(Official Hive Translator)
The another way to P2Ps - "the Zealot's pathway"
(Rated as: excellent)
This is one more gem from Zealot's collection of syntheses, submitted by him several days ago to HyperLab. Needless to say, i grew kinda tired of saying compliments to this most extraordinary researcher - so i won't repeat them once again - just let me say as a preface that what you're about to read is truly awesome, if you like chemistry, it'll drive you nuts - it's REALLY cool.
He desired that this route to substituted phenylacetones was called 'Zealot's pathway' - and under this name it will bee engraved into the plates of Russian clandestine chemistry - please keep this credit of his work if you're going to experimentally reproduce or replicate this info.
1) Resacetophenone - Gesch reaction.
The mixtr of 10g resorcinol, 6g MeCN, 50 ml dry ether (dried/kept over KOH) and 4 g ZnCl2 there is bubbled thoroughly dried HCl. The mixtr warms up slightly and ZnCl2 gradually dissolves. In a half an hour the liquid beecomes opaque and then turns into a slurry. When the precipitate ceases to form, HCl stream is discontinued and after several hrs there is added 50 ml aqua (w/cooling!). The aqueous layer is washed w/ether and boiled for 1/2 hr. On cooling there precipitates a significant qtty of resacetophenone. The mother liquor is xtracted w/ether. The combined yield constitutes 9,6 g = 70% of theory. Resacetophenone crystallizes from water as long needles, melting at 144-145 C.
".....The point of the procedure is that under the influence of diazomethane phenyl radical migrates relatively to the carbonyl atom. If phenyl and hydrogen/haloid compete (like, e.g., in case of benzaldehyde or benzoyl chloride) - there forms an acetophenone, or beta-haloacetophenone; if a phenyl and an alkyl compete - there is formed a P2P; if an alkyl and methyl - methyl migrates.
In the rxn there is used a triple equivalent of diazomethane, 1st the hydroxy groups get methylated, then the chain methyl "insertion" takes place. I.e., essentially three stages at once."
Now, I was so astounded w/this statement that i actually asked Zealot to skan and email me the ref from the book that he got this idea from. It is called 'Reactions of the Organic Compounds', authored by Robert Fuson (spelling?) - as Zealot says, "...anyone who reads this book will beecome the 1st amongst the equal ones, and the equal amongst the 1st ones". The DejaVu (for the ones who don't know - UTFSE, this plugin is available online) of these pages is available at http://moonlight.ionichost.com/penetrati
10g resacetophenone is dissolved in 50 mls ether, added 0,1 g finely powdered CuCl and w/intensive stirring and RT there's added over an hour-1,5 hrs 200mls ethereal solution of diazomethane, made from 90 mls 40% KOH and 30g nitrosylurea (containing approximately 8,4-8,3g diazomethane). The rxn is carried on until the eruption of gas bubbles completely ceases. The ethereal solution i washed w/50mls aqua and evaporated. The obtained product is rextallized as follows: dissolve in 60:40 IPA/aqua, drip in water until complete turbidity and cool.
Yield 11,5g (91% of theory)
The Leuckart-Zealot reaction ("...sorry for my immodesty") gave a 88% of theory yield of the amine base.
Now - of course, you all want to hear the trip-report...It was submitted to me by email shortly afterwards, but even bee4 it i was speculating (judging by the numerous data that i've gathered by now - about which i could've gone at length - but i won't - see, at least, PiHKAL) - that the compd should bee active in MDA-mescaline dosages - go figure yourselves (Yellium - remember that discussion of ours 'bout the antipsychotics?) Any way, that's what he says:
"............so - about the dosages and the effects. The effect there is, and it cannot not to bee In doses beelow 200 mg, it's non-psychedelic, no psychotomimetic effects, no delirium............... Nothing resembling ketamine w/its wild hallucinations............Nothing also close to a schizophrenic episode or oneiroid or hypnogogic states................(Please keep in mind that in Russia there's very little culture around psychodelics, and the terminology he uses is consequently VERY different).
In 200 mg - slight synesthesia, euphoria, but no motor activity. Enhancement of visual and audial perceprions......... for me, it was a sharp euphoria from music..................not anything trance-like, but rather the general pop-art...........The synesthesia points at the psydhedelic direction, but.................. i didn't try it above 200 mg - i just didn't like to puke...i generallly don'thave that body composition...............many people i know don't like to pukeLOL!!!!! .........i am not distinguished by an endurable personality, physically speaking........ so, it is quite possible that there will bee other people than myself who'd get mescaline experiences from this compouind....................
That's currently it...................
I, of course, want to make two mentions:
1) The Renowned Bibliophil of Hyperlab, Garin, scannned and upoaded all the info there was on diazomethane onto his site at http://chembook.narod.ru. I WILL translate whatever you want me, oh my dear brothers, from that document - there is quite something.
2) If one was to make use of a phluoroglucinol in this rxn, one'd arrive at TMA-6 Zealot just didn't have any phluoroglucinol.
3) May i humbly suggest that in all the other cases, suggested by Assholium for gettin' acetophenones (like acetylations w/GAA and polyphosphoric acid (said never got a yield beelow 80%)) - would yield an acetophenone quite suitable fo all the followin reactions w/diazomethane.
Nice post Antoncho, but don't forget that diazomethan is a bit complicatet to work with.
But I'm still impresed wit the "Leuckart-Zealot" reaction. That was the news off the month.