Sciencemadness Discussion Board

1-bromo-3,4-methylenedioxybenzene uses

Klute - 1-9-2009 at 12:35

I was kindly given a small amount of 1-bromo-3,4-methylenedioxybenzene, and I'm not sure of what I want to do with it..

Converting it to piperonal could be an option, using a grignard for example, but it would be much more easier to start from piperontl alcohol and do a TEMPO-catalyzed oxidation or an Oppenaeur with aluminium isopropoxide and paraformaldehyde, which is said to work particularily well on this substrate.

I'm pretty sure the methylenedioxy bridge can make very nice smelling product.

This document describs the formation of the grignard and a few uses.. I guess I could form the grignard reagent and react it with acetaldehyde, and oxidize the alcohol formed to the acetophenone..
Or even making safrole, which isn't illegal to posses in France I think.. Never smelled safrole!
What else could be done using the grignard? Any ideas?

I was thinking of doing an enolate reaction with acetone to get to the controversial phenylacetone, although I will have to check if this isn't illegal in France.. I never encoutered this product and I suppose it smells nice..
The reaction seems pretty simple, DMF, t-BuOK, acetone.
Apparently acetylacetone and CuI can be used to get to the piperonylacetone, although I recall Bandil trying this at the HIve and only getting the starting product back.. But he used sodium carbonate as a base, surely usign NaH or t_BuOK to form the enolate would be better..

EDIt: the grignard reagent could be additioned to propyleneoxide to form the Arylpropan-2-ol, which could then be oxidized.. QUite a lengthy procedure, especially if you have to prepare the propylene oxide yourself (acetone --> chloroacetone --> chloropropanol --> propylene oxide)!

Anymore suggestions?

This product can be easily prepared by bromination of cheap benzodioxole, so I wont mind doing several tests.. Hey, if I try the enolate synth, at least someone would have tried it, after all theses years!



[Edited on 1-9-2009 by Klute]

JohnWW - 1-9-2009 at 14:16

Quote: Originally posted by Klute  

(cut) Or even making safrole, which isn't illegal to posses in France I think.. Never smelled safrole!
What else could be done using the grignard? Any ideas?
I was thinking of doing an enolate reaction with acetone to get to the controversial phenylacetone, although I will have to check if this isn't illegal in France.. I never encountered this product and I suppose it smells nice..

I would advise you against contacting your local Pigs (what do you call them in France? - Gendarmerie or Flics, I think) for an opinion as to whether this or that chemical is "illegal" in France, because it would draw their attention to yourself. Knowing how universally corrupt they are, they may even start to keep you under surveillance, in the hope of being able to frame you for some alleged offense that you did not commit.

As for possible uses of the stuff, I suggest that you look up the phrase "1-bromo-3,4-methylenedioxybenzene" on Google.fr. From this, it appears that it can be used to prepare a Grignard reagent with which to introduce the 3,4-methylenedioxyphen-1-yl group into an organic compound containing another polar group, for synthesizing certain pharmaceuticals and (piperonyl ethers) insecticides. It can also be used for making some boric acid esters. It is closely structurally related to safrole and piperonal, which have side-groups in place of the Br atom, and which could be made from it by Grignard reactions.

See (several processes are patented, and some articles are restricted):
http://www.freepatentsonline.com/3711517.html
http://www.freepatentsonline.com/6794529.html
http://www.patentstorm.us/patents/6939985/description.html
http://www.patentgenius.com/patent/5514773.html
http://www.faqs.org/patents/app/20090105474
http://linkinghub.elsevier.com/retrieve/pii/S095741660400373...
http://linkinghub.elsevier.com/retrieve/pii/S003194229800270...
http://pubs.acs.org/doi/abs/10.1021/jo051901z
http://www.rsc.org/ejarchive/P1/1996/P19960002157.pdf
http://pubs.acs.org/doi/abs/10.1021/jo047751u
http://doi.wiley.com/10.1002/adsc.200404102

[Edited on 2-9-09 by JohnWW]

Klute - 1-9-2009 at 17:49

Yes, Flic is the word :)
I will contact local university and see if I can get some info on this, or simply on the net.
I don't think safrole is plin illegal, it's still possible to buy safrole oil here I hear, although I have never encoutered it unfortuanly.
The phenylaectone might be another case though, I think that compound might be completly illegal to make. ANybody haev more info on this concerning europeens?

Boronic acid looks like a good idea, especiallyu I wanted to try some suzuki and other palladium-mediated couplings..

smuv - 1-9-2009 at 21:08

If you make the grignard reagent, might as well react it with N-methylpropyleneimine. :p

Watch out with grignards as under some conditions they deprotonate a methylene proton of the dioxolane ring

You could also make sesamol.

Klute - 1-9-2009 at 21:19

Yes, sesamol looks nice too.
This could even be a way of preparing 2-methoxy-4,5-methylenedioxybenzaldehyde, if someone wanted to make some MMDA-2 (PIHKAL #133), for a legal MDMA analogue, active at 25-50mg..

It's strange how that 3,4-methylenedioxyphenyl is unconsciously related to drugs..

EDIT: Ok, I think I need to precise that I have no intention of making any MDMA from this product. I have indeed considered the synthesis of several precursors, but that's is du to the fact that they are the compounds having the 3,4-methylenedioxy bridge which are the most discussed on the internet. I see noth├žing wrong in considering the preparation of safrole or piperonylacetone as long as these will not be used to make MDMA. I am not encouring anyone to make some MDMA, honestly I think 1-bromo-3,4-methylenedioxybenzene isn't a vital precursor owing to its low availability and high price, compared to things like safrole or piperonal.

And I'm no adept of chemistry-oriented masturbation. (don't ask)

[Edited on 2-9-2009 by Klute]

jon - 3-9-2009 at 22:21

mmda now jon has never tasted this, the sn2 between iodo alkanes and ammonia does yeilds 90 % in ipa expiriments have shown that primary alcohols interfere with this nucleophile but iodo alkanes give excellent yeilds of primary amines in ipa.
20-1 stochiometry.
if one were to theoretically attempt such a thing with myristicin

ChemistryGhost - 1-8-2012 at 05:17

Can 1-bromo-3,4-methylenedioxybenzene be synthesized from Sesamol?:P

zoombafu - 1-8-2012 at 12:05

Do a grignard reaction. You've got the bromine atom right there, just find some cool compound that you can make with the combination of it and another molecule. (not safrole of course). I personally think that a well done grignard reaction is the most fulfilling chemical reaction there is.