Kate Moss (Member)
09-10-99 04:01
No 103784
      Piperonal ---> MDA  Bookmark   

Ok I know there is plenty of information out there about using piperonal as a precursor to MDA but I'm going to ask anyway.

What is the easiest method for the process?  By easy I do not mean requiring no lab skill, I mean using easily obtainable chemicals.  I read methods of using nitroethane, which I can't synthesize right now or find, isn't there any way around this? 

Could someone point me in the right direction. 

Thanks

Kate

 
 
 
 
    Kate Moss
(Member)
09-10-99 09:16
No 103786
      Re: Piperonal ---> MDA  Bookmark   

I'm sure the answer is no, or someone would have done this already but my question is a follows -

Could someone do the Buchener reaction to ethanol using (NH4)2SO4 NH3 to get nitroethane plus the base?

 
 
 
 
    Kate Moss
(Member)
09-10-99 09:31
No 103787
      Re: Piperonal ---> MDA  Bookmark   

Is phloroglucinol difficult to obtain?  I suppose starting w/ ethylbromide wouldn't be to bad. That damn ethylamine is the only thorn in my side these days.

Kate
 

 
 
 
 
    Kate Moss
(Member)
09-10-99 09:36
No 103788
      Re: Piperonal ---> MDA  Bookmark   

Sorry to keep rambeling here.  Having taken a look at your page on it, I'm starting to feel better about the whole thing. 

Thank you much for the help.  Tell that crazy Puerto Rican neighbor of yours I say hi.

Kate

 
 
 
 
    Rhodium
(Administrator)
09-10-99 19:02
No 103785
      Re: Piperonal ---> MDA  Bookmark   

There is no good way around nitroethane if you want to start with piperonal, but on my page, at  http://rhodium.lycaeum.org/chemistry/nitroalkane.html  there is a few syntheses available.
 
 
 
 
    Cherrie Baby
(Member)
09-12-99 00:54
No 103789
      Re: Piperonal ---> MDA
(Rated as: good read)
 Bookmark   

There is an alternative to nitroethane. The Darzens' glycidic ester synth. You need alpha-halo-propionic ester. A chloro or bromo will do fine and an methyl or ethyl ester is OK; typically the ethyl ester of alpha-chloro-propionic acid. The synth uses a substituted benzaldehyde, such as piperonal, a strong base and the alpha-halo-(propionic ester). It can be done with just KOH or NaOH as the base provided that a phase-transfer catalyst is used. The glycidic ester is converted to MDP2P easily. [CA 112(1):7280f; Chim. Acta Turc. 16, 227 (1988)]

An alternative to the alpha-halo-propionic ester for a Darzens is chloro-acetonitrile. [JCS Chemical Communications. 902 (1977); Synthetic Communications 16, 983 (1986); Bulletin Chemical Society of Japan, 53, 1463, (1980)].

 
 
 
 
    halcyon
(Member)
09-16-99 00:19
No 103790
      Re: Piperonal ---> MDA  Bookmark   


Drone and I had a quick convo about this about a month or so back (I was doing most of the listening, of course  .

but basically, instead of making the phenylnitropropene intermediate which needs that nasty /watched/ precurser nitroethane, you make the nitrobutene using nitropropane...

with the former, you'd reduce the propene to MDA or MDP-2-P, but with the latter, you'd reduce the butene to make J (alpha-Ethyl-3,4-methylenedioxyphenethylamine; PiHKAL, pg 698.), or MDP-2-but...

Sources: drone's ramblings,
PiHKAL

------------------
.x[ PLUR ]x.
halcyon; Kinetic Pharmaceuticals

 
 
 
 
    Siamese
(Junior Member)
09-21-99 12:42
No 103791
      Re: Piperonal ---> MDA  Bookmark   

From Pihkal #94 J:

Efforts to prepare this ketone by the iron and acid reduction of the appropriate nitrostyrene (1-(3,4-methylenedioxyphenyl)-2-nitro-1-butene, mp 64-65 C) were thwarted by the consistently unsatisfactory yield of the
precursor from the reaction between piperonal and 1-nitropropane.

A shame, it sounds nice.

 
 
 
 
    Rhodium
(Administrator)
09-21-99 20:24
No 103792
      3,4-Methylenedioxyphenyl-2-nitro-1-butene
(Rated as: excellent)
 Bookmark   

3,4-Methylendioxyphenyl-2-nitro-1-butene
A solution of piperonal (10.0g, 67 mmol) and n-Butylamine (19.4g, 267 mmol) in 100ml benzene was stirred at reflux for 6 hours. The water (1.2 ml) generated during imine formation was removed with a dean-stark trap. The reaction mixture was cooled to room temperature and the solvent evaporated in vacuo to yield the intermediate imine as a yellow oil. The imine was dissolved in a solution of nitropropane (6.2g, 70 mmol) and glacial acetic acid (20 ml) and stirred at reflux for 30 minutes. The reaction was then poured over crushed ice and acidified with concentrated HCl to pH 2 to yield the nitrostyrene as a dark green solid. The solid was isolated by filtration and recrystallized from IPA. Yield 8.4g, 63%.

Reference:latest addition (10-19-04):
Methods for the Analysis of 1-(3,4-Methylenedioxyphenyl)-2-Butanamine and N-Methyl-1-(3,4-Methylenedioxyphenyl)-2-Propanamine (MDMA)
F. Taylor Noggle, Jr., C. Randall Clark, Shridhar Andurkar, and Jack DeRuiter
Journal of Chromatographic Science, Vol 29, 103-106 (1991) (../rhodium/pdf /forensic/mdma-bdb.analysis.pdf)
 
 
 
 
    Wizard X
(Moderator)
09-22-99 05:45
No 103793
      Re: Piperonal ---> MDA  Bookmark   

Using a dean-stark trap for all aldehyde + nitroalkane condensation rxn, ALWAYS GIVES better yields.
 
 
 
 
    Rhodium
(Chief Bee)
11-18-01 04:26
No 237908
      Re: Piperonal ---> MDA  Bookmark   

Post 103789 (Cherrie Baby: "Re: Piperonal ---> MDA", Chemistry Discourse) is worth looking up. This thread also has other interesting data.
 
 
 
 
    PolytheneSam
(Master Searcher)
11-18-01 15:29
No 238027
      Re: Piperonal ---> MDA  Bookmark   

Two good articles to look at on the subject (using alpha-halo acetic and propionic esters) are:
Amines Related to 2,5-Dimethoxyphenethylamine I and Amines Related to 2,5-Dimethoxyphenethylamine II in JACS, Jan 1940, pages 161-167.

http://www.geocities.com/dritte123/PSPF.html