01-07-04 08:34
No 480923
Hi bees!
I have searched and searched this site for information on this topic, but i have not found anything that directly describes the scheme i have pondered.
Well the basic idea came from Post 475109 (Lego: "Amphetamines/PEAs w/o benzaldehyde or nitroethane", Novel Discourse), where they bromomethylate benzene in 86,5% yield with a VERY easy procedure. It's almost a shake'n'bake procedure.
Is there any particular reason why this method has not been tested with benzodioxole? In Post 360218 (Rhodium: "3,4-Methylenedioxy-1-bromobenzene Synthesis", Newbee Forum), the chief says that benzodioxole is brominated in super high yields(91%) to 3,4-methylenedioxy-bromobenzene. Obviously this means that the methylendioxy bridge activates the correct sites on the aromatic ring. The only problems i can think of are the following:
1)
The bromomethylgroup is o,p-activating, compared to a bromo substitutent. This might lead to bis-bromomethylated compounds. However, in Post 475109 (Lego: "Amphetamines/PEAs w/o benzaldehyde or nitroethane", Novel Discourse), the same thing should apply. That is, that the group would activate the o,p-position for further bromomethylation, yet this does not happen when the reaction is run carefully. Any ideas if this would work or not?
2)
Perhaps the methylenedixoy-bridge does not like the bromomethylether formed in the reaction. Will the MD bridge get ruined from this reaction?
Those are the two only arguments that could ruin the route. If they do not, the rest would go like this:
i)
Benzodioxole is quite cheap and unwatched(44 euros / 100 g). This is bromomethylated ala Post 475109 (Lego: "Amphetamines/PEAs w/o benzaldehyde or nitroethane", Novel Discourse)(the one w/o HBr) to yield 3,4-methylenedioxy-bromomethylbenzene.
ii)
The compound from reaction i is purified and dried thoroughly, to be used in a grignard reaction. 3,4-methylenedioxy-bromomagnesiumbenzene
iii)
With the magnesium-grignard compound at hand, this is reacted with acetonitrile also described here (../rhodium /phenyl
iv)
The product from iii is either reduced rigth away with borohydride to give MDA or hydrolysed with water to give MDP2P. In the afforementioned text on rhodiums site, Poodle describes a 75-80% yield on regular P2P, and 80% when reduced directly to amphetamine.
Anyone have reasons why this would not work? If it did work it sure would be an easy way to the goodies IMO
. The only timelimiting reaction is the bromomethylation which takes about 16 hours. The rest can be done in less than a days work...Regards
Bandil
Drugs = Fun; Drugs <> Money
(Hive Bee)
01-07-04 11:15
No 480944
Thanks for the detailed description. Lego had the same idea some days ago, it is the logical conclusion of the bromomethylation method.
But for MDP2P Lego suggest another route:
1) Bromination of 1,3-benzodioxole, e.g. Regioselective Bromination of Aromatics Using KBr/Oxone (../rhodium /oxone.
2) Reaction with acetylacetone to get MDP2P: Post 464635 (Lego: "P2P from bromobenzene/CuI/Acetylacetone", Methods Discourse)
For phenethylamines this method is great, if instead of acetonitrile sodium formate is used. This will yield the substituted phenylacetaldehyde which can form the oxime and bee reduced to the amine with any of these methods:
../rhodium /alhg.ox
../rhodium /oxime.t
../rhodium /redamin
../rhodium /oxime2a
../rhodium /mdaoxim
Post 470658 (psyloxy: "oxime reductions w/ Ca and Pd/C NH4COOH", Novel Discourse)
Post 476580 (Chromic: "Al/Hg on ketoximes", Methods Discourse)
Post 477266 (Lego: "Reduction of oximes with zinc/ammonium formate", Novel Discourse)
Post 442691 (Lego: "Reduction of an aldoxime with Zn/HCl", Novel Discourse)
Post 413177 (Lego: "Reduction of ketoximes with Zn/NH3", Novel Discourse)
The candle that burns twice as bright burns half as long
(Chief Bee)
01-07-04 17:59
No 481028
For phenethylamines this method is great, if instead of acetonitrile sodium formate is used.
Huh? This makes no sense to me... Could you clarify?
The Hive - Clandestine Chemists Without Borders
(The Archetypical "Good Guy")
01-08-04 02:44
No 481139
Lego>
Is there any particular reason why the method you mention is preferrable over the one I suggested when it came to MDP2P? Do you think the yields will be superior by this method? The only drawback i can see is that you can't work with grignard reactions with to much THC in the blood
.edit: ohhhh, by further studies of the P2P method i sure can se why it's preferable. Is it really as easy as it looks? Guess thats another project that has to be tested!
As for chloromethylations thats a road I will never take again. I toyed around with them some time ago and boy are they ever tedious. That HCl gas flying around really sucks. The bromomethylation looks so easy in comparison.
Also the method i mentioned hardly requires any wierd chemicals or anything. Everything can almost be bought in 7-11
But swim will definately try the bromomethylation route out if noone objects about a flaw in the line of thought!
Regards
Bandil
Drugs = Fun; Drugs <> Money
(Hive Bee)
01-08-04 03:08
No 481146
@Rhodium:
For phenethylamines this method is great, if instead of acetonitrile sodium formate is used.
Huh? This makes no sense to me... Could you clarify?
Is there any particular reason why the method you mention is preferrable over the one I suggested when it came to MDP2P? Do you think the yields will be superior by this method? The only drawback i can see is that you can't work with grignard reactions with to much THC in the blood
Lego meant these articles on your page:
Aldehydes from Grignard reagents with formic acid (../rhodium
/grigna
@Bandil:
Most bees have serious troubles with Grignard reactions, so Lego considers the bake&fry-method with the acetylacetone to bee superior for this substrate. Your method will work for sure, too, although Lego is not really sure if the methylendioxy group will survive the concentrated sulfuric acid completely.
THC will bee superior for Grignard reactions as the addition has to bee done carefully and slowly, much better than meth
The candle that burns twice as bright burns half as long