Yeah, maybe you're right. This all started when I saw that picture in Post 238753 (https://www.thevespiary.org/talk/index.php?topic=12355.msg23875300#msg23875300)
(Rhodium: "MDMA from only aliphatic precursors", Serious Chemistry), which basically showed closing the methylenedioxy ring on a eugenol derivative with a 75% yeild. I really haven't been able to get it out of my mind since. Does that SynGen program give references to the reactions it uses?
I sell crack for the CIA
I don't know what exactly will happen to eugenol, but even if it produce only a 30% yield this is the way to go, since eugenol can be had for less than €20/liter.
I don't have any refs right now, but I have seen several ones over the years. Strong aq. acids will demethylate phenolethers. Look what Mr. Shulgin says:
The amphetamine metabolite, 4-hydroxyamphetamine hydrochloride (4-HA), was prepared by heating 5.0 g 4-MA in 20 mL concentrated HCl at 15 lbs/in. After recrystal-lization from aqueous EtOH, the product weighed 3.8 g and had a mp of 171-172 °C.
http://www.erowid.org/library/books_online/pihkal/pihkal097.shtml (http://www.erowid.org/library/books_online/pihkal/pihkal097.shtml)
I've seen several other reactions where phenolethers were refluxed with H2SO4, and at least partial demethylation took place. para MeO will hydrolyse the fastest, ortho-MeO the slowest. But they all will eventually come off.
If eugenol won't work satisfactorily then use something else. Vanillyl-methyl-ketone for example.
I'm not fat just horizontally disproportionate.
The reflux should most preferably be done under inert atmopsphere (as dihydroxyallylbenzene is sensitive to oxidation). A tightly packed CaCl2 moisture protection tube should keep most of the air out of the reaction flask though.
I was referring to protecting the dihydroxyallylbenzene as the diacetoxyallylbenzene (acetylation of it all with acetyl chloride or acetic anhydride) while isolating/purifying it, it might help against decomposition. Some data on the dihydroxyallylbenzene can be found in https://www.thevespiary.org/rhodium/Rhodium/chemistry/allylpyrocatechol.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/allylpyrocatechol.html)
For suggestions on how to perform the H2SO4 demethylation, I think Osmium is more qualified to write an outline on how it should be done.
What is the best distillation vacuum you have available in your lab?
Here it is!!!
However the yeild is only 50% and it takes quite allot of LiCl. Hmm I wonder if you could recover the LiCl?
Patent EP1136481 (http://l2.espacenet.com/dips/viewer?PN=EP1136481&CY=gb&LG=en&DB=EPD)
A solution of 354 ml (2.30 mmol) of eugenol and 292 g (6.89 mol) of lithium chloride in 3.7 1 of N,N-dimethylformamide was refluxed for a total of 44 hours (h), and, after 4 h, 18 h and then 7 h, a further 292 g (6.89 mol) of lithium chloride were added each time. After cooling, 2 1 of toluene were added and the resultant precipitate was filtered off with suction and extracted with toluene. The organic extracts were combined and concentrated on a rotary evaporator. After flash chromatography (ether/pentane, 1:1, Rf = 0.37) on silica gel, 173 g (50%) of 4-allylcatechol were obtained.
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