These last three theoretical methods have no real kinship to any of the major categories or precursors. The first is the one that has caused Strike more despair than any other. It was once a Top Ten recipe in the first edition. But it was a reckless gamble on Strike's part and Strike paid for it. Here is what Strike wrote last year...
If you read the excellent book called "Recreational Drugs" by Professor Buzz  you may come across a little recipe in the amphetamine section for something called N-acetyl-phenethylamine. So what the hell is that? Well, actually it happens to be one step away from being an amphetamine but no one makes this clear to all the novices reading the book. Strike means to say that even novices just reading for pleasure need a little help here and there. It's a pity because this is a really good recipe using unwatched chemicals and is a more direct way of aminating safrole or allyl-benzene without having to go through the making of an intermediate such as MD-P2P or P2P. Actually, Strike is under the distinct impression that Professor Buzz got this recipe from the progenitor of underground chemistry books: "Psychedelic Chemistry" by Michael Valentine Smith. Unfortunately, both these authors simply copied commentary from the actual scientific article  without any elaboration towards the final outcome.
This is almost a one-pot production and uses a simpler borohy-dride catalyst (NaBH4) than others that are out there. These catalysts are very clean in their action yet very gentle on the molecule as a whole. Before this method is started, there is one bit of preparatory work that needs to be done by the evil underground chemist. The method calls for the use of anhydrous mercuric nitrate (Hg(N03)2) but the only commercially available form is a monohydrate (has one molecule of water attached, bubbal). So the chemist buys (or makes) the white, crystalline monohydrate. Next, if the chemist feels she is going to get really attached to this method then she's going to want to invest in a little toaster oven that she will never, ever put food in again. This toaster is placed in the hood or in the backyard because any possibility of vaporized Hg would be bad. In a beaker or mom's Pyrex meatloaf dish is weighed 100g of Hg(N03)2.H20 then the beaker is placed in the toaster oven which is set at approximately 220°F and remains there for about an hour. The beaker is cooled and reweighed. If the stuff is 5% lighter (95g) then the water is gone. The mercuric nitrate is then ground up with a spoon (spoon thrown away) and used right away because if it sits around its going to gain water from the air.
To do the reaction the chemist places a flask in an ice bath on top of the stirplate and into it is added 100mL acetonitrile (CH3CN) and 65g anhydrous mercuric nitrate. A small separatory funnel that has 33g of safrole or 24g allylbenzene is placed over the flask so that everything looks just like that of fig. 9. The safrole is then slowly dripped in so that the temperature stays between 20-28°C. A yellow precipitate will form as the mercuric nitrate latches on to the safrole. After the addition is finished, the ice bath is removed and the solution stirred at room temperature for 1 hour.
After 1 hour 200mL of 3M NaOH is slowly poured in followed by 200mL of 0.5M NaBH4 in 3M NaOH (a stock solution of this is made by mixing 120g of NaOH into enough water to make an even 1000mL, then 19g of NaBH4 is mixed in). At first things will grey then blacken slightly as elemental mercury is released and starts to fall to the bottom of the flask, and the droplets of product oil will appear. The solution is stirred for 1 hour and a slight amount of heat can be applied to hasten the reaction. After 1 hour, 200mL saturated NaCI solution is stirred in, the whole thing extracted twice with 50mL of ether and the ether removed by simple distillation to afford the intermediate 'N-acetyl-MDA' or 'N-acetyl-amphetamine'. Phooey!
This happy acetyl intermediate is just one hydrolysis away from being MDA or benzedrine. By hydrolysis Strike means that by using simple acid or base one can chop off that acetyl group that is stuck to the nitrogen and replace it with a hydrogen thus giving the chemist her final freebase. Hydrolysis is going to show up a lot in this book so lets discuss the two ways to do it. To that acetyl oil sitting alone in the bottom of the flask is added either 500mL of 15% aqueous HCI solution (HCI in water, bubba!) or 500mL of 20% aqueous NaOH with 100mL ethanol and the solution refluxed for 5 hours. MDA is now in the pot. If the chemist hydrolyzed with HCI then she basifies the solution with concentrated NaOH solution until the pH is 9 and all the little droplets of freebase oil have been released. She then extracts the oil with either benzene, ether or DCM (chemists choice), dries the solvent through Na2S04 and distills away the solvent to get product. If NaOH was used to hydrolyze then solution is cooled, extracted with ether, dried and distilled to give product. Either way the yield is ~80%.
The method Strike just described was an extension of an earlier published report  in which things were produced a little differently but bear description here because it has applicability as an alternative for those unwilling or unable to do the previous, unbelievably easy process. Besides, it's good to see how science progresses.
The acetonitrile and mercuric nitrate amounts remain the same except they are to be accompanied by 12.6g of fuming nitric acid (see chemicals section) in the reaction flask. Then, with cooling, the safrole or allylbenzene is added just like before. The reaction is immediate and takes no more than 20 minutes of stirring after which 100mL ice cold dH20 is slowly added. Next, with vigorous stirring, saturated sodium chloride solution is slowly added until a pronounced precipitate forms. This yellowish mass is the chloride,
not hydrochloride, of the acetamino-safrole intermediate (don't ask). The chemist wants to keep these crystals so the solution is vacuum filtrated and the filter cake washed with a little clean dH20. 40g of the filter cake is scrapped into a flask containing 160mL dH20, 14 mL 6M NaOH and 0.4M of 2% sodium amalgam (a catalyst, see chemicals section) and the solution stirred for 3 hours. Again, the precipitate will grey and elemental mercury will fall to the bottom of the flask. After 3 hours the solution is decanted into a filter (the mercury stays behind in the flask), and the flask with mercury is washed with 100mL ether which is also decanted into the afore mentioned filter. The ether drips through the filter cake then the filter is washed through once more with 100mL fresh ether. Both ether washings are cqmbined and distilled to give N-acetyl-MDA which can be hydrolyzed in the same manner as before.
The acetyl intermediate formed by the reaction is another species that one could use LiAIH4 on to strip the oxygen rather that hydro-lyze [26, 27], To reduce the intermediate one can use the exact method as was used in the Leuckart reaction or one can substitute tetrahydrofuran (THF) in place of ether as the solvent. In using THF the reflux goes for 24 hours instead of 4. After refluxing and cooling, 50mL dH20 in 100mL THF is added, then 50mL 15% NaOH, and finally 100mL more dH20 forming a white precipitate. The solution is vacuum filtered, the filter cake washed with 50mL THF and both the filtrate (the liquid stuff) and the THF washing are combined and removed by vacuum distillation to give freebase MDEA (-80-85%).
Yeesh! That was what Strike wrote last year. And the sad truth is that it did not work! The reason why is the way Strike proposed getting 'anhydrous' mercuric nitrate. The baking of commercially available mercuric nitrate monohydrate was actually destroying most of the compound. Aside of that this recipe works! It really does.
So what can be done about the mercuric nitrate problem? The authors in the original paper from which this recipe came from, clearly call for an amount of mercuric nitrate that is exactly equal to an anhydrous form. Had they used the available monohydrate they would have used an increased amount of the salt to compensate for the added water in order to get an exact molar ratio. But the article just don't read that way! Strike, nor anyone Strike has talked to, has any clue on how to make anhydrous mercuric nitrate. Does that make this method impossible?
Surely one would hope not. What if one just used the mercuric nitrate monohydrate that is at hand. One's only real concern would be if the monohydrate water would interfere with the acetonitrile in a competing oxymercuration reaction. But could it really considering the massive excess of acetonitrile present? All Strike can say is that someone, somewhere is gonna try it. And Strike would really, really like to hear about it.
The next weirdo method is a contribution by Ritter. This one is Ritter's combo contribution whereby she gives all of you a novel synthesis for making the valuable nitroethane (this is also included in the Chemicals section). Then Ritter gives you something to think about by hypothesizing how this nitromethane synthesis can be applied in a similar manner to make a beta-Nitropropane (not propene) from bromosafrole. From there one can reduce using methods Strike isn't even gonna get into here!
"Ref: JACS 79, 2507 (1957) Tetrahedron Vol 46. No.21 pp7443-57, 1990 Nitro Compounds By Ritter
Nitroethane and 1-(3,4 methylenedioxy) 2- nitropropane This method of producing the above mentioned nitro compounds is by far the best Ritter has come across yet. The problem with standard nitroethane synthesis is that the -N02 source most commonly used is silver nitrite (al la Merck Index citing). Needless to say, this is going to be an expensive compound to make as it is not available commercially but must be synthesized from costly silver nitrate. The other methods mentioned in Vogels 5th masterpiece
which use DMSO and sodium nitrite produce low yields of the desired product because other nitrous compounds that are formed compete with formation of the desired product. This improvement prevents those unwanted nitrous compounds from ever forming leaving you with a 80% or higher yield of the desired nitro compound. In the case of 1-(3,4 methylenedioxy) 2- nitropropane existing methods for its production in the literature usually start with the nitropropene and reduce it to the desired nitropropane which can be easily reduced to the desired amine. There is no need to try to make this intermediate nitropropene which uses watched chemicals (piperonal and nitroethane) anymore. Bromosafrole will react in the following synthesis to yield 80% or greater of the 2-nitro compound which can be reduced abazillion different ways to MDA.
Now the goodies: Nitroethane
Ethyl bromide 32g, 26.0 ml (.3mol) or Ethyl iodide 46g, 24ml (.3mol) is poured into a solution of 250 ml Dimethylsulfoxide (DMSO) or N,N Dimethylformamide or N-methylpyrolidone (DMSO preferred), 36 grams sodium nitrite (that's NaN02 pyromaniacs, not sodium nitrate) and 52 grams phloroglucinol dihydrate. This stuff is expensive but it can be recycled. Stopper all this in a flask with a good magnetic stirring bar and stir it in a room temp, water bath for 2 hours or until an emulsion forms. At this point dump all into 600ml ice water and extract w/ two portions of 200ml methylene chloride. The MeCI2 extracts are washed w/water three times then dried w/ anhydrous magnesium sulfate then evaporated off in a fractional distillation setup, collecting the fraction that boils at 113-116'C at atmospheric pressure as pure nitroethane. Expected yield about 20 grams. That's not a ton of product but this reaction can be scaled to any size you can dream of and yields will stay in the 80% range.
Synth for 1-(3,4 methylenedioxy) 2- nitropropane
This compound is made the exact same way as above only .3 mol (72 grams) bromosafrole is substituted for the bromoethane. Some extra DMSO may need to be added to facilitate stirring. Except for this the reaction proceeds as stated above. When the reaction is completed and MeCl2 extracts are evaporated, the raw product is suitable for reduction, no vacuum distillation is needed to purify the nitro compound. Just subject it to one of the many reductions out there that will reduce an aliphatic nitro group (note this is NOT a nitroalkene). AI/(Hg) in I PA should work fine. There are also many exotic NaBH^/transition metal salt combinations that will easily reduce the nitro group, not to mention straight catalytic hydrogénation. One mistake not to make would be to try a dissolving metal reduction such as tin/HCI. The boiling acid will destroy the methylenedioxy bridge and leave you with a frustrating mess of tar. Also don't forget to check out the new Ammonium Formate Catalytic Hydrogen Transfer Reduction detailed in Synthesis Feb. 1988, pp 91-95."
The last recipe deserves to be last: The Ritter Reaction [not affiliated with the above Ritter]
Allylbenzene N-acetyl-Amphetamine Amphetamine
This method was designed to produce an acetyl intermediate just like that in the failed recipe a few paragraphs above using only sulfuric acid and acetonitrile . This reaction works, in theory, in a so-so manner on allylbenzene but not on safrole. This method will not make X for many reasons. So why does underground literature and DEA forensic scientists keep claiming that it does? Strike doesn't know either. Let's see what the man who invented this, Dr. Ritter, had to say back in 1952: "several attempts to obtain amides from...safrol (sic) were fruitless.", What makes all these people think that this will work unless no one did their homework. This is another sore spot of Strike's and - 199-
now Strike is going to bitch for one entire paragraph and will then rejoin you for the recipe at the beginning of the subsequent paragraph.
Concentrated sulfuric acid, which is called for in this experiment, will break the ether bonds of methylenedioxy ring structure on safrole. This allows the resultant phenols to dimerize and polymerize with other injured safrole molecules. If one included this with the natural protic destruction that H2S04 is going to cause on the rest of the molecule then this method becomes very untenable for X. Another contention Strike has is with the idea that cyanide procedures meant as a Ritter reaction nitrile source for the conversion of tertiary alcohols and t-butyl primary alcohols  will work on a straight-up allylbenzene as has been suggested. This, in fact, does not work well at all on both allylbenzene and safrole. Let say, for example, that there was a group of 'scientists' that, upon the suggestions from certain sources, invested in some expensive and elaborate equipment to safely perform the Ritter reaction using cyanide (a way that supposedly produces higher yields than acetonitrile). Let's suppose that both allylbenzene and safrole were tried with not one active compound being produced. Next, let's suppose that these scientists were so pissed off that they had every oil fraction from the beginning of the procedure to the very end analyzed by mass spectrometer and found that all one ends up with is crap, crap, crap, and some unreacted precursor. Maybe someone has a way to use these cyanide procedures that work. But as far as Strike is concerned, they are not worth the hassle and/or risk.
Hey, Strike is back. Anyway, the only people this procedure is going to help are those interested in speed, and the only applicable version is going to be the one using acetonitrile. It's pretty simple though, and the chemicals needed are very basic. 59g allylbenzene in 200mL acetonitrile is stirred in an ice bath to a temperature of 10°C then 270mL H2S04 is slowly dripped in so that the temperature remains at around 10°C. An alternative to this would be to mix the acetonitrile and H2S04 together and then drip the allylbenzene in. Either way, after addition is complete, the ice bath is removed to allow the temperature to rise. The temperature will rise slowly to around 50°C, then start to rapidly climb towards 80°C. Most methods give the impression that this solution is going to stop getting hotter at 80°C, but it won't. At around 60-70°C the chemist should plunge the reaction flask back into the ice bath. If the chemist does not keep this in mind then the reaction will go super-critical and the chemist will have a horrible sulfuric acid vapor cloud in the house. The reaction color progresses from a light orange to black after the temperature rise. The reaction mix is poured into 400mL ice cold 15% NaOH solution in a PP container. If more NaOH is needed to make the solution basic then so be it. The N-acetyl-amphetamine is removed by extracting with ether then removing the solvent, or by decanting the oil which will form a layer on top. The oil, dirty as it is, is hydrolyzed with 15% HCL for 10 hours just as was done above and in the Leuckart reaction. The freebase isolated in the same way.
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