I was looking through Rhodium's site the other day, dreaming up all the ways to whip up some mind warping matter. And this one kinda caught my eye. I havent relly heard of to many bee's on this board talk about this method. Has anybee ever sucessfuly done this starting from black pepper?

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A clean lab is a happy lab:)

What method? A link would be nice. Im sure it can be done, but I cant think of an easy way to change a benzaldehyde into a phenylacetone in a reasonable manner.

                                                  PrimoPyro

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Vivent Longtemps La Ruche!

Here it is.............

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdp2p.piperonal.html

and there's also this thingy:) 

https://www.thevespiary.org/rhodium/Rhodium/chemistry/piperine.txt

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A clean lab is a happy lab:)

Ah yes, I completely forgot about that method.  

Yes it works, and Ive heard a few bees saying that this principle works quite well, and is favorable to many other ketone production methods.

                                                   PrimoPyro

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Vivent Longtemps La Ruche!

The substituted phenylnitropropene can easily be reduced in smallish batches with acetic acid and palladium on carbon to produce an amphetamine product.

Or for the brave, do a LAH reduction in THF.
Or catalytic hydrogenation.

If you really can't stand MDA and demand MDMA, go the Fe/HCl route...extracting from pepper has never been practical in my experience.

TheFiend

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Pacing around and gibbering to myself...

P.S. I've been meaning to try something larger-scale than the acetic acid catalytic hydrogenation...

I've been working on an another method of catalytic hydrogenation--I'll do a write-up...

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Pacing around and gibbering to myself...

.... SWI'a friend of mine (Russian) has successfully extracted piperine from pepper w/acetone - on sitting for some days crystals formed apontaneously. I also have at hand some 3 or 4 different ways to extract properly piperine. Go ahead, ask if you want (too busy now)

SWI'Vitsh, that friend of mine, says all them previous experimenters were completely wrong in the following steps. Piperine is not easy to hydrolyze!

Also - the oxidation step is quite dubious and needs research - there is, however, no doubt that the proc on Rh's (piperonal from isosafrole) will not work. Again, i can give more details and ideas if someone's interested.

Antoncho

> there is, however, no doubt that the proc on Rh's (piperonal from isosafrole) will not work

Huh? The methods described on my page for that transformation will definitely work (or did you mean that they weren't directly applicable to piperic acid?).

Also, 3base have written this nice document:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/piperonal.pepper/index.html

There's a few steps here folks. Somebody rigged up a erlenmeyer with a couple of hundred grams of off the shelf black pepper and threw in some EtOH and let sit. After filtering organic matter out and drying the EtOH off, one gets a mixture of different isomers of piperine (4 to be exact) but never the less they all react with caustic hydroxides to form piperonylic acid + piperidine byproduct(don't worry there's not enough of this to collect for other uses, so let it evaporate)which is then oxidised to piperonyl. Ethyl nitrate is as easy as making HCl from sulfuric acid, and somewhat the same setup but here you won't be collecting gas. The equation goes EtOH+H2SO4--> Ethyl Sulfate + (K or Na)NO3 --> Ethyl nitrate + (Sodium or Potassium) Bisulfate and sulfate. If you decant quickly after the reaction sequence you can save the trouble of separating those byproducts later (even though some purification is needed) The sulfates will crystallize at the bottom then slow dissolve back into the solution. Catch them as crystal and It will save a lot of trouble. Decant. Purify, etc. Now piperine yields I've read are anywhere from 2.5% to 7% of the weight of the pepper used. Mind you this will produce small amounts of MDA in the order of 4 to 5 grams per run per 100 g of pepper. By hey how hard is it to get 100-200 g of black pepper,EtOH,Na or KNO3,H2SO4,KOH? The nitrates used in the Ethyl nitrate run can also used to make nitric acid with can oxidise piperonylic acid to piperonal. I've also read that MnO2 can be used but who wants to purify that out of batteries? I've dreamed up MDA from alkaline batteries, black pepper, stump remover and alcohol. How much more over-the-counter could it be?

Wait--in your dream, 4 to 5 grams of MDA were forthcoming from 100 grams of pepper?  Or is this an exaggeration?

Maybe this deserves some revisiting...

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Pacing around and gibbering to myself...

Dear Rhodium!

By saying that the procedure won't work i simply implied that oxidation of piperic acid w/Na2Cr2O7 is not possible. It was noted by Uemura, that this treatment will destroy the acid all the way to CO2 and water, and confirmed by Vitsh - he experimented w/alkaline, acidic and neutral pHs, and at different temps, too - none of them worked.

Now, in an old book i once read that piperonal was industrially prepared from potassium piperate - that's the rationale of cleaving the amide first - to get it water soluble - with KMnO4 at 3 C.

If SWIM ever starts to experiment on this, he'll undoubtedly check out this method 1st.

Antoncho

Fuchicoma:
(1) > ... they all react with caustic hydroxides to form
piperonylic acid + piperidine ...
do you realy mean piperonylic acid ? usualy piperine is
degradated by e.g. KOH to piperic acid + piperidine

(2) > ... which is then oxidised to piperonyl ...
what do you mean with piperonyl ?

(3) > ... nitric acid with can oxidise piperonylic acid to piperonal ...
oxidation of piperonylic acid leads to CO2, piperonal can be
made by reduction of piperonylic acid or by oxidation of
piperonyl alcohol see

None

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/piperonal.pepper/index.html#conversion)

(4) please describe what you exactly do in this procedure
with Ethyl nitrate and HNO3 ?

it seems that you muddled the chemical names, but
if you have refs on this topic then don't hesitate to
post them here ...

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"Whatever there is to learn has to be learned the hard way."
Castaneda's teacher Don Juan Matus

Antoncho:
 > I also have at hand some 3 or 4 different ways to
extract properly piperine. Go ahead, ask if you want (too
busy now)

> Now, in an old book i once read that piperonal was
industrially prepared from potassium piperate - that's
the rationale of cleaving the amide first - to get it water
soluble - with KMnO4 at 3 C.

i'm highly interested in everything about this topic.
please send everything over to me what you think would fit
in my paper

https://www.thevespiary.org/rhodium/Rhodium/chemistry/piperonal.pepper/index.html

every contribution(small or big) is wellcome: hints, refs,
complete recipes, ...

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"Whatever there is to learn has to be learned the hard way."
Castaneda's teacher Don Juan Matus