this was posted over at pnaut by user 7royals. Dont know if he is here but there is no one at pnaut anymore.

looks like the most OTC amphetamine synth i have seen (would this give amphetamine or methamphetamine?)

i dont really think it is responsible to encourage anybody to play around with amphetamines or methamphetamines.. but you guys are grown ups you can handle yoursleves.



Thought I would share this with everyone. Inspired by Twodogs. Basic outline, figure out ratios and numbers by yourselves.

Jasmorange Dealkylation:

Add Xylene (excess) and FeCl3 in round bottom, add Jasmorange. Reflux until dealkylation is complete by TLC. Remove dealkylated Jasmorange from reaction mixture (distillation/precipitation/etc.)

Aldoxime:

Twodogs method or Sonsons, I prefer Sonsons since it is quicker. You will not isolate solid aldoxime, if you do please share. Only liquid aldoxime has been recovered, haven't found any references to physical characteristics of this aldoxime.

Amide:

Twodogs method.

Amine:

Twodog method works. Higher yields obtained by mixing water, NaOH, bleach together and chilling. Then add amide and stir for atleast an hour or two. Better to stir in the cold overnight. Bring temp up to 80C and hold for 30 minutes. Cool, extract, etc.


Try it out and post results if you'd like.

oh few more things -
Jasmorange = 2-methyl-3-p-tolylpropanal right?
so you expect to remove a methyl group from a phenyl ring with just FeCl3? thats weird man. never heard of it. I think the poster has confused a few things -
FeCl3 is used to dealkylate phenyl ethers like vanillin, benzodioxole, etc... not to remove alkl groups attached to a phenyl ring!!!!!!! this is basic organic chemistry.
another thing is FeCl3 high temp reflux of the aldehyde. It might also cyclize. (ala friedel crafts type).
also, you can see how dumb the poster is, since he is using xylene as a solvent. If FeCl3 would be able to remove a methyl group from a phenyl ring, then xylene would loose at least one of its methyls as well.
anyway, i call BULLSHIT

you could however use this to make para-methyl-amphetamine.

Who would ever be possessed of the desire to synth para-CH3-amphetamine? that stuff is going to metabolise to the corresponding ephedrine, and be godawful toxic. Heard tell from a russki guy on a forum somewhere, forget where, you know what the reds are like when it comes to their drugs...crazy loco bastards alright, and then some. The guy in question said, and I quote 'this is the one drug that really scares me'

Look at mephedrone, meTHedrone, the cathinone versions, as well as PMA. PMA is plain friggin' nasty stuff, very, very steep dose response curve, a little may be enjoyable, Shulgin seemed to like it in his PIHKAL report(s) on it, but a little more and its hypothermia, potential 5HT syndrome (which many posters on bluelight have said is an awful, painful miserable thing to go through, but the reality of it is so much worse, worse than you could believe. My dear lady went through it, and collapsed, totally immobile, in agony. She thought she was going to die, and was scared shitless. My girl doesn't scare easily, she has a spine and will of steel, to put it mildly, but that scared the everfucking jumping jesus christ on a bike mother of fuck out of her, but she couldn't move to get help, just stuck there, thinking it was the end for her, and by the time it had lessened enough to move, things were getting better to a slight degree, and the fear for her life was over, although in her case it wasn't caused by anything recreational, she doesn't touch anything of the sort, but rather, a sudden, unpredictable reaction to daily SSRI treatment in addition to sumatriptan to treat one of the awful migraines she gets)

Mephedrone/methedrone are just as nasty, a few deaths, plus reports of skin discoloration, longterm chest pains, severe hypertension, intermittent tachycardia/arrythmias in some cases. From internet reports, its possible those two beta-carbonyl derivatives are LESS toxic than 4-methylamphetamine, but 4-MA seems, maybe to be even worse than PMA.

Avoid the lot of them like one would wish to avoid being fucked in the arse with a rusty length of fire ant infested razorwire, covered in the blood of a lassa fever patient.

At least if you haven't a death wish. About the only use for para-monosubstituted amphetamines I can think of, would be to painfully murder an enemy who does not yet realise he has earned one's enmity, with some plausible deniability as far as it being an obvious intentional extermination goes.

Any chance of a link to the Beckmann protocol? I have other interests in mind for it, but similar, stopping at the intermediae isocyanate, distillation of said isocyanate then reaction with one of the more potent GABAergic agonist alcohols, such as 2MTB, or better yet, ethynylcyclohexanol, or something like placidyl.

Legal prodrug here, since one never actually synthesizes the amphetamine itself, merely its isocyanate, and forms a carbamate, which will act as a prodrug, the carbamate hydrolysing on contact with stomach acid, forming the amine and the carbocation corresponding to the alcohol, which will rearrange to the alcohol quicker than one can say 'fuck the cops in the arse with a rusty bread knife'

nk40ouvm : ive never heard of FC dealkylation. I will look it up. But to me it seems that even if this can be reasoned in theory, simple FC conditions will not give appreciable yields. Otherwise this would have been a known procedure for aromatic dealkylation which is a pain in the ass no matter what method you go about it!

Tsathoggua : your idea sounds interesting. there is no need to distill the isocyanate. if you have an excess of the alcohol it is possible to proceed from the amide straight to the carbamate. This works best for the non easily oxidized alcohol (methanol, ethanol). with t-butanol (product expected to be BOC-amide) you get mostly oxidation of the alcohol and no trapping of the isocyanide. if you are interested in the reference, let me know.
most amides ive tried work well with methanol to product the methyl-carbamate. only problem is that hydrolysis is a pain in the ass, requiring prolonged alkali hydroxide reflux (usually 15-20 hours are needed for complete conversion).
the nickel catalyzed beckmann rearrangement can be found here -
"Isomerization of Aldoximes to Amides under Substantially Neutral Conditions.", Lamar Field, Patricia Barnett Hughmark, Susan Holroyd Shumaker, W. Stanley Marshall,
JACS, 1961, 83, p1983.
The experimental part can be summed up into : Add 600ml xylene to 1 mol of aldoxime. add 20mmol (2mol%) nickel acetate tetrahydrate followed by 2ml of piperidine and reflux for a minimum of 6 hours. let cool to r.t. The amide usually crystallizes out of the xylene and is collected by filtration followed by washing with xylene. Yields are usually very good.
some notes from experience -
the piperidine is absolutely needed. i have not tested other secondary amines. the piperidine supposedly forms a complex with the aldoxime, perhaps even exchanging with the hydroxylamine to form an enamine which then apparently reacts with the nickel much better. this theory is based on the article mentioned and  (A. Bryson  and F. P. Dmyer, J. Roy. Soc. N. S. Wales, 1940, 74, 455, 171). without piperidine the yields are crap and the product is very dirty requiring tedious purification.

post reaction, the nickel acetate is still present. it does not dissolve (at least not completly) in the xylene. as you may or may not it is dangerously toxic and carcinogenic. care should be taken when working with if you appreciate life. If the end product of your synthesis is for human consumption you HAVE to clean the formed amide somehow and remove the nickel acetate. crystallization from boiling xylene works, however you need to take care to keep it as close to boiling while filtering since most amides will precipitate upon slight cooling. another good way of purifying the amide is vacuum distillation, but this is dependent on the amide and your skills. most of the amides ive worked with required short path or even bulb-to-bulb distillation.

it seems logical to assume that other secondary amines might be suitable for this reaction, morpholine and n-ethyl-n-benzylamine are some common ones used in enamine synthesis, so these might merit investigation, if you are so inclined (also since piperidine isnt OTC).

i love the way the guy makes out as though hes done it, sly dog.. he also goes "thought i would share this with everyone" and "figure out quantitys for yourselves" as though hes giving us pearls.. haha i have never seen a bullshitter like that

i love the way the guy makes out as though hes done it, sly dog.. he also goes "thought i would share this with everyone" and "figure out quantitys for yourselves" as though hes giving us pearls.. haha i have never seen a bullshitter like that

It's kind of easy to identify the guys who got all their ideas from reading the Wikipedia page on amphetamine.

Hey Tsathoggua could you perhaps elaborate on 4-MAR's toxicity? If you could redirect me to some literature or have anything to say about it, please do!

Dont FC alkylations require a halogen compound?

letters may i ask what yields was when piperidine was added in the beckman?
 attempts without-
(from memory and assuming the aldoxime was good quality)
 attained 70% yields most of the time without its use.(once established parameters of reaction)
the amide quality was clean,  found to crop in 3 goes most efficient, the first two crops would produce once a single cold wash had been done a slightly off white crystal amide.
the third crop (or last one) sometimes was contaminated with a little sticky brown substance which might require 2-3 washes to clean thoroughly. others found single crop more effective, and less time consuming (perhaps they have better lab skills lol)
the brown shit appeared most when or the amide was hard to clean when,
too much nickel acetate was added (above 2.5mmol)
over reflux..
and after the 5hour reflux when raising temps to enable the thermal reaction ~ @119c? if temps went to high at this point im not sure exactly how high, perhaps 127c yields reduced a lot too perhaps 30-35% and brown shit was in abundance. it made initial amide crystallisation more of a bitch too.

(i edited out my q about friedal crafts dealkylation, found the answer myself)
second q, would fecl3 be superior over alcl3 to o-demethylate eugenol, in some cases it is noted to be advantageous over alcl3, producing less tar, and of course is less toxic.