Amphetamines And M Eth Am Ph Etam Ines From Phenylacetones
With all of that MD-P2P and/or P2P lying around, there's a good possibility that an evil underground chemist might turn it into final product. Dear God! The thought of it just sickens Strike! But what can ya do? And what againx were those final products? Why it's these suckers right below:
So without further ado, here's the recipes you've been looking for!
METHOD #1: Strike's extra special, blue ribbon favorite. Guaranteed to put the starch in your socks! This is the cleanest, highest yielding procedure for making MDA from MD-P2P that Strike has ever known. It is absolutely impossible to fuck up.
The catalyst needed is called sodium cyanoborohydride (NaBH3CN). It is not very common but there are few 'places' that still sell it. It is very prone to take up water out of the air so the chemist makes sure that she doesn't leave it sitting out all night. The method is simplicity itself.
Into a large flask or glass tea jug is dumped 200g MD-P2P (or 150g P2P) oil, 920g ammonium acetate, 2000ml methanol (MeOH) and then 73g of powdery sodium cyanoborohydride (NaBH3CN). Rapid stirring is started, and some nitrogen from a baby nitrogen tank is blown into the airspace of the flask to dispel the air and the flask is immediately covered with foil. The clear, light yellow solution stirs at room temperature for 24hrs.
That's it! The MDA has now been made. The solution is completely clear with not one iota of tar produced, and all of this achieved at room temperature with no pressure needed. Strike told you this was good. The solution is now cleaned up a little and the MDA isolated.
The methanol is vacuum distilled from the flask (this occurs between the temperature of 50-60°C), then allowed to cool. Sometimes upon cooling the concentrated mixture will polymerize into a big, white gummy mass. This will go away in the next step. To the concentrate is added 2000mL 3N HCI solution which will dis-
solve any polymerized mass (No, Strike still ain't gonna tell you how to calculate '3N'. You really need to learn to calculate Normality & Molarity. Sigh! But in this case 3N = 3M which is approximately a 10% HCI solution). The entire solution can, if desired, be poured into a PP container. Here is where the chemist comes to a slight variation in what is normally considered washing and extracting. The MDA is , at this point, an acid loving species and is actually going to stay in all that HCI solution even if that solution is mixed with an organic solvent. This gives the chemist an excellent chance to recover all of the valuable, unre-acted MD-P2P which is not acid loving and will go into the solvent. So the chemist extracts the HCI/MDA solution with a few hundred ml_s of DCM (a.k.a. methylene chloride, or dichloromethane) and saves the DCM to recover the MD-P2P for later use. Technically, the concentrate is supposed to be dissolved in DCM and then 'extracted ' three times with about 500ml_ of 3N HCI each. Strike's way works just as well.
After the DCM is separated from the HCI/MDA, it's time to release the MDA from the water. To do this the chemist has to make some saturated sodium hydroxide solution. A saturated solution is made by dissolving as much sodium hydroxide as possible in an amount of water (say, 500mL). This NaOH solution should be chilled in the freezer. So, the chemist is going to place her MDA/HCI solution in a PP container and chill it in an ice bath tray with stirring. Next she starts adding the cold NaOH solution in small increments so that bubbling wont get out of hand. The solution will start to get warm and slowly turn basic. At around pH 9 beautiful, clear-amber beads of MDA freebase oil will appear all about the solution (most of it settling at the bottom) and the chemist adds a little more base to insure an excess so that all MDA will separate out. This is one of the more pleasant events of drug chemistry.
Now the chemist need only extract the MDA oil from the water with some DCM. Yes, this time the MDA will go into the DCM. The chemist merely pours about 400mLs of DCM into the container and stirs it really well for a few minutes while she watches TV. As much of the water as possible is poured off or separated
in a separatory funnel and then the DCM layer is dried through 100g of sodium sulfate ( see methodology chapter). The DCM is then removed by simple or vacuum distillation to afford a clear, light-amber MDA freebase. This oil is so clean as is that it can be crystallized without distillation. If one wanted to, they could distill it to get rid of the color impurities, but there is so little contamination and, besides, what little there is will separate out in the process of crystallizing the product for consumer usage (see Crystallization chapter).
The yield here is 80-90%. No, that is not bullshit! This method has not been given the proper credit it deserves and sometimes has been dismissed without due process. Does Strike sound defensive? You bet! Strike has been in the science game for a long time and knows that bitterness, doubt and contempt abound. But that's ok, because those who do not use this method simply get hammered by those who do!
For those chemists that prefer MDMA or meth, this method can work for them too , Everything about the catalytic reduction remains the same except that instead of using ammonium acetate as the amine source, one is going to use 1000g methylamine hydrochloride (see the Chemicals section on how to make). The screwier thing about this procedure is that someone is going to have to babysit that stupid flask for 24-36 hours checking the pH every now and then. The reaction has to remain neutral (pH 6-8, bubba!) the entire time, but that ain't going to happen because the dissociation products from the methylamine are going to start to turn things basic. So someone has to keep it neutral by checking the pH with pH paper and adding a couple of drops of straight-from-the-bottle concentrated HCI. Aside of the two changes, the reaction, cleanup and yield remain exactly the same.
METHOD #2: By far the most popular method currently available. This is a really convenient way to convert P2P or MD-P2P into meth and MDMA ('ecstacy'). It is a very clean procedure, akin to that of the NaBH3CN method, using amalgamated aluminum catalyst made from ordinary household foil [26, 28]. When Strike was reading all the underground literature on the use of household
aluminum foil to reduce ketones, Strike thought that it was probably a bunch of baloney because this procedure was always dumped in the backwash of conversion examples so it didn't look as if it merited much consideration. In fact, this procedure works very well and is super easy but the yield is a little low (50-60%). But since the catalyst is plain old aluminum this procedure will prove to be the perfect 'foil' (ha ha!) for those who can't get their hands on other high-powered catalysts. Strike did say that this method will produce methamphetamines, but the trade-off for those spoiled babies that just have to have this kind of drug is that they are going to have to use a watched chemical: the dreaded methylamine. It's pretty groovy that this book has gone this far without having to rely on any controlled substances except for precursors. As one of the most watched chemicals of all, methylamine is going to have to be made. In the chemicals section of this book is an easy method for making the form of methylamine that is required for this method which is methylamine hydrochloride (CH3NH2.HCI).
Here's how the chemist proceeds. Next to the cheetos, the pathetically unemptied ashtray full of cigarette and joint butts, the rave fliers and the decomposing cat carcass the budding chemist may find her roll of aluminum foil. 50g of the foil is cut up into 1 in x 1 in squares and chunked into a big flask or glass sun tea jug. Older methods suggest that those pieces of aluminum foil be washed with some dilute aqueous NaOH, drained, then washed three more times with fresh dH20. This is meant to 'clean' the surface of the aluminum before it is amalgamated. This really isn't necessary but can be done if desired.
Either way, the happy little foil pieces end up lying at the bottom of the flask ready to be turned into a catalyst. To do this the chemist
pours a solution of 1.3g mercuric chloride (HgCI2) dissolved in 1700mL dH20 and stirring is started. The Hg starts to immediately react with the aluminum. Effervescent bubbling will be fierce and the solution will start to get really hot. This is allowed to continue for 15-30 minutes during which time the stirring solution will get cloudy grey with metal particles from the degradation of the aluminum.
There are a couple of notes to consider here. Just about all of that powdered dust is amalgamated catalyst, which is great except that almost all of it will be lost in the next cleanup step. One can make up for the loss of catalyst by increasing the aluminum batch size, but care is necessary in doing this. There is a danger point in making too big a batch of AIHg. Beyond the size of a 150g of Al, the reaction may overwhelm the water it is in and a boiling, volcanic steam cloud may erupt. It can get freaky! Also, the amount of HgCI2 should not be increased beyond the ratio given here because it will pulverize all the aluminum very quickly leaving nothing but dust.
After 15-30 minutes the water is decanted from the catalyst leaving just enough to cover the metal chunks. If the catalyst is exposed to air it quickly degrades. The aluminum is then washed 4 times with fresh dH20 decanting each washing so that a little water remains to cover. In the clean water the catalyst looks to be frosted with grey dust and is now ready for the big reaction. After the last decanting the chemist, in rapid fire succession, dumps the following ingredients into the flask holding the catalyst in the exact order as follows:
(1) 76g methylamine-HCI in 76mL dH20
(2) 230mL isopropyl alcohol
(3) 183 mL 25% aqueous NaOH solution
(4) 67g MD-P2P or 50g P2P
(5) 440mL isopropyl alcohol
The flask is placed in a plastic tray because an ice bath may be necessary and stirring is again started. Ice is added as necessary so that the temperature stays below 50°C and the solution stirs this way for 3 hours. Usually, the temperature never seems to rise over 30°C no matter what one does. Some folks say that heat is necessary. Strike does not think it is. The solution looks very heterogenous. By this Strike means that all sorts of junk is swirling around in the flask. Amber beads of P2P go flying by as do chunks of foil, grey dust, and frosted beads of oil.
After 3 hours the stirring is stopped and the solution allowed to settle. By this time just about all the foil will have turned to dust, which is going to make the next step of vacuum filtration very difficult because it will plug up the filter paper in a second. So the chemist lets it settle, then pours off the liquid through the vacuum filtration setup (see methodology section). The flask is rinsed with 100mL methanol, the methanol poured through the grey filter cake and the filter cake discarded. All of the filtrate is placed in a flask and vacuum distilled to remove all the methanol, isopropyl alcohol and water which will leave the chemist with oil and junk in the bottom of the flask.
The cleanup of this oil is exactly like that which was done in Method #1. The oil is dissolved in about SOOmL of 3N HCI and the solution extracted with TOOmL of DCM. The chemist remembers that in this particular case the MDMA or meth is going to stay in the HCl/water but that unreacted, valuable MD-P2P or P2P is going to be in that DCM so it, of course, is saved. The HCI/MDMA solution is then basified with concentrated NaOH so that at around pH 9 the happy little beads of final, freebase product will appear in the solution. As usual, the oil is extracted with DCM, dried through Na2S04 and the DCM removed by distillation. The final product here is usually a little darker in color than the product achieved in Method #1, but it is still remarkably clean and may be crystallized as is with the crystallization process removing most of the color impurities. Of course the chemist may wish to vacuum distill to afford clear product. The average yield with this method is 60-70%.
METHOD #3: This is a simple one pot version of Method #3 except that ammonia is used instead of the watched methylam-ine.HCI so one can make MDA instead of MDMA . This is
pretty low yielding and can get messy. It is strongly suggested that one consider doing #2 above before trying this method. 54g (0.3M) MD-P2P or 40g P2P, 200mL ethanol, 200mL 25% aqueous ammonia solution (ammonium hydroxide), 40g aluminum grit (a.k.a. powdered aluminum or finely minced aluminum foil) and 0.3g HgCI2 are stirred together. The mixture will heat itself up pretty good so an ice bath can be applied to insure that the reaction doesn't get too violent. When the reaction has simmered down, the solution is refluxed for 2 hours; then the solution is vacuum distilled to remove all the ammonia and methanol. What's left is water, MDA and particulates. This solution is basified with 120g KOH or NaOH to release the freebase oil which is then extracted with ether. This ether is then itself extracted with 3N HCI, the ether discarded and the freebase liberated from the HCI by basi-fying again with NaOH to give clean freebase with a yield of approximately 30%.
METHOD #4: This here method was contributed by a scholar named Ritter. She is adamant about this method and considers it a major breakthrough. Ritter wants to do what was done in Method #2 except without the insidious methylamine.
"Who Needs Methylamine Anyway? by: Ritter, edited by The Professor
Dedicated to Eleusis
The following procedure may prove to be one of the largest advances in the field of MDMA chemistry since the perfection and dissemination of the Wacker oxidation procedure for producing MDP2P. This reaction is based on a published process that somehow has escaped discovery by underground chemistry until -104-
now. Methylamine is no longer a stumbling block in the aluminum amalgam reductive alkylation method of producing MDMA as this procedure produces this impossible to obtain and fickle to make material, in situ, during the reductive alkylation of MDP2P to MDMA from very common nitromethane. Nitromethane when subjected to the simplest of reductions forms methylamine, so why not make methylamine at the same time MDMA is being produced instead of going through the hassle of making it separately?
Nitromethane is a very common material. Just go down to your local drag strip and pick up a gallon or two for doping your high performance cars fuel. It's also available up to 40% pure in RC model fuels. Simply fractionally distill the nitromethane (bp 101°C) out of the model fuel mixture and you're ready to go. If methanol is present in the fuel formulation, some will azeotropically distill over with the nitromethane lowering its boiling point slightly, but this does not present a problem.
So, how does this whole thing work? It's as simple as it sounds. An alcoholic solution of nitromethane and MDP2P is dripped into a mass of amalgamated aluminum immersed in alcohol first reducing the nitromethane to methylamine, allowing the Schiff base of the amine and ketone to form which is then further reduced to the desired MDMA.
Set up a 2 liter two or three-neck flask with an addition funnel and a reflux condenser and provide with a heat source. Not much heat is needed here so anything from a water bath on a buffet range to a heating mantle is fine. Stuff 55 grams of one-inch squares of aluminum foil into the flask. An important topic must be addressed here which has been formerly neglected to a confusing degree -the proper type and thickness of foil. The problem with aluminum amalgam reductions is that their reaction rate is dependent on three major factors, and depending how you play these factors you may either have a complete failure or an explosion, or better yet if you follow this advice a perfect yield! These factors are the mentioned foil type, the degree of amalgamation allowed by HgCI2
solution before ketone and amine are reacted, and finally, the temp the reaction runs at. Thick foil tends to react slowly at a low temp and very thin foil, such as generic food grade aluminum foil, tends to react so fast and exothermically you can literally shit your pants! The aluminum, which produced the best results, is widely available to the industrial biological community in the form of 4" x 4" sheets ,04mm thick neatly separated from each other with a sheet of tissue paper. It is used for sealing flasks and the like before they are autoclaved. For those of you who can't get this, don't worry. Heavy Duty Reynolds Wrap will work fine, only a more careful eye must be kept on the reaction rate. Others have reported success using cut up pie tins. The main idea is don't use real thin foil.
Fill the seperatory funnel with 50 grams of MDP2P and 50grams or 39ml nitromethane dissolved in 200ml methanol. In another 1 liter vessel add 1.5g HgCI2 (mercuric chlohde) to a liter of methanol and allow all solids to dissolve. Very carefully (HgCI2 is deadly poisonous!) pour the methanolic solution of HgCI2 onto the aluminum foil pieces in the flask and stand back and watch the magic begin. If ail of the foil isn't covered by the methanol just add more until it is. In a few minutes effervescence will begin and the reaction may be started. After about 5-10 minutes the bubbling should be sufficient and you may start adding the methanolic mixture of nitromethane and MDP2P drop by drop from the seperatory funnel. As time progresses the reaction may heat up to the point of boiling and refluxing of the alcohol will occur. This is no problem as the 65°C boiling point of methanol is perfect for this reaction (I know many disagree, but dream about this and you'll see!) The addition should take roughly one hour and the mixture should be allowed to react for at least 4-6 hours after or until all pieces of aluminum are reacted into a gray suspension. Temperature control needs to be addressed here. If the reaction proceeds under ideal conditions, it will run exactly as described above. In less than ideal and more commonly, the reaction will start to slow down halfway through requiring external heating to maintain a good reaction rate. If the Greater Powers really are against you, an addition of another gram of HgCI2 in methanol solution added to the mix will kick it back in.
Now the easy part -isolating your product. One of the most attractive features of this new synthesis is that the standard AI/(Hg) amination mixture must be tediously filtered to separate the product from the spent aluminum hydroxide sludge at this point. The following remedies this most frustrating step and will probably give many a new outlook on the potential of the AI(Hg) reduction.
Mix up about 1.5 or 2 liters of 35% NaOH solution and allow to cool. Slowly add the gray aluminum gook produced in the first reaction to the NaOH solution and pour into a large seperatory funnel. Two distinct layers will appear after sitting for maybe an hour, the top being a reddish alcoholic solution of product and the bottom garbage NaOH/AI(OH)3. Simply separate off the garbage bottom layer and discard. Don't worry, there's no product tied up in it, and remember that no filtration is needed anywhere in this recovery process compared to other synths out there! Take the top layer and evaporate off the methanol to give an amazing yield of impure amine and a little bit of water. Unscrupulous souls not worth their weight in shit can take this product and crystallize it directly but there is a lurking deadly poison in it at this point— sol-vated mercury salts! These can be easily removed by dissolving the crude product in about a liter of toluene and washing it with several portions of water in aseperatory funnel and finally with a saturated NaCI solution. Dry the toluene with about 50g anhydrous MgS04 made by heating drug store epsom salts in the oven at 400'F for an hour, cooling then powdering. After sitting for an hour or until the toluene is no longer cloudy, chill the dried toluene solution of freebase in the freezer and bubble away with HCI gas to produce beautifully pure MDMA hydrochloride crystals. If they are a little discolored they can be easily cleaned up with an acetone rinse to pristine purity WITH NO MERCURY CONTAMINATION!
METHOD #5: This method is extremely easy to do but can be messy. One needs to read everything Strike says in this section to get things straight, though. This method is called the Leuckart reaction and it converts P2Ps into amphetamines or methamphet-amines as shown below. This method is very simple to do but has been grossly misreported, especially where its applicability to X production is concerned. The method that's been floating around the longest for X is the one found in Chemical Abstracts , This method works but it is very messy and the yields suck (about 20%). Strike is going to detail how this method works, but a few paragraphs away Strike is going to lay down lots of ways that this method can be better for both X and speed production.
23g of MD-P2P or 17g of P2P that was made by any method and 65g formamide (HCONH2) is poured int a small Pyrex flask (sorry, glass is a no-no here). If one wanted to make meth or MDMA then one would use 60g of a chemical called N-methylformamide instead of formamide. However, this chemical is extremely watched because of its use in this recipe so it is not something Strike would expect an underground chemist would use.
This flask is placed [Figure 11]
in an oil bath which
is merely an aluminum sauce pan with enough corn oil in it to equal the height of the liquid in the flask. A thermometer is placed in the flask and another one placed in the oil so that the whole setup looks like figure 11.
Stirring is started and heat is applied so that the oil and reaction mix achieve a temperature of about 120°C in about an hours time. It is at this point that C02 bubbles will begin to emerge signaling that the reaction has begun. Some amount of ammonia will start to be given off at this point so the apparatus, if not already in a hood, should be placed in one. It is from this point that the solution will start to turn from its clear yellow color to that of a more orangy hue. The temperature of the solution is allowed to slowly climb until it reaches the blistering temperature of 190°C. It is held at this temperature for 5 hours then allowed to cool. What the chemist will have at this point is a thick, gooey mass of black tar that has probably gotten so thick from polymerization and evaporation that even the magnetic stirbar has been halted.
When cool, 100mL ether is added to the flask to dissolve all the tar and then the black tar/ether is poured into a separatory funnel. The ether is washed once with 100mL dH20, the upper ether layer separated away and the water extracted once with 100mL fresh ether. The two batches of ether are combined and the solvent removed by simple distillation leaving the chemist with a black mass of oil in the bottom of the flask. Next, the chemist pours 8mL of methanol into the flask, swirls to mix the tar with the MeOH then adds 75mL of 15% HCI. This solution is refluxed for three hours during which time the whole solution becomes black. The chemist is using HCI to hydrolyze the formyl intermediate. The solution is allowed to cool then is basified with concentrated NaOH solution until pH 9 is reached. The chemist won't really need to check the pH with litmus paper because, as usual, dark drops of MDA oil will appear all about the surface of the solution as a pleasant indication. All that is left is for the chemist to extract the MDA with ether or DCM and distill away the solvent. However, separating the solvent layer from the water layer is a bit tricky in this case because the two layers are so equally black that it may require a lot of squinting and a flashlight to spot the inter-
face between the two. Needless to say, the oil obtained is way to filthy to use and must be vacuum distilled to afford clean yellow MDA freebase. The distilled freebase is really pure, but to Strike, the effort to get this sorry yield is not worth it, especially if this is tried in large batch amounts. By large Strike means an attempt at conversion of at least 200g MD-P2P or P2P.
If ever there was a reaction that was batch size independent then it has to be this one. A chemist can try to process 200, 500 or even 1000g of P2P using this version of Leuckart and never recover more than 100g no matter how careful she is. This procedure is more in line with those who wish to make steady reasonable supplies of X and should not be used to process more than 100g of P2P at a time. In fact, it shouldn't be used to make any drugs at all. You see that would be illegal.
Strike's mission with this book is to provide as many methods for a conversion as possible. Slight corrections to a recipe can make a great difference; and to become a truly great chemist one should be aware of both the good ways and the bad ways and what it was that made one recipe a poor one and another a good one. Then, when a chemist comes across other or future experiments, she can make a more educated assessment as to its worthiness. This whole Leuckart business is a good example. The Chemical Abstracts article has been around so long and its merits so few when there have been so many blatantly better recipes staring illegal chemists in the face. Not until very recently has some correction been made in some of the underground literature. Folks interested in speed manufacture should read this closely. It all relates in every way to the betterment of methamphetamine synthesis.
If one is using formamide or N-methylformamide then one is not going to have the advantage of creating formic acid as a breakdown product, so the idea is to have formic acid already in the reaction mix. To do this one takes the 65g of formamide and mixes it with 30g of 88% formic acid, places this flask in the oil bath and attaches a simple distillation set up to it as shown in figure 12. Since the formic acid has some water in it the chemist is going to remove that water by heating the oil bath to 160-170°C and allowing the water to distill over with no vacuum. When no more water distills over the chemist allows the reaction flask to cool, adds the 23g of MD-P2P, reattaches that distillation setup and allows the mix to slowly rise in temperature to 160-170°C. The reaction stays at this temperature for 5 hours, any longer makes little difference. Also, if the temperature rises above 170°C then destruction, not production, will occur. The distillation setup is there to condense any product that happens to exit the reaction flask. This distillate is returned to reaction while things are still hot. Using formic acid effectively doubles the yield.
The Leuckart reaction was originally conceived using a chemical called ammonium formate (HCOONH4) which is very similar to formamide (HCONH2) . It is pretty much believed that this molecule donates its ammonium part to the P2P and then the formate part turns into formic acid (HCOOH) which then acts to reduce the intermediate into its stable formyl derivative (don't ask).
Other ways to do this reaction would be to use what the dudes did in the old days: ammonium formate , This way uses 60g of ammonium formate, no formic acid, and a distillation setup. Another combination that works equally well is 1:1 formic acid and ammonia in place of formamide. It is also perfectly fine to remove the water under the distillation setup, then replace it with a reflux condenser and conduct the reaction under reflux for the 5 hours . In fact, reflux is a good way to do any of these Leuckart reactions.
These strategies reduce the amount of tar immensely and keeps the reactants together a lot longer under reaction conditions that are more amenable to production. Whichever way was used, the chemist is going to have a cooled solution of formyl intermediate, and formamide etc. There are a couple of ways to process this stuff from here that are better and more convenient than the original way [22,31],
Instead of washing the reactants with water, extracting the product with ether, removing the ether then hydrolyzing, why couldn't one just hydrolyze right off the bat in the original reaction pot? As it so happens this can be done. The chemist can put 200mL of 30% aqueous NaOH or 200mL 30% HCI right into the flask and reflux for 5 hours. Using NaOH to hydrolyze has two advantages: it is gentler on the methylenedioxy ring structure of the X molecule and it is faster to process. After hydrolysis is over and the solution has cooled all one needs to do is extract with ether to obtain the MDA oil because using NaOH means that the MDA stays as an oil throughout. A really frugal chemist can do one extra thing to help herself out. She can take that ether/MDA layer and mix it with a few hundred mLs of 3N HCI. This, as usual, will cause the MDA to go into the water layer but what is going to be left behind in the ether besides tar is going to be a lot of unreacted, valuable P2P. The chemist saves that layer to deal with its P2P payload at another time. Meanwhile, all that remains is for the chemist to release the MDA from the water/HCI by basifying and extracting with ether.
Of course, there are a couple advantages to using HCI as the hy-drolyzer. Since using hydrochloric acid means that all that fat MDA or amphetamine is in the water solution, the chemist can vacuum filter the solution to get rid of all the tar and crap which will give a remarkably clean water solution. The X is released by basifying and extracting with solvent.
Since the formamide reaction solution is going to be a lot cleaner than the tarry mess of the original recipe, the chemist has yet another option to explore. Instead of hydrolyzing in the reaction pot, the chemist can add 500mL of clean dH20 and stir just like in the crappy original method except that this time the chemist is going to look for a heavy oil layer that will settle at the bottom. The up
per water layer is decanted from the oil layer. That water, by the way, can be acidified with HCI to form crystals of formamide that can be isolated for reuse. The heavy oil layer, alone at the bottom of the flask can be hydrolyzed as is with either 10% HCI or 10% NaOH. The chemist, by now, should know the general differences and outcomes of hydrolyzing with either of these two compounds.
By utilizing the improvements stated above in any combination preferable to the chemist, convenience will be enhanced and yield will jump from around 20% to that of 50%. Not bad, but there is one more oddball form of the Leuckart reaction that was devised specifically for X production and produces a yield of 70%! This little procedure  has been around for 40 years and has, until recently, failed to be reported as a superior Leuckart conversion method by underground sources. This sort of thing really frustrates Strike.
This procedure works equally well for both X and speed production. The set up used is the same as fig. 12 (remember, no vacuum) and into the reaction flask is placed 275 mL formamide, 80g MD-P2P or 70g P2P, and 55mL of 9% glacial acetic acid (50mL dH20 and 5mL glacial acetic acid, bubbal). This is slowly heated to 140-150°C in the oil bath and kept there for 5 hours. The lower the temperature at which a sustained reaction (bubbling) can occur the better. Suffice to say that 150°C should not be passed. Very early on the water and glacial acetic acid will have distilled over and can be discarded.
After 5 hours the reaction is stopped and the flask cooled. The formyl-MDA can be isolated and hydrolyzed by any of the ways Strike just mentioned a few paragraphs back, but this method offers a third, very convenient way which should be tried. What the chemist does is forget about letting the flask and its contents cool. Instead, she removes the oil bath, places the flask back on the stirplate (distillation setup still attached), attaches a vacuum and distills off all the formamide. What remains is a dark, heavy formyl-MDA precipitate that is allowed to cool down while the chemist makes up a solution of 150g potassium hydroxide (KOH), 500mL ethanol and 125mL dH20. This solution is poured into the
flask with the formyl-MDA residue, the condenser from the distillation set is plopped in vertically and the solution refluxed for a mere 30 minutes. The solution is then acidified with concentrated HCI solution, the distillation setup reattached and all the ethanol distilled off under vacuum. What is left is MDA and aqueous HCI and from this the MDA is liberated, as usual, by basifying with NaOH, extracting with solvent, drying the solvent and distilling to get MDA in 70% yield.
Dear readers please take notice: Not once has the flask left the stirplate since the formamide and P2P reaction started up to the last point where MDA freebase was liberated. That's pretty damn convenient. Technically, the Leuckart reaction can continue as a one pot synthesis from the last part of P2P cleanup right up to final product.
The last thing that Strike has to say about the Leuckart reaction is the use of LiAIH4 as a method of making the final freebase out of the formyl intermediate. What we have gone over so far is the method of boiling the formyl intermediate one gets from the formamide reaction with HCI to hydrolyze the species. What happens when one does that is that the bond between the nitrogen and the N-carbon gets ripped apart allowing the amine to form. But if one uses LiAIH4 instead of HCI, what happens is that the double bonded oxygen of the formyl species gets stripped away without any carbon-nitrogen cleavage [26, 27], The result is that one gets MDMA instead of MDA! And without having to use the restricted N-Methylformamide to do it.
To make MDMA from the formyl intermediate obtained by the Leuckart reaction the chemist is going to have to distill it to get the clean-yellow oil first. That black crap one gets from the formamide - 115 -
reaction is too dirty. 50g of cleanish N-formyl-MDA or amphetamine is dissolved into 300mL anhydrous (dry, bubba!) ether. This mixture is slowly dripped into a flask containing 38g LiAIH4 in 200mL anhydrous ether and the reaction mix refluxed hard for 4 hours. The chemist makes sure that there is really cold water coursing through the condenser and that there is a drying tube placed on top of that condenser. After four hours have passed 100mL of dH20 is poured into the flask to destroy any remaining LiAIH4. The ether layer is separated, vacuum filtered and extracted with 3N HCI. The MDMA or meth is, of course, now in the HCI water, not in the ether. That water layer with product is separated from the ether and the MDMA is liberated with NaOH to give MDMA or meth (90%).
Well, that's about as rounded an education on Leuckart reactions as Strike can give. Strike feels that after reading all of those similar, repetitious steps, one can start to get a good feel for where a product is at any given moment. Stuff like what happens to MDA when it's mixed with acid or base, or what happens to ketones (P2P) under the same circumstances. One can see now that it is possible to not only isolate safrole and P2Ps chemically but that the same can be true for the final MDA or meth freebase oil. Repeated washings with acid or base and solvent can effectively clean up a compound to an almost presentable state without the use of vacuum distillation. It can happen, one only needs have confidence in the chemistry.
METHOD #6: -17.8g MD-P2P and 300mL 40% aqueous methylamine is stirred at reflux for 30 minutes then 15g NaBH4 is added over a 10 minute period and refluxed for 1 hour longer (an even longer reflux time than that would be better). The reaction mix is cooled on an ice bath and carefully acidified with concentrated HCI yielding a thick white precipitate. The aqueous acid layer is washed with DCM or chloroform (discard the solvent) and basified with NaOH to release the freebase, which is taken up with ether and distilled to give MDA (yield =30%). Are you starting to see how all this chemistry is just the same bullshit over and over again, with the only differences being an odd chemical here or there?
METHOD #7: --This turns a P2P into an intermediate called a ketoxime which is then reduced to give MDA or benzedrine. To a solution of 25g MD-P2P or 18g P2P in 40mL ethanol, I0g hydrox-ylamine hydrochloride and 20mL dH20 is added a solution of 6g NaOH in 20mL dH20. This mix is then refluxed for 2 hours, diluted with 100mL dH2Op acidified with HCI and extracted with ether to give a thick, red oil upon removal of the solvent. 10g of this ketoxime intermediate, 100g acetic acid and 50mL dH20 are stirred together, then 300mL of 3% sodium amalgam catalyst (see chemicals section) is slowly added, then the solution stirred for 6 hours. The solution is basified with NaOH, extracted with ether and then the ether is extracted with 3N HCI. The free base is released from the acid water, extracted with ether, blah, blah blah. The yields from this type of procedure have been reported as high as 90% . However, these results are from a group in the Netherlands which happens to be right next to Belgium. And from Belgium there came a punk that did Strike dirty. Yeah, you know who you are you piece of shit! If Strike doesn't catch up with you before Strike dies then Strike will definitely be waiting for you in hell, you coward! Anyway, there has also been proposed a way to reduce that ketoxime intermediate using NaBH* instead of the harsher sodium amalgam .
METHOD #8: A very promising and tasty looking method contributed by some person named Feck. Don't know who or where this guy came from. But one day a care package with some very startling research articles appears in Strike's mailbox from this Feck character. This one was the best because it actually used P2P as an experimental subject . So you already know the method works on our favorite ketone species!
The article was a complex read for such a simple process. Strike has done Strike's best to interpret this article correctly for you. First off, even though the reaction is fairly simple, the authors have a lot of caveats about the materials needed. Important is the finding that the pH must remain between pH 7-9 or nothing will happen. Next, the granulation of the magnesium was found to be critical as well. Chunky old magnesium turnings were found to
give much higher yields than the finer powdered magnesium. The purity of the particular Mg used was 99.5%. The last note is that an excess of amine produces max yields.
The versatility of this reaction is quite apparent. One can use ammonium acetate to make MDA or amphetamine, or methylamine in methanol for MDMA. But methylamine is optimal because it gives higher yield and less byproducts. Also, if ammonium acetate is used, one must use either ammonia (NH3) or a primary amine (any of one's choosing, Strike supposes) in place of the triethyla-mine in the reaction.
In articles like this one, the scientists don't have the time nor the space to write out the details and amounts of reactants used for every single substrate they tried things on. So they pick just a few of the precursors they tried and use their numbers as an example of how the reaction typically goes. All one does is just substitute an equal amount of their favorite phenylacetone for the one in the example while keeping everything else the same. This will not be too big of a stretch of the old imagination with the first example below. The example ketone is just phenylbutanone. One little carbon more than phenylacetone, but a methyl ketone nonetheless (don't ask). They react exactly the same. As it so happens this first example is also the one using ammonium acetate to make MDA. Sweet!
"1-Methyl-3-phenylpropylamine—In a 250 cm3, single-necked flask were combined 4-phenylbutan-2-one (7.41 g, 50mmol), AcONH4 [ammonium acetate] (38.54g, 500mmol), Mg (6.08g, 250mmol) and 70% aqueous MeOH (100 cm3). The flask was capped with a mercury filled bubbler [feel free to substitute this one], to reduce escape of NH3, and the mixture was stirred at 20-25°C, for 12h. If the reaction was not complete (TLC), additional AcOH (6.0g, 5.7cm3, 100mmol) and Mg (2.43g, 100mmol) were added and the stirring continued for an additional 12h. The mixture was poured into water (600 cm3) to which NaHC03 (50g) was then added: the whole was then internally steam distilled until 500 cm3 of the distillate collected. It was made alkaline (pH >12) with 50% aq. NaOH and extracted with CH2CI2 (3 x 50 cm3). The com bined extracts were dried (K2C03), filtered and evaporated on a rotatory evaporator."
Strike is stopping the quotation here because the chemist is a point where she can exercise here own options. What the chemist has left after evaporation (or distillation) is freebase residue with some contaminants. The chemist can work this up as usual which would be to do a little more acid/base clean up like has been done with all freebase recipes. Or crystallize the final product for recreational use. The authors continue by making an oxalate salt out of their freebase. One can make whatever salt they want out of an amine freebase. Making an HCI, like what naughty chemists normally do, is just one way of doing things. Here is the rest of the experimental. We're continuing right where the last sentence above ends.
"The residue was dissolved in MeOH (20 cm3) and added slowly, with stirring, to a solution of anh. Oxalic acid (5.40g, 60mmol) in MeOH. Complete precipitation was effected by adding Et20 (50 cm3) to the mixture and cooling it to -20°C."
They are actually using crystallization to purify the amine from any non-amine contaminants. They later freebased the crystals and fractional distilled to get pure amphetamine with a yield of 50%.
Wow! That looked pretty good, huh?! The following example is one of the paper's experimental examples of using Methylamine as the amine source. This allows one to get MDMA or Meth. The authors used methylamine in methanol. That means they are using the MeNH2 freebase, not MeNH2HCI . The authors explain that they made their methylamine/MeOH solution by dripping (Strike thinks) aq. 40% methylamine onto solid KOH and bubbling the liberated MeNH2 into ice cold methanol. One can do this, or buy a gas cylinder of MeNH2 gas which can be bubbled into the methanol or whatever.
"N-Methyl-1,5-diphenylpentan-3-ylamine — Into a 250 cm3, sin-glenecked flask, were combined 1,5-diphenylpentan-3-one (7.15g, 30mmol) [<-insert said P2P here!], a solution of MeNH2 in MeOH
(5.4/770/ dm3, 44.5 cm3, 240mmol), and Mg (3.28g, 135mmol). AcOH (14.4g, 13.75 cm3, 240mmol) was added with a pipette below the surface of the liquid and the flask capped with a mercury-filled bubbler, to reduce escape ofMeNH2. The mixture was stirred vigorously, at 20-25°C, for 12h. If the reaction was incomplete (TLC), additional Mg (0.73g, 30mmol), MeNH2 solution (11.1 cm3, 60mmol) and AcOH (3.6g, 3.4 cm3, 60mmol) were added and the stirring continued until completion (3-6h). Work-up afforded the monooxalate salt (6.72g, 65%)."
METHOD #9: This method is not '#9' because it is bad. It's just that it, and #8 above, are still in the experimental stage as far as underground chemists are concerned. So Strike placed the less tested methods down here so as not to confuse people too much.
But this method has been generating more rabid attention than any other in the underground. Feck sent Strike some articles on it. Osmium emailed Strike some of the same references [56, 57]. Everyone is talking about it. And for good reason. It is essentially the second generation of reductive amination using superclean, gentle catalysts. Just think of it as Method #1 - except that the NaBH3CN has been replaced by a more workable catalyst: Sodium Triacetoxyborohydride [NaBH(OAc)3],
This catalyst works in a similar manner to NaBH3CN except that it does not suffer from the same potential toxicity that NaBH3CN does. It is also different in that one can synthesize the damn stuff rather easily in one's own garage, as opposed to NaBH3CN which will require a very complicated and dangerous cyanide generation apparatus as is shown in the Chemicals section of this book. The following is about all Strike has on the making of the catalyst NaBH(OAc)3 :
"Treating a benzene suspension of sodium borohydride (4 equiv.) With glacial acetic acid (3.25 equiv.) And refluxing the mixture for 15 min under nitrogen, after the initial rapid gas evolution subsided (ca. 3 mol of H2 liberated) [No Smoking!], gave a clear solution of NaBH(0Ac)3."
As you are about to see, the standard methods for using the NaBH(OAc)3 catalyst call for it to be in a dried, powder form. Strike supposes the benzene in the above reaction can be distilled off to leave dry catalyst. But don't quote Strike on that! Maybe it could be made in situ in the DCE solvent of the reaction to come (don't ask). Aw hell! Just go and buy the shit!
Anyway, with catalyst in hand it is time to proceed with the reductive amination . As far as Strike can see, this method will not work well in making MDA. It will not use ammonium acetate in the same way as NaBH3CN. So one is stuck with making MDMA or meth using this method. And without further ado, here's your recipe:
(a) The amine [methylamine] and carbonyl compound [P2P] are mixed in 1,2-dichloroethane and treated with NaBH(OAc)3. THF, CH2CI2, or CH3CN may also be used as solvents [but a longer reaction time will be necessary].
(b) Acetic acid (1-2 mol equiv) may be used in reactions of ketones [the paper says that AcOH acts as an accelerator to speed up the reaction with the P2P. But without it, the reaction will still go to completion. It will just take longer to do.]
(c) Reactions are normally carried out using the free amines [ie methylamine freebase. One can saturate the reaction solvent with MeNH2 before starting in order to achieve this]: however, the amine salt [ MeNH2HCI ] may be used. In this case, 1-2 equiv of Et3N [triethylamine] is added to the reaction mixture. The Et3N must be removed from basified product prior to salt formation."
And here's the two representative methods one would use. Just imagine the carbonyl precursor as a P2P and the amine as methylamine. Visualize man!
"Method I. This procedure is used for most ketone reactions. A representative example is the reductive amination of cyclopenta-none [P2P] with hexamethyleneimine [MeNH2]: Hexamethyl-eneamine (1.0g, 10mmol) and cylclopentanone (0.84g, 10mmol) were mixed in 1,2-dichloroethane (35mL) and then treated with
sodium triacetoxyborohydride (3.0g, 14mmol) and AcOH (0.6g, 10mmol). The mixture was stirred at room temperature for under a N2 atmosphere for 24 h until the reactants were consumed as determined by GC analysis. The reaction mixture was quenched by adding 1N NaOH and the product was extracted with ether. The ether extract was washed with brine [NaCI solution] and dried (MgS04). The solvent was evaporated to give the crude freebase (1.6g, 96%).
Method II. The above procedure is followed without the addition of glacial acetic acid. The reaction mixture remains cloudy throughout the reaction. This procedure is more appropriate with most aldehydes and unhindered aliphatic ketones [which P2Ps happen to be], A representative example is the reductive amina-tion of 4-pyridinecarboxaldehyde [P2P] with ethyl 2-piperidinecarboxylate [MeNH2]: Ethyl 2-piperidinecarboxylate (1.57g, 10mmol) and 4-pyridinecarboxaldehyde (1.07g, 10mmol) were mixed in 1,2-dichlorvethane (35mL) and then treated with sodium triacetoxyborohydride (3.0g, 14mmol). The mixture was stirred at room temperature under N2 atmosphere for 24-30 h. The reaction mixture was quenched by adding aqueous saturated Na-HCOs, and the product was extracted with EtOAc [ethyl acetate]. The EtOAc extract was dried (MgS04), and the solvent was evaporated to give the crude freebase (2.4g, 96.7%)."
Both those methods look pretty equal to Strike. Still, Strike tends to think that the Method I looks like it's the best of the two. There are some definite advantages that this method has over the NaBH3CN one. But all in all, they look about even to Strike. It's great to have options though. Isn't it?!
METHOD #10: You girls need to know that Strike is not just listing every method that produces a precursor or makes a final product. There are hundreds out there. Many make the product but are too hard, too expensive or too low yielding. Many are a combination of both. There are special criteria that makes a method worthy of inclusion in this book. Often, a method has been reviewed by many people before it makes it for consideration. When there is no one person that has actually tried a particular method on our special precursors, then that method had better have a lot of merit and unique potential.
This really crazy looking method is one of them. There are a lot of things about it that make it very attractive. The first is the author of the article: Rajender S. Varma. You will see in the Nitropropene section of this book (and in references from many other parts of the book) that this guy has been making a lot of strangely applicable advances in catalysis, amination, and reduction of amphetamines and related compounds. It is uncanny how often Strike has come across this person's work. It is like he is the Shulgin of basic precursor and amphetamine progress. Go figure!
The other attraction is the method itself: clay, a Sears microwave oven and the most lightning-quick results ever imagined! Someone sent Strike this method via fax, but dumbass Strike did not get the person's 'name'. But you know who you are, Bra'!
Anyway, there have been two very hot topics in chemistry lately: clay & microwaves. Both have been shown to do remarkable things in preparative organic chemistry. And this article Strike has , has combined both to produce some stunning reductive ami-nations of ketones to final amine products. The procedure involves mixing naked ketone, the amine, some clay and some NaBH4 in a beaker and zapping it in the microwave for only a couple of minutes. That's it. The general procedure is as follows:
"Typical Procedure. The synthesis of N-phenyl-p-chlorobenzylamine is representaive of the general procedure employed. A mixture of p-chlorobenzaldehyde (0.7g, 5mmol), aniline (0.455g, 5mmol) and montmorillonite K10 clay (0.1g) contained in a 25mL beaker was placed in an alumina bath inside the microwave oven and irradiated for two min. The in situ generated Schiff's base was mixed thoroughly with freshly prepared NaBH4-clay (5.0mmol of NaBH4 on 1.72g of reagent) and water (1mL). The reaction mixture was again irradiated for 30 sec (65°C). Upon completion of the reaction, monitored on TLC, the product was extracted into methylene chloride (3x15mL). The removal of solvent under reduced pressure provided pure N-phenyl-p-
chlorobenzylamine in 90% yield."
This next one is a power pulse modification for using lower boiling point amines (read why later on below):
"N-d-PropyDaminocvcloheptane: A mixture of cylcloheptanone (0.56g, 5mmol), n-propylamine (0.46g, 7.5mmol) and K10 day (0.1g) contained in a small beaker was placed in an alumina bath (heat sink) and irradiated for 6 min in a MW oven at its 20% power using pulsed method (one min cooling between two successive irradiation of 2 min each). The in situ generated Schiff's base was mixed with sodium borohydride (0.19g, 5mmol) and K10 clay (1.53g) to which water (1mL) was added and the reaction mixture was irradiated in MW for 45 sec at its full power. Upon completion of the reaction, as monitored on TLC, the product was extracted into methylene chloride (3x15mL). The removal of solvent under reduced pressure gave the free base in 79% yield. HCI salt (EtOAc-MeOH)."
Can you see what happened there? Ketone and amine react to give final freebase. Very nice. The authors even suggest that simpler matrices such as alumina or silica might work in place of clay. But, regardless, there is one small problem. The authors did not use any of the amines that an underground chemist would. As a solventless system, the authors had to use amines that were liquid or solid at or above room temperature. The lowest boiling amine they used was propylamine. And it was a borderline case causing them to use a modified pulse method so that it would not get too hot and escape the reaction matrix.
So you can see that to make MDA or MDMA using either NH3 or MeNH2 one is going to have to think of a way to keep them in the fray. Strike's first impulse is to dissolve the amine in a solvent. But what solvent? And would the reaction even work in any solvent? Rhodium thinks that maybe an aqueous amine solution would work considering the clay is moistened with water anyway.
Well, when in doubt ask the guys who wrote the article. And that is just what Strike did. The co-author of the method was a very kind
and helpful man. When asked how he would modify his method to involve either NH3, MeNH2, or EtNH2 , he, said that DMF (Dimeth-ylformamide) would be the first choice for solvent. DMSO would be the second choice. He indicated that water may work, but that experimentation would need to be done to be sure.
So now we have a modified method where one has ammonia, methylamine or ethylamine freebase saturated in a small amount of DMF. The author next suggested that a power pulse protocol would not necessarily be needed, but that the power output from the microwave should be between 20-40% of full power. Also, the water in the clay would still be needed for the reaction.
Lastly, Strike asked what he thought about the scalability of this process. Can it be upped to 1 mol or more? He said he was up to 50mmol and said no decrease in yield was apparent. The time of irradiation also did not need to be any longer than the written protocols.
So what the hell are all of you waiting for?! Nuke it!
That is about all Strike has for this section. But Strike is well aware of all the ways that P2Ps can be converted to amphetamines or methamphetamines using catalysts such as palladium black, Ra-ney-nickel and platinum in complex pressure apparatuses often using injections of hydrogen gas. These ways of conversion are relatively clean, with good yields, but they are not what this book is about. Strike feels these ways to be too involved for those looking to make a decent profit while avoiding overly-complex setups or expensive catalysts. These ways of conversion are meant for those who are intent on enormous yields, founding an empire and being placed in a correctional facility for a good part of their lives. Don't get Strike wrong, there's absolutely nothing wrong with these methods; and if one is interested in this sort of thing and wishes to become a professional drug lord, then they would definitely want to invest in the chemicals and proper construction of the type of apparatus necessary to do these pressure reactions.
Apart from the academic literature, one should read the book "Secrets of Methamphetamine Manufacture" by Uncle Fester . This book explains all about the in-home applications of these pressure methods. Strike, however, emphasizes reactions that are purely chemical.
Continue reading here: Pnitropropenes
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