Author Topic: Piperonal ---> MDA  (Read 2567 times)

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Kate Moss

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Piperonal ---> MDA
« on: September 10, 1999, 04:01:00 AM »
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


Rhodium

  • Guest
Re: Piperonal ---> MDA
« Reply #1 on: September 10, 1999, 07:02:00 PM »
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.

Kate Moss

  • Guest
Re: Piperonal ---> MDA
« Reply #2 on: September 10, 1999, 09:16:00 AM »
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

  • Guest
Re: Piperonal ---> MDA
« Reply #3 on: September 10, 1999, 09:31:00 AM »
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

  • Guest
Re: Piperonal ---> MDA
« Reply #4 on: September 10, 1999, 09:36:00 AM »
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


Cherrie Baby

  • Guest
Re: Piperonal ---> MDA
« Reply #5 on: September 12, 1999, 12:54:00 AM »
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

  • Guest
Re: Piperonal ---> MDA
« Reply #6 on: September 16, 1999, 12:19:00 AM »

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

  • Guest
Re: Piperonal ---> MDA
« Reply #7 on: September 21, 1999, 12:42:00 PM »
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

  • Guest
3,4-Methylenedioxyphenyl-2-nitro-1-butene
« Reply #8 on: September 21, 1999, 08:24:00 PM »
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)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mdma-bdb.analysis.pdf)

Wizard X

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Re: Piperonal ---> MDA
« Reply #9 on: September 22, 1999, 05:45:00 AM »
Using a dean-stark trap for all aldehyde + nitroalkane condensation rxn, ALWAYS GIVES better yields.

Rhodium

  • Guest
Re: Piperonal ---> MDA
« Reply #10 on: November 18, 2001, 04:26:00 AM »

Post 103789

(Cherrie Baby: "Re: Piperonal ---> MDA", Chemistry Discourse)
is worth looking up. This thread also has other interesting data.

PolytheneSam

  • Guest
Re: Piperonal ---> MDA
« Reply #11 on: November 18, 2001, 03:29:00 PM »
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