eugenol >> mmda (bromo snag)

[blue]

this bee has been fantasizing about a dream that goes from vanillin >> mmda for quite a while, however there is one big stumbling block. Nitroethane. (can't get it and a monumental pain to synth it)

wracking my brain for an alternative route to hearts desire, it has occured to me that eugenol is the allybenzene equivalent of vanillin. so here is what i propose,

eugenol >> bromine in MeOH >> 3methoxy,4hydroxy, 5bromo allybenzene >> NaOH >> hydroxyeugenol ( 3methoxy,4,5hydroxy allybenzene) >> >> methelenation viaDCM, NaOH, DMSO >> 3methoxy,4,5methlenedioxy allybenzene (looks alot like myristicin, hmm?)

this allybenzene can then be isomerized to the propenylbenzene, run through a pseudonitrosite synth to yeild the nitropropene and reduced by a multitude of methods to the beolved amino derivative.

unfortunately the most questionable step is the 1st. i am unsure whether the bromination technique outlined by Os and Rhod in the MMDA synth will bromintate the 5 position in the ring or whether it will brominate the beta carbon on the tail. if it does want to go to the beta carbon, any suggestions how to inhibit this allowing dominant bromination at the 5 position?

more than one way to skin a cat(maybe) feel free to point out any other shortcomings above.

is it soup yet?

[Osmium]

The bromine will add to the unsaturated side chain, forming the dibromopropane before it has any chance to react with the aryl nucleus. This means you have to somehow protect the side chain, and since I know of no easy way to do that right now you might as well start with the 'ketonized' eugenol/isoeugenol.

[blue]

that is exactly what i was afraid of. shit. wasn't planning to dream via ketone, rather nitro. would converting isoeugenol to the b-nitropropene effect the same protetion, allowing bromination at 5 position to proceed?

is it soup yet?

[Osmium]

That's a very interesting question.
Probably not. And even if it does work, you will most likely run into problems at a later stage, e.g. when trying to methylate that phenolic OH.

[hypo]

Has anyone ever heard of the 2C analog of MMDA??

[yellium]

Shulgin's claissen rearrangenement is out of reach?

[psychokitty]

Another fascinating prospect is the synthesis of 3-methoxy-4-allyoxy-allybenzene from eugenol (via NaOH, PTC, and allylbromide) >>> ketone (by any of the available methods) >>> and then to the final unsubstituted amine (Leukart or whatever).  This compound is mentioned by Shulgin in the big book, seems to hold a lot of promise theoretically (according to its phenethylamine analogue, that is)and is virtually unknown as an active substance.

--PK

[Rhodium]

PK: on what page is this compound mentioned?

http://rhodium.lycaeum.org

[yellium]

MEPEA, #123 

(oi, can my title get altered as a prize for knowing pihkal trivia?)

[blue]

yellium - not out of reach, just very involved, actually another way around the nitroethane via the aldehyde that i have looked at is to convert the aldehyde into a propenylbenzene via that bromoethane variation on the gringard that nichols and shulgin came up with (looks sweet), i was torn between that route and the one proposed above.

also wanted to exhaust the eugenol possibilties because it looked like a more direct route intitially, but i am not so sure.

is it soup yet?