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piperine, piperidine, piperonyl and pepper
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Would you be willing to contribute for research?
not interested
3%
 3%  [ 1 ]
Definately, and can't wait,
96%
 96%  [ 26 ]
Total Votes : 27

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Ephoton

Joined: 03 Jul 2005
Posts: 72
2474.98 Points
View Single Post10054
re: piperine, piperidine, piperonyl and pepper

 Wed Sep 14, 2005 2:08 pm		 Reply with quote
my post further up this page says sodium nitrate this is a typo it is nitrite Smile
sorry
i also remeber reading somthing about making chloropropionic acid from
lactic acid.
seemed possible.
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Ephoton

Joined: 03 Jul 2005
Posts: 72
2474.98 Points
View Single Post10136
re: piperine, piperidine, piperonyl and pepper

 Fri Sep 16, 2005 2:19 pm		 Reply with quote
disolve pepper in methylated spirits. 1 gram of piperine will disolve in 15ml of
alc
filter
mix with water and leave a night or two
pipperine and pipperic acid do not disolve readily in h2o
Smile Merck
peace
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CherrieBaby
chouchou
Joined: 01 Mar 2005
Posts: 67
3070.02 Points
View Single Post10663
re: piperine, piperidine, piperonyl and pepper

 Tue Oct 04, 2005 1:34 am		 Reply with quote
I think methanol may be best for extracting piperine. Methanol boils at 65C so is easier to remove afterwards. It's also cheap and easy to buy.

After extrating the piperine and hydrolysing it to piperic acid I bet you could oxidise it with alkaline copper sulphate. I think a mole ratio of about 1:6:14 / piperic acid:CuSO4:NaOH would work best.

See these 3 for an experimental discussion:

* http://www.sciencemadness.org/talk/viewthread.php?tid=4465
* https://www.synthetikal.com/synthforum/viewtopic.php?t=414
* USP US2516412

This is what I think would happen:

MDP-CH=CH-CH=CH-COOH + 6 CuSO4 + 14 NaOH -->
MDP-CH=CH-CH=CH-COONa + 6 CuO + 6 Na2SO4 + 7 H2O + NaOH

MDP-CH=CH-CH=CH-COONa + 6 CuO + NaOH -->
MDP-CHO + NaOOC-CH=CH-COONa + 3 Cu2O + H2O

Piperic acid : MDP-CH=CH-CH=CH-COOH
piperonal: MDP-CHO

I wonder whether it would be beneficial to add tartrate? CuSO4 / NaOH / tartrate is Fehlings solution. the CuO formed is complexed with tartrate and becomes available in solution as an oxidising agent.
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CherrieBaby
chouchou
Joined: 01 Mar 2005
Posts: 67
3070.02 Points
View Single Post10696
re: piperine, piperidine, piperonyl and pepper

 Wed Oct 05, 2005 9:17 am		 Reply with quote
MistaMiyagi describes a theoretical process of the oxidative cleavage of piperic acid using CuO

https://www.synthetikal.com/synthforum/viewtopic.php?t=414

but unfortunately that procedure is only speculative. MistaMiyagi admits he "never saved a copy of the thread before the Hive went down". I did, and I am able to confirm that the posts which MistaMiyagi condensed were those of hCiLdOdUeDn.

Hey hCiLdOdUeDn, if you're here now can you tell us all whether your experiments worked? We're all very interested.

These ideas are based on US patent: US2516412, entitled "Method of synthesizing syringaldehyde" and is dated: 1950-07-25

I actually have a HTML version of that patent and can confirm that the procedure provided by Antoncho at the Hive is as in the patent. Most of the reactions in the patent have nothing to do with oxidations of aromatic substitured alkenes.

The only other thing of relevance in the patent to alkene oxidation is the remark
Quote:
when a substantial amount of syringaldehyde was needed for synthetic work recourse had to be taken to oxidation of lignin with alkali and nitrobenzene and separation of the syringaldehyde from the other aldehydes present by the method of Hibbert and co-workers [J. Am. Chem. Soc. 61, 2198 (1939)]
The author (Pearl) gives no specific reference to the oxidative cleavage of alkenes with CuO but does reference one of his own articles (JACS, (1942), pp 1429-31) which I haven't read. I discovered this post to the hive by hCiLdOdUeDn - it reads remarkably similar to MistaKiyaki's post which leads me to the conclusion this and another of hCiLdOdUeDn's posts (also see below) are what MistaMiyagi condensed.
Quote:
Author: hCiLdOdUeDn (Hive Bee)
Date: 12-10-02 02:06
Post No. 387976
Subject: Can someone confirm that copper sulfate under ...

Can someone confirm that copper sulfate under basic conditions would oxidize piperic acid into piperonal with higher yields then KMnO4?

The method seems simple. Just throw in your piperic acid, NaOH, CuSO4, and water. Reflux for 8hours, then filter through a buchner funnel, wash the filter cake, and acidifiy filtrate with HCl. Then extract with DCM and remove DCM to leave impure piperonal crystals? Is that method doable?

If the DCM contained unreacted piperic acid or piperidine, and piperonal, then couldnt a bee do a bisulfite adduct to purify piperonal purification??

Seems like a good route if one cannot find safrole!
Later (in the same thread) hCiLdOdUeDn mentions his experiments. At no stage does he say that his experiments worked.
Quote:
Author: hCiLdOdUeDn (Hive Addict)
Date: 02-17-03 04:19
Post No. 408765
Subject: Hmm.. alanine. Where can I get this OTC?

Hmm.. alanine. Where can I get this OTC?

I am still doing the pepper-->piperonal experiments. After more reading, I have found alot of sources confirming piperic acid does oxidize to piperonal (not like I didnt believe you Rhodium...I DID...I just needed proof ).

Today Ive just processed oleoresin from blackpepper. This stuff is cool. From reading its a matrix of turpenes and about 70% crystalline piperine. The hard part is isolating the piperine from the turpenes and oil...but after experimentation 10mL of boiling 70% Isopropyl alcohol to 7g of oleoresin produced 5g of crude piperine after cooling the IPA. Letting it stand for 48hours left a layer of nice dark yellow crystals. After recrystalization from ethanol...little clear yellow crystal shards weighed out at approx 4g.

Im going for the route from post Antoncho: "Double bond ox. cleavage (to aldehyde) with CuO" (Chemistry Discourse) from Antoncho. Hopefully, piperic acid can be oxidizied into piperonal.

Im trying this at a smaller scale. This is my plan (which will be performed VERY SOON):

5g Piperic acid
25.6g Hydrated Copper Sulfate
16.9g Sodium Hydroxide
205g H2O

This will be placed in a 500mL RB flask refluxed for 8hours with good magnetic stirring.

After the solution cools, I vacuum filter it. This should leave precipatated red cupric oxide because the action of the Benedicts reagent oxidizing the carboxylic acid into the corresponding aldehyde. I will wash the cupric oxide through the filter with warm ethanol and add this to the mother solution.

After that I throw everything into a 1L sep funnel and acidify until neutral. I then extract 3x 50mL DCM. Pool the DCM and evaporate to leave something....

Perhaps bisulifte/metabisulfite could purify piperonal. Destruction could be done with sodium carbonate or NaOH.

These are just thoughts. Anyone care to mention a better idea?

I know it probably needs alot of tinkering before it can work but does piperic acid need to be in suspension or does it need to be dissolved in the solution to work?
I don't recommend following hCiLdOdUeDn's method. Better to stick to the ideas in the patent (US2516412).

Also of interest:

British Patent: 774,608 mentions the following oxidation using manganese dioxide.
Code:

          O
Ar-C=C<  -->  Ar-C=O  +  O=C<
   |             |
The article from Rhodium "aldehyde.txt" describes an oxidative cleavage using NaHCO3/KMnO4

The article I uploaded (below) describes large scale oxidative cleavage using dichromate.

I have uploaded 5 articles which may be of interest to people:

http://rapidshare.de/files/5891157/Piperonal.zip.html

1) British Patent 774,608, 1957, "A Process for the Preparation of Aromatic Carbonyl Compounds from Aryl Ethylenes"
2) US Patent 2,516,412, "Method of Synthesizing Syringaldehyde"
3) Oxidation of a Propenylbenzene (Asarone) to benzaldehyde (2,4,5-Trimethoxybenzaldehyde) using NaHCO3/KMnO4
4) Cervený, Kozel & Marhoul, "Synthesis of Heliotropin", Perfumer & Flavorist 14, pp13-18, 1989
5) Arctander, from "Perfume and Flavour Chemicals, 1969, Heliotropin, pp183-4
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stooge

Joined: 11 Feb 2005
Posts: 56
1401.36 Points
View Single Post10704
re: piperine, piperidine, piperonyl and pepper

 Wed Oct 05, 2005 5:28 pm		 Reply with quote
obtaining the piperonal is less a problem then getting nitroethan in swis' eyes (err swis means "in his opinion", how ever) - or is there anything to do with piperonal without nitroethan? that would be great ...

swis also wonders what to do with the black, oily stuff that was left after filtering the crystalls ...
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kurupira

Joined: 18 Sep 2005
Posts: 3
92.10 Points
View Single Post10705
Re: re: piperine, piperidine, piperonyl and pepper

 Thu Oct 06, 2005 2:00 am		 Reply with quote
stooge wrote:
...is there anything to do with piperonal without nitroethan? that would be great ...


Maybe you could condensate it with MEK, do a Baeyer/Villiger oxidation and saponify the enol-ester to get MDP2P like here..

just speculating...
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