Verdict on the Bromosafrole route?

iodide · Fri Jun 24, 2005 7:16 pm

When I used to lurk at the hive about 5 years ago, I remember that a big controversy in the area of phenethylamine synthesis was whether the bromosafrole method actually worked. People were claiming success while others were asking for proof, and it was quite fun to read.

What ever came of that? Judging from the lack of discussion or it, am I safe to assume that it doesn't work? It seemed like an easy, forgiving reaction.

2spun · The Resistor

is that for
bromosafrole to mda or mada?
swiy thinks only from read's he's not try'd it yet so can give not a frist hand.
But it work better for mda,( form what swiy has read ).
swiy has not found yet any solid info for mdma? via bromosafole

ApprenticeCook · DILLIGAF

More so iodosafrole but it became one of the many taboo subjects at the hive..
Check over at WD for my thread in the advanced dreaming forum regarding the amination of halosafrole with gabriel reagents, i have a polish chem journal article giving experimental detail and the basis of the mechanism and conditions which must be addressed when designing a gabriel reagent.

There was much discussion in that thread which lead to some interesting findings. The use of sacchrin as the gabriel reagent was one of psychokittys thoughts which would work according to the information within the article i reference in the thread posts.

-AC

2spun · The Resistor

Righton,

thanks bro .

ApprenticeCook · DILLIGAF

oh also my thread was relating to halosafrole to MDA, to reach MDMA as the final product you must use a different gabriel reagent or alkylate MDA ala shulgin in phikal.

-AC

ApprenticeCook · DILLIGAF

The thread at WD -->
https://161.57.220.246/forum/topic.asp?TOPIC_ID=2304

The reference pdf from that thread -->
http://rapidshare.de/files/2625309/Polish_J._Chem_-_A_Facile_Synthesis_of_Primary_and_Secondary_Amines.pdf.html

Have fun!
-AC

ApprenticeCook · DILLIGAF

Fast Microwave-Assisted N-Alkylation of Phthalimide in Dry Media.
http://www.cyf-kr.edu.pl/~pcbogdal/synlett/

"New method of synthesis of N-alkylphthalimides {via} alkylation of phthalimide in 'dry' media under microwave irradiation has been elaborated. The reactions were carried out with high yield (50-90%) by simply mixing of phthalimide with an alkyl halide which was adsorbed on potassium carbonate. The irradiation of the mixtures in a domestic microwave oven leads in a remarkable short time (4-10 min.) to the desired N-alkylphthalimides."

"the syntheses were carried out by simply mixing of phthalimide with 25% excess of an alkyl halide and a catalytic amount of tetrabutylammonium bromide (TBAB). The mixtures were adsorbed on potassium carbonate and irradiated in an open Erlenmeyer flask in a domestic microwave oven for 4-10 min."

With the exception of the TBAB this looks rather nice dont you think?

-AC

sony · Fri Jul 08, 2005 3:01 pm

Nice article, but dont you agree that ammonia or methylamine are too volatile for this solventless microwave alkylation? Smile

Ephoton · Fri Jul 08, 2005 3:19 pm

dry ice condensor out of the top of the microwave sony ?

ApprenticeCook · DILLIGAF

ammonia or methylamine? where are they in the above microwave proceedure?
Its pthalimide, alkyl halide (eg bromosafrole), cabronate support and tbab.

-AC

loki · guinea pig

that writeup specifically talks about pthalimide. it has two keto groups attached to the alpha N carbons. it is possible that formamide may react the same way but some sort of measures would be need to make it work due to temperatures. A massive excess of formamide may do the trick, since formamide is fairly easy to come by... reflux may not even be neccessary in, for example, a volumetric flask, as the glass would not heat by the time the reaction was finished.

just gotta get some tetrabutylamonium bromide and you're home and hosed. i don't see why this reaction would not work, possibly the only concern would be ensuring that everything is dry.

edit: if this method works it opens up a world of possibilities for alternative methods of alkylaminations

sony · Sat Jul 09, 2005 7:41 pm

ApprenticeCook · DILLIGAF

sony if you read what the gabriel method is you would fully understand.
It is the formation of an amine from a halide by the use of (normally) potassium phthalimide, the phthlaimide joins to the halide and then you acidify this formed intermediate and the phthlimide breaks off forming phthlic acid and the amine.

-AC

sony · Sun Jul 10, 2005 4:39 pm

My bad.

Just looked up the reaction mechanism and dont you actually need to basify the reaction (as the Phthalimide is acidic)?

http://www.organic-chemistry.org/frames.htm?http://www.organic-chemistry.org/namedreactions/gabriel-synthesis.shtm

This is indeed very interesting, as this could prove to be a relativeley easy route.

As for OTCness:

How would you guys think saccharin would subsitute for phtalimide ?

Some other PTC's might be used aswell, sony does not know what kind of PTC's are in shampoo's for example but perhaps PEG 400 might work here.

loki · guinea pig

looks to me like succinimide would work the same way, that benzene ring has nothing to do with the reaction.