Author Topic: PMA and PMMA  (Read 2662 times)

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wolfx

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PMA and PMMA
« on: September 09, 2001, 04:50:00 PM »
I looked into PHIKAL, main index, for anethole, and I was directed to # 97, which for my surprise was PMA. I figured out, though, that Shulgin uses anisaldehyde and NOT anethole for this synthesis. After looking a bit more for similar compounds, I found # 130, PMMA. I have the following assumptions, I would like someone who knows more organic chemistry than I do to confirm :

1) There is a typo in the index, it should say anisaldehyde and not anethole.

2) Looks like anethole used with performic method OR Oxone method, followed by reduction with ammonium acetate would yield PMA. With MeAm one would get PMMA.

By the way, I am only interested in the chemistry, I don't plan to make any of the two. Looks like both are similarly dangerous stuff. I though this was interesting enough to post. For those who don't know, I reiterate PMA is DANGEROUS, it is reponsible for several deaths, some wrongly atributed to MDMA. PMMA looks similar.
W.

Karl

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Re: PMA and PMMA
« Reply #1 on: September 09, 2001, 04:57:00 PM »
Anethole is the propenyl benzene of anisole, while anisalaldehyde is the benzaldehyde.

wolfx

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Re: PMA and PMMA
« Reply #2 on: September 09, 2001, 05:28:00 PM »
I looked in ChemFinder and could get the anisole molecule to come up. But, unhappily my knowledge of Organic Chemistry is not enough to understand the implications of what you have said. Could you or someone else extend a bit more , I would like to learn about it by the way.
W.

Rhodium

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Re: PMA and PMMA
« Reply #3 on: September 09, 2001, 05:41:00 PM »
1) Why anisole points to PMA in Pihkal is because anisole is mentioned in the extensions and commentary section of entry #97.
2) Correct, ansisole can be a starting material for both PMA and PMMA.

foxy2

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Re: PMA and PMMA
« Reply #4 on: September 09, 2001, 05:41:00 PM »
Look at chemfinder it will show you the difference.
And here

https://www.thevespiary.org/rhodium/Rhodium/chemistry/yadontsay/




You will see the difference between allyl benzenes and propenyl benzenes.


Do Your Part To Win The War

wolfx

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Re: PMA and PMMA
« Reply #5 on: September 09, 2001, 06:11:00 PM »
Dear Rhod, you are right, I found the reference to anethole at the end of # 97, so it is not a mistake.
Thanks, W.

Rhodium

  • Guest
Re: PMA and PMMA
« Reply #6 on: September 11, 2001, 10:47:00 AM »
jasium: Anisole is methoxybenzene. You mean Anethole, which is 4-methoxypropenylbenzene.

improv_chem

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Re: PMA and PMMA
« Reply #7 on: September 12, 2001, 09:01:00 AM »
Wow, back up a bit.  What is this magical method to make PMA from the ketone?

"Looks like anethole used with performic method OR Oxone method, followed by reduction
                      with ammonium acetate would yield PMA. With MeAm one would get PMMA."

Is this reduction with ammonium acetate occuring in a hydrogenation device under pressure or is it some other beautiful method which has evaded my attention?
Getting the ketone should be a piece of cake with oxone other than the large volumes of solvents and rxn mixture.  Is there any easy way to get this to PMA without a bomb or some exotic chem(like NaBH4) that one can't easily make or get otc at a hardware store?
If not, is PMMA any good at all?  I mean as something to get one high, not to sell.
Just peaked my interest a little because i had a dream the other night that this little buzzing insect was flying around a still and some anise oil. :P

-improv :)

Let's play with nature a little, I'm sure we can make her a little higher....

Rhodium

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Re: PMA and PMMA
« Reply #8 on: September 12, 2001, 09:45:00 AM »
The reductive amination can be performed with an aluminum amalgam reduction, commonly called Al/Hg. The search engine is good for finding out how to do it.

improv_chem

  • Guest
Re: PMA and PMMA
« Reply #9 on: September 13, 2001, 12:19:00 PM »
I am familiar with Al/Hg reactions with MeAm but I thought it would not work well with NH3.  If one was to perform an Al/Hg reaction with NH3 in alcohol instead of MeAm would a decent yeild of PMA be obtained?
Any tips could be very useful.
-improv

Let's play with nature a little, I'm sure we can make her a little higher....

Rhodium

  • Guest
Re: PMA and PMMA
« Reply #10 on: September 13, 2001, 12:22:00 PM »
No, using ammonia or its salts will at best give 30% yield with Al/Hg, probably lower.

hypo

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Re: PMA and PMMA
« Reply #11 on: September 13, 2001, 12:40:00 PM »
a friend tried Al/Hg with NH4Cl + NaOH (from TCBE), yield was in the region of 0%.

you could try to go via oxime. oximes can be reduced with Na, Al/Hg, Urushibara-Ni and probably more.

Chromic

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Re: PMA and PMMA
« Reply #12 on: September 14, 2001, 10:54:00 AM »
Hypo, do you have a writeup for oxime formation / reduction using Hg/Al? (of either pmp2p or mdp2p?)

hypo

  • Guest
Re: PMA and PMMA
« Reply #13 on: September 15, 2001, 01:33:00 AM »
no writeup, sorry. if i had one i would post it! my friend has other projects on his backburner, but maybe i can convince him to try that reaction again.

oxime formation is super easy:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdaoxime.html


MeOH was replaced with EtOH. all sizes where multiplied with 10. a tiny bit more of water was needed to dissolve the NaAc. product can take longer to crystalize (a day).

the al/hg reduction is basically your standard reduction with the following differences:
- use excess of Al (used 10x, next time will try using less)
- before adding the oxime, add some H2O and 4 eq. of AcOH
- let run for 12 hours.
- workup is a little bitchy (lots of unreacted Al). best would probably be to basify with lots of NaOH, wait until all Al has reacted, extract multiple times with alcohol and evaporate under vac (or would the water vapor carry away product?). then do your favorite A/B. filtering of the Al(OH)3 sludge did not work (it was sucked through!). what my friend did was messy: extract with toluene and wash with water. but the washing water separated in two phases(!), so he added some toluene and separated. you get the picture.

yields were an estimated 50% (back then he had no good scale!)
hth.