posted 02-04-99 12:45 PM         

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Boy, this dream pissed The Cook off thoroughly quite a few times. I would awake to nothing. (How Frustrating, when you KNOW it works)
But the other night, she locked the doors, pulled the blinds, and stared at her spice rack. Oxidation seems to be the big problem in this dream, but check out:
http://www.lycaeum.org/~rhodium/chemistry/aldehyde.txt
Looked sound. Let's do the Math.
15g Asarone ->.072 Mol
40g Bicarb -> .476 Mol
25g KMnO4 -> .158 Mol
So it's roughly a 1:2:5 oxidation(maybe 1:2:6?), and for a 50% yield, it's worth a shot.
Who, What, Where, etc:
Piperine is extracted from B. Pepper with an organic solvent. Duh. Anhydrous alcohols are fine, ether is much cleaner. Solvent is evap'd to leave yellow crystals.
Hydrolize with NaOH in Alcohol. (MeOH/EtOH both verified)
Oxidize with Potassium "Yeild Killer" Permanganate, to get a flask full of chopped-up molecules :-).
Procedure:
-100g Black Pepper, refluxed in MeOH for 20 min. Filter, Evap. MeOH to yeild yellow crystals. Dissolve in Acetone, filter (If needed), then recrystallize Piperine, mp:131<-NOT BAD!!! (Sorry, she forgot to dream it's weight.)
-Piperine added to NaOH in MeOH. refluxed till MeOH is gone, leaving Sodium Piperidiene and Piperic Acid as a Brown tar, crystallizing to yellow gunk upon cooling. -100ml dH20 added, solution was heated to boiling. Soln. acidified using HCL, giving a yellow suspension, and brown oil floating on top.
-Solution was cooled, then ugly, chunky, yellow piperic acid was filtered. Filter cake was dissolved in acetone, and NaCl filtered out. Recrystallize, Note the change of odor.
-A 1:2:5 oxidation was dreamed, similar to the asarone oxidation.
2.18g (.01 Mol) Piperic Acid was suspended (Suspended, it DON'T dissolve) in 150ml boiling dH20, containing 4.2g (.05 Mol) Sodium Bicarbonate. To this hot solution, 3.16g (.02 Mol) KMnO4 [Well, some didn't dissolve] in 75ml warm dH20 added with an eyedropper over about 40 min. (Notes ream an addition funnel, or lose your mind from boredom. Keep this slightly exothermic reaction CONSTANTLY stirred.)
->During the additon of the permanganate, she dreamed that the pepperish smell subsided almost completely, with the formation of a NEW, milder, marshmallow-y good smell. Mmmmm.
/* The Cook thinks that the oxidation could be done 'on the fly', using the smell as an indicator. (If you're good) But last time she dreamed that, she oxidized it all into pipenylic acid. OOPS! */
-The warm brown solution was filtered to leave a slightly yellow/tan solution. This was chilled overnight, as per the asarone oxidation, but the crystals were TINY!
[Actually, this 'failure' has been a reoccurring dream, the main cause of the frustration in this rxn]
-The Cook cursed the slightly cloudy solution, and in a fit of rage, added 25ml IPA. (To kill any remaining oxidizer) She dumped the solution into a pyrex dish, and set it on the heater for a few days.
-The next time she slept (48h later), she dreamed the solution had evaporated into off-white, glassy chunks(YES!!). There was also some brown MnO2 at the bottom, and some tartaric acid, but that's not important. What is important is: that shit can be filtered/ recrystallized to give just over 1g of luscious translucent Piperonal rocks. MP was dreamed to be 41, so it ain't Lab Grade, but it ain't bad either, bees. She dreamed this substance had a wunnerful, indescribable odor that could be likened to marshmallow with a slight fruity, cherry overtone. It smelled so good, she ate it all, and died later that day, leaving no evidence or record other than this. So if any bees are feeling frisky, she'd like to know HOW BIG it can be scaled. If you dream the answer, point your flask towards hell, and yell real loud! ;-)
-cook (Still tryin' to keep it real)

When you see the Southern Cross for the first time, you understand now why you came this way.

posted 02-04-99 05:56 PM         

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An alternate synthesis of 3,4-methylenedioxyphenylacetone starts originally from piperonal. A
suspension of 32 g electrolytic iron in 140 mL glacial acetic acid was gradually warmed on the steam
bath. When quite hot but not yet with any white salts apparent, there was added, a bit at a time, a
solution of 10.0 g of 1-(3,4-methylenedioxyphenyl)-2-nitropropene in 75 mL acetic acid (see the
synthesis of MDA for the preparation of this nitrostyrene intermediate from piperonal and nitroethane).
This addition was conducted at a rate that permitted a vigorous reaction free from excessive frothing.
The orange color of the reaction mixture became very reddish with the formation of white salts and a
dark crust. After the addition was complete, the heating was continued for an additional 1.5 h during
which time the body of the reaction mixture became quite white with the product appeared as a black
oil climbing the sides of the beaker. This mixture was added to 2 L H2O, extracted with 3x100 mL
CH2Cl2, and the pooled extracts washed with several portions of dilute NaOH. After the removal of
the solvent under vacuum, the residue was distilled at reduced pressure (see above) to provide 8.0 g of
3,4-methylenedioxyphenylacetone as a pale yellow oil.

hellman

posted 02-04-99 05:59 PM         

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woops!.

SYNTHESIS: (from piperonal) To a solution of 15.0 g piperonal in 80 mL glacial acetic acid there
was added 15 mL nitroethane followed by 10 g cyclohexylamine. The mixture was held at steam-bath
temperature for 6 h, diluted with 10 mL H2O, seeded with a crystal of product, and cooled overnight
at 10 °C. The bright yellow crystals were removed by filtration, and air dried to yield 10.7 g of
1-(3,4-methylenedioxyphenyl)-2-nitropropene with a mp of 93-94 °C. This was raised to 97-98 °C by
recrystallization from acetic acid. The more conventional efforts of nitrostyrene synthesis using an
excess of nitroethane as a solvent and anhydrous ammonium acetate as the base, gives impure product
in very poor yields. The nitrostyrene has been successfully made from the components in cold MeOH,
with aqueous NaOH as the base.

posted 02-04-99 08:51 PM         

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Well as I was saying before I pushed the wrong button. See http://www.chemfinder.com/
and search on paroxetine also known as Paxil. A common antidepressant. If you'll notice breaking the ether linkage of Paxil yields, Piperonal.
I suspect there are many more suprises in the pharmacopia of the antidepressants.

------------------
... smell the whiskey burnin down copperhead road.
cdu4.cduniverse.com/programs/hurlPNM.exe?/75693633/~aa-457027/0092625_0101_00_0002.ra

posted 02-10-99 03:52 PM         

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"think about how many times, I have fallen,
spirits are usin' me, and I hear the voices callin'..

Southern Cross is a cool old song by Crosby Stills and Nash.......

posted 02-11-99 12:27 PM         

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In trying to validate the cook's isolation and conversion above I found:

Methanol is too hard to get to just pour liters of into pepper and boil away, so I used denatured alcohol. So to a pound of pepper I added 600ml of denatured alcohol and boiled away for about 30 minutes. Filtered the pepper out and saved for another boil later. Evaporated the alcohol leaving a black sticky goo with some yellowish solids in it. Dissolved as much of the stuff as I could with acetone and filtered.

The yellow solids didn't dissolve, but a lot of black tar did. Now I have yellow sticky powder (there's still some of the black gunk in it) and black tar. Both smell like pepper.

The yellow stuff won't dissolve in acetone like he indicated, so there's no hope of recrystalizing this way. The black stuff won't crystalize, it's some kind of tar. I think what's needed is to get the rest of the tar out of the yellow stuff and then proceed with it. The black tar can be diluted with 95% drinking alcohol and used as a spice.

opinions?

posted 02-11-99 04:22 PM         

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I tried this too.

It makes for a fuck of a mess.

Got the yellow powder and the brown tar. The tar sticks to e-thing like, well, like TAR, I guess......

We probably should work on it....

posted 02-17-99 06:39 AM         

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Just to let you guys know.

When attempting to extract piperic acid/chavacine (E/Z isomers) from the pepper, I have found the best method is to soxhlet extract with EtOH - it doesnt have to be that dry either! Also , for good yields you need a hell of a lot longer than 20 minutes, try 6 hours to get a good yeild!

Peace, love and empathy

Fan of Shulgin

posted 02-17-99 06:48 AM         

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P.s - when I say piperic acid/chavacine I do mean piperine ( I had skipped the alkali induced cleavage).

And another thing - if you can get soxhlet apparatus then just make your own version! Its easy to make with plastic tubing and filter paper!, and it really will stop all that black crap getting into the ethanol solution of piperine!

All times are CT (US)