piperine, piperidine, piperonyl and pepper

joe_aldehyde · huxleys associate

hey syn, just to get things right - i think that you're somehow messing up the names for the respective compounds? piperine is a piperidine-amide of piperic acid, and piperonyl is 1,3-Benzodioxol-5-ylmethyl-something, but not a compound itself. you sure mean piperonal. sorry to be a nomenclature nerd Wink

besides that, if Bromine were OTC, there is also the method of brominating piperic acid to tetrabromopiperic acid and subsequent decomposition in hot dilute NaOH. this method has only been described in the exercise section of some chemistry book (reference is in the respective file mentioned above), but as to the yields of this method, i've not been able to dig anything up.

anyways, i have pepper oleoresin, bromine and hot dilute naoh (eyes on me!), so i could give it a shot. i also got lots of chromate solution and salts, but would this even be worth the try as chromate salts are not at all otc, right?
PCC (pyridinium chlorochromate) would be the best reagent imo, but now thats something surely not OTC plus...we're all male i guess, and we still need our balls...my children will be taught how to make drugs when they come of age Smile

Star-light · Blacklight bulb

biobrew · Tue May 31, 2005 3:32 am

Anyone have a referance on the color of piperine. It seems that a lot of referances that swim has run accross refers to piperine as a pale to yellow solid. And US patent 6054585 refers to recrystalizing in EtOH which really isn't a good choice for resolving piperine. The best choice for a recrystalization solvent seems to ethylacetate, But is this OTC? True piperine crystals tend to be chunky prizmatic clear crystals. Swim has this the isolation of piperine over 30 times.....ouch, that stuff really hurts

taking up the oily oleoresin in ethanoic KOH should push out the crude piperine into yellow needles, but it has been two years since swim did this. This procedure should be environmentally friendly and no need for any bromine or anything else besides solvents and A/B, well at least B

The Ethanoic KOH is crucial as i believe that NaOH wont go into ethanol

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Guest · Tue May 31, 2005 5:19 pm

Joe,

The nomeculture should be fine,

I think the confusion is from another thread that is on Pyridine, which can also be made from pepper, but from the piperidine side,

Let me explain more,

Inside pepper there is about 10% piperine.
Piperine can be broken up into piperidine, and piperic acid.
Piperic acid upon mild oxidation with Kmno4 eventually yields Piperonyl.

There should be plenty of threads on the reaction of piperine to piperonyl.
You see when you break down the piperine, it breaks down into its constituents,,

If you added the structure of piperic acid, and piperidine, you would get piperine,

The other thread (pyridine) deals with the other part of the salvaged molecule.
Here we are dealing with phenylethlamine part,

A lot of people have had success changing piperonyl into MDMA

syn
-hope this clears it up

biobrew · Tue May 31, 2005 8:52 pm

Whoops

guess i skipped a few posts. Rolling Eyes

Will an ozonolysis work here. Cut the hell out of everything then hopefully isolate the aldehyde. Ozone generators aren't that expensive and aren't too bad to build if I remember from some MJ forums.

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primathon · modified

LINK: DIY Ozone Generator Plans

Dope_Amine · Wed Jun 01, 2005 3:12 pm

In looking at literature with piperine as a reactant, general transformations:

-conversion of amide to ester or carboxyllic acid (Bioorganic & Medicinal Chemistry, 12( Cool

, 1905-1920; 2004)

- selective epoxidation of db next to amide (Tetrahedron Letters, 35(2), 279-80; 1994)

-reduction of both conjugated db's w/ H2 & Pd

-reduction of *only* db next to amide (Tetrahedron Letters, 39(7), 677-678; 1998)

-1,4 hydrogenation w/ Mg (Synthetic Communications, 29(21), 3799-3804; 1999)

-double epoxidation w/ MCPBA (Bollettino Chimico Farmaceutico, 136( Cool

, 532-534; 1997)

-formation of cyclic unsat. sulfoxide (w/ amide on one side and methylenedioxyphenyl on other) (Organic Letters, 3(22), 3565-3568; 2001)

-reduction of carbonyl group only (Bioorganic & Medicinal Chemistry, 12( Cool

, 1905-1920; 2004)

-conversion of piperdine to other alkylamines

The conversion of 1,3 diene to 2-ene seems to be promising to me since it de-conjugated the amide/carbonyl...

stratosphere · Tue Jun 07, 2005 5:39 pm

is there a high yield way from piperidine to 4-piperidone?

Bluechip · Sun Jun 19, 2005 11:00 am

I know this is a bit round about,
But coulnt we take the oxidation all the way to piperonylic acid (as this seems to happen anyway),make the calcium salt of the MDbenzoic acid and react with Ca formate to produce the benzaldehyde/piperonal?

Im sure I remember someone mention this in the past.

stooge · Sun Jun 19, 2005 2:16 pm

@stratosphere:
once, in the old days (...) swim asked the same question at the hive and RHOdium himself (yes! he talked to me! i am blessed:)) said that wouldn't be possible ...
or ... is it?!??

stratosphere · Sun Jun 19, 2005 5:05 pm

wow, rhodium spoke to you personally, you are blessed Smile

i can't see why an oxidation would be selective of the 4 position, nor do i see any way to seperate the products of a "shotgun" oxidation plus the yield would be so bad.

i have a crazy idea unsupported by any references i can find, that if you protonate pyridine the resonance structure shares the plus charge between the 4 carbon and N, the one with the + charge on the 4-carbon would have 2 alkene bonds between the 2,3carbons and the 5,6 carbons, so if you catalytically hydrogenated it , it could potentially add 4 hydrogens to the 2,3,5,6 position, leaving you with a carbcation at 4 which should hydrolyze to give 4-hydroxy-piperidine.

to see if this works i would just have to find an atricle about someone trying catalytic hydrogenation of pyridine under acidic conditions.

a silmiliar vain could be tried on nicotinic acid followed by decarboxylation.

stooge · Mon Jun 20, 2005 12:21 am

sorry, i'm a little dumb, didn't understand a word you where saying there - but if there are any otc ways to piperidone i know someone who's VERY interested Smile

oh, btw - what would be a good use for 4-hydroxy-piperidine?

stratosphere · Mon Jun 20, 2005 12:31 pm

4-hydroxy-piperidine could be oxidized with chromate to 4-piperidone.