylacetone solution should be distilled through a Claisen adapter packed with some pieces of broken glass to effect fractionation. The first of the toluene should be distilled at normal pressure to remove water from solution azeotropically. The b.p. of the azeotrope is 85° C, while water-free toluene boils at 110° C.

    When the water is removed from solution, turn off the heat on the distillation, and carefully apply a vacuum to remove the remainder of the toluene. Then with the vacuum still on, resume heating the flask, and collect the substituted phenylacetone. Methylenedioxyphenylacetone distills at about 140° C and 160° C using a good aspirator with cold water. A poor vacuum source leads to much higher distillation temps and tar formation in the distilling flask. The yield from the reaction is close to 150 ml of phenylacetone. Its color should be clear to a light yellow. The odor of methylenedioxyphenylacetone is much like regular phenylacetone, with a trace of the candy shop odor of the safrole from which it was made.

    A higher-boiling phenylacetone like 2,4,5-trimethyloxyphenylacetone is better purified as the bisulfite addition product, unless a vacuum pump giving high vacuum is available. To make the bisulfite addition product, take the residue from the filtering flask, dissolved in some toluene and freed from catalyst as described above, and pour it in a beaker. Next, add 3 volumes of sodium bisulfite solution prepared by adding sodium bisulfite or metabisulfite to water until no more dissolves. Shake or vigorously stir for a couple of hours to convert the phenylacetone to the solid bisulfite addition product. Filter out the solid, then regenerate pure phenylacetone by putting the solid into a round-bottom flask, adding an excess of saturated solution of sodium
    bicarbonate in water, and refluxing for a couple hours. After cooling, the phenylacetone should be extracted out with some toluene. The toluene should then be removed under a vacuum, and the residue stored in a freezer until conversion to the amphetamine. All phenylacetones are sensitive to light, and should be stored in the freezer.

    The above cooking procedure is the best way to process allylbenzenes to the corresponding phenylacetones. Sassafras oil, as previously mentioned, is 80-90% safrole. Calumus oil, if its country of origin is India, consists of about 80% of the allyl isomer of asarone:

    It too can be purified by distillation under a vacuum to yield fairly pure allyl-asarone. Its boiling point is 296° C at normal pressure and about 170° C with aspirator vacuum. More details on this Indian calamus oil can be found in Chetn. Abstracts column 6585 (1935), also Current Science, Volume 3, page 552 (1935).

    My search for calamus oil of Indian origin came up empty. In fact, the health-food store in my town, which is well-stocked with various oils for use in aromatherapy, had never heard of the stuff, nor was it listed for sale in their catalogs. This left one alternative: dig up the roots of North American calamus, and steam-distill the oil out of them.

    While searching for calamus in my area's swamps, bogs and ponds, the damaging effects of the spread of purple loosestrife was obvious. This imported plant from Europe has taken over much of the former habitat of the calamus plant. Here in America, the loosestrife is free from the insect that keeps it under control in Europe by feeding on its seeds. The state paper-pushers have been thinking for years about importing the bug, without ever getting off their butts and doing it.

    I suggest this project to somebody out there in the reading public so that
    it can finally get done while there is still some native flora left. After a lot of searching, I finally found a large patch of the American calamus. (See Figure 4.) The time for harvesting the roots of the calamus is in the fall after the killing frost. The frost brings the oil down out of the leaves and
    into the root for winter storage. The roots are about a foot long, an inch or so in diameter, and run horizontally in the soil at a depth of a few inches. They are best dug out using a fork, taking care not to pierce the root, as this will cause loss of oil during drying. The dug-up roots should be rinsed free of dirt, and the tops cut off there in the field. (See Fig 5.)
    The roots should then be taken home and allowed to dry at room temperature for a week or two. Take care that they do not get moldy!

    Once dried, oil can be distilled from them. This is done by first grinding up the roots in a blender or with a Salad Shooter, and piling the ground-up roots into a large pressure cooker. A good-sized pressure cooker will take a load Of 10-15 pounds Of Calamus plant root and fibrous rootlets.

    Next, add a few gallons of water, a couple handfuls of salt, and mix. The oil can now be distilled. Attach a five-foot length of copper tubing to the steam exit on the lid of the pressure cooker. Its diameter should match that of the steam exit so that steam is not lost here, and should be tightened into place with a pipe clamp. The tubing should then be led downward into a pail of ice water, and back up into a dark-glass 40 or 64 ounce beer bottle. The ice water cools the steam, turning it into water which collects in the bottles.

    Heat is applied to the pressure cooker, bringing it to a boil. Heat as fast as is possible without bringing over foam or having uncondensed steam escape. When a couple of gallons have been distilled out, stop the heating and add a couple more gallons of water to the pressure cooker. Continue this process until 4-5 gallons of water have been collected.

    This process is a steam distillation, and is the way most plant oils are obtained. The steam distillate in the beer bottles contains calamus oil
    floating on top of the water and clinging to the glass. Calamus oil produced from American plants is reddish brown, and has a strange,
    pleasant and sweet odor. For more detailed information on calamus oil see The Chemergic Digest August 30, 1943, pages 138-40, and Soap, Perfumery and Cosmetics August 1939, pages 685-88.

    The oil is obtained by first saturating the steam distillate with salt, then extracting the oil with toluene (obtained off the shelf in the hardware store's paint section). About a gallon of toluene is plenty to effect the extraction. Then the toluene is removed by vacuum evaporation in a large filtering flask to yield the calamus oil as a residue in the filtering flask after the toluene has been evaporated. The yield is about 200 ml from 15 pounds of roots.

    Calamus oil obtained from sources other than India differs from the Indian oil in two important respects. The amount of asarone in the oil is much lower than the 80% found in the Indian oil, and the position of the double bond is propenyl rather than allyl:

    The asarone is obtained in pure form from the oil by fractional distillation under a vacuum. Asarone boils at about 170° C under good aspirator vacuum of 15-20 torr. The asarone fraction should be collected over a 20-degree range centered on 170° C. I found the yield of asarone from American plants to be about 15% of the oil, giving 30 ml from 15 pounds of root.

    Asarone is a light-sensitive material, and as such, should be stored in
    the fridge or freezer. Upon standing in the fridge, it will crystallize, allowing further purification by filtering. The m.p. of the pure substance is 67° C. Asarone is listed as a cancer-suspect chemical, along with half the other substances in the world. In reality it is not particularly harmful. See Chem. Abstracts 1931, page 169. It also doesn't have any pronounced drug effect at reasonable oral dosage. See Dr. Shulgin's comments on the substance in Pikhal.

    With the double bond in the propenyl position, we come to the next major advance over the disappointing procedure cited in the beginning of this chapter. See European Patent 0,247,526 titled "A Process for 3,4-dimethoxyphenylacetone Preparation." This process uses a simple electrochemical cell to convert the propenyl-benzene to the corresponding phenylacetone in very high yield. The procedure given also works with 2,4,5-trimethoxypropenylbenzene (asarone), and probably also with iso-safrole. It is my opinion that it will work with all propenylbenzenes.

    There are great advantages to the use of an electrochemical cell in
    clandestine synthesis. The solvents and the salts can be reused over and over again, making for a very low profile. The reagent doing the transformation is electricity, available at the nearest wall socket. The transformer, multimeter and alligator-clip wiring can all be obtained at Radio Shack with zero suspicion attached. This method comes with
    my highest recommendation.

    To do the reaction, a 1000 ml beaker must be rigged up as shown in Figures 6 and 7. A central piece of stainless steel having a surface area of about 100 cm2 actually in contact with theGraphite anodes (2) solution is securely clamped into place down the center of the beaker. On each side of this stainless steel piece, securely clamp into place two pieces of
    graphite, roughly equal in size, having a total surface area in contact with the solution of about 70 cm2. All three of these electrodes should run
    straight down into the flask, and a constant distance of 1 cm should
    separate the surface of the anodes from the Electrochemical cell used to convert a cathode. This is verypropenylbenzene to the corresponding phenylacetone.

    important, as the anode-to-cathode distance determines the voltage at which this cell runs. It is also very important that shorts between the anode and cathode be prevented. The current must flow anode-to-cathode through the solution, not through a short! Then into the beaker place a magnetic stirring bar, 25 grams of NaBr dissolved in 100 ml of water, 500 ml of acetonitrile, and 20 grams of asarone. Note now the depth of the solution in the flask, and be sure that the required amount of electrode surfaces are in the solution. I depicted graphite sheet anodes, in Figures 6 and 7, but the more commonly available graphite rods will work as well.

    Now, using alligator-clip wiring, attach one clip to the central stainless steel cathode, and run it to your DC transformer where it is connected to the black or negative pole. Another approximately one-foot long section of alligator-clip wiring is attached to each of the Stainless steel cathode
    graphite anodes; i.e. the alligator-clip on one end gets attached to graphite anode A, while the alligator-clip on the opposite end of the wire
    gets attached to graphite anode B. Then remove some insulation in the
    center of the wire, and make an electric connection to the positive and red pole on the DC transformer.

    Next, begin vigorous magnetic stirring of the solution, turn on the transformer, and adjust the output of the transformer so that it is pushing a constant current of about 3.4 amps. All three of the electrodes should be fizzing away at this point. If one appears dead, dig the alligator-clip into it to make better contact. Continue passing electricity until 24,000 coulombs have been passed through the solution. A coulomb is defined as 1 amp-second, so this takes about 2 hours at 3.4 amps. The patent states that the temperature must be kept in the range of 10-306 C, so watch to make sure that the current doesn't heat up the solution too much. Surround the beaker with ice if this occurs.

    The electrochemical cell makes the following compound, an epoxide. When the required amount of current has been passed, turn off the juice and the stirring, and pour the contents of the beaker into a sep funnel. Allow it to stand for about Vi hour for the phases to fully separate. An aqueous phase settles out at the bottom of the sep funnel, in spite of the fact that water and acetronitrile are miscible. This water phase contains the NaBr. It should be separated off and saved for reuse.The acetonitrile phase contains the product. It should be poured into a distilling flask, and the solvent removed under a vacuum. By packing the receiving flask in dry ice during this process, the acetonitrile can be recovered for reuse.

    The residue of epoxide product left in the flask should be diluted with 150 ml of ethyl acetate, and poured into a 500 ml flask. Flush the flask with nitrogen, then add 1.5 grams lithium iodide, and reflux for 5 hours. The lithium iodide catalytically transforms the epoxide to the phenylacetone.

    After the 5 hours of reflux are over, allow the mixture to cool, then pour it into a sep funnel. Wash the ethyl acetate solution with 50 ml of water to recover the lithium iodide into the water solution. Separate off the water layer, and evaporate the water to recover the lithium iodide for reuse. The ethyl acetate solution should be dried over some anhydrous sodium sulfate, then the ethyl acetate evaporated off to give about 20 grams of 2,4,5-trimethoxyphenlyacetone. This light-sensitive substance should be stored in the freezer.

    Method Two

    Acetonitrile is a quite poisonous solvent, dangerous both in inhalation from the fizzing electrochemical cell and by absorption through the skin. It has been my experience that just spilling a little bit of it on your skin is enough to give you head rushes and make you feel uncomfortable. The use of acetonitrile can be avoided without loss of yield by using the alternative procedure in Example 6 in the patent.

    The electrochemical cell is constructed in exactly the same way as in the first method. Then into the electrochemical cell put 400 ml of dimethylformamide, 200 ml of water containing 27 grams NaBr, and 20 grams asarone. Check the level of the solution, and make sure that the amount of electrode surfaces are the same as in the first method. Then begin stirring, and pass the current through the solution exactly as in the first method.

    When the 24,000 coulombs have been passed, pour the contents of the beaker into a sep funnel, dilute with 1000 ml of a 20% solution of salt in water, and extract four times with 200 ml portions of ethyl acetate. The combined extracts, amounting to 800 ml, should be washed twice with 200 ml portions of a 20% solution of salt in water.

    The ethyl acetate solution contains the product epoxide. It should be evaporated under a vacuum to a volume of about 200 ml, then reacted with lithium iodide just as in the first method to yield about 20 grams of 2,4,5-trimethoxyphenylacetone.

    Recycling of solvents is possible with this method too. Ethyl acetate can be recovered during the vacuum evaporation by use of a dry-ice trap. The dimethyl-formamide can be recovered by vacuum distillation.

    The Journal Method

    A very effective alternative method exists for converting propenyl benzenes to phenylacetones. I know through mail received from the reading public that this method gives a yield of about 80% when used with isosafrole. Similar results can be expected when used with asarone.

    In spite of the high yields and simplicity of this reaction, I can't recommend its use. That's because this procedure uses thallium(III) nitrate to oxidize the propenylbenzene to the corresponding phenylacetone. The thallium(III) nitrate gets reduced to thallium(I) nitrate. Both of these heavy-metal compounds are very poisonous and, unlike organic chemicals, the heavy metals persist forever in the environment, and accumulate in the body. You want a bunch of thallium around the house about like you want to be kicked in the teeth with a heavy pair of boots.

    A further bad aspect of this method is its high cost. 100 grams sell for $150, and the high molecular weight of the compound means that a lot of it has to be used to get a moderate amount of product. One pound of thallium(ni) nitrate is required for a 1-molar batch.

    This method can be found in Tetrahedron Letters No. 60, pages 5275-80 (1970). To produce a one mole batch, dissolve one mole of propenylbenzene in some methanol, and put it into a one-gallon glass jug. In a beaker, dissolve one mole (448 grams) of thallium(HI) nitrate trihydrate in methanol. Then pour the thallium solution into the jug with the propenylbenzene, and stir at room temperature for 5 minutes.

    The thallium(I) nitrate formed by the reaction comes out of solution. It is
    removed by filtration. The propenylbenzene has at this point been converted to a ketal. This is hydrolyzed to the phenylacetone by shaking the filtrate with about 2000 ml of 1 molar sulfuric acid solution in water for about 5 minutes. The phenylacetone is then extracted out with a couple of portions of tolulene. This extract is then washed with 5% NaOH solution, then distilled or purified by conversion to the bisulfite addition product.

    Production of TMA-2, MDA, etc. from the Corresponding Phenylacetone

    There are three good methods for converting the phenylacetone to the psychedelic amphetamine. Choice number one is to use reductive amination with a hydrogenation bomb with Raney nickel, ammonia and alcohol solvent. See Journal of the American Chemical Society, Volume 70, pages 12811-12 (1948). Also see Chem. Abstracts from 1954, column 2097. This gives a yield of about 80% if plenty of Raney nickel is used. The preferred conditions for use with MDA is a temperature of 80 C, and a hydrogen pressure of 50 atmospheres.

    The drawback to this method is the need for a shaker device for the bomb, and also a heater. The use of platinum as the catalyst in the bomb works great when making MDMA, but gives lousy results when making MDA. There may be a way around this, however, for serious experimenters. It has been found in experiments with phenylacetone that a mixture of ammonia and ammonium chloride produces good yields of amphetamine (50%) when used in a bomb with platinum catalyst. Methylenedioxyphenylacetone is quite likely to behave similarly, along with other phenylacetones.

    To use this variation, the following materials are placed in the 1.5 liter champagne bottle hydrogenation device described in Chapter 11 of Secrets of Methamphetamine Manufacture, Third Edition.

    .5 gram platinum in 20 ml distilled water. If this platinum is in the form of
    PtO2 instead of reduced platinum metal catalyst obtained with borohydride, the experimenter must now reduce the platinum by pressurizing the bottle with hydrogen and stirring for about an hour.

    Next 100 ml of methylenedioxyphenylacetone is added along with 40 grams NHUCl, 500 ml methyl alcohol saturated with ammonia gas, and 50 ml NHjOH. The bottle is then set up as seen in Figure 17 in Secrets of Methamphetamine Manufacture, Third Edition. The hydrogenation is done as described in that section.

    When the reduction is over, the contents of the flask are filtered to remove the platinum metal for reuse. Some crystals of NH4C1 are also filtered out; they are rinsed down with some water to remove them. Next the filtered batch is poured into a 1000 ml round-bottom flask, a few boiling chips are added, and the glassware is set up for refluxing. Plastic tubing is attached to the top of the condenser and led outside. The mixture is boiled under reflux for one hour to force out the excess ammonia.

    Next, the solution is allowed to cool, and made acid to congo red (about pH 3) with hydrochloric acid. Now the glassware is set up as shown in Figure 3 of Secrets of Methamphetamine Manufacture, Third Edition, and the solution is evaporated to about one-half its original volume under vacuum. A fair amount of crystalline material forms during the acidification and vacuum evaporation.

    Next, 400 ml of water is added to the solution, and then it is extracted with about 100 ml of toluene. The toluene layer is thrown away because it contains garbage. The batch is now made strongly basic by adding lye water to it. It should be remembered here that it is very important to shake the batch well once it has been basified, to make sure that the MDA hydrochloride gets neutralized. Finally, the MDA is extracted out with a few hundred ml of toluene, and distilled under vacuum. The boiling point is about 160fi C under aspirator vacuum. The yield is about 50 ml.

    Another very good choice of a method for converting methylenedioxyphenylacetone to MDA is the Leuckardt reaction. In this case formamide is used instead of N-methyl formamide. When used with phenylacetone to make amphetamine, only the very high-grade 99% material will work. In the case of methylenedioxyphenylacetone, however, the much more commonly available 98% formamide works just fine. See Chem. Abstracts from 1952, column 11246, and Austrian patent 174,057. In this variation, 40 ml of methylenedioxyphenylacetone is mixed with 100 ml of freshly vacuum-distilled formamide, 2 ml glacial acetic acid, and 20 ml water.

    This mixture is heated up to about 130° C, at which point bubbling should begin, then the temperature is slowly raised to keep the bubbling going, as described in Chapter 5 of Secrets of Methamphetamine Manufacture, Third Edition, until a temperature of ISO° C is reached. This should take at least 5 hours. The yield is 70%.

    Processing is then done just as in the case of meth. The formamide is destroyed by boiling with lye solution. In this case, the ammonia gas produced is led away in plastic tubing. The formyl amide is then separated, and hydrolyzed by refluxing in a mixture of 60 grams KOH, 200 ml alcohol, and 50 ml water for an hour. After the reflux, the mixture is made acid with HC1, and the alcohol evaporated away under a vacuum. The residue is then diluted with water, and the freebase obtained by making the solution strongly alkaline to litmus by adding lye solution. The freebase is then
    extracted out with some toluene, and distilled.

    This procedure is no doubt applicable to all phenylacetones. In the case of 2,4,5-trimethylphenylacetone, I would first try this with only half as much added water. Those phenylacetones containing the methylenedioxy grouping, I would use just as stated.

    The last choice is a very simple, but also very time-consuming (several days!) reaction. Sodium cyanoborohydride in methanol with ammonium acetate and methylenedioxyphenylacetone at pH 6 react to give disappointing yields of MDA. See Pikhal by Dr. Shulgin in the section under MDA for full cooking instructions.

    This method is general for all phenylacetones, as Dr. Shulgin used it on quite a variety of them, all with similar low yields. In all of these methods, once the freebase is obtained in pure form by distillation (the boiling point of the amphetamine is similar to the phenylacetone), the freebase should be converted to the crystalline hydrochloride derivative. This is done by dissolving about 50 ml of freebase in about 400 ml ether or toluene, then bubbling dry HC1 gas through the solution, and filtering out the crystals to dry. See Chapter 5 of Secrets of Methamphetamine Manufacture, Third Edition for a full description.
     
  2. ancient powers

    ancient powers Member

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    A Complete MDMA Synthesis for the First Time Chemist

    Introduction

    Thanks to Strike, Rhodium, Ritter, Osmium, r2d3, Semtex Enigma, Spiceboy, ChemHack, Labrat, Eleusis, Ketone/LabGrrrl, and a personal hero, Dr. Shulgin. And to the object that made this possible - the Internet.

    Disclaimer: This is for theoretical argument only. IF someone chooses to follow this synthesis, note that the product has been 'Scheduled 1' by the United States Government, and offenders can be prosecuted. In no way do I condone this activity.

    This is a hypothetical synthesis for: 3,4-methylenedioxy-N-methylamphetamine. Or MDMA.HCl. Or Ecstacy. The synthesis as described 1. does not put off nasty fumes, 2. requires suspicious chemicals, and therefore is 3. perfect for the clandestine chemist. The synthesis itself can be performed in a series of weekends or in a straight shot. If one were to follow this exactly - with no shortcuts - buying everything they're told - doing exactly what is written - they and they're friends will have a lovely spring. For those who think they are better than the instructions as written - be prepared to screw it up at least 4 times before success (or you finally figure out I'm right). Be prepared to invest ~$800. Be prepared to read and learn. It's also a good idea when investing in chemicals to buy 5x what is needed for a synthesis - this way you can repeat it without buying it again. Read the whole thing before you start. There is some prep-work that can be done ahead of time, or while you're distilling. Good luck.

    Overview:

    1. Distillation: of Natural Oil to obtain pure Safrole
    2. Rxn: Formaldehyde + Ammonium Chloride -> MethylAmine.HCl (MeAm.HCl)
    3. Rxn: Safrole -(Wacker Oxidation(PdCl2+Benzoquinone))-> MDP2P
    4. Distillation: of Reaction contents to yield pure MDP2P
    5. Rxn: MDP2P -(Al/Hg Amalgam (MeAm.HCl) -> MDMA oil
    6. Crystallization: (MDMA oil + HCl in IPA/Xylene) (anhydrous conditions)

    What you need:

    This list is the basics. Do not even start this without ALL the Chemicals and Apparatus.

    Apparatus and Glass:

    · http://www.amazon.com/exec/obidos/ASIN/0471387320/qid=996507700/sr=2-1/ref=aps_sr_b_1_1/104-5586371-4861548"]'The Organic Chemistry Lab Survival Manual' by James W. Zubrick. (A must, throughout this text, pages from this book will be mentioned. ~32$) (and very handy pictures of glass set-ups)
    · Distillation Apparatus(1x500mL and 1x1000mL Round Bottom Flask, 1x250mL Round Bottom Flask, condenser, distillation adapter, vacuum adapter, thermometer adapter) (Get Ground Glass Joints. These are the best. 19/22 or 24/40 - my first set was 19/22 - and is still used to this day.)
    · Thermometer (0°C to ~300°C)
    · Stand (Home Depot - (2x10in., flange, 2 ft. of ½in pipe))
    · Clamp (Buy it. Trust me its worth it) (for holding the glassware to the stand - these support several hundred dollars in glass - buy a nice one!)
    · Hotplate/Stirrer combo (got to have it, its worth it) (www.labx.com - spend $200)
    · Magnetic stir bar (look on the Web) (teflon coated)
    · Water Aspirator (or a good vacuum source. But aspirators are cheap <$20)
    · Boiling Stones (for distillations. Small shards from a broken coffee mug)
    · Tubing (about 10ft. total (3 meters) - hardware store - vacuum tubing is better than dialysis tubing - but both will work)
    · Vaseline (not much - for coating of the ground glass joints)
    · Measuring Cups (Prefably pyrex, and in milliliters (mL))
    · 10 various sized glass containers/bottles (250mL, 500mL, 1L, 2L etc)
    · Scale (a three beam analytical balance are great - and can be found for less than $100 - www.balances.com - they can weigh as much as a kilo and as little as 0.1g - perfect!)
    · pH paper (chemical supply) (just one roll will do - ~10$) (nothing specific, just need to tell the difference between an acid and a basic solution)

    Chemicals:

    · Safrole (160g)(sassafras oil, yellow camphor oil) (Natural/Essential Oil distributor)
    · Dimethylformamide (DMF) (350mL) (Diethylformamide or Formamide will work)
    · p-Benzoquinone (Quinone, Benzoquinone) (120g) (Photo Shop, or Chem supply)
    · Palladium Chloride (PdCl2) (2g) (Photo Shop, or chem supply)
    · Methylene Chloride (DiChloroMethane, DCM) (this can be distilled from automotive solvents (just go into Nationwise, PepBoys, Sears, AutoZone And read the labels) Or a Liter can be bought from a Chem supplier.)(Zip-Strip furniture polish remover)
    · Hg-salt (1 gram of: HgCl2, Hg(NO3)2, Hg(acetate)2, HgCl, It can be anything, and 1g should last you a long time.)
    · Isopropyl Alcohol (IPA, Pharmacies 91% Isopropyl Alcohol will be available)(get +3L)(don't get the 70% stuff) (or you can get pure stuff from a chem supplier)
    · Epsom Salts (Magnesium Sulphate) (MgSO4) (grocery store/pharmacy) (Spread out on a cookie sheet, and bake in the oven at 200°C for 3hr to dry them - pretty useless if you don't dry it)
    · Thick Al foil (heavy duty, or pie pans from the Grocery store)
    · Muriatic Acid (31.45% HCl)(Pool pH down, Driveway cleaner, ~3$/gallon)
    · Sodium Hydroxide (NaOH) (Drain Cleaner Crystals) (Read these labels, Get the stuff that is JUST NaOH.) (Red Devil Lye, Lye - Hardware Store)
    · Ammonium Chloride (NH4Cl) (Photo Store or Chem Supplier)
    · Paraformaldehyde (Hardware store) (called Mildewcyde or DiGas - made by the same people who brought you Damp-Rid - hint-hint)
    · Peanut oil (this is a high boiling oil that we will use as an oil bath on the hotplate/stirring plate combo)
    · Acetone (for cleaning your glass and crystal work-up) (Paint Section of Hardware Stores)
    · Xylene (for crystallization) (paint section - thinner - get it specifically)

    1. Distillation: of Natural Oil to obtain pure Safrole.

    A Comprehensive Description of this Step by Chromic

    Set up for a vacuum distillation like on page 53 of Zubrick. Always put a little Vaseline on the ground glass joints - this way they won't stick when you try to take them apart. Put as much Natural oil (Sassy, Camphor, ect) as you have, but not more than 300mL, into the 500mL Round Bottom Flask (RBF) with several Boiling Stones. Put one of your 250mL RB flasks as the receiving flask. Set up your Water Aspirator Vacuum, in the sink (this may require setting this up a day before - parts, trips to the plumbing store, etc.) and attach the vacuum hose to the aspirator and then to the vacuum adapter on the distillation set up. Start turning up the heat slowly! SLOWLY! The slower you do it, the better/purer your safrole will be. At normal pressure safrole boils at 232°C - but under your vacuum, it may boil at anywhere from 110-160°C. Whatever temp it starts to come over at - make a note of it. And if the temp is higher than 160°C - check your seals on the tubing and glassware - More than likely there is a little leak. Remember that Vaseline! At the end of the distillation, you should have a water white oil that really refracts light - And has a lovely smell - a little like potpourri.

    Distillation set-up: Set up the distillation set-up on your bed, before you try to put it together on the stand. You will get a good idea about how the pieces go together, and become familiar with the fragility of the whole thing. Read Zubrick for advise about where to place the clamp.

    The Peanut Oil: A bowl with a flat bottom rests on the Hotplate. It is filled with Peanut Oil. The distillation flask sits in the bowl but not touching the bottom, so that the Hotplate heats the bowl, the bowl heats the Peanut Oil, the Peanut Oil heats the distillation flask. This is VERY effective. And will be perfect for all your distillation needs - especially if you do it under vacuum.

    Step 2. (2 hour work + 4 hours wait + 4 hours work)

    2. Rxn: Formaldehyde + Ammonium Chloride -> MethylAmine.HCl

    In your 500mL RBFlask: (Thanks ChemHack/Labrat!) Set up for distillation (not vacuum). In the distillation flask (your 500mL RBFlask) put: 108g of NH4Cl, 120g Paraformaldehyde (molecular ratio 1:2, remember this when scaling up!) and 320ml of water and several boiling stones. Start heating very SLOWLY. Remember to turn on the water in the condenser!

    At 80°C a clear solution was obtained. Heating continued - The temperature was maintained for four hours at 104°C (this temp is VERY important - if you over shoot it - don't worry - bring it back down and try to stabilize it at 104°C) Once you've got it at 104°C start the stop watch and do it for 4 hours. At 104°C, a small amount of distillate will come over - very slowly - this is good. We are removing methylal, and methylformate from the reaction contents and therefore driving the reaction to the right - or getting more of what we want.

    After four hours and while the solution is still hot, set up to vacuum distill (IE its already set-up - now just add the vacuum hose!) - but don't turn on the vacuum yet. Turn up the heat. Within 30 minutes or so - liquid should start coming over - the internal temp of the mixture should not go over 200°C - Keep distilling off the liquid until 1/2 of the solution remains - (IE distill off half of the solution.) Then, take your flask off the Hotplate and let it sit in an ice/water bath. Crystals should start to form in several minutes. Filter off these Ammonium Chloride Crystals. Now set up for distillation of the remaining liquid again - Add a couple more boiling stones. Distill off half of the remaining liquid. When half remains (or a 1/4 of the original solution), turn the vacuum on SLOWLY! VERY SLOWLY! - you don't want the whole mess of liquid jumping out at you. At some point the whole mass will crystallize into a yellow-white solid. This is ~95% MethylAmine.HCl, ~2% Ammonium Chloride, and 3% DiMethylAmine.HCl. This is fine for the next step. It may be a little wet, but if you let it crystallize hot (spontaneously in the flask with heat) it should be fairly dry. Seal it in a wide mouth jar until needed.

    As a way to check your product - if you live in a relatively humid area, you can put a crystal of your product on the table - walk away - and when you come back a small puddle of water will be on the table where your product was. MethylAmine.HCl is said to be HYGROSCOPIC. Another way is to put 20mL of water in a cup then add 5g of the NaOH to it. Stir to dissolve. Now, drop several crystals of your product into it - it should smell like rotting fish + ammonia. If you do the same with Ammonium Chloride, it will just smell like ammonia.

    You'll recover about 1/3 of the ammonium chloride for recycling and after a lot of evaporating. You'll get ~80g of pure (95%) MethylAmine.HCl, which corresponds to ~80% yield. Congrats. This can be stored at room temperature, forever. I've heard of people using 40+ year old MethylAmine.HCl with excellent results.

    Paraformaldehyde is the polymerized form of formaldehyde - but unlike most polymerization processes - this one is reversible - so Paraformaldehyde and formaldehyde can be interchanged at will. If all you can get is formaldehyde solution - remember that if its 37% formaldehyde then 100g of the solution contains 37g of formaldehyde - or just go ahead and change your amounts in the flask to - 324g of 37% Formaldehyde Solution, 108g NH4Cl, 205mL water.

    Step 3. (2 hours work + 7 hours of wait (sleep?) + 1 hour work)

    3. Rxn: Safrole -(Wacker Oxidation (PdCl2+Benzoquinone))-> MDP2P

    This step has been called the Wacker Oxidation. It uses PdCl2 as a catalyst to put and oxygen across a double bond. This step has been worked over many times so do not change the amounts for the fabled 'scale-up'. If you do this correctly, you will have more MDMA.HCl than you know what to do with. (Thanks Strike!)

    Procedure:

    Put the following into your CLEAN 1000mL RBFlask:
    300mL of dimethylformamide (DMF), 50mL of tap water, 120g of p-Benzoquinone 2g of Palladium Chloride (PdCl2), Magnetic Stirbar. (PS - Don't skimp on the catalyst!)
    Start the stir bar on 'slow stir'. Mix 160g of Safrole and 50mL DMF in a cup/jar. Drip the Safrole/DMF Mix into the solution at room temp (30C) over 30min time. After the addition, the solution was dark reddish orange. Almost black. Make sure the stir bar is spinning - Now - Walk away. Go to bed. Go somewhere else. Set your watch alarm to wake/remind you 7 hours later. NOTE: This reaction requires NO additional heating! Just stir!

    Strikes comment: "After 4.5 h the solution will progress on its own to +45°C. Obvious exothermic reaction. After 7 h solution will be back to ~30°C."
    The reaction mix was flooded with slightly acidic water (~50mL of Muratic Acid (HCl) in 1.5L of water). The oil fell out of solution to the bottom. It was black/blood red in color. This is when its nice to have a Big Sep Funnel.

    Now we need to define several things. The upper layer (in this case!) Is the aqueous layer - IE it's the layer that contains the WATER - the bottom layer is the organic layer (in this case!). IE it contains oil and other ORGANIC type molecules (IE the stuff you want!).

    After you flood the reaction contents shake the container to mix the solution, give it about 10 minutes to settle - two layers will form. The upper aqueous layer was a lighter blood red/pink. The upper aqueous layer was decanted from the oil (IE it was poured off). The aqueous Layer washed with 2x100mL DCM (Methylene Chloride / DiChloroMethane). If you can't see the layers, hold the container up to the light, so that the light shines through the container. Keep the DCM washes - They contain the goods.

    You now should have about 200mL total of DCM washes. You should also have about ~100mL of the 'Organic Layer' that you separated from the reaction contents. Pour the DCM washes and the Organic layer together. Now wash the DCM/Organic layer with 2x150mL 10% NaOH (30g NaOH in 270mL water). This will remove the other reaction by-product - hydroquinone. If you don't do this step the hydroquinone will clog your condenser when you try to distill. Keep the DCM/Organic layer. The NaOH layer (Aqueous: is still on top) can be tossed. (Thanks Osmium!)

    You can stop here and wait for another day - put the DCM/Organic Layer into the freezer.
    Define Washes - 100mL of DCM was poured into the aqueous layer and then the aqueous layer+DCM was shaken so the two would mix - then it was put down to let it settle out again. When it was settled (notice that the layer now is a different color) the aqueous layer was poured off again into another jar where it was washed again with another 100mL portion of fresh DCM = 2x100mL washes.

    Step 4. (4 hours work)

    4. Distillation: of Reaction contents to yield pure MDP2P

    Pour the DCM/Organic layer into your CLEAN 500mL RBFlask. Put several boiling stones in too. Set up for vacuum distillation.

    This time we are going to collect a particular fraction in the flask - there is DCM (BP 40°C), water (BP 100°C), DMF (153°C), safrole (232°C), ketone (BP est. ~290°C), and polymerized crap (BP ~300°C+)

    Now remember when we distilled the safrole? What temp did it come over for you? Well - that temp plus approximately 25°C is the temp that the ketone will come over under vacuum. For example, if your safrole comes over at 150°C, then the ketone will come over at 175°C. If your safrole comes over at 130°C then your ketone will come over at 155°C. Get it?

    WEIGH the receiving flask! Write the weight on a piece of tape and tape it to the flask!
    Start your vacuum distillation by first turning on your vacuum - if you remembered your boiling stones, then it will begin to boil immediately. This is the DCM coming off first. The boiling may be very vigorous, So watch it, and be prepared to vary the pressure so it won't fly into your receiving flask. Turn on the heat (Hotplate) SLOWLY! and let the temp climb to just over the temp at which safrole came over (SLOWLY: it should take at least 2 hours to reach that temperature - if you do it in under 2 hours you are going WAY to fast). You are going to have to change the flask, when the temp gets to above the safrole temp. This is a bit tricky, because you are going to have to release the vacuum. Release the vacuum at the pump/aspirator and change the flask quickly - you may just dump it out, rinse it once with acetone, or IPA (IsoPropylAlcohol) - and put it back. Start the vacuum immediately, but be careful here, because the Organic layer that you are distilling might jump out of the flask and into the receiving flask - so if you can - vary the vacuum so that the vacuum comes on GRADUALLY! (IE with an aspirator, turn on the water slowly.) The ketone oil is a clear white/yellow hint of green oil. Re-weigh the flask for your yield calculation - you should have over 100g of ketone.

    With an aspirator you can vary the vacuum when you are turning it on. You simply turn on the water slowly. IE Increase water pressure slowly. By turning it off, you can make water jump into the receiving flask because there is a 'vacuum' in the distillation apparatus and it will suck water out of the aspirator - SO - when you turn off the vacuum, do so by removing the hose from the aspirator - while the aspirator is going. You can also vary the vacuum by removing the hose PARTIALLY - This will take some practice so play and have fun.

    Strike's excellent post read: "With high vacuum at 100-140°C ~18g safrole came over. At 166°C came over ~125g ketone." When she did this method...
    Keep the ketone. Smell it. Look at it. Look at how it refracts light. For the brave: taste it. Note all of these 'properties' and remember - After you have judged its properties, put it in the freezer. Note: it won't freeze. It will become a very viscous liquid.
    If you try to distill the ketone at atmospheric pressure (no vacuum), you will get to about 220°C and then the whole flask will polymerize. Total waste of effort, time, and precursors. So don't mess around and get a vacuum source.

    The ketone is unstable. It won't explode or anything, but if left to its own devises, it will rearrange. And then it will be useless. At room temp, it will rearrange in about a week - depending on where you live - if you keep it in the freezer - it can last months - FREEZER! After its in the freezer you can stop for today.

    Step 5.

    5. Rxn: MDP2P -(Al/Hg Amalgam (MeAm.HCl) -> MDMA oil

    (Thanks Ritter, Osmium, Shulgin!)
    This is called the Al/Hg Amalgam. This process utilizes the electronegative properties of the Aluminum. Now, something that most people don't realize, is that all aluminum is actually coated with Al2O3. This is the oxidized form of Aluminum. We will remove this part of the foil so that the aluminum can reduce the imine with elemental Al.

    This reaction actually has two parts. First, there is the ketone -> imine condensation. This reaction reacts the ketone with methyl-amine to form an imine - water is produced as a product. Second, the imine is reduced (Hydrogen is added across the double bond) to the amine. The condensation really needs anhydrous (no water) conditions, and the reduction actually needs water - so there is a fine balance here - IE don't mess with the procedure.

    What you need to have prepared ahead of time:
    · CLEAN 500mL RBFlask.
    · 20g of thick aluminum foil cut into ~1cm squares.
    · 0.1g of Hg(salt) (any mercury salt will do, not Hg Metal) (Note: Hg=Mercury)
    · Disposal Jug (milk jug)
    · 1L of Clean water
    · 25mL of 25% NaOH solution (dissolve 25g NaOH in 75g of water, then 25mL of it)
    · 50g of MethylAmine.HCl dissolved in 300mL of 91% Isopropyl Alcohol
    · 40g of 'ketone' dissolved in 50mL of 91% Isopropyl Alcohol
    · Cool water bath. (A milk jug with the top cut off)
    · Ice (don't screw around, buy a bag) (or have at least several kilo's handy)
    Set up your stand and clamp so that, when the flask is clamped to the stand the bottom of the flask is about 4 inches (10cm) from the table top. This is so that you can put the heating plate and stirbar combo under it. Have your thermometer already in its thermometer adapter so you can throw it in the flask at any second.
    Prepare the following, put them in a jar and have them ready at a moments notice:
    · 50g MethylAmine.HCl dissolved in 300mL 91% Isopropyl Alcohol
    · 40g 'ketone' in 50mL of 91% Isopropyl Alcohol

    It is very important that these are ready before you start! BEFORE YOU START!
    20g of Al squares are put into the 500mL RBFlask. They are covered with ~350mL of H2O (water). 0.1g of Hg(salt) (or just a very small spatula) is placed in with the Al squares, and given a good stir. Amalgamation was allowed to proceed until there was the evolution of fine bubbles the formation of a light grey precipitate, and the appearance of occasional silvery spots on the surface of the aluminum. (Thanks Dr. Shulgin!)
    Basically here the Al2O3 is being destroyed, the water is reacting with the Al2O3 to form Al(OH)3 and H2. This should take between 15 and 30 minutes. Just be patient.
    When amalgamation is complete, pour out the water into the milk jug. Pour in another ~350mL of water and carefully shake the flask to stir up the contents. Pour it out into the jug. Do it again with another ~350mL of water. So basically, you wash the Al pieces with 2x350mL of water. Dump out as much of the water as you can in 10 seconds or so - then immediately go to the next step - leave the Al foil in.

    This will remove most of the Hg from the solution. Don't worry, the Hg will be completely removed in the successive washes during the work up. If you let the Al squares sit in between washes, they will heat up and re-form the Al2O3 in a matter of seconds. So be quick and have the ingredients ready for the procedure.

    Now, immediately, add in THIS order:
    · 50g MethylAmine.HCl dissolved in 300mL 91% Isopropyl Alcohol
    · 40g 'ketone' in 50mL of 91% Isopropyl Alcohol, then drop in a Magnetic Stirbar. Try to get the stirbar going - it might take several minutes.

    Now drip this in 25mL of 25% NaOH solution over several minutes. Put the thermometer in the solution. Start being very paranoid about the temperature. The temperature of the reaction flask must not climb above 60°C. Its best if the temp is kept around 50°C. Stirring is necessary so, with the heat off, stirbar on, flask sitting in the cool water bath. When the temp gets to about 50°C, put several chunks of ice in the bath. If the temp falls below 40°C, take some of the ice out. But whatever you do, make sure the temp remains below 60°C. The whole time you are doing this the contents are a grey sludge. Remember to keep the stirbar going! If the stirbar is difficult to start going. Don't worry, trying to get it started seems to work just enough.

    At some point you'll notice that the temperature is not rising like it had been (in about 4 hours or so). You have reached the end of the ketone -> imine condensation - Look inside the reaction flask and see if you still see any pieces of Al foil - if you do - continue stirring until the Al foil has been depleted. This reaction should go no less than 6 hours.
    Now, after you are convinced that the reaction has stopped (6 hours later) - IE the temp of the solution is room temperature, and there is no more foil chips in the mix. Pour in 25mL of the 25% NaOH solution. Stir the contents some more, and then let the stirbar stop and then let the solution rest for at least 30 minutes. The NaOH solution will make that grey sludge into a filterable consistency. If you can't tell there has been a change in the consistency - put in another 25mL of 25% NaOH solution. The grey sludge should abruptly change from a uniform grey to a chunky white/grey blob. Then in a matter of minutes the whole thing will be resting on the bottom of your flask.

    The reaction contents will settle out. The grey sludge will settle to the bottom, and a clear yellow liquid will rise to the top. Pour off the clear yellow liquid. Save it. Put 200mL of 91% Isopropyl Alcohol into the reaction contents, stir the solution, so that the whole thing is disturbed and swirling in the flask and again wait. Pour off the 2nd clear yellow liquid once it settles. Add the 2nd clear yellow liquid to the first. Do this several times, or until the clear liquid is no longer yellow.

    This is an extraction out of the reaction contents. The more you do this process, the higher your yield. So don't do it once and get excited and try to complete it with just the first extraction because you will just waste half of your product. You've gone this far - don't fuck it up now.

    After you have gotten as much of the yellow liquid out as you could. Put the grey sludge in the same milk jug waste container. Dispose of it properly - the milk jug contains elemental Hg - Not a lot - less than 0.1g. But you should dispose of it properly. Not down the sink. Take it to a High School or A University, To the Chemistry department - tell them you broke a thermometer, and then couldn't figure out what to clean it up with.
    Set up for vacuum distillation (Boiling Stones!) but we're not going to distill. We are going to evaporate the Isopropyl Alcohol (IPA) from the reaction contents. Under an aspirator vacuum, the IPA should come over around 35°C. Make sure you get the alcohol out. When the alcohol is close to being gone - the solution might spontaneously separate in your distillation flask. Not to worry - the top layer is probably your product, and the bottom is water. Don't try to separate it, just dump the whole thing into the next procedure.

    The next two paragraphs out line a procedure known as an Acid/Base extraction. This works very well for our target molecule, and any molecule that contains an amino group. If the next two paragraphs are not done, then plan on not having any crystals when you're done.

    After the alcohol has all gone, Take the brown oil that is left and put it into 500mL of ~0.5M HCl solution (470mL water + 30mL of Muriatic Acid). Stir or shake it up. A lot of the brown oil should go into the acid solution. Now pour into this solution 30mL of DCM. Shake again and let it settle. You will notice two layers formed - The top layer is the Aqueous layer - which CONTAINS your product, and the bottom layer contains the DCM, polymerized crap, and non Nitrogen containing molecules. Pour off the top layer (That CONTAINS your product) and discard the DCM layer. Wash the Aqueous layer again with 30mL of DCM, and repeat the process. NOTE that the AQUEOUS LAYER CONTAINS THE PRODUCT - DO NOT DISCARD THE AQUEOUS LAYER! You can discard the DCM washes, because they contain nothing useful what-so-ever. Discard!
    Now, slowly add 50mL of 25% NaOH solution to the aqueous layer. When you do this the Aqueous layer will turn a milky white and may heat up just a little bit. Not to worry. A light brown oil will fall out of the solution. This is your product (in the freebase form).

    Before collecting it, wash the 'now basic' Aqueous layer with ~50mL of DCM. Shake and let it settle out. Pour off the top Aqueous layer, and KEEP THE DCM THIS TIME! The DCM washes CONTAIN THE GOODS! Wash the aqueous layer twice more with 50mL of DCM. Combine those DCM washes that contain your product, and continue.

    Set up for vacuum distillation, and once again, just boil off the DCM (Boiling Stones!). There might be a little water in it, so this time when you are boiling off the DCM, let the temp of the distillation flask reach ~50°C for several minutes. That should be good enough. You should have a light brown oil in the flask - it kind of looks like thick Newcastle Beer.

    Step 6 (2 hours work)

    6. Crystallization (MDMA oil + HCl in IPA/Xylene)

    This must be done in anhydrous conditions. If its not, then you will not get crystals. Anhydrous means 'no-water'. If water is present, then you can expect to get crapola.

    Procedure:

    This first step can be done ahead of time. Like, during a distillation or reaction: Get a fresh bottle of 91% Isopropyl Alcohol, and pour out approximately 100mL. Now get some of your DRY Magnesium Sulphate (Epsom Salts) (about 100mL worth) and dump it into the 91% IPA. There might be a little heat evolution, but not to worry .... Shake it up and then let it sit till the MgSO4 settles out. Pour off the IPA, and then put more fresh MgSO4 into it (about 100mL worth). Now shake the bottle and let it sit for 15 minutes. You must do this at least three times - It really is much better to do it four times - Why fuck it up now right? After three times you will have 'Dry' IPA. You can actually do this while you are distilling or waiting for a reaction to proceed.

    Make a mixture of 100mL 'Dry' IPA and 150mL Xylene. Pour it into the flask that contains the MDMA oil, and drop the stirbar in too. Stir so that the whole thing is mixed up real well - Now drip in Muriatic Acid slowly. Test with pH paper every 5 drops or so - keep adding the Muriatic Acid until the pH of the solution is 5-6 - or just barely acidic.
    Set up for vacuum distillation, and distill the solution, distill this with the stirbar in instead of the boiling stones - IE When the solution has reached a pH of 5-6 - Start distilling. Be careful not to let the solution get above 120°C - When a lot of the solution has boiled away, crystals will spring to life in the flask. Under vacuum, the solution should never get above 70°C.

    Filter these with a coffee filter, suspended over a jar - This gets the excess IPA/Xylene out. Scrape the crystals on to a plate and let the crystals dry, by letting the IPA/Xylene (mostly Xylene at this point) evaporate - this might take several hours - a 60 Watt lamp 6 inches (20cm) away from the crystals shining brightly helps. Stir the crystals to promote even heating.

    The crystals will be a brown-yellow color. Now scrape the crystals into a jar, and pour ~20mL of acetone onto them. Swirl the mixture. The crystals won't dissolve - but a lot of the brown will. The brown-acetone is poured off, and the acetone wash is repeated.

    After the acetone wash, dry the crystals. You should have around 15g of dry crystals. That's 150 hits. The now 'almost white' crystals have melting point values over the range from 145-153 ° C, depending on how much water was in there during crystallization. And these crystals are ready for consumption. 60mg is not enough. 80mg is great for my wife. 100mg is a great dose. 125mg is balls-to-the-wall. 150mg is too much. For me at least. Fun for me is actually 80mg MDMA+70mg MDA in one pill. WHOH. But I guess you'll have to do another synth - right?

    If you have completed this, congrats. Fucking Fantastic. Now Teach Someone Else! If you do - we WIN! Dig it?
     
  3. ancient powers

    ancient powers Member

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    Manufacture of "Ecstacy"
    from Chemical Abstracts 52, 11965 (1958)

    For Informational Purposes Only. The authors & distributors do not advocate the use of illegal drugs and assume no liability for the use or misuse of this information . The procedures described are dangerous and should not be attempted by persons inexperienced in Organic Laboratory techniques.

    This formula is exemplified for MDA (3,4-Methylenedioxy- phenylisopropylamine); substituting N-methyl formamide results in MDMA or N-methyl MDA (Ecstacy).

    To a cooled mixture of 34 g 30% H2O2 and 150 g formic acid, add dropwise a solution of 32.4 g (0.2M) isosafrole in 120 ml acetone, (keep temperature below 30 degrees) Let stand twelve hours and evacuate in vacuum. Add 60 ml methanol and 369 g 15% sulfuric acid to the residue and heat on a water bath three hours. Cool, extract with ether or benzene and evaporate in vacuum the extract to give 20 g 3,4,-methylenedioxybenzylmethyl ketone.

    Add 23 g of above ketone to 65 g formamide and heat at 190 degrees for five hours. Cool, add 100 ml H2o2, extract with benzene and evaporate in vacuum the extract. Add 8 ml methanol and 57 ml 15% HCL to residue, heat on water bath two hours and evaporate in vacuum (or basify with KOH and extract the oil with benzene and dry, evaporate in vacuum) to get 11.7 g MDA.

    The above occurs as a yellowish brown oil; this is active orally, but somewhat inconvenient; to convert to powder (salt) form, reflux in Hydrochloric acid and evaporate.

    Safrole, an allyl benzene, occurs naturally in oil of sassafras, about 70%. Can be extracted with simple distillation. It is con- verted to isosafrole (a propenyl benzene) by adding equal weight of KOH flakes and absolute ethanol and heating on steam bath or refluxing for 24 hours; dried and evaporated in vacuum or added with two time its volume in water and extracted with ether or methylene chloride and dried, evaporated in vacuum. Hexane is used for recrystalization.

    Formamide and N-methyl formamide are closely watched by the DEA. Many people have been busted by small suppliers where it was easy to get; those are "sting" operations that tail the buyer home.
     
  4. ancient powers

    ancient powers Member

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    Sassafras oil is an orange-colored liquid with a smell just like licorice. It is a complex mixture of substances which is easily purified by distilling.

    To obtain pure safrole from sassafras oil, the glassware is set up as shown in Figure 13 in Chapter Three. The distilling flask is filled about 2/3 full of sassafras oil, along with a few boiling chips, and then vacuum is applied to the system. A little bit of boiling results due to water in the oil, but heat from the buffet range is required to get things moving. Water along with eugenol and related substances distill at the lower temperatures.

    Then comes the safrole fraction. The safrole fraction is easily spotted because the "oil mixed with water" appearance of the watery forerun
    is replaced with a clear, homogenous run of safrole. When the safrole begins distilling, the collecting flask is replaced with a clean new one to receive it.
    The chemist is mindful that the safrole product is 80-90% of the total volume of the sassafras oil. Under a vacuum, it boils at temperatures
    similar to phenylacetone and methamphetamine.

    When all the safrole has distilled, a small residue of dark orange-colored liquid remains in the distilling flask. The distilled safrole is watery in appearance, and smells like licorice. With a liberal supply of safrole obtained by distilling sassafras oil, work can then commence on converting it into 3,4 methylenedioxyphenylacetone.
     
  5. ancient powers

    ancient powers Member

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    Methylamine

    Methylamine is very high on the do-not-everpurchase-through-regular-commercial-channels list. As such, any meth production scheme that uses the phenylacetone route will also have to produce its own methylamine. This is no great challenge, hi the days before methylamine became commercially available, researchers and practical cookers in industry always had to make their own. To our benefit, they left good directions for us to follow. See Organic Syntheses, Collective Volume 1, pages 347-9.

    The reaction to produce methylamine is cheap, but requires a lot of labor. Two molecules of formaldehyde react with ammonium chloride to produce a molecule of methylamine hydrochloride and formic acid. Both starting materials are easily obtained in 5-gallon-pail or 50#-bag sizes from commercial chemical outlets serving industry.

    The glassware is set up as shown in Figure 11 in Chapter Three. The chemist places 1000 grams of ammonium chloride and 2000 ml of 35-40% formaldehyde in the 5000 ml flask sitting in the pan of oil. (These chemicals need not be a very high grade; technical grade is good enough.) He puts a thermometer in the oil next to the flask and heats the oil to 105° C or so, with the aim of heating the contents of the flask to about 100° C or so. A thermometer inserted into the flask is used to monitor its temperature. A bubbling reaction kicks in, and a condensate made up of formic acid and methyl collects in the receiving flask. When this distillation slows in a couple of hours, raise the temperature inside the flask to 104° C, but no
    higher. Continue heating at this temp until no more distillate comes over (4 to 6 hours). Periodic applications of aspirator vacuum to the batch will increase yield of methylamine because it pulls the CO2 out of the reaction mixture.


    Then he turns off the heat and removes the flask from the pan of oil. Some liquid will have collected in the 2000 ml flask; he throws it out and rinses the flask with water. The 5000 ml flask is set in a pan of room temperature water to cool it off. A good amount of ammonium chloride crystals precipitate from the solution. He does not want these chemicals, so he filters them out. He returns the filtered reaction mixture to the 5000 ml flask and again sets up the glassware as shown in Figure 11. A 250 ml flask is used as the collecting flask. The reaction mixture should be clear to pale yellow.

    He turns on the vacuum source and attaches it to the vacuum nipple of the vacuum adapter. He boils off the water and formic acid in the reaction mixture under a vacuum. Heating the flask in the oil pan speeds up the process, but the oil is not heated above 100° C. When the volume of the contents of the flask is reduced to about 1200-1300 ml, he turns off the vacuum and removes the flask from the oil pan. The flask is put in a pan of room temperature water to cool it off.

    Some more crystals of ammonium chloride come out of solution. He filters out these crystals and pours the filtered reaction mixture into a 2000 ml flask. He sets up the glassware as before, and again boils off the water and formic acid under a vacuum. He does not heat the oil above 100° C. When the volume of the reaction mixture has been reduced to about 700 ml, crystals of methylamine hydrochloride begin to form on the surface of the liquid. It looks a lot like a scummy film.

    When this happens, the vacuum is disconnected and the flask is removed from the oil bath. The flask is placed in a pan of room temperature water to cool it off. As the flask cools down, a lot of methylamine hydrochloride crystals come out of the solution. When the flask nears room temperature, it is cooled off some more with some cold water. This will cause even more methylamine hydrochloride to come out of the solution.

    The chemist filters out the crystals and puts them in a Mason jar. The crystals look different from the crystals of ammonium chloride, so he should have no trouble telling the two apart. These crystals soak up water from the air and melt, so he does not waste time getting them in the Mason jar after they are filtered.

    He pours the filtered reaction mixture into a 1000 ml round bottom flask and again sets up the glassware as shown in Figure 11. He reattaches the vacuum and continues boiling off the water and formic acid under a vacuum. When the volume of the mixture reaches 500 ml, he removes the flask from the hot oil and places it in cool water.

    As it cools off, more crystals of methylamine hydrochloride appear. He filters the cold reaction mixture to obtain these crystals. He transfers them to a beaker and adds 200 ml of cold chloroform to the beaker. He stirs the crystals around in the chloroform for a few minutes, breaking up any chunks. This dissolves any dimethylamine hydrochloride in the product.

    He filters the crystals in the beaker, then puts them in the Mason jar along with his first crop of methylamine hydrochloride crystals. He throws away the chloroform and returns the reaction mixture to the 1000 ml flask. He boils the reaction mixture under a vacuum again. When its volume reaches about 150-170ml, he turns off the vacuum and removes the flask from the hot oil.

    He pours the reaction into a beaker and stirs it as it cools down, to prevent it from turning into a solid block. Once it has cooled down, he adds 200 ml of cold chloroform to the slush. He stirs it around with a glass rod for a couple of minutes, being sure to break up any chunks. The mixture is then filtered. The crystals of crude methylamine hydrochloride are kind of gooey, so it may not be possible to filter out all the chloroform.

    This batch of crystals is added to the Mason jar along with the rest of the crude product. The yield of crude product is around 425 grams. It absorbs water easily from the air, and melts. Its smell has been described as "like old woman's pussy." The main contaminant of the crude product is ammonium chloride, along with some dimethylamine hydrochloride, and some of the reaction mixture. The 425 gram yield of crude product is therefore deceivingly high.

    Purification would best start with drying under a vacuum. This could be conveniently done by placing the crude crystals into a large vacuum flask, stoppering the top of the flask, and applying aspirator vacuum for about half an hour. Gentle heating of the flask with warm water during the vacuum drying helps speed along the process, as does some shaking around of the contents of the vacuum flask. If one has an aspirator that likes to spit water back into flasks under vacuum, then one should use a vacuum pump. Now to get nice and pure crystals of methylamine hydrochloride, we leave those crude crystals in the filtering flask, and add around 3/4 of a quart of 190-proof vodka to the crystals. One hundred- ninety-proof vodka won't dissolve ammonium chloride, but it will dissolve methylamine hydrochloride when it is hot. Leave the top of the filtering flask stoppered to prevent steam from getting into the flask, then warm up the flask using hot water.

    Water fresh off the stove, almost boiling hot, would be best. Swirl around the flask as it warms to get the methylamine hydrochloride dissolved. Once the alcohol solution gets hot, stop swirling to let suspended crystals settle out. Then decant off the alcohol solution, taking care to keep the crystals inside the flask. Filtering is necessary. Then put the alcohol which has been decanted from the flask in the freezer. As it gets cold, methylamine hydrochloride crystals will come out of solution. When the alcohol is good and cold, filter to collect these pure crystals of methylamine hydrochloride. Store them in a Mason jar with a lid.

    Return the filtered cold alcohol to the filtering flask containing the crude product. Once again heat the alcohol with swirling to dissolve some more methylamine hydrochloride. Then let the suspended crystals settle once again, and decant the alcohol as before, and cool that down in the freezer to get another crop of pure methylamine hydrochloride. A few cycles through this process will get all the methylamine hydrochloride soaked out of the crude product and recovered as pure recrystallized methylamine hydrochloride.

    The yield of pure methylamine hydrochloride will be around 350 grams or so. Sometimes, the methylamine hydrochloride is used directly as such in the reaction, such as, for example, in reductive alkylation using aluminum foil as the reducer. More generally, the free base is used. To obtain a strong solution of methylamine in water, 100 grams of methylamine hydrochloride is placed in a flask with 50 ml water.

    This is chilled in an ice-salt bath to a temperature nearing 0° F. Then a cold solution of 60 grams of NaOH in 100 ml water is slowly added with stirring. The addition must be slow enough, and the cooling strong enough, to avoid losing the free base as a gas. Methylamine solution produced in this way is roughly comparable to the commercial 40% methylamine, except that it also contains salt, and maybe a little NaOH if too much was added.

    This solution should either be used immediately, or stored in a tightly stoppered bottle. Refrigeration of the solution is optional, but desirable. The reader should be aware that chloroform is a poison for Raney nickel catalyst, so if that particular method is going to be used in meth production, the crystals must be vacuum-dried. Also, it is possible that the excess NaOH may interfere with methods using catalytic hydrogenation. I can't say. If it does, an apparatus like that in Figure 18 can be used to boil out the methylamine free base into a stirred, chilled solution of alcohol.

    Other methods of making methylamine exist, but they are not well-liked by the pioneers mentioned at the beginning of the chapter. Presented here is their preferred method. For example, it can be made in 71% yield by reacting methyl iodide with hexamine, also known as hexamethylene tetramine. Good directions for making this substance from ammonia and formaldehyde can be found in Home Workshop Explosives by yours truly. The production details for methylamine are found in the Journal of the American Chemical Society, Volume 61, page 3585 (1939). The authors are Galat and Elion.

    It can also be made by degrading acetamide with Clorox. See Journal of the American Chemical Society, Volume 63, page 1118 (1939). The authors are Whitmore and Thorpe, and the yield is 78%. It can also be made via the Curtius reaction in a yield of 60%. See Helvetica Chimica Acta, Volume 12, page 227 (1929). The authors are Naegeli, Gruntuch and Lendorff.
    References Journal of the American Chemical Society, Volume 40, page 1411 (1918).
     
  6. polymer

    polymer Senior Member

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    very nice!
     
  7. Gratefully Dawg

    Gratefully Dawg Member

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    Very thorough. I tip my hat to you. You seem to have truly mastered the art of extraction. I think you should be the one running the make your own drugs class. Liroy doesn't ever do anything.
     
  8. comradechristophe

    comradechristophe Member

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    i say again a gentleman and a scholar...

    all i need is some chemicals and some time.
     
  9. ancient powers

    ancient powers Member

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  10. C123-473

    C123-473 Member

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    (BTW, You can get LSA crystals from an A/B...)
     
  11. ancient powers

    ancient powers Member

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    Methylamine Synthesis
    by ChemHack
    -----------------------------------------------------------------------
    The way I figure it, Hexamine is a lot less nasty (fume-wise) to make then Ammonium Chloride and just as easy.

    The Hexamine and the Ammonium Chloride procedures are essentially the SAME. Adding HCl to Hexamine causes it to degrade into Ammonium Chloride and Formaldehyde and is not a nasty reaction AT ALL, just raises the temp a little bit.

    If you want methylamine.hcl the easy way then follow my advice. Make your hexamine the way that you have been. Boil away all the water in a stovetop safe glass frying pan. (a Teflon pan coated regular pan will also work) This produces a buttload of nasty fumes but in my opinion the smell of ammonium is not as bad as having HCl gas in the air as you would if you just made ammonium chloride directly. You want to do it in a separate room with a window if you don't have a fume hood. The fumes of formaldehyde are worse than HCl so make sure that the solution you are boiling away has excess ammonium instead of excess formaldehyde.

    Once you boil all the liquid away you will be left with white hexamine powder. Add the HCl and stir it around real good. Some heat will be evolved. Let it sit overnight and in the morning there will be a buttload of Ammonium Chloride crystals sitting in the bottom of your flask.

    Rig up a large reflux device by attaching a long hose to the top of a large glass bottle. Now put the bottle in a pot and add cooking oil. If you put to much oil in then the thing will float so be careful. Now just heat the oil up until the thing starts bubbling. Turn off the heat and swirl it around. Notice how it continues bubbling even after it is no longer boiling? Tiny bubbles? That is CO2 being released.

    Now heat it again and this time let it keep bubbling. Swirl it around a lot to make sure the evolved gas can get out. I like to use a big-ass hose as the "reflux" area and then stick a smaller hose through it down into the solution. Attach the smaller hose to a fish tank bubbler and let the bubbler do the stirring for you. This will also help blow the evolved CO2 out of there. To make sure your little bubbler hose wont melt or distort because of the heat, test it in boiling water first.

    After a couple of hours the thing will no longer bubble when it is not boiling. The boiling point will go up from 100 to about 108. This is a good sign that the reaction is done. For 340g of hexamine I let it go 5 or 6 hours total but some of that time was just heating it up.

    Oh yeah, heat and cool slowly when using a regular bottle because the glass can't take quick temperature swings when it is that hot. The last thing that you want is a bunch of nasty formaldehyde/methyamine/ammonium water boiling below a layer of hot oil!

    When your heating is done allow it to slowly drop to room temperature on its own. Maybe best to just leave it overnight again. A bunch of ammonium chloride will fall out of solution again. Filter this off and set it aside for later.
    Using the same frying pan, evaporate the liquid solution. Again, there will be nasty fumes. If you have boiling flasks and an aspirator you may choose to use that instead because you suck those fumes right down the drain.

    Personally, I don't have any 2 liter boiling flasks and I don't wanna wait to do successive smaller amounts. I just boil them away in the spare bedroom with the windows open. Go back and check often because you don't wanna boil all the water away and scorch your goodies.

    At some point during the evaporation, more ammonium chloride will start to come out. Remove it from the heat and cool quickly. Then filter out the crystals and set them aside with the others.

    Put it back on the heat and let it go all the way until it is mushy. It won't get completely dry but don't worry about it. Take it off the heat and it will get nice and solid. Scrape this stuff up and combine it with the other crystals. You now have a much of methylamine and ammonium chloride.
    Get two large flasks with pouring spouts. Pyrex measuring cups work great. Put the crystals in the larger one. Pour a couple hundred mls of hardware store denatured alcohol in the other one and heat it to boiling in the microwave. Add the boiling alcohol to the crystals and stir like mad for a few seconds. The alcohol will probably take on a yellowish tint. The less yellow the better because that means you have fewer by-products but don't worry if it is bright yellow. You can worry if it is orange.

    Pour the hot alcohol off into a separate container. Put this container in the freezer and go smoke a cigarette. When you come back to the freezer you will see magic crystals!

    Keep repeating the procedure with fresh alcohol until you don't get any more crystals. Then do it one more time for good measure. The bright white crystals left in the measuring cup are ammonium chloride. Load them up in funnel with a coffee filter and pour one last bit of hot alcohol over them. Add the alcohol to the other and spread the ammonium chloride out on a plate to dry.

    Now put all of the alcohol extracts (even the ones that solidified) back into your frying pan and evaporate. Be extra careful to notice when no more alcohol is coming over because it might still be slushy even though all the alcohol is gone. These are the liquidy impurities. Once all the alcohol is gone the temperature in the frying pan will go way up so pay attention!

    Purification:

    Once the alcohol is all gone remove it from the heat and allow it to cool down and get nice and solid again. If you have any chloroform then now is a good time to use it. It dissolves the di-methylamnine impurities but leaves the good stuff behind.

    If you don't have any chloroform then pour out about 100mls of alcohol and put it in the freezer until it is very cold. Add the cold alcohol to your methylamine and impurities and stir it around real good. Not very much of the solid will dissolve but the alcohol will take up a bunch of the yellow crap leaving the crystals much lighter. Decant off the cold yellow alcohol and repeat with fresh cold alcohol until you reach the point of diminishing returns. This is the somewhat subjective point where you are starting to get more of your good stuff than yellow stuff.

    With this first round you can probably go until the cold alcohol coming off the crystals is completely clear. Put these crystals in an airtight container. They are the purest ones but you can still get lots more.

    Now evaporate the yellow alcohol as before. You will get a somewhat more mushy yellow product than before. Repeat the purification with fresh cold alcohol as before but this time adjust the amount of alcohol down because you have fewer crystals to purify. If you are really careful then this second batch of crystals, although much smaller, will be almost as pure as the first batch. If so then put them with the first batch. Otherwise put them in a sealed "Not-So-Pure" contianer.

    You can continue the process over and over again until you are left with an orange sludge that pretty much dissolves completely in the amount of alcohol needed to get the orange liquid away from the paltry amount of powder. It is probably a waste of time to take it this far because you've already got a load of perfecty good, relatively pure methylamine.hcl.

    Next time you want to make more you'e already got a bunch of ammonium chloride to start with so you can skip the hexamine step and instead add the ammonium chloride to the formaldehyde and boil from there without any HCl.

    --------------------------------------------------------------------------------
    force: "I did not dry it thoroughly- it seemed to be more like paste than powder, so i mixed this with HCL..."

    Well this is the reason that you never got hexamine powder. If you would have been more patient you could have dried the hexamine out into a fluffy white powder.

    Adding HCl to hexamine causes it to break down into formaldehyde and ammonium chloride! When you tried to "evaporate" this mixture...well everyone knows that when you heat formaldehyde and ammonium chloride together they react leaving methylamine hydrochloride, formic acid, carbon dioxide, and garbage. If the temp goes above say 110C you will also get some di-methylamine. It is the methylamine, not the hexamine, that is soaking up water from the air and melting.

    If you are intent on ruining your hexamine this way (haha) then the best thing to do is heat the hexamine/HCl mixture under reflux for a few hours until the temp reaches 110C. If you just evaporate it straight away most of the formaldehyde will escape as gas before it can react to form methylamine. Be careful with the reflux because a lot of CO2 gas will be released causing the boiling flask to bubble over. If you don't see any bubbles by the time it reaches 102C then take off the reflux apparatus and stir it briefly with a glass rod (you could use a chopstick instead.) This should get you on the way with thousands of tiny gas bubbles. The gas bubbles generally look smaller and more numerous than bubbles from simple boiling. You WANT these bubbles to come out of solution so that the CO2 doesn't stay in solution.

    If you don’t already have a stirring solution then one nifty way to stir it while it is refluxing is to find some small hi-temp plastic hosing that you can run down through the condenser to the bottom of the boiling flask. Connect the hose to a fish tank bubbler to force bubbles into the solution to agitate it.
    Anyway, depending on the size of your batch you should expect to heat it for several hours. Stop the heating when the temp goes above 110C. If its been over 100C for 4 to 5 hours but the temp is still sitting at 108 you can stop adding heat but continue to stir. If the tiny gas bubbles are no longer coming off even when stirred by hand then it is safe to assume that you are done. One interesting thing to note is that even though the gas bubbles probably won't start to come off until you reach about 100C, once they do start you can remove the heat and they will continue to come out until the temp drops into the 80s.

    When you are done heating allow the mixture to slowly come to room temperature. Lots of little white crystals will fall out of solution. They are ammonium chloride and you should filter them off and put them in a big ass jar. Then evaporate the remaining liquid on a steam bath. You really don't want to just put it in a frying pan and heat on the stove because the temp will go to high. Also, if you have an aspirator I STRONGLY recommend that you use it because there are some seriously nasty fumes that come off and it is best if they are sucked down the drain. If you do it in open air then, in my opinion, the only acceptable way to do it is in a separate room of your house with the window open and a fan blowing. The fumes will burn your eyes and lungs and I'm not kidding one bit!

    Don't cheat on the drying like you did with the hexamine and it will be much easier to purify your product. As you dry it out it will reach the point where it is a little mushy at 100C but quickly hardens as it cools. Now you have a bunch of white to beige-ish yellow chunks of methylamine and ammonium chloride. Scrape this stuff up and put it in the big jar.

    Go to the hardware store and buy a gallon of denatured alcohol for ~$10. Estimate the amount of alcohol that would be required to cover the crystals with about an inch of alcohol. Put this amount of alcohol in a microwave safe (pyrex) measuring cup and heat it to boiling in the microwave. Pour the boiling alcohol into the jar of crystals, replace the lid, and shake the hell out of it for a minute or two. Bright white crystals of ammonium chloride will quickly settle to the bottom. Carefully decant off the alcohol (which should still be fairly hot) into another container. The alcohol will have probably have taken on a yellowish color but it is actually good if it hasn't. Repeat the process with more boiling alcohol and add this alcohol to the first. For good measure do it one last time with about half as much alcohol. This time instead of merely decanting the alcohol, hot filter it. Sparkly crystals of ammonium chloride should be left behind in the filter cake.

    Evaporate the combined alcohol extracts to leave methylamine.hcl. Make sure it is good and dry and then wash with chloroform to get rid of any di-methylamine that might be hanging around.

    If there was any water in your product before you did the initial alcohol extraction then there is probably still a bit of ammonium chloride in your product. Add boiling alcohol with stirring and see if all dissolves. If it doesn’t then this is the ammonium chloride that escaped with the water the first time... filter it out.

    Once you get rid of all that ammonium chloride you can do a cool trick with your mehtylamine.hcl. Add just enough boiling alcohol to dissolve all of your product and then let it cool down slowly without stirring. It will crystallize into a huge chunk of fairly pure methylamine. Now put it in the freezer to reduce the solubility even more. When it is good and cold you can take it out and pour the small amount of methylamine laden alcohol into an evaporating dish. If you skipped the chloroform wash then this alcohol will contain mostly yellowish di-methylamine garbage and the solid chunk of crystals will be your clean stuff.

    Points to remember:

    Ammonium Chloride is not soluble in alcohol.
    Methylamine.hcl is much more soluble in hot alcohol than cold.
    Both are soluble in water. Minimizing water aids separation.
    Methylamine.hcl is not soluble in chloroform.
    The dimethylamine(?) impurities are more soluble in alcohol than methylamine.

    If you read what people have written about the separation most will tell you that methylamine.hcl and ammonium chloride look different. This is really only true AFTER you separate them. In a homogenous mixture it is much more difficult to point to any particular grain and identify.
    With a mixture of methylamine.hcl and ammonium chloride, leaving it exposed to the air results in a mushy mess.
    --------------------------------------------------------------------------------
    Now for some clarifications on my previous post:

    There is no reason that you need to totally dry your hexamine at the beginning except to know what your TRUE YIELD of hexamine really is. You want to know how much you actually have so that you don't add too much HCl. Any extra HCl you add will come back to haunt you if you plan on evaporating the stuff in the open air. It is easy to add too much based on the weight of the hexamine because it is capable of holding a HUGE amount of water. I evaporating to dryness the first time you make hexamine and keeping careful notes of how much formaldehyde and ammonium hydroxide was used. On subsequent runs you can use this information to more accurately estimate the amount of hexamine likely to have been produced and avoid the long wait for dryness.

    "If its been over 100C for 4 to 5 hours but the temp is still sitting at 108 you can stop adding heat but continue to stir. If the tiny gas bubbles are no longer coming off even when stirred by hand then it is safe to assume that you are done."

    To clarify, if you remove the heat but continue stirring and gas bubbles DO continue to come off then you are NOT yet done. Continue heating. You should be able to tell the difference between the tiny gas bubbles and the larger "boiling bubbles" without removing the heat but since the gas bubbles will continue to come off below the boiling point this is a good way to be certain.

    I don't if there is an upper limit to the size of this reaction. The largest glass container for sale at my local supermarket is a 1.5 liter apple cider jar. The OceanSpray bastards have replaced all of their glass bottles with plastic ones so this cider bottle is all that is easily available to me. The cider jar easily withstands the heat if you do it slowly. Plunging a jar full of room temperature liquid into a pot of hot oil results in a cracked bottle and a nasty oil/water mess! The key is to start with everything at room temp and raise the temp slowly. Even starting at room temp, immediately cranking the power up to max results in a cracked bottle. Three feet of 1/2" inner diameter hose from the hardware store cemented into place through the lid of the bottle makes for a perfectly effective air-cooled condenser. This method makes it easy to remove the condenser for a quick manual stir to get the gas bubbles going and the tube is wide enough to run the small fish-tank bubbler hose down through the middle of it and into the liquid to provide bubble-agitation.

    This setup is good for processing the hexamine from 4 packets of mildewcide with a yield of ~190g of very pure methylamine.hcl and quite a bit of unpure material that seemed like to much of a pain in the ass to recover.

    Cost of materials:

    4 packets of mildewcide --> ~$6 (~$1.50 each)
    Muriatic Acid --> ~$2/gallon (there will be lots left over)
    Ammonium Hydroxide --> ~$10/gallon (lots left over)
    --------------------------------------------------------------------------------
     
  12. vedaddy

    vedaddy Member

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    thanks a lot for this easy guide. Can i get the cactus at a garden store or do i have to order it online? Where do you get citric acid, and NaOH that doesnt involve buying online?
     
  13. vedaddy

    vedaddy Member

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    i was also wondering if you can replace NaOH with Janitorial strength ammonia?
     
  14. ancient powers

    ancient powers Member

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    The Methylamine FAQ v2.0

    Table of Contents

    1 Introduction/What's New?
    2 Questions/Answers
    3 Making Methylamine via Hofmann Rearrangement (Hypohalite version)
    4 Making Methylamine via Schmidt Rearrangement
    5 Making Methylamine HCl via Formaldehyde
    6 Making Acetamide from Acetic Acid & Urea
    7 Making Acetamide from Ethyl Acetate & Ammonia
    8 Making Absolute Ethanol

    -------------------------------------------------------------------------

    Introduction/What's New?

    This document deals with the preparation of Methylamine and Methylamine Hydrochloride from non-restricted precursors. Both of these compounds are currently extremely difficult to purchase legitimately or otherwise. This is the third major version of the FAQ, and in this version I am adding more physical data on the syntheses as well as a new reaction called the Schmidt Rearrangement which might be more attractive to some. Also, the astute observer will notice I changed the ratios of reactants in the Hofmann as well as scaling it down by 5 times. This is the result of empirical testing to better accomodate the person with small scale glassware (like myself).

    Please note that I am not a chemist by trade, but I have taken great pains to insure the accuracy of all information, including empirical testing. While this means I am not an authoritative reference, it also means that a non-chemist can put this information to use.

    What's New? v1.5: I have tested many variations on the Hofmann process in order to make it more efficient and easier. In my empirical testing, I have come up with several process improvements that make life with Hofmann so much easier and much more efficient to boot. For one thing, I have sucessfully performed it without having to use any ice in the reactants, reducing the volume of reactants by over 50% (and less volume is less one has to distill to get the good stuff). Yield hasn't suffered at all, and though slightly more time is required to perform the first step, distillation has been effectively doubled in speed (good for those of us with 500mL flasks and such to work with). Also, I added a new process that some may find more convenient called the Schmidt Reaction. It is very similar to the Hofmann, but please note that I haven't tested it nearly so much. Perhaps in a future "final touch" version I will put more empirical data into it.

    What's New? v2.0: I must warn against selecting the Schmidt reaction to make the product, as my experiences it with it have been less than pleasant. Do try to use a fume hood of some sort if you wish to pursue this otherwise highly attractive method. Also, I have re-written the Formalin/Ammonium Chloride method with a more practical view in mind. This new write-up makes it much more worthy of consideration - live and learn, eh? In addition, I have added another preparation of Acetamide which uses all OTC (well, except for the Calcium Oxide) reagents and is both cheap and easy.

    -------------------------------------------------------------------------

    Questions/Answers

    Q1) What is Methylamine or Methylamine Hydrochloride?
    A1) Methylamine, or more correctly Monomethylamine, is of formula CH3NH2, a simple primary amine. It is a noxious, acrid gas which is quite nasty and a tad on the explosive side. For this reason, it is usually sold or prepared as it's hydrochloride salt, or as an aqueous solution of about 40% concentration. The HCl salt is in the form of white deliquescent crystals, and is frequently substitutable for the aq. soln. in many synthesis preparations.

    Q2) What is this lovely compound used for?
    A2) Methylamine/HCl has a number of uses in which it is impossible or highly impractical to substitute. Several examples are:
    Methylamination of Hydroquinone to result in the ring structure p-methylaminophenol, the Sulfate of which is the photographic developing agent Metol. Aqueous Methylamine (40%) is used to prepare animal hides for taxidermy, especially when it is vital to preserve the hair. Synthesis of complex ring structures via the Mannich Condensation in conjunction with an aldehyde and a ketone. And, of course, it is a necessary for the preparation of several drugs (both legal and otherwise).

    Q3) Where can I get it?
    A3) You can't unless you happen to be in an industry that uses it or are prepared to sign your privacy away to the DEA. That's why this FAQ exists; so you can make it yourself. Besides, if you can't make it with the data provided in here, you have no business messing with it anyway.

    Q4) What are the legal implications of having it?
    A4) Well, it is required by any chemical supply institution that they take down all sorts of data on anyone attempting to purchase a kilogram or more of either the aqueous solution or the salt, but it has been my experience that no place will sell it to an individual in any quantity. I even have a friend who owns his own photography business and he says he couldn't buy any as well. I could go off on a long pedantic spiel about how ridiculous this is, but why bother. Possession of Methylamine is not a felony, in any amount, though you may violate some hazardous waste and/or zoning rules above a certain quantity. It's not the kind of thing you want to store next to your bed, anyway. If you have it in conjunction with other compounds, such as P-2-P or MDP-2-P, then if for some reason the DEA came a'knockin', you could be prosecuted for Conspiracy to Manufacture Amphetamines, which could be damaging to your lifestyle and health (see Code of Federal Regulations 21 for more info).

    Q5) Can I make it?
    A5) Definitely. If you have half a clue and some reasonable grasp of chemistry fundamentals, you can make a good chunk of methylamine in an afternoon. I am covering three individual processes in this FAQ that I feel are relatively easy but, primarily, because they give good yields. The ones I cover are:
    Hofmann Rearrangement of an Amide to an Amine
    Schmidt Rearrangement of a Carboxylic Acid/Anhydride to an Amine
    Aldehyde to Amine
    Also, it is possible to make it from completely over the counter materials if one chooses the Hofmann rearrangement and synthesizes the Acetamide from Urea and glacial Acetic Acid (synthesis included as well). And as a free bonus, I am including the most common preparation of Anhydrous (Absolute) Ethanol from grain alcohol or denatured alcohol.

    Finally, I would be remiss if I did not mention that there are several other processes for producing amines, though I have not treated them. Some other processes to consider among the hundreds are:

    Methyl Chloride + Ammonia in an ether solution (CH3NH2 + NH4Cl)
    CH3OH + NH3 at 300C
    CH3NO2 (Zn/HCl) -> CH3NH2*HCl
    etc...

    For further reference, consult these references:
    Organic Reactions vol. 3
    Vogel's Practical Organic Chemistry
    Organic Syntheses, vol. 1
    On to the syntheses...

    -------------------------------------------------------------------------

    3) Synthesis of Methylamine/Methylamine HCl via Hofmann Rearrangement
    There are two approaches to producing an amine from an amide using the Hofmann rearrangement reaction. One way is to react the primary amide with an alkaline-halide solution (eg - Sodium Hydroxide and Bromine). The other method is to use an alkaline-hypohalite solution (eg - Sodium Hydroxide and Calcium Hypochlorite). The astute observer will notice that there is no chemical difference in the two processes. One produces the Hypohalite in situ, the other uses the Hypohalite itself. Substitution of various halogens/halides/hypohalites/hydroxides is acceptable, but I feel I have picked the best combination of maximal yield and ease of availability. Feel free to prove me wrong ;-). Also, at least one text specifies that Sodium Hypochlorite produces much higher yields than Sodium Hypobromite. This delicious vindication is expected since Chlorine is a more reactive halogen than Bromine. Now, we are going to use Calcium Hypochlorite, in the form of powdered pool shock, because concentrated Sodium Hypochlorite is a rare, unstable creature indeed. Our yield will not suffer in the slightest because of this.

    The main example presented will be the alkaline-hypohalite method as it is the easiest to acquire the necessary chemicals. It is of interest to note that the alkaline-halide method is much easier to perform, processwise, in that it is more forgiving of sloppy technique.

    The general theory behind the process is that the hypohalite will convert the amide to a haloamide. This then spontaneously changes to the isocyanate when heated and decomposes to the amine from the water present. In effect, all that happens is that a Carbonyl (CO) group is stripped off the starting amide to yield the corresponding amine. Yields pre-purification are around 80%, post-purification average around 65%. Certain uses of the resulting amine will not require purification, though, so it will be left up to you whether or not to perform those steps.

    To make methylamine we start with Acetamide. The general, unbalanced reaction process is thus:

    CH3CONH2 + Ca(OCl)2 ----> (CH3CONCl)2Ca++ + H2O
    then
    (CH3CONCl)2Ca++ + NaOH ----> CH3NH2 + Na2CO3

    CAUTION Methylamine is a poisonous, noxious inflammable gas. It has a strong ammonia/rotting fish-like odor. It's not as bad as Chlorine gas, though, which can be produced if one is careless in the beginning!

    You can scale these reactions up or down within reason. What is reasonable? I can't say, but I have done batches from .01 to 1 mole with no difficulty. The key problems in scaling this reaction have to do with heat gradients in the flask and inadequate stirring. Use your own judgement, keeping in mind that this is not an industrial process.One reference to keep in mind (Thanks to J.W. Smith for sending this one) concerns the first step of the reaction. Whitmore and Thorpe, J. of the Amer. Chemical Society, Vol 63, April 1941, p1118

    "It was necessary to allow several hours for the formation of the N-chloroamide before heating to degradation temperature. With this modification it was possible to prepare methylamine...consistently in 78% yield."

    In my experience, this is a true statement. Please remember to keep the reactants well iced, though. Now, to begin:

    In a large mixing bowl which can contain a smaller stainless steel mixing bowl, prepare an ice bath with water and salt to bring the temperature down to -10C or so. Setup your glassware for simple distillation with magnetic stirring beforehand because certain steps need to be performed quickly. Use a vacuum adapter to connect to the receiver flask, and attach some rubber or polypropylene tubing to the vaccum nipple to connect to a bubbler setup (a funnel inverted in a beaker, or a plastic aquarium aerator tube). The distilling flask should be sitting in in a stainless steel bowl with nothing in it (you will add pre-heated oil to the bowl).

    NOTE In order to make this as painless as possible, please observe the following recommendations: 1) Keep the mixing bowl temperature as close to 0C or less as possible; 2) Keep the Hypochlorite solution as it is being added as close to 0C or less as possible; 3) After half the Hypochlorite solution has been added, place a plastic bag with 50-100g ice/salt/water mix into the bowl to help keep temperatures low (use this instead of directly adding ice to the reactants, which adds a considerable volume of water making the process less volumetrically efficient); 4) Purchase an 8lb bag of ice ahead of time!

    Next you will prepare three solutions.

    10g of Acetamide in 20mL of distilled water.
    16.4g of Calcium Hypochlorite (Pool shock) in 50mL of hot distilled water
    24g of Sodium Hydroxide (Lye) in 40mL of cold distilled water

    This last solution should be prepared slowly as it is quite exothermic. Set all three aside in a freezer. Now prepare the mixing apparatus which will be a stainless steel "mixing bowl" suspended in the ice/salt bath made earlier. We use a stainless steel bowl here so that heat transfer will be maximal, while preventing any corrosive interaction. A glass bowl will not be sufficient for larger scale preparations as it will not conduct heat fast enough to prevent the reactants from going over 10C (at which point the Haloamide will decompose and you'll have to start over). Take the Sodium Hydroxide solution out of the freezer once it is cool, but not cold.

    After the bowl has been sitting in the ice bath for a few minutes, add the Acetamide solution. Stir well until the solution has cooled to -10C. Now, slowly add the Hypochlorite solution to the mixing bowl in bursts of no more than a couple mL while stirring vigorously. If you do this perfectly, there will be no fizzing or bubbling at all. This depends on how cold you keep the mixture, and how slowly you add the pool shock! Realistically, the considerable heat evolution of the reaction will make adding the last few mL a trying task! Keep an additional 50g of ice on hand to throw directly into the mixture if necessary. This solution may evolve Chlorine gas so you should obviously perform this step under a fume hood or outside). Keep stirring until it has calmed down and turned a turbid colorless to light green Let it sit for 2 hours, stirring occasionally and making sure that it never gets warmer than 5C.

    After the 2 hours is up, add the Sodium Hydroxide solution quickly with stirring. The solution should immediately turn a chalky, milk white. That's because a lot of Sodium Carbonate just got generated. You no longer need be concerned over it's temperature, so you can leave the solution in this state overnight if perhaps the hours have passed by too quickly and you've suddenly realized it's 2:00am.

    Preheat a water bath on the stove (or wherever) to about 80C and place the stainless steel mixing bowl in it. Once the temperature of the solution hits about 65C, take the bowl out and set aside while stirring all the while. This is where it rearranges, and the reaction is exothermic enough to sustain it's temperature nicely. If you find the temperature climbing past 80C, immerse the bowl into some cold water briefly. After about 15 minutes the temperature will start to fall, at which point you should transfer the whole mess to the distilling flask. Before you continue you need to choose whether you want to make the hydrochloride salt or the aqueous solution of Methylamine, though.

    Heat the flask using an oil bath to 100C after adding this solution to effect gentle boiling which will drive off the Methylamine as a gas. In my experience, misbehavior is likely to occur at this point. One particular problem to watch out for is the sucking back of bubbler solution (be it plain water or 6N HCl) into the receiver flask. I don't know why the pressure in the distilling flask would go below atmospheric, and therefore cause this to happen, but it has several times with me. Needless to say, this results in a serious mess and botches the whole process (I have found a cure for this by using an automotive one-way vacuum valve, like a PCV).
    Continue heating the flask contents until you have collected around 100mL of distillate in the receiver.

    For the aqueous solution: Place 18mL of cool distilled water into your bubbler setup. The expected, not theoretical, yield of Methylamine from this amount of reactants is 7 grams. I have used a plastic aquarium aerator tube as the bubbler with excellent results. Sure beats using an inverted funnel.
    For the HCl salt: Do exactly as above except use 6N Hydrochloric Acid. 6N HCl may be produced by diluting 60.4mL of "Muriatic Acid" to 100mL with distilled water. Evaporate the bubbler solution to dryness then add 15ml of water, 10mL 10% NaOH soln. and heat gently to a boil with constant motion until dense white fumes appear. This will remove the Ammonium Chloride. Remove from heat while stirring as it cools down. Pulverize the dry residue, then reflux with absolute Ethanol for several minutes. Filter the refluxed soln. on a heated Buchner or Hirsch funnel, then distill the alcohol off the filtrate until crystals just begin to form. Allow the soln. to cool naturally to room temperature, then cool further in an ice bath. Filter the solution on a chilled Buchner funnel with suction. The yield of Methylamine Hydrochloride should be around 55% of the theoretical.

    To clean the white residue off of your glassware, dump some muriatic acid straight from the jug onto them and swirl.

    References:
    Journal of Chemical Education, v14, pg542
    Organic Reactions volume 3
    Vogels Elementary Practical Organic Chemistry, pg574
    -------------------------------------------------------------------------

    4) Methylamine/Methylamine HCl via Schmidt Rearrangement

    This reaction is quite similar to the Hofmann Rearrangement, but it reacts a Carboxylic Acid with Hydrazoic Acid to generate the desired amine. Like the Hofmann, it has wide application and versatility, yet also has excellent yields in many cases. It will also preserve the chirality of the starting Acid/Anhydride, which is not of interest to us, but an important fact to note.

    The restrictions on this process are that the starting Carboxylic Acid must not adversely react with either Sulfuric Acid or Hydrazoic Acid. It would be a crime if I didn't also mention that the Schmidt Rearrangement has much greater application than just making amines from carboxylics, but that is well beyond the scope of this FAQ. See Organic Reactions v3 for more details.

    To make Methylamine or the HCl salt using the Schmidt Rearrangement, you start off with glacial Acetic Acid. You might be saying to yourself, "Damn, why bother with the Hofmann!" since glacial Acetic Acid is so easy to get, but, there is a drawback... And that is Hydrazoic Acid, which is not easy to get. As well, Hydrazoic Acid is extrememly poisonous and should not be handled without a fume hood under any circumstances. Really. This is coming from a guy who has no problem distilling Ether solutions in his kitchen, so take it seriously. Why bother, then? Well, because you can generate the Hydrazoic Acid in situ using Sodium Azide and conc. Sulfuric Acid. I have not personally tried this because I don't have a powder addition funnel. Anyway, Sodium Azide is not too hard to come by through chemical supply houses and Sulfuric Acid is easy to acquire in the form of Instant Power Drain Opener. This reaction must be performed in an area of adequate upward ventilation, or at least with the air flowing away from you.

    NOTE In the initial testing of any undesireable interaction between Sodium Azide, Acetic Acid and Sulfuric Acid, I mixed 5mL of each into a small cup underneath my "fume hood". Though I smelled nothing, within seconds my head felt like it was expanding, my heart started racing, and I felt more weak and confused than normal. I just barely escaped and recovered in 15 minutes, but, Needless to say, this procedure is a tad on the dangerous side. You have been warned.

    Theory behind this reaction is:

    R-COOH + NaN3 ---H2SO4 ---> intermediates ---H2O---> R-NH2 + CO2
    The intermediates in making amines are isocyanates (O==C==N) just like the Hofmann Rearrangement. The isocyanates are decomposed with water, just like the Hofmann. In fact, there is a lot of similarity between the Hofmann and the Schmidt reactions. Before I detail the synthesis steps, I should note that if you wish to generate the Hydrazoic Acid in the flask by adding Sodium Azide, you might need a powder addition funnel. This bit of equipment is quite pricey and it's likely you won't have one, so the first part of the synthesis details how to make the Hydrazoic Acid separately.

    There are three variations on this process you may choose from:

    Add Hydrazoic Acid to a Carboxylic Acid/Benzene or Chloroform mixture (O.React. claims this is the preferred method).
    Add Sulfuric Acid to Carboxylic Acid/Hydrazoic Acid/Benzene or Chloroform mixture (this is my prefered method).
    Add Carboxylic Acid/Hydrazoic Acid/Benzene or Chloroform mixture to Sulfuric Acid or Sulfuric Acid/Benzene or Chloroform mixture.

    a) Preparation of Hydrazoic Acid

    CAUTION This compound is EXTREMELY EXPLOSIVE and HIGHLY TOXIC! I am not exaggerating! Do not, under any circumstances, allow the acid to heat above room temperature (bp: 37C). Use latex gloves to handle, and dispose of small quantities using plenty of water followed by dilute baking soda/water.

    Prepare a paste out of 65g Sodium Azide (1m NaN3) and 65mL of water in a beaker. Add 400mL of either Chloroform or Benzene to this paste (depending on what you have available, but be consistent later on) and stir well. Dump this mixture into a round bottom flask situated in an ice/salt bath, drop in a stirrer magnet, attach a Claisen adapter, addition funnel, and thermometer. Let this mixture cool to 0C.

    Place 49g of cold concentrated Sulfuric Acid into the addition funnel, but only after you make sure the stopcock is turned OFF. Ever so slowly add the acid to the flask, dropwise, such that the flask contents stay around 1C, and never go over 5C. This might take a while, be patient. After all is added, pour the flask contents into a separatory funnel (ventilation is absolutely required here) and separate out the aqueous layer. Your HN3 is dissolved in the Chloroform/Benzene layer. If you wish to determine the exact concentration of the acid, you may titrate it, but the reaction generally goes to completion with no secondary hydrazides forming as long as you kept the temperature where I told you to. Some HN3 might have gone to the aqueous layer, but mostly the resulting Sodium Sulfate will crowd it out. The resulting concentration, then, is the moles of Hydrazoic Acid over the the total moles of HN3 and your solvent (Chloroform = 117g/m, Benzene = 78g/m).

    b) Making the Amine (All Variations)
    Setup your glassware for simple distillation with a claisen adapter, three way adapter, pressure-equalized addition funnel, water cooled condenser, vacuum adapter and receiver flask to catch any condensed solvent vapors.

    c) Specifics for Variation 2

    Drop your stirrer magnet into the flask and add 250mL of Benzene or Chloroform (take your pick), Next, add .25 moles glacial Acetic Acid (15g) then .5 moles Hydrazoic Acid with stirring. Warm this solution to about 40C using a water bath. Make sure all joints are air tight. Add 20mL concentrated Sulfuric Acid very slowly. The reaction is mildly exothermic, so take care and watch the temperature. The reaction finishes within 2 hours. The amine is in the sulfate salt form. To convert to the hydrochloride salt form, first add an equinormal amount of 10% NaOH solution and stir well. Next, extract the free amine with ether and bubble HCl gas through it to precipitate out the crystals. Filter to recover.

    -------------------------------------------------------------------------

    5) Methylamine HCl from Formaldehyde and Ammmonium Chloride
    This is the least desirable of all three processes. The yields are lower than the two rearrangements, and it requires substantial labor to get a decently pure product. Not "labor" as in difficult but "labor" as in a lot of it. I would suggest this only for those who have a large supply of Formaldehyde available to them (note - N. Coffey found formaldehyde at Home Depot - look for "Mildewcide" and dissolve it in enough water to make a 37% solution to depolymerize the paraformaldehyde).

    Place 250g of Ammonium Chloride and 500g of technical Formaldehyde (37%, Formalin). Rig the flask for simple distillation such that a thermometer extends into the reaction mixture, and a Liebig or West condenser. Heat the mixture on the steam bath until no more distillate comes over, then turn up the heat and hold the reaction temperature at 104C until, once again, nothing else comes over. This should take from 4 to 5 hours. The distillate may contain interesting things, so check out footnote 1 for details on what to do with it. Next, the reaction flask should be cooled rapidly to room temperature by immersion into first a warm water bath (60C) swirled, and then an ice bath. Filter the solution on the vacuum Buchner funnel to recover ~62g of Ammonium Chloride crystals. Concentrate the filtrate using moderate vacuum and gentle heat until the volume is reduced to half. Filter the mother liquor once again after cooling quickly to yield a second batch of Ammonium Chloride, ~19g.

    Transfer the filtrate to a ceramic evaporating dish and heat on a water bath until a crystalline scum forms on the top. Cool the dish quickly then filter the mess on the vacuum Buchner to yield ~96g of Methylamine Hydrochloride. Concentrate the filtrate once again to obtain a second crop of crystals, ~18g. Concentrate the filtrate a third time as far as possible using the water bath, then store the dish in a vacuum dessicator loaded with Sodium Hydroxide in the bottom for 24 hours. Add Chloroform to the residue left in the crucible to dissolve out Dimethylamine Hydrochloride (distill off the Chloroform to recover - good stuff) then filter on the venerable old vacuum Buchner funnel to yield an additional ~20g of Methylamine Hydrochloride, washing the crystals in the funnel with a small portion of Chloroform (~10mL).

    Purification of the Methylamine HCl is in order now, so transfer all of the crude product to a 500mL flask and add either 250mL of absolute Ethanol (see end of FAQ for preparing this) or, ideally, n-Butyl Alcohol (see Footnote 4). Heat at reflux with a Calcium Chloride guard tube for 30 minutes. Allow the undissolved solids to settle (Ammonium Chloride) then decant the clear solution and cool quickly to precipitate out Methylamine HCl. Filter rapidly on the vacuum Buchner funnel and transfer crystals to a dessicator (see Footnote 3). Repeat the reflux-settle-cool-filter process four more times if using absolute Ethanol, or two more times if using n-Butyl Alcohol. The yield of Methylamine HCl should be 100g.

    -------------------------------------------------------------------------
    Footnotes

    Footnote 1 - The byproducts of the first step are Dimethoxymethane and Sodium Formate.
    Footnote 2 - The Methylamine solutions in all steps should be cooled rapidly to promote smaller crystal formation.
    Footnote 3 - According to the original document, centrifuging is the most satisfactory method of drying products because of their hygroscopic nature. I suggest warming in an oven on a glass dish then transfering to a vacuum dessicator loaded with either concentrated Sulfuric Acid or Sodium Hydroxide in the bottom. It is not normally necessary to have absolutely dry Methylamine HCl anyway.
    Footnote 4 - The solubility of Ammonium Chloride in absolute Ethanol is 0.6g/100g at 15C. The solubility in n-Butyl Alcohol is neglible, even at its boiling point. If you use n-Butyl Alcohol, you will only need to perform 3 reflux/filter operations to obtain sufficiently pure Methylamine Hydrochloride.

    References to this section:

    Sharp & Solomon, J. Chem. Soc. 1477 (1931)
    Werner, J. Chem. Soc. 850 (1917)
    Sommelet, Compt. rend. 178, 217 (1924)
    Hofmann, Ann. 79, 16 (1851)
    -------------------------------------------------------------------------

    6) Synthesis of Acetamide from Acetic Acid and Urea

    Urea is conveniently obtained as a constituent of many fertilizers and so it is easily obtained. Sources have indicated that a 50lb bag can be purchased for $15 in the US. It is of less than ideal purity from this source, so some washing will be in order (with what?). Glacial Acetic Acid is easily obtained from photographic supply stores in high purity and for cheap as well. This reaction produces Acetamide with such purity that the product does not even need to be recrystallized (the reaction goes to completion with no side products).

    The reaction is:

    CH3COOH + NH2CONH2 ----> CH3CONH2 + CO2 + 2NH3
    Place 125g Urea and 125g of Acetic Acid in a 500mL round bottom flask in preparation for simple refluxing with magnetic stirring and without cooling water (or use cooling water heated to about 80C). Attach condenser, claisen adapter and place thermometer so that the bulb is around 1cm from the bottom, fully immersed. Heat on the mantle gently to bring the temperature of the mixture to 150C in 20 minutes. The mixture should be refluxing in the condenser, and probably subliming in it as well unless heated "cooling" water is used. Push any crystals back down as necessary. Hold at reflux until the temperature rises to 195-200C (approximately 1.5 hours) Allow to cool, then rearrange the condenser for distilling (its really preferable to use 80C water in the condenser). Heat to collect nearly pure Acetamide starting at 200C with most coming over from 214-216C. If the product smells strongly of mice (as in the rodents), then recrystallization from warm methanol is in order. To recrystallize, take 50g of Acetamide, dissolve in 40mL warm Methanol, add 100mL Ether to crash it out and allow to stand. If no crystals have formed after an hour or so, gently scratch the inside of the beaker with a glass rod. If your product is only faintly odorous and is colourless to white, then it is considered pure. Melting point is 80.5C.

    -------------------------------------------------------------------------

    7) Synthesis of Acetamide from Ethyl Acetate and Ammonia

    Ethyl Acetate is allowed to mix with concentrated Ammonia solution for several days to make Acetamide. This is a very attractive method because all the reagents involved are easy to acquire and cheap.

    a) Preparation of Ethyl Acetate from Ethanol and glacial Acetic Acid
    Dehydrate at least 100mL of grain alcohol to yield absolute Ethanol. 74mL (58g) will be required. Add this quantity of Ethanol to a round bottom flask with 225g glacial Acetic Acid and 3g of concentrated Sulfuric Acid. Heat at reflux on an electric heating mantle for 12 hours then attach a Vigreaux or Hempel fractionating column to distill off the crude ester at 76-77C. Change receiver flasks and recover the excess of Acetic Acid, bp 118C. Wash the first receiver contents with a half volume of saturated Sodium Bicarbonate solution then add 50g of anhydrous Sodium Sulfate (the salt of Sulfuric Acid and Sodium Hydroxide, dried in an oven at >100C for several hours) and distill the pure dry ester once again. Yield should be greater than 70g.

    b) Reaction of Ethyl Acetate and Ammonia to make Acetamide
    Add 44g of Ethyl Acetate and 90mL of concentrated Ammonia solution (~28%) to a 500mL round bottom flask with a stirrer magnet. Plug the neck with a thermometer in a thermometer adapter and stir gently for 48 hours or until the mixture becomes homogenous (stop the stirrer occasionally to check). Attach standard distillation apparatus but leave off the receiver flask at first, connecting a short piece of rubber tubing to the receiver adapter which is submerged in a beaker of dilute HCl (10-20%). Heat gently on a mantle to drive off the excess ammonia into the beaker. When no more bubbles come over then attach the receiver flask and commence distilling acetamide from 170C up, rapidly. Run 80C water though the condenser to prevent clogging. Once distillation slows to a crawl, remove the receiver flask and set aside in a hot water bath (80-90C). Clean up the glassware used for the distillation then use the receiver flask as the distilling flask and a glass container with screw-lid top as a receiver. Run 80C water through the condenser as before, and redistill the Acetamide, which should come over completely at 216C using the heating mantle. Yield should be greater than 24g.

    -------------------------------------------------------------------------

    8) Preparation of Absolute Ethanol from Grain Alcohol

    Absolute, or 99.5% water-free, Ethanol is frequently necessary in many organic operations. It is quite easy to prepare from the azeotrope with water such as "Everclear" brand grain alcohol, "moonshine" or "Rectified Spirits" (an old term for the same thing).

    Dehydrate 75g of fresh anhydrous Calcium Oxide in a vacuum dessicator for 24 hours (a bit redundant, I know) or heat in an oven at 200C for 2 hours, then immediately transfer to the vacuum dessicator until use. Setup glassware for simple refluxing with a water-cooled condenser and a Calcium Chloride guard tube. Place 350mL of Ethanol into the flask, quickly add the Calcium Oxide and hold at gentle reflux on the water bath or heating mantle for 6 hours. Allow the mixture to stand overnight, then distill off the alcohol, discarding the first few mL (it may be more convenient to just vent the condenser to the atmosphere for the first couple of minutes after distillation has commenced). Yield should be better than 315mL. Store the absolute Ethanol in a tightly closed glass container as it will pick up water from the air rapidly.

    - eleusis@netcom.com - The Methylamine FAQ v2.0 - 01/21/96 -
    See also:
    MDMA Synthesis Notes.
    Good information on acetamide.
    Newest MDMA Synthesis.
    Phenethylamines i Have Known And Loved, part two, by Alexander Shulgin.
    The 3,4-methylenedioxy-n-methylamphetamine (MDMA) synthesis from PiHKAL.
    Syntheses that suck for methamphetamine.
     
  15. ancient powers

    ancient powers Member

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    How To Manufacture Meth -- True Iodine Recipe
    by MethodMan


    NOTICE: TO ALL CONCERNED certain text files and messages contained on this site deal with activities and devices which would be in violation of various Federal, State, and local laws if actually carried out or constructed. The webmasters of this site do not advocate the breaking of any law. Our text files and message bases are for informational purposes only. We recommend that you contact your local law enforcement officials before undertaking any project based upon any information obtained from this or any other web site. We do not guarantee that any of the information contained on this system is correct, workable, or factual. We are not responsible for, nor do we assume any liability for, damages resulting from the use of any information on this site.


    No lies here folks this recipe will manufacture methamphetamine this will get you into trouble if you do this BE CAREFUL!



    First of all let's talk about supplies:
    • 1 Case Regular Pint size Mason Jars ( Used for canning)
    • 2 Boxes Contact 12 hour time released tablets.
    • 3 Bottles of Heet.
    • 4 feet of surgical tubing.
    • 1 Bottle of Rubbing Alcohol.
    • 1 Gallon Muriatic Acid ( Used for cleaning concrete)
    • 1 Gallon of Coleman's Fuel
    • 1 Gallon of Acetone
    • 1 Pack of Coffee Filters
    • 1 Electric Skillet ( If you don't know what i am talking about I will have pics later)
    • 4 Bottles Iodine Tincture 2% (don't get the decolorized it won't work)
    • 2 Bottles of Hydrogen peroxide
    • 3 20 0z Coke Bottles (Plastic type)(with Lids/caps)
    • 1 Can Red Devils Lye
    • 1 Pair of sharp scissors
    • 4 Boxes Book Matches (try to get the ones with brown/red striker pads)
    • 1 pyrodex baking dish
    • 1 Box execto razor blades single sided
    • 1 digital scale that reads grams
    • 2 gallons distilled water \
    • 1 Roll Aluminum foil tape
    That's what you would have to go buy if you wanted to make meth.
    First things first -- the Iodine Crystals. Take one 20 oz, plastic Coke Bottle and pour 4 Bottles 2% tincture into it.

    Add Hydrogen Peroxide to this. Use only 1/2 a bottle of Hydrogen peroxide. After this you know, the gallon jug that the Muriatic acid comes in take the cap off and fill this cap level with the acid. Add the acid to the coke bottle (Place in a freezer for at least 30 mins).

    While the Iodine crystals are being made we are going to extract the Pseudo from the Contacts. You are going to need a towel for this so go get one. Take the pills out of one box, add it to one of the mason jars fill with rubbing alcohol just enough to cover the pills let set for 3 minutes. Remove pills and take the towel and wipe the top coating off the pills this will remove the wax. Do the same with the other box of Contacts as well, after this add those wiped off pills only 10 to a clean mason jar. On top of this add 1 bottle of Heat do the same for the other box of Contact. Let these two mason jars with pills, heat stand for 30 minutes. Then shake the jars till pills are completely broke down then let the jars sit again for 4 hours or until the Heats is completely clear. Once clear siphon the heat off (Not the powder stuff at the Bottom you don't want this it will fuck your dope up).

    Well anyway siphon the heat off with a piece of the surgical tubing siphon this into a pyrodex baking dish place in microwave on high till the heat is almost evaporated. Take out of microwave. Now plug up your electric plate set the pyrodex dish on this on about 180 deg continue evaporating till you get a white powder on the pyrodex (Careful not the burn the pseudo if it turns yellow it's burned) after you get it dried take a razor blade and scrape this powder up. (Put this aside for later use)

    Now we are going to get the red phosphorus from the book matches take a pair of scissors and cut along the edge of the phosphorus do the whole four boxes of match book matches then take 1 small coffee cup will work to this coffee cup add about 1/4 the way with Acetone dip the match book strike pads into the acetone for 10 seconds this will loosen the phosphorus so it will be easier to scrape with the razor blades. (Put the phosphorus in an empty match book box to let dry. Now it's time to get the iodine crystals get a clean mason jar on top of this place 1 coffee filter and pour the contents of the iodine +muriatic+Hydrogen Peroxide into the filter ( do it slowly don't over pour) well once you get though with the filtering on top of the coffee filter will be a black substance ( This is iodine crystals) dry them by wrapping in more coffee filters till you get a pretty good thick pile around the original filter place on ground and step on it to get the rest of the liquids off save this for the cook.

    next take your digital scales weigh your pills first say you had 2 grams of pill powder then weigh out an equal amount of iodine crystals then for the phosphorus divide the total weight of pills by 3 3 will go into 2 1 time so if you had 2 grams pill powder you should have 2 grams iodine crystal 1 gram phosphorus Now its time to make the cook jars you will need 2 clean mason jars with lids 1 foot surgical tubing poke a hole in both jar lids place one end of the tubing into each jar lid and seal with foil tape (buy this at Wal-Mart for about $ 1.60 well anyway seal off the tubes as well as you can so you should have 2 mason jars with lids that have surgical tubing foiled taped and sealed.

    ok this is the cook in one mason jar add distilled water in it fill it half way close the lid on it. now get you hotplate hot first at 180 degrees F when the plate get hot then its time to add the Iodine+pill powder to the other mason jar not the one with water in it once you get both Iodine and pill powder to the jar add 6-10 drops of distilled water to this place it on the hotplate now add the phosphorus once you put this in the jar there is going to be a imediatereaction place the other lid with hose onto the jar screw on tightly then turn your hotplate up to 400 degrees f let this cook for 1 hour to an hour and a half the best way to tell when it is done is when the contents of the cook jar doesn't boil anymore once this has happened turn the hotplate off and let the jar cool so you can touch it now its time to see if we have dope once it has cooled open the lid and you should smell rotten egg like smell if it has this smell congrads you have dope now we have to remove the dope from the black gooey substance to this jar add about 1/4 cup of distilled water and seal the jar with a lid that has no holes in it and shake the jar till all the substance on the bottom of the jar has come off into the water

    next take another clean mason jar and place a coffee filter and filter the cook jars contents though the filter now on the filter is your phosphorus save this for another cook later on just putt it in a dry coffee filter and put it somewhere dry and safe now you have a jar filled with a yellow honey looking substance if its this color you have done good at cooking the dope now to this add Coleman’s fuel fill the jar about full just leave enough room for shaking now add 1-2 table spoons red devil lye let the jar sit for about 5 mins then place lid on the jar and shake the hell out of it then sit the jar somewhere to rest for about 30 mins

    Now we are going to pull the dope out of the Coleman fuel and the product is going to be 90% methamphetamine to do this fallow what I say exactly siphon the Coleman fuel into an empty 20 oz coke bottle siphon off much as you can trying not to get the substance off the bottom of the jar once you have the Coleman fuel in the coke bottle add about 4-6 coke bottle caps of water to this now add one drop of muriatic acid to the coke bottle place lid on bottle and shake the hell out of it place upside down so it want fall and get your hotplate hot 400 degrees f on top of the hotplate

    place a clean pyrodex bowl on it now take the coke bottle still upside down and loosen up on the cap let the water drain into the pan don't get any Coleman fuel into the pyrodex bowl now the water will evaporate while it is doing this take a coffee cup add acetone to it fill it 1/4 the way up now once the water has dried on the plate take plate off with gloves and add a small amount of acetone to the pyrodex bowl it will sizzle swirl it around and if all works out good there will be crystals all over the pyrodex bowl scrape up with a razor and enjoy Methamphetamine :) This with 2 boxes of Contacts will make anywhere from 2-3 grams meth....
     
  16. ancient powers

    ancient powers Member

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    The Matchbook Red Phosphorus Bible
    [ Back to the Chemistry Archive ]



    Materials:

    5 Gallon Bucket
    Drill (1/2" chuck)
    Mud/Paint/Concrete Mixer
    Coffee Filters
    Strainer (big enough to fit over pot and bucket opening)
    2 gallon Cooking Pot
    Tin Snips or Scissors
    200 Matchbook Boxes
    2 Gallons Acetone
    Sulfuric Acid
    Hydrochloric Acid
    Water
    Iodine


    Extracting Red Phosphorus from Matchbooks:
    1. Rip off matchbook covers. Line up as many matchbook covers as you can cut through with tin snips or good, sharp scissors. Cut out and save all the striking strips.
    2. Drill 3/4" hole in the lid of the 5 gallon bucket. Put the mud mixer through 3/4" hole in lid and into the drill.
    3. Dump the 200 matchbook boxes worth of striking strips (10,000 striking strips) into the 5 gallon bucket. Pour 1.5 gallons of acetone into the bucket. Cover bucket by inserting mud mixer then snapping on the lid.
    4. Mix Contents for about 5 minutes. Check to see if strips are mostly white on account of the phosphorous/glue being washed off. If not then continue mixing.
    5. Take off the lid and pull out mixer. Put the strainer on the cooking pot and pour all the acetone in. Pull out all strips from strainer and bucket and place on clean table or in a bowl. The strips will be covered in residual red phosphorus, so rinse them by placing the strainer on bucket and throwing a handful of strips in it. Then slowly pour some of the acetone in the cooking pot, through the strainer until strips are clean. Empty strainer into garbage. Continue until all strips are rinsed.
    6. Pour all the acetone/RP into the cooking pot. Let the RP settle for about 15 minutes. Slowly pour off the acetone. Keep pouring as long as the acetone is pretty clear. The last bit of acetone will be reddish colored. Filter this through a coffee filter in the strainer. Scrape the mushy RP back into the pot or dry the filters, roll and ball them up well, then unfold. All the RP will fall right out in a dust.
    Cleaning Matchbook Red Phosphorus:

    Sulfuric/hydrochloric acid wash: (This can be done as 2 different washes) With mushy RP in cooking pot, pour enough 1:1 water/sulfuric to cover the glob. (It's optional now to add heat or not. If so then add no more than enough for a light boil) Mix contents for 5 to 10 minutes. Add an equal amount of hydrochloric acid and continue mixing for 5 to 10 minutes. If heat was applied take off now. Add an equal amount of cold water. Filter through a coffee filter in the strainer. Scrape the chunky RP off the filters back into the cooking pot. (This will eat up a lot of small paper fibers, hair, cotton, lint or whatever.)

    Acetone wash: Add enough acetone to cover the globs and chunks of RP. (Again you can add heat if you like. Bring it to a controlled boil.) Mix for 5 to 10 minutes. Let cool or add a little cold water. Filter RP same way and return it to pot. (This will remove any glues or other acetone solvent junk.)

    Water wash: Add enough distilled water to cover the RP globs. Bring this to a boil for 5 to 10 minutes. Filter out the RP and leave in filters to dry out. When dry roll and ball up filters then brush out dust. Collect dust in a baggie and store. (This is a general cleaning to remove any chemical residue.)

    Other washes: Any of the following solvents have been safely used to wash RP... Methanol, Ethanol, Denatured alcohol, Isopropanol, Toluene, Xylene. These would be done the same as written above.

    Screening: Put the RP in a stainless steel screen or plastic/steel mesh style coffee filter and run acetone through it. The RP is washed through the screen with the acetone, and any particles larger than the screen apertures are filtered out.

    Washing order:The order does not matter as long as the RP is finished off with an acetone wash then a distilled water wash.

    Prefiring Red Phosphorus

    React RP/I2:Weigh out your RP and put it into a bottle. Add half as much I2 to it and shake it up. Add (dropwise) H2O2 when not reacting. Continue shaking and adding drops of H2O2 until it's done reacting.

    Filter out RP: After prefiring add water and shake. If it won't loosen up then put the bottle in boiling water for 5 minutes. Filter the water/RP/I mix. Wash the RP with acetone then water. Dry it out, baggie and save for a rainy day.

    Note: Make sure drill has a 1/2" chuck.

    This was compiled from many sources and through trial and error was refined to what you see. It was written to be printed up and used as a reference for anyone like swim that hasn't been able to get lab grade RP. Swim's current run was scaled down using a 2 gallon bucket with 114 boxes! It took over 3/4 gallon of acetone to extract the RP. Clean up will be H2SO4/HCl, acetone, H2O, prefire, acetone, H2O, done!

    Swim is expecting to yield about 250mg per box. They're hoping to end up with an even ounce.
     
  17. vedaddy

    vedaddy Member

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    thanks a lot, can i just get NaOH drain cleaner...know any good brands that just have NaOH?
     
  18. ancient powers

    ancient powers Member

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    Procedure for Obtaining Pure Ephedrine,Pseudoephedrine or PPA From Stimulant and/or Cold Pills


    No aspect of methamphetamine manufacturehas changed so radically in the past few years as the composition and availability of the OTC "stimulant" pills which are useful as raw-material feed-stock for methamphetamine production.

    Back in early '92, when I penned the third edition to this book, ephedrine pills were available by mail order. These pills were quite well-suited for a very simple water extraction to get out the active ingredients, because they were about 30-40% active ingredient, and the fillers were mostly nonwater soluble. Sudafed pills were almost that easy to extract, except that they had a red colored coat that had to be soaked off in solvent before commencing a water extraction of them.

    Since that time, the mail-order outfits have been heavily leaned upon. Several of their heads are now in the slammer. Other such companies have been taken over and are now agents of the enemy. I wouldn't trust most of them as far as I could spit. All ephedrine orders now must be accompanied with photocopies of driver's licenses, etc. Ephedrine is now on the chemical diversion list with no minimum threshold quantity. To quote one of the DEA's top dogs on this matter: "We're keeping track of where they are going."

    Pseudoephedrine, aka Sudafed, and PPA, aka phenylpropanolamine or Dexatrim, are now subject to close sales scrutiny as well due to the Meth
    Act of 1996, passed in response to the 4th edition of this book. A single sale limit of 24 grams of base, which corresponds to a little under 500 of
    the 60 mg pseudoephedrine pills or a little over 300 of the 75 mg phenylpropanolamine pills, has been established. Mail-order pill companies are now required to turn over, on a regular basis, a complete customer list with names and addresses and amounts purchased.

    As a result, it must be emphasized that the procedures given in this chapter are most suitable for making "stash" amounts of meth or dexedrine. Large pill purchases will attract the heat like blood in the water does sharks. The recipes given in this chapter can easily be scaled down to whatever amount of pill feedstock one is able to obtain.

    Retail store sales aren't federally regulated, but the prices there are very high compared to the mail-order prices. Starting in 1998, Wal-Mart began limiting sales of all cold medicines (read: ephedrine, pseudoephedrine
    and phenylpropanolamine) to three packages per customer. Try to buy more and the cash register throws a fit. Some localities in areas such as California have passed ordinances decreeing similar retail sale limits. State laws may be coming imposing similar limits. Some states have gone so far as to declare pseudoephedrine a Schedule 5 drug which must be dispensed one package at a time by a pharmacist. Unless one is willing to spend all day shopping for pills, it may be difficult to accumulate thousands of them.

    An alternative to the use of ephedrine pills is what are called "herbal extract" pills. These don't at present come under reporting requirements because they wear that "herbal" label. These pills are loaded with ephedrine, so expect laws to be passed shortly bringing them under reporting requirements.

    They are at present available by mailorder at a reasonable price. Ads can be found in our favorite sleazy magazines. I would suggest using a fake name and a rented mailbox when ordering them.

    Another source of ephedrine is the herb Ma Huang, which is the source of those herbal extract pills, and the natural source of ephedrine. It contains
    around 8% ephedrine, along with some pseudoephedrine. This material too isn't under reporting requirements as I write this, but stay tuned. That could change at any moment. I've looked for this herb at my local health food stores with no success, but your area may be better stocked.

    The "doctoring" of the pills over the past several years has been similarly dramatic. In the case of ephedrine pills, the first thing which was done
    was to add more filler to make them less suitable to a simple water extraction. The more filler, the more water required to extract the active ingredient, and the more inert pill-gunk co-extracted.

    This gunk had a bad effect on the methproduction reactions, which follow the GIGO principle. Then the pill doctoring became more scientific. The insoluble filler was replaced by some type of water-soluble fiber which played much greater havoc with the ensuing reaction if no purification beyond just water extraction was done. Even in the case of making cat, it would screw up the reaction by causing the entire reaction mixture to take on a milkshake consistency upon neutralization with NaOH. The gunk equally filled the water
    and toluene layer (which, by the way, were pretty hard to spot because of the floating gunk).

    The floating gunk could be filtered out of the toluene layer, and the hydrochloride then precipitated, but the octane numbers were greatly reduced below normal.

    The next version of ephedrine pills contained 25 milligrams of ephedrine along with 100 milligrams of guaifenesin. They were available at gas stations and other stores because they came under the definition of "mixture" in the Chemical Diversion Act, and so were not regulated. These 100 milligram guaifenesin pills were followed by 200 milligram guaifenesin pills, which is what are on the market now. The definition of mixture" has been changed so that ephedrine pills containing guaifenesin are just as reportable
    as the others.

    The best extraction procedure to use has changed a lot with the passage of time, and the introduction of new pill formulations. I'll go through the various pill extraction techniques which have been used over the past decade so that the reader can have a sense of history on this subject.

    It's also wise to cover the old methods because many of the old techniques can be made useful again with some tweaking to counteract the effects of new polluting ingredients in pills. Let's start with the basic pill extraction procedure. It's an extension of the old standard water extraction
    procedure that was so successful with the old mini-thin ephedrine pills. It also used to work fine with the old types of pseudoephedrine pills. By
    substituting 1-2% HC1 solution for the water in this extraction, it can also be used to extract Ma Huang, and the "herbal extract" pills.

    The first step is to grind the pills. A mortar and pestle gives the best grind size, as overly fine grinding makes the subsequent filtering steps more difficult. With herbal extract pills and Ma Huang, the initial grind should be done in a blender, mixing the substance to be ground with its initial grind charge of 1-2% hydrochloric acid (hardware store muriatic acid diluted 15-30 fold) and blenderizing at medium high speed until small particles are obtained.

    The next step after the grind is to determine whether these pills need to be degummed and desplooged. The ephedrine-guaifenesin pills are really loaded with gum. They must be degummed and desplooged by soaking the ground up pills in toluene, then filtering. Other types of pills I've come across aren't so loaded with this ingredient, although it may be more prevalent in the future.

    Failure to degum and desplooge these pills results in a milkshake later when the water extract is made basic and extracted with solvent. It also
    really slows up the filtering of the water extract. I think this emulsion-forming ingredient is some type of fatty acid which forms a soap when sodium hydroxide is added later on to free base the ephedrine, or whatever.

    Toluene is also quite good at removing guaifenesin from pills. Colored pills should be tested with solvent. If toluene is going to be used as the extractant at the end of this procedure, check to see if toluene dissolves
    the coloring matter. If it does, then soak the ground up pills in toluene and filter to remove the color. Ditto if Coleman camper fuel is going to be
    used as the final extractant. Allow the ground up pills to dry after desplooging so that the solvent is removed from them.

    Then water extraction is done. Mix 1,000 ground up pills with 350 ml of water, and stir for about an hour. Another variation is to just mix 1,000 pills with 350 ml water, and after the pills have softened, mush them up and stir for an additional hour.

    Now the pill mush should be filtered. Vacuum filtration through a Buchner funnel is greatly preferred, because it will suck the filter cake dry, giving better extraction with less use of water. The need to keep the amount of water used to a minimum arises from the fact that the "pill extraction deterrents" are less soluble in water than the desired ingredient, so the more water used, the more effective they are. It may be difficult to get the mush to filter easily through filter paper, so a preliminary filtering through clean white cotton cloth cut like a filter paper will be helpful in these cases.

    The filtrate should be clear, and very bitter tasting, as it contains the active ingredient. Hopefully, most of the pill fillers didn't dissolve, and they are sitting in a filter cake in the Buchner funnel.

    Now take this filter cake of pill sludge, remove it from the filter, and mix it with an additional 300 ml of water. Stir this around for an hour, then filter this. If a Buchner funnel was used, this is enough water to extract the pills. If only gravity was used to aid filtration, then the pill sludge should be soaked with a final 100 ml portion of water, and filtered.

    To the combined filtrates, add a dash of hydrochloric acid to suppress steam distillation, and boil its volume down to about 200 ml. With pseudoephedrine, this isn't so important because it isn't as water-soluble as ephedrine or PPA free bases, but the volume should be reduced some for it, too.

    Now let the solution cool, and then add 20% NaOH or lye solution with stirring or shaking until the solution is strongly alkaline to litmus paper.
    Indicating pH paper should say 12+. A pH meter may not be as useful as paper for this reading. The solution at this point should smell strongly of the kind of fishy free bases.

    Extract the water solution with about 100 ml of toluene. This solvent can be found in the paintthinner section of the hardware store or paintsupply outlet. If you can't find this solvent, Coleman camper fuel will work almost as well. The water layer should remain a liquid, and the toluene layer should be clear and transparent. If the particular "deterrent" formulation results in a milkshake consistency, just estimate how much isthat top 100 ml of solvent, separate it off, and filter it. Rinse the filtered out gunk with solvent.

    Repeat this extraction with two additional portions of toluene. With the ephedrine-guaifenesin pills, extract with petroleum ether, hexane or
    Coleman camper fuel. The combined toluene extracts should be placed in a 400 ml beaker and allowed to sit for a few hours. This serves two purposes: first, entrained water will settle to the bottom of the beaker and stick to the glass. When it is poured into a fresh beaker, the water will be removed.

    The second reason involves an observation I made some time ago with one particular "deterrent" formulation. In that case the water layer became almost solid after the second toluene extraction, because the solvating action of ephedrine free base was lost for these fillers. The toluene
    extract in this case, upon standing, grew a mat of white solid about %- to '/z-inch thick on the bottom of the beaker. After letting this mat grow, and pouring the solution off of it, all proceeded well from that point.

    Once the toluene has been poured into a fresh
    beaker, dry HC1 gas should be bubbled through it
    to precipitate pure ephedrine, pseudoephedrine or
    PPA hydrochloride. This is done just like the
    bubbling to get meth hydrochloride in Chapter
    Five. The yield from 1,000 25 mg ephedrine pills
    is about 20 grams, from 1,000 60 mg pseudoephedrine
    pills about 50 grams, and from 1,000
    75 mg PPA pills is about 65 grams.
    With Ma Huang and herbal extract pills, the dilute
    acid solution used as extractant should be
    boiled down to concentrate it, just as with pills.
    Then take some toluene and extract the acid solution
    concentrate. This will remove coloring and
    other plant material, but not the desired ephedrine.
    One, of course, has to wait for the solution
    to cool before doing a solvent extraction or the
    solvent will boil and fume and make a mess on
    you.
    Then after extracting the acid concentrate, this
    concentrate should be made strongly alkaline by
    adding lye solution and shaking. We now have
    free base as in the pill example. It can be extracted
    out with toluene, just as with pills, and the
    hydrochloride collected by bubbling with HC1,
    just as with pills.
    Another pill extraction procedure which was
    briefly touched upon in the fourth edition of this
    book has proven quite useful when extracting
    those 200 milligram guaifenesin pills. Through
    the fifth edition of this book and partway through
    the life of the sixth ed until roughly the beginning
    of 2004, this method also was very effective in
    extracting the various brands of pseudoephedrine
    pills.
    First the pills are finely ground in a blender.
    Shaking the blender some while it is running will
    help to get large pill chunks off the bottom of the
    blender and into the blades. Next one can pour
    the powdered pills into a beaker, and desplooge
    with roughly one ml of toluene for each pill used.
    Stir it around for about half an hour, then filter.
    Spread the pill mass out to air dry. I'm not really
    Chapter Fifteen
    Methamphetamine From Ephedrine or Pseudoephedrine;
    Amphetamine From PPA
    certain if this step is absolutely necessary. Feel
    free to skip the toluene desplooge step, and see if
    it makes any difference.
    Return the dried pill mass to the beaker, and
    add about 4 grams of lye for each 100 of the 25
    mg ephedrine pills used. Stir this in. Then slowly
    add 91% isopropyl rubbing alcohol, or hardware
    store denatured alcohol or 190-proof vodka, with
    stirring, until a moderately runny paste is
    achieved. Too much alcohol could make it difficult
    to precipitate the hydrochloride crystals at the
    end of this process. Using water instead of alcohol
    can result in a regrettable mess, especially if
    too much water is used. That extraction deterrent
    formulation really kicks in with water, and a horrendous
    milkshake emulsion easily forms. Stick
    to alcohol.
    Stir this fairly light paste for about half an hour.
    The lye dissolves, and produces the free base of
    the ephedrine. We now extract out the ephedrine
    free base.
    Add 50-75 ml of Coleman camper fuel for each
    100 pills used, and stir this mixture for about half
    an hour. Then filter the mixture. Doubled up coffee
    filters or lab filter paper will be fine enough to
    catch the pill particles. A clear blue filtrate should
    result. The blue color is from the camper fuel; it
    causes no problems.
    Return the pill mass to the beaker, and add another
    50-75 ml of Coleman camper fuel for each
    100 pills used. Stir this for about half an hour,
    then filter.
    The combined clear blue filtrate is now ready
    for bubbling with dry HC1. This is done just like
    in all the other examples where we bubble dry
    HC1 to get the crystalline hydrochloride product.
    The blue color of the camper fuel doesn't color
    the crystals at all, so long as it is sucked away using
    a Buchner funnel and vacuum flask. If you
    don't have such equipment, a final rinse of the
    crystals with toluene will wash off the camper
    fuel.
    Camper fuel evaporates quickly, and doesn't
    leave a lingering smell on the crystals of ephedrine
    hydrochloride. One can expect to get close to
    100% extraction of the pills by this method, so
    121
    long as the pills were finely ground in the first
    place. Your Uncle has tried and likes this method!
    Others have also used this method, and offered
    their variations on the techniques. Suggested refinement
    number one is to replace the Coleman
    camper fuel with the naphtha, a common solvent
    which one can pick up at the hardware store.
    People have found that naphtha evaporates away
    faster than Coleman camper fuel, and that it is
    also a considerably cleaner solvent than camper
    fuel.
    Suggested refinement number two is to do
    away with the isopropyl alcohol/lye mixture for
    the free basing of the pills. Instead what they
    suggest is to take the ground up and toluenedesplooged
    pills, and wet the pill mass with a 5%
    solution of lye in water. After a bit of mixing, the
    wetted pill mass is spread out on wax paper to
    dry. Once the water has evaporated away, the free
    based pill mass is then extracted with naphtha or
    camper fuel, just as given above.
    All of these methods use a lot of solvent, and so
    produce a lot of waste solvent. The question naturally
    arises, "What do I do with my waste solvent
    after it has been used?" There is an easy answer
    to this. One should never pour waste solvent
    down the drain, or dump it into the ground, or
    otherwise dispose of it haphazardly. What one
    should do is store the used solvent in champagne
    bottles or other containers that can be sealed up.
    Then at the earliest convenient moment, pay a
    visit to the waste oil recycling drop off point.
    These can be found in most any town. Just pour
    your waste solvent into the waste oil container.
    The waste oil will be recycled as a fuel, and your
    solvent will do no harm there.
    The years 1999 through 2001 brought with
    them a series of unfortunate events for meth
    cookers. Bad news item number one was the pulling
    from the shelves of products containing
    phenylpropanolamine. This unfortunate occurrence
    was due to a number of strokes traced back
    to taking too much Dexatrim and related products.
    The resulting lawsuits and FDA restrictions
    meant the end for OTC (Over-the-Counter)
    phenylpropanolamine.
    Secrets of Methamphetamine Manufacture
    Seventh Edition
    122
    Of even greater significance for meth cookers
    has been the gradual appearance of and now market
    domination by a series of "doctored" OTC
    pseudoephedrine pills. These pills first showed up
    in Australia in late 1999. The parent company
    distributing these "gak" pills chose Australia as
    their test ground because if people keeled over
    from ingesting the mile long list of "inert ingredients"
    the publicity in the US would be much easier
    to kill. One must also consider that the price
    that a lawyer can extract for a dead Aussie is
    much less than an American lawyer could get for
    dead Americans. Add to that the fact that the
    Aussies had a nice and growing clandestine meth
    "problem" based upon pseudoephedrine pills. The
    Aussies were the perfect test market for these
    new pills.
    Once Warner Lambert demonstrated that their
    new pill formulations didn't seem to kill people,
    and also showed that the new pill formulations
    confused the hell out of clandestine chemists trying
    to extract them to use as raw material for
    meth cooking, the pills moved to the US. Then, as
    of Spring 2001, was very hard, regardless of
    brand, to find a pseudoephedrine pill which one
    could extract by the old method of grinding the
    pill, and extracting with water or alcohol. These
    "simple extractions" should now be considered to
    be completely worthless for the pills now on the
    market.
    The new pseudoephedrine pills can be recognized
    by looking at the list of inert ingredients on
    the pill package. The list of ingredients will be a
    mile long, and will include such things as povidone,
    crospovidone, lactose, carnauba wax, acacia
    gum, Xanthane gum, soaps like stearic acid or
    magnesium strearate, polymers with many names
    like Polyox or Pluronic. They may also choose to
    say "may contain one or more of the following"
    or they may just say, for ingredients, see US Patent
    6,136,864 or World Patent 00/15261. These
    patents make for great reading. I'm mentioned
    over and over. Check them out.
    The two Fester-obsessed jackasses at Warner
    Lambert Pharmaceuticals who have devoted their
    working life to me will go nameless here. What
    won't go unnoticed is the fact that they and their
    parent company are making a killing off these
    new pills, charging $15 per hundred for them.
    Generic versions also using their formula charge
    almost as much while paying royalties to them.
    They didn't bother to cut me in on the gravy train
    while getting rich off me, so it was time to send
    them back to work.
    The new pseudoephedrine pills were roughly
    modeled after the gas station ephedrine pills. This
    should come as no surprise, since the same crew
    was responsible for them It is also possible to extract
    them by a roughly similar method to that
    used with the gas station ephedrine pills. The difference
    at present is that the new pseudoephedrine
    (Sudafed) pills are much more heavily loaded
    with waxes like carnauba and gums like acacia.
    Dragging these waxes and gums into a meth production
    batch will kill the yield, and make isolating
    any product very hard. The whole idea behind
    these patents, which claim to make "illicit drug
    product impossible," is that they are formulated
    so that the "gak" which has been added gets
    brought over through the extraction process into
    the batch, thereby ruining any batch.
    A method which works on these new pseudoephedrine
    pills is to first grind them in a
    blender. It is hard to get a fine grind because they
    are so gummy. Then soak the ground-up pill mass
    in at least 3 ml of toluene for each pill used. Stir
    the mixture from time to time, and after a couple
    hours of soaking, filter off the toluene, and allow
    the pill mass to dry. Then free basing using isopropyl
    alcohol/lye or lye solution in water can be
    done just as given previously. This is fooled by
    extraction of the free base using toluene rather
    than naphtha or camper fuel. There is no need to
    use the naphtha to extract these pills since they
    don't contain guaifenesin. After a couple extractions
    with toluene, the pooled toluene extracts can
    be bubbled with dry HC1 to get nice looking
    crystals of fairly pure pseudoephedrine. With the
    present formulations on the market, this procedure
    will give a clean enough pseudoephedrine to
    Chapter Fifteen
    Methamphetamine From Ephedrine or Pseudoephednne;
    Amphetamine From PPA
    make meth. Further cleaning of the pseudoephedrine
    crystals could be done by taking the crystals,
    and for each gram of crystals, dissolving it in 10
    ml of water. Add lye with strong shaking until the
    pH of the water is 12+ to pH paper. Now extract
    the water with some toluene, and bubble the toluene
    extract with dry HC1 to get really pure pseudoephedrine.
    This procedure worked well until late 2003, although
    towards the end of that period, new pill
    ingredients were added that required the product
    pseudoephedrine to be soaked in a little cold
    methyl ethyl ketone (MEK) and then filtered to
    get a clean product. Then a new generation of gas
    station ephedrine pills appeared which were completely
    unextractable by the old method. Within
    six months, the same formulation had spread to
    the pseudoephedrine pills as well, and clandestine
    chemists everywhere were stumped as to how to
    defeat this new menace.
    I had foreseen the emergence of this threat, and
    in the sixth edition of this book suggested using
    steam distillation when they made their way to
    the market. It turned out that steam distillation
    worked OK with Ma Huang and herbal ephedrine
    pills. The result with gas station ephedrine pills
    was bad because of a combination of foam producing
    ingredients they contained. Pseudoephedrine
    pills proved to be impossible to steam distill
    successfully using standard methods.
    The culprit behind this plague for meth cooks
    was US Patent 6,359,011, again by those two
    jackasses Nichols and Bess at Warner Lambert.
    This Patent relied heavily upon polymers to mess
    up the extraction and isolation of ephedrine or
    pseudoephedrine from pills, and included polymers
    which mimic the solubility of ephedrine and
    pseudoephedrine so that chemical methods of isolation
    of the product was next to impossible. The
    polymers would be pulled into whatever product
    could be isolated from the pills, and they would
    proceed to kill any reaction used to convert the
    ephedrine or pseudophedrine into meth.
    I love a good challenge like this from "the
    man." It's always been my belief that playing offense
    is much easier than playing defense, so I
    123
    knew the Patent holders were in a losing game.
    The question was just how to crack this new and
    heavily polymer dependent formulation.
    After about a month of thinking about the subject
    in my spare time (oh, there is so little of
    that!) and a couple of weeks of experimentation
    again in that very rare spare time, I hit upon the
    Achille's Heel of all formulations dependent
    upon polymers.
    Polymers are built up of smaller subunits linked
    together into long chains. The most common
    linkage used in the pill additives is the ester link.
    When I was a kid, I used to watch Granny Clampett
    cook lye soap by the Cement Pond. She was
    cleaving ester links in fat to make soap. If Granny
    can cleave esters, so can I to get something more
    interesting than lye soap. I knew that once the
    links were broken in the polymers, they would no
    longer have the solubility characteristics which
    make them such a problem.
    There are two general methods for cleaving esters,
    be they in polymers or anywhere else. They
    are alkaline hydrolysis and acid hydrolysis.
    Granny was doing an alkaline hydrolysis of the
    ester links in fat by the Cement Pond using lye,
    which is NaOH. For the cleavage of the pill
    polymers, the more general chemical method is
    called for. That method is hydrolysis using potassium
    hydroxide (KOH) in alcohol solvent.
    To put this method into use, I revived the old
    alcohol extraction method. To hydrolyse, the alcohol
    should be the azeotropic mixture. This
    gives maximum yields, as less or more added water
    cuts the yield of the desired product. There are
    two commonly available azeotropic alcohols.
    They are 95% ethyl alcohol, exemplified by 190-
    proof vodka and hardware store denatured alcohol,
    and 91% isopropyl alcohol found in the bandage
    section of your local drug store. I chose the
    latter for my work because it doesn't have as
    great a smell as the denatured alcohol found in
    the hardware store.
    The extraction method I discovered doesn't require
    the pills to be pre-soaked in solvent to remove
    their copious supply of gums and waxes
    prior to extraction. The KOH hydrolysis removes
    Secrets of Methamphetamine Manufacture
    Seventh Edition
    124
    them as well as the new breed of polymer additives.
    Simply add the Sudafed pills to a blender,
    and grind them up. When the dust settles inside
    the blender, empty it onto a plate and then use a
    spoon to crush any pill bits and pieces which escaped
    grinding in the blender. When finished
    with that job, just put the ground up pill mass into
    a beaker or measuring cup with a pour spout.
    An example batch size of 100 Sudafed pills
    containing 30 mg each of pseudoephedrine will
    require about 250 to 300 ml of alcohol to extract
    completely. Measure out about 100 ml of alcohol
    and add it to the pill mass, then stir. An orange
    red solution will start to form immediately as the
    pills extract. Swirl or stir around this mixture
    from time to time for about an hour, then it is
    time to collect the first extract.
    Generic Sudafed pills obtained from Walgreen's
    are very closely formulated according to
    the previously mentioned Patent. Obtaining the
    first extract from them is very simple. Just pour
    the mix through a coffee filter and collect the filtrate.
    Brand name Sudafed pills and Wal-Mart
    store brand pills are of a bit more advanced formulation
    which plugs filters. For them, just let the
    pill sludge in the beaker settle for about an hour,
    then pour off the alcohol solution from the pill
    sludge. Try to keep as much of the pill mass in
    the original container as possible.
    If filtering was done, then return the filtered pill
    mass to the original beaker or cup. Then add another
    roughly 100 ml portion of alcohol to the pill
    mass for another extraction. If pouring off of the
    first soak was done, then just add another 100 ml
    portion of alcohol to the pill mass. Let the next
    pill soak proceed for an hour or so like the first
    one with some swirling or stirring. Then filter or
    decant off the second alcohol soak just like the
    first one.
    Finally, do a third alcohol soak of the pill mass
    with another roughly 100 ml of alcohol just as before.
    By now, the alcohol extracts are becoming
    pale in color, indicating that the pills are nearing
    complete extraction. Filter or decant this soak just
    like the previous ones.
    If the pills being used allowed one to filter,
    then the next step can be done immediately. That
    step is hydrolysis with KOH. If filtering was
    skipped due to filter plugging pills, then let the
    extracts settle overnight to shed floating crap. I
    am told that putting some sand into the filter one
    is using defeats the filter plugging qualities of
    these new pills, so do give this a try. It is far more
    preferable to filter the pill extracts, as this allows
    more complete extraction.
    Now for the big part of the show, the KOH hydrolysis.
    The combined alcohol extracts are now
    poured into a Pyrex beaker. A Mr. Coffee pot will
    do fine if you don't have a beaker. Put it on a
    stove top at medium heat, and then add 10 grams
    of KOH pellets for each 100 of the 30 mg Sudafed
    pills extracted. If one has picked up the new
    60 mg Sudafed pills, then one would use 20
    grams of KOH per one hundred pills, and of
    course, the amount of alcohol required to extract
    them would be double as well. Do avoid the new
    120 mg Sudafed time release pills, as they are of
    a gooey formulation you don't want to mess with.
    The goo is their time release mechanism, and is
    unlikely to spread to the lower dose pills.
    The question which is likely to pop into one's
    head at this point is "Where do I get KOH?" This
    close chemical cousin of lye, NaOH, is pretty
    easy and safe to get from those mail order chemical
    outlets that advertise in the classifieds sections
    of some magazines. Keep the order to KOH, and
    there will be little chance of bad things happening
    as a result. An alternative source can be found at
    everybody's favorite department store which is
    open 24/7. Head to the plumbing section, and you
    will find a product which is roughly 50% KOH
    and 50% NaOH. This can be used in a pinch, just
    by upping the amount used to about 15 grams per
    hundred pills. One can also do some Internet
    shopping. Search under "soap making." KOH is
    used to make soft soap. One can also search under
    "hide tanning." KOH is used in that craft as
    well. Avoid solutions of KOH in water, as the alcohol
    already has the best amount of water for the
    reaction in it. If you can only get a KOH solution
    Chapter Fifteen
    Methamphetamine From Ephedrine or Pseudoephedrine;
    Amphetamine From PPA
    in water, boil it down. In no case just use NaOH,
    as it doesn't work. Also avoid getting hardware
    store drain openers which contain KOH plus
    bleach. The bleach will simply destroy the pseudoephedrine
    or ephedrine in the extract and leave
    you with nothing. KOH pellets can also be found
    at pool supply stores as pH Up (caustic potash).
    As the KOH pellets dissolve into the alcohol
    extracts, they begin to chew up the polymers,
    gum and waxes in the pills. This only happens
    when the alcohol solution is at or near boiling, so
    a gentle boiling of the alcohol is needed. Adjust
    the heat setting on the stove top accordingly.
    Within a few minutes of boiling with the KOH,
    you will note that the original red orange color of
    the alcohol extract is fading rapidly, and that an
    oily layer is forming at the bottom of the beaker,
    or Mr. Coffee pot, whichever you are using. Continue
    to gently boil for half an hour, then set aside
    to cool. With the variety of pills exemplified by
    the Walgreen's store brand which closely follows
    the Patent formulation, you will have a coffee
    colored oil layer at the bottom of the beaker, and
    a weakly colored alcohol solution containing the
    pseudoephedrine you want floating above it. Just
    pour this mix into a sep funnel and let the oil settle
    to the bottom and drain it off to get rid of the
    crap you just destroyed. We can now move on to
    the evaporation and getting product portion of the
    process.
    With the brand name Sudafed pills and the
    Wal-Mart store brand pills, the ones which
    plugged up the filters, the KOH boil takes a bit of
    a different course. With these pills, as the KOH
    dissolves in and the alcohol gets boiling, the red
    orange color fades, and the solution turns milky.
    Don't be alarmed by this, as the milky appearance
    is caused by little white flakes of crap which you
    have destroyed. Boil in this case for half an hour
    just as with the previous example. The only difference
    is after it is done boiling. In this instance,
    let the solution cool and settle overnight, or at
    least for several hours. The white flakes will settle
    out leaving a clear alcohol solution containing
    the pseudoephedrine, and a mat of gooey white
    flakes overlaying a layer of gak oil on the bottom
    125
    of the beaker. When fresh, this oil will most times
    be yellow colored, but in a few hours it too will
    turn coffee colored. The white flake mat is gooey,
    and given a few hours it sticks to itself. Then in
    this case, one can just pour off the alcohol solution
    from the white flake mat and oil layer to get
    a clean alcohol extract.
    Now to get the product! Pour the cleaned alcohol
    extract into a clean beaker, or a Teflon-coated
    pan. Then simmer down the alcohol extract.
    There are two points here to be wary of. Point
    number one is that alcohol is flammable, and
    mildly toxic. Be sure to use a good draft of air to
    clear the vapors away from the boiling spot. Alcohol
    isn't nearly as flammable as naphtha or
    other solvents, but fire precautions need to be observed.
    Point number two concerns the last phases of
    the evaporation. It is VERY important that one
    not boil down the solution to dryness. This will
    result in a yellow colored product that is crap. As
    the solution gets to nearly all evaporated down,
    switch to boiling water heat, or just letting it
    evaporate with some aid of heat and blowing off
    the alcohol vapors. It is far better to let a bit of alcohol
    remain than burn the product!
    Now the remaining product in the bottom of the
    flask will consist of left over KOH, pseudoephedine
    free base, and assorted crap. Start by adding
    about 50 ml of water for the 100 pill batch example
    to the beaker. Swirl it around, and let it work
    for a few minutes. Then pour it into a sep funnel.
    Homemade substitutes for sep funnels are easily
    constructed. Check out Jack B. Nimbles' book for
    starters to get some ideas. Then add 50 ml of
    toluene or xylene to the beaker to dissolve your
    product. Swirl and let it work for a few minutes,
    then pour that too into the sep funnel. Chase the
    residue in the beaker with a little bit (about 15
    ml) more toluene (that means add a bit more!)
    and pour it too into the sep funnel.
    Now we are on our way home. Shake that sep
    funnel for about half a minute, and let it set to settle
    the layers, hi the case of the close Patent formulation
    pills, the water layer will look like
    Pepto-Bismol. Using the pills which give a milky
    Secrets of Methamphetamine Manufacture
    Seventh Edition
    126
    look upon boiling, this color will not be seen in
    the water layer. Drain off the water layer, and add
    about 50 ml of water for this 100 pill example.
    Shake the toluene or xylene layer again with this
    fresh water. Now let things settle in the sep funnel.
    You should have a clear toluene solution
    floating above a reasonably clear water layer.
    Drain off the water. Now check the toluene
    layer. It should be just clear solution. If there is
    floating crap in it, pour it through a coffee filter.
    This will give you a clear toluene or xylene solution
    containing the pseudoephedrine free base.
    Let it set in this beaker for a couple of hours to
    settle any water you dragged in. Then pour it into
    a clean beaker, and bubble the solution with dry
    HC1 gas. You will get roughly 70% yield of the
    possible pseudoephedrine available from the pills
    after you filter out the pseudephedrine hydrochloride,
    and rinse the product with fresh toluene or
    xylene. This is the same HC1 bubbling procedure
    which has been used throughout this book, and
    for the last 20 years. Become familiar with it!
    Gas station ephedrine pills extract and behave
    in a very similar fashion to the pseudoephedrine
    pills, except that they don't give the color change
    while they are boiling in the alcohol and KOH.
    They aren't colored in the first place, so that is to
    be expected. The same procedure can be used on
    them to get similar yields of good product. The
    complication with them is that they contain
    guaifenesin. To remove most of the guaifenesin
    from the pills, they should first be ground up in a
    blender, then add 2 or 3 ml of toluene or xylene
    for each pill used to the ground up pill mass and
    with stirring let it soak out the guaifenesin for a
    few hours. Next filter the pill mass to remove
    most of the toluene, then spread the pill mass out
    to dry on a plate. Once dry, the extraction with
    91% isopropyl alcohol followed by boiling with
    KOH is done just like in the procedure for Sudafed
    pills, hi this instance, naphtha should be used
    as the solvent to extract the residue from the
    beaker, and to bubble HC1 gas with. This solvent
    is used instead of toluene or xylene because it
    doesn't dissolve the guaifenesin still left in the
    pill extract.
    I know what you are going to say at this point:
    "That seems like a complicated procedure." Actually,
    it's really simple. It's just that I put in all
    the possible details for you. It's just an extension
    of a method which was used to extract the pills
    from the mid 90's. One could even add the old
    method of blowing into the bottom of the beaker
    to get rid of the last of the alcohol to reveal big
    crystals of pseudoephedrine. Now add to that
    KOH boil, and destroyed crap removal, and you
    have the exact same method which was used
    roughly 10 years ago with the pills that I prescribed
    a solvent pre-soak and water extraction
    for. Extraction methods do turn a circle. If this
    method seems complicated to you, check out my
    website www.unclefesterbooks.com. The Cookin'
    Crank with Uncle Fester video will make it all
    just as plain as it really is.
    The next reasonable question is.. "I just can't
    get KOH!" I worked out a method just for people
    like you, but the yield is closer to 50% rather than
    the 70% gotten from my original method. Dig
    harder for KOH, but here it is:
    The pill extraction is done exactly like before,
    except when it is time to boil the pills add instead
    20 grams of KC1. This is salt substitute found at
    your grocery store. Read the label, and get the
    brand that just says KC1 with a couple of other
    minor ingredients. Then as the pot is warming up
    to a boil, slowly, with stirring add 10 grams of
    NaOH (lye) per one hundred pills used. The best
    stirring tool is a rubber spatula, and stir well because
    the alcohol can only dissolve around one
    gram per 250 ml alcohol, and you want that bit of
    KC1 to react to make KOH plus NaCl. This is
    making KOH on the sly. The addition of NaOH
    should take about 20 minutes, with lots of stirring.
    A big snow fest of NaCl crystals in the solution
    will be seen during this process.
    About the time that the last of the NaOH has
    gone into solution, it's time to boil this mix. During
    the course of a half hour boil, the initial red
    orange color of the alcohol will fade to a shade
    Chapter Fifteen
    Methamphetamine From Ephednne or Pseudoephedrine;
    Amphetamine From PPA
    which is best described as melon. Then set aside
    the beaker, and allow the mixture to cool and settle.
    The next thing to do is to pour the alcohol solution
    off of the settled layer of salt on the bottom
    of the beaker. Using a coffee filter makes this
    separation much more efficient. Then the alcohol
    solution is carefully boiled down, just as in the
    previous example. When it gets close to being
    evaporated down to the bottom of the beaker, its
    best to let the evaporation finish by itself at room
    temperature, or with mild heating.
    Now add about 50 ml of water to dissolve the
    salt, KOH and NaOH in the bottom of the beaker.
    Let it work for about 10 minutes, and pour the
    water solution into a sep funnel. Then put about
    50 ml of toluene or xylene into the beaker to dissolve
    the residues of pseudoephedrine in the bottom
    of the beaker. Let that soak work for about
    10 minutes, then add this also to the sep funnel.
    Finally, chase the last bits of product out of the
    beaker with a rinse using about 10 or 15 ml of
    toluene or xylene. Pour this into the sep funnel as
    well.
    The sep funnel is then shaken hard for about 20
    seconds, and set aside to settle. What is left of the
    orange color will go into the water layer at the
    bottom of the sep funnel. A lot of floating crap
    will be seen, as well as a fairly clear toluene layer
    at the top.
    Now drain off the water layer. You will note
    that the floating crap is in both the water layer
    and the toluene layer. You don't want to be draining
    off and throwing away the toluene, because
    that is where your product is. It's better to be
    leaving some of the water rinse in the sep funnel
    at this stage than throwing away your toluene
    product layer.
    When the water layer has been drained away,
    add 50 ml of clean water to the sep funnel, and
    shake again. When the mix inside the sep funnel
    settles in a few minutes, you will see a nicely
    clear toluene layer at the top mixed with floating
    flakes of crap, and a lightly colored water layer at
    the bottom mixed with floating flakes of crap.
    Drain off the water layer, and pour the toluene
    127
    layer through a coffee filter to remove the floating
    crap.
    Rinse out the sep funnel with water to remove
    clinging flakes of crap from the glassware, then
    pour the filtered toluene back into the sep funnel
    and drain off any water which carried through the
    filtration. Then pour the toluene layer into a clean
    beaker and let it set for an hour or so to shed any
    water still entrained in the toluene. Finally, pour
    the toluene into a clean beaker and bubble dry
    HC1 gas through it to get crystals of pseudoephedrine
    hydrochloride. Filter them out with a
    coffee filter, rinse them with a fresh portion of
    toluene, and spread them out on a plate to dry.
    The yield in this case will be around 50% of the
    maximum possible. In the case of 100 of the 30
    mg pseudoephedrine pills, that will be around a
    gram and a half of product.
    This variation isn't as good as the one using
    only KOH pellets, but it does avoid any problems
    associated with getting them as it uses instead
    KC1 salt substitute and lye. I tried one more variation
    on this procedure. That variation was to use
    water to extract the pills, and then to the filtered
    water extract I added 3-5% by weight of sulfuric
    acid and boiled for about 45 minutes. I obtained
    the product by making the solution basic by adding
    lye to the solution when it was cool, and then
    extracted the product with toluene, washed it a
    couple of times with water, filtered the toluene
    extract, and then bubbled dry HC1 gas through it.
    In that instance I got less than 50% yield of a
    product which was still dirty and would need to
    be recrystallized to be used successfully in making
    meth.
    The alcohol extraction followed by boiling
    KOH treatment procedure should once and for all
    put the pill formulators out of the polymer additive
    game. It has been my greatest pleasure to
    wreck their Patents, and fill their work lives with
    consternation and dread. As they lay in bed trying
    to sleep while muttering my name, I have only
    one suggestion for them. If you had cut me in on
    the gravy train from those Patents, I might have
    been persuaded to keep quiet about this.
    Secrets of Methamphetamine Manufacture
    Seventh Edition
    128
    The pill formulators have one more card to
    play, and we may see it sometime soon. That card
    is to replace the natural "d" isomer of pseudoephedrine
    with the synthetic "1" isomer. Reduction
    of this "1" isomer would then give only the
    very weak "1" isomer of meth. A Patent has already
    been published claiming that the "1" isomer
    of pseudoephedrine works just as well as the real
    McCoy for cold relief. If this new product should
    come to replace the pseudoephedrine presently on
    sale, the following procedures will prove very
    helpful. One can racemize "1" pseudoephedrine to
    "d,l" pseudoephedrine. Reduction of this product
    would then give "d,l" meth, which is a very nice
    buzz indeed. In fact it is much better than the
    strictly "d" isomer meth one generally gets from
    ephedrine or pseudoephedrine as the starting material.
     
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