P2P's from aryl halides and acetylacetonate

[Nicodem]

It seems strange that the methylenedioxy-bridge should make it THAT unreactive?

No, it does not seam strange at all. The strange thing would be if two so strongly deactivating groups for the nucleophilic aromatic substitution (NAS) would allow the reaction to give the so much wanted product .
What is known about 2-nitro-4,5-methylenedioxo-(meth)amphetamine?
It might bee interesting if you would nitrate your bromodioxole as a nitro group ortho to the bromine would better activate it for NAS. It should be possible to aminate the resulting P2P without reducing the nitro with NaBH4. And most importantly it would bee a new compound, probably without the neurotoxicity of MDMA since that position 2 would be blocked for the metabolic hydroxylation. If I remember corectly the 2-bromo and 2-methyl compound still retain some of the MDMA activity (about 1/2) but are predicted to bee non-neurotoxic.
However I'm not sure if the nitro group would attack only that position.

Is it certain that the carbonate is a strong enough base to deprotonate the acetylacetone?

It should. In water Na2CO3 is just strong enough (pKa 10.3) to deprotonate acetylacetone (pKa 9), but in DMSO Na2CO3 should be an even stronger base.

[Bandil]

Anyone interested in the writeup i made of the entire "reaction"? It's probably a good idea to store it somewhere... Maybe a digest would be a good idea? Then i can make a compilation of all the arylhalides i get to test.

I'll only bother with making it, if theres interest in it!

Regards
Bandil

[amine]

Looking at the original text the acetylacetonate is produce via reaction with KOH/NaOH, and then dedydrated to get the Potassium/Sodium Acetylacetonate.

Bandil, you do think that preparing the electrophile via this method could produce different results?

I'm not sure why sodium carbonate was used, but is it strong enough to deprotonate the acetylacetone to the acetonate? I know that alpha carbon should deprotonate easily since its stablized by those oxygens. But maybe something stronger needs to be there.

edit: recalling o-chem classes, generally the claisen condensations used bases like NaOEt et. al. I'm sure the carbonate wasn't strong enough. Hopefully preparing the potassium/sodium acetylacetonate and then adding it to the solution may give better yields, I see no reason to why the that methylenedioxy bridge would deactivate the so severely.
If it is indeed the bridge, maybe starting with 5-bromo-1,3-benzenediol would provide better result, and then one could close the bridge with a methylenation reaction using dcm and a ptc?

edit 2: Looking over psychokitty's notes on synthesis of mdma precursors from eugenol, the paper talks about methylenation of the 3,4-dihydroxy(methyl)amphetamine to the desired product in 70-78% yields depending on whether the amine is protected or not.

Swim has been looking over this preceedure for quiet some time now, as it was his next project. Good luck Bandil! Swim is convinced this method can work!