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Author: Subject: Piperic acid oxidation to Piperonal
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[*] posted on 9-9-2005 at 19:11
Piperic acid oxidation to Piperonal


Does anyone have a tried and tested method for the oxidation of piperic acid to pieronal?

The most commonly known route of KMnO4 in THF or PTC/Alcohol has pretty bad yields, is there a better yielding route that anyone has used before? A workup would be better even again...

Any help would be greatly appreciated...
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[*] posted on 9-9-2005 at 20:36


Someone had the same question some time ago at the Hive ....here are some of the comments then, which I hope will help you make some choices........solo

Quote:


Everyman
(Member)
09-13-98 15:48
No 172238
Oxidation of Piperic Acid (Pepper to Piperonal)

Cherrie Baby recently mentioned Piperine - Piperic Acid - Piperonal as a good route.
This guy here :

http://www.lycaeum.org/~rhodium/chemistry/piperine.txt

seems to have had trouble with the oxidation of Piperic Acid via KMnO4, reporting *piperonyl, piperonylic acid and/or piperonyl acetone in varying quantities.*

Would some sort of catylised Oxidation work better? Someone recently said something about KMnO4 being non-selective. Perhaps there is a better route?

If this could be made to work in reasonable yeilds youd be looking at Piperonal OTC for $100/Kilo.

Perhaps its not that tempting now, but in a few years it may be.

So has anyone got any ideas?





Everyman
(Member)
09-17-98 19:36
No 165765
Oxidation of Piperic Acid (Pepper to Piperonal)






spiceboy
(Member)
09-18-98 09:58
No 165766
Oxidation of Piperic Acid (Pepper to Piperonal)

Try sodium dichromate in acid solution. It seems to be gentler than KMnO4.



Cherrie Baby
(Member)
09-19-98 04:30
No 165767
Oxidation of Piperic Acid (Pepper to Piperonal)

Uranium - for those special disco-biscuits that glow on the dance floor?
I think ozonolysis is a possibility. Patents exist for the manufacture of piperonal from safrole. Strike forgets that dichromate is 1) not OTC and 2) produces toxic chromate waste products. But... ozonolysis is difficult to control.





dpHarma
(Member)
09-19-98 22:45
No 165768
Oxidation of Piperic Acid (Pepper to Piperonal)

how about high intensity UV, from a germicidal lamp.
dpHarma





Everyman
(Member)
09-20-98 15:49
No 165769
Oxidation of Piperic Acid (Pepper to Piperonal)

Cherrie - Any chance of a brief description of the ozonolysis process or a ref on one of those patents?
When you say difficult to controll is that as in by-products, or explosions?





Piglet
(Member)
09-21-98 12:39
No 165770
Oxidation of Piperic Acid (Pepper to Piperonal)

using O3: H.E.Carter 'Journal of Biological Chemistry' vol.36 p4273-8 (1966) - 96%
(also CAS vol.50 16890g).
using K2Cr2O7 (like SP said): 'J.Chem.Ind.Tokyo' 23 p56-79 (1920).

Good luck finding that second reference!





spiceboy
(Member)
09-21-98 18:44
No 165771
Oxidation of Piperic Acid (Pepper to Piperonal)

you can too get dichromate OTC.....
Go to a Ceramic Supply in your area...I found the shit way, WAY cheaper than any chem or photo supply....



Piglet
(Member)
09-21-98 18:52
No 165772
Oxidation of Piperic Acid (Pepper to Piperonal)

Dichromates are controlled as poisons in the UK. Destroys rivers and what not. Still, I for one am not messing with 03. There is a design for an O3 generator in Vogals.
KMnO4 will most likely give you acid. I think...



Sailor Moon
( )
09-21-98 22:20
No 165773
Oxidation of Piperic Acid (Pepper to Piperonal)

It is time to call Drone 342 and inquire as to the possibilities of using a milder oxidant such as hypochlorite. I have heard her espouse this idea several times....



Cherrie Baby
(Member)
10-01-98 01:16
No 165774
Oxidation of Piperic Acid (Pepper to Piperonal)

Jerry March - (pages 1181-82) on oxidative cleavage of double bonds:
With ordinary solutions of permanganate or dichromate the yields are generally low and the reaction is seldom a useful synthetic method; but high yields can be obtained by oxidising with KMnO4 dissolved in benzene containing the crown ether dicyclohexano-18-crown [J. Am. Chem. Soc. 94, 4024 (1972); J. Org. Chem. 43, 1532 (1978)

With certain reagents the oxidation can be stopped at the aldehyde stage, and in these cases the products are the same as the ozonolysis procedure. Among these reagents are:

chromyl trichloroacetate: Liebigs Ann. Chem. 659, 20 (1962)
t-butyl iodoxybenzene: Tetr. Lett. 26, 4955 (1985)
KMnO4 in THF-H2O: J. Org. Chem. 51, 3213 (1986)
NaIO4-OsO4: J. Org. Chem. 21, 478 (1956)

That KMnO4 in THF looks very enticing - I'll mail the procedure ASAP.





spiceboy
(Member)
10-01-98 19:26
No 165775
Oxidation of Piperic Acid (Pepper to Piperonal)

What about attempting to slow the rate of KMnO4 oxidation ala the 'cold cat' method?
The supposed knock on that was that the permanganate would overoxidize the p'fed...blahblahblah

but it doesn't if treated correctly.
diluting the FUCK out of it and chilling it seems to really take a lot of oomph out of the Rx.....????





Piglet
(Member)
10-01-98 19:35
No 165776
Oxidation of Piperic Acid (Pepper to Piperonal)

KMnO4 is weaker in alkali media. Maybe in ammonia solution?



Cherrie Baby
(Member)
10-03-98 02:45
No 165777
Oxidation of Piperic Acid (Pepper to Piperonal)

The following abstract appears to contain a mistake - it talks about making MDP-acetyl carbinol by fermenting vanillin with yeast. I thought I'd flashed back to acidtopia when I first saw it - funky yeast - yeh!! They probably meant via fermentation of piperonal. US pat. 3338796 will, hopefully, have more info. on MDP-acetyl carbinol.
MDP-acetyl carbinol is easily reduced to b-Me-MDP-glycol, from which MDP2P can be obtained by our dear friend the Pinacol rearrangement. The total process is untried so yields are as yet unknown. But everything is very OTC.

Piperonal can, itself, be obtained by oxidation of piperic acid (from pepper) with KMnO4 in THF or with PTC. [see the references above, in my previous post]. The amount of KMnO4 used must be strickly limited so as not to over-oxidise to the MD-benzoic acid.

I hope to get this patent next Monday.


Chemical Abstracts Vol. 67, 1967, page 8432, 89797u
Converting veratraldehyde to L(-)3,4-dimethoxyphenylacetyl carbinol. John W. Rothrock (to Merck & Co. Inc.). U.S. 3,338,796 (Cl. 195-28), Aug. 29, 1967, Appl. Aug. 19, 1964, and Oct. 13, 1966; 2 pp.
L(-)3,4-Dimethoxyphenylacetyl carbinol (3,4-(MeO)2C6H3CH(OH)Ac) is produced by contacting veratraldehyde with a growing acyloin-producing culture of Aerobacter aerogenes ATCC 211; the product is isolated by extn. and crystn. Thus, medium contg. com. yeast ext. 20, dextrose 20, MgSO4 7 H2O 0.5, KH2PO4 0.2, and Na2HPO4 0.2 g./1., with pH adjusted to 7, is inoculated with a strain of Saccharomyces cerevisiae; the medium is aerated and agitated at 28° for 48 hrs. The agitation and aeration are stopped. Vanillin is added to give a concn. of 4 g./1. The agitation and aeration are resumed and continued for 7 hrs. to produce L-3,4-(methylenedioxy)phenylacetyl carbinol. The fermentation broth is sterilized and filtered to remove the cells. The filtrate is satd. with NaCl and extd. 4 times with 1/3 vol. of EtOAc. A crude product is obtained after evapg. the EtOAc. A by-product of the fermentation process is removed by crystn. from an EtOAc-petroleum ether soln. of the crude product. The mother liquor contains the desired product, the solvents are removed by evapn. and the residual oil is subjected to partition column chromatog. using diatomaceous earth and a solvent mixt. of C6H6-EtOAc-MeOH-H2O (9:1:5:5). The fractions eluted are vanillyl alc., vanillin, and a mixt. of vanillic acid and L-3-methoxy-4-hydroxyphenylacetyl carbinol. The last fraction is fractionally crystd. from a mixt. of EtOAc-petroleum ether to remove vanillic acid. The mother liquor contg. the product is further purified by extn. by aq. Na2SO3 to ext. acetyl carbinol as a bisulfite. The bisulfite addn. product is decompd. by addn. of an excess of an aq. soln. of Na2CO3. The product is extd. with EtOAc. The ext. is evapd. to a small vol. to cryst. L-3-methoxy-4-hydroxyphenylacetyl carbinol; m.p. 69-73°, [a]D23 = 211° (c 1.02%, acetone). L-3,4(Methylenedioxy)phenylacetyl carbinol, m.p. 44-6°, [a]D25 = 228° (c 1.2% EtOAc), and L-3,4-dimethoxyphenylacetyl carbinol were also produced by the method. S. P. Marino






Cherrie Baby
(Member)
10-14-98 05:20
No 165778
Oxidation of Piperic Acid (Pepper to Piperonal)

Last post was a little off topic but the same error occured in the patent - as well. So that's a grand total of 1 author, 2 patent examiners and 1 Chem. Abstracts transcriber who failed to notice the obvious error - 1 mentioned previously!!

Everyman Are you serious about the pepper? - I don't have time to do this until about 12 days from now but I've figured everything out in theory and have all the refs.
Isolation of Piperine from Black Pepper - J. Chem. Ed. 70(7), 598-9 (1993)

Hydrolysis to Piperic acid (might not be needed (at Rhodium's)

Oxidative cleaveage to Piperonal with cetyltrimethylammonium permanganage - see Synthesis 1984, p 431-3. They also give details for making CtMe3N MnO4 from CtMe3NBr - but I can't see why CtMe3NCl shouldn't work just as well (CtMe3NCl is ubiquitous in loads of OTC skin & Hair products) - I intend to try this first with fabric conditioner - it's cheaper but is less hydrophilic (so might not work!).

Also J. Chem Research - Synopses 1986, p 458-9 for "Cetyltrimethylammonium Permanganate: a Useful Reagent for the Selective Oxidative Cleaveage of Aryl-substituted Olefins"

R4N+ MnO4- is one reagent to use - expected yield of piperonal ~ 74% with this:

The benzylic alkene of piperic acid should cleave to aldehydes (either side) and other, purely aliphatic alkene group will give a diol.

Alternatives are to use (2) aq. KMnO4 with substrate in THF - it might work - see J. Org. Chem. 51, p 3213 (1986). Or (3) PTCs, which include: Crown ethers (too expensive), TDA-1 - see Synthetic Commumications 17 p 647-55 (1987), Dimethyl polyethylene glycol - see J. Org. Chem. 43, p 1532, (1978).

General Procedure for the Oxidative Cleavage with CTAP

To a stirred solution of the alkene substrate (1 mmol) in DCM (7 mL) was added a solution of CTAP (1 mmol) in DCM (6 mL) at 25°C. After 2-6 h, diethyl ether (50 mL) was added and the reaction mixture was filtered through a pad of Celite and anhydrous MgSO4. The filtrate was concentrated in vacuo and the crude product was purified by chromatography on silica gel to afford the pure carbonyl product. [From: J. Chem. Res. (S), 1986, 459]

Note (mine): CTAP: cetyltrimethylammonium permanganage.

Why do they add diethyl ether and not more DCM? Surely better to stick with just one solvent so that it can be recycled?

Cetyltrimethylammonium Permanganate, CTAP

To a stirred solution of potassium permanganate (3.168 g, 20 mmol) in water (100 mL) at 20°C is added, dropwise over 20 min, a solution of CTAB - Cetyltrimethylammonium Bromide (8.02 g, 22 mmol) in water (100 mL). A fine violet precipitate forms immediately. Stirring is continued for 30 min, the precipitated product is isolated by suction, washed thoroughly with water, and dried in a dessicator over phosphorus pentoxide in vacuo for 3 h at room temperature to give the salt as a fluffy violet solid; yield: 6.5 g (80%). The reagent is stored in a brown bottle in the refrigerator. [From Synthesis 1984, p 431]

Notes: a suitable alternative to CTAB is CTAC aka Cetrimide or Cetrimonium Chloride - found in hair conditioners. [A small cosmetics company would have no difficulty getting hold of mucho supplies of this in mega quantities]

An alternative dessicant to the P2O5 is KOH or NaOH? Why not? Dessication is essential and these quaternary ammonium compound are very hygroscopic.






The Cook
(Member)
10-19-98 07:41
No 165779
Oxidation of Piperic Acid (Pepper to Piperonal)

The other day, I was eating breakfast when I tried to dump some black pepper on my eggs.
It seems that someone had unscrewed the lid!
As pepper poured over my food, I became so irate that I passed out and dreamed I was watching a show called Ghetto Precursors-It was a generalization of several runs.
Here's what was on it.
Someone put 1 cup of blk pepper in a snapple bottle then added a goodly amt of IPA (drygas)
They capped it and shook like hell and the IPA turned yellow/brn. Then they filtered out the pepper from the yellow IPA, and heated the filtered IPA to dryness.
They were left with roughly 15-20g of yellowish powder. When they washed it with acetone, it looked much cleaner.
The yellow powder was dumped into the now clean snapple bottle, and IPA was once again added. Sodium Bicarbonate was also added, about 2 Tbsp(but more was added if it was consumed). This mixture was boiled to dryness in the microwave, stopping periodically to stir/let the soln calm down.
Before it boiled dry, it formed two layers, the bottom one was light yellow, the top was brown/dark yellow.
Again, IPA was added and the crystalline mush was filtered to give about 10-15g of lt. greyish crystals. The people on the show could not get this shit to melt! Even when it was heated extremely hot, it only turned white.. I guess they burned off some imputities, though... Oh, well.
They then added the white crystals to some hot dH2O, but solubility was bad, even with stirring. Then some .5 molar soln of KMnO4 was added, with stirring. What it looked like they were doind was: They heated the mixture, added some KMnO4 soln, and stirred until the purple turned brown. I could see that the crystalline mass at the bottom of the jar was being digested, as the entire soln turned chalky tan. As soon as the KMnO4 soln was not immediately used (i.e. it stayed purple for a few sec.) IPA was added to quench the soln (although the show said IPA sometimes fucked up cat synths). Now the soln was allowed to cool, and some ether/hexane was added to try to extract whatever made the mixture turn yellow again. The show said be careful with ether, especially doing dumb shit like adding it to hot water. (overboil)
The ligroin (ether/hexane) was sep'd in a ghetto sep funnel (ziplock bag-cut off corner).
This ether extraction was repeated several times, at different temperatures. All ether solns were mixed, and evaporated at steam bath temp (>100)to give funky looking yellow oil.
SO WHAT???, I asked! then the people on the show threw the plate of yellow oil in the fridge and it froze quickly into a very pale yellow-almost white (when broken up)
crystalline mass.
Wow, I thought, those bastards made a pepper extract that's liquid at room temp, but a solid when cooled. It's kinda waxy looking, and rather unspectacular. Then the show ended, and the announcer said next week, at the same bat time, same bat channel, they would couple this nasty shit with nitroethane... i wonder why they'd want to..
Anyway, that's the bizarre ass dream I had, Sorry if it's rambling or hard to follow, my memory is kinda foggy from the pepper overdose. Anyway, here are some things I remember them saying as they worked.
1)As they filtered the pepper from the IPA..
"Damn this shit smells peppery"
2)One got the yellow pepper extract on his face...
"Ouch, this burns like pepper on my face"
3)After the acetone wash of above extract.
"Boy, that's bright yellow"
4)When they boiled the yellow extract with bicarb...
"Look! 2 layers! How'd that happen"
5)After above reflux
"What happened to my yellow powder? All I have now are whitish crystals!"
6)While adding the permanganate...
"Hey, that funky pepper smell is changing into a more pleasant odor!"
7)After yellow oil extraction...
"This doesn't smell like pepper very much at all!"
8) While playing with room temp melting point.
"This stuff should be kept in the freezer!"

Once again, I apologize for any and all typos, and sorry I didn't have their measurements, the program said it would make the whole game too easy.. Post any related dream stories. This seems to be QUITE ineffiecient, but if blk pepper is $5.00 a pound, it ain't that bad. Plus, it's OTC.

*I miss ZWITTERION's kitchen chemistry tales.





The Cook
(Member)
10-19-98 07:48
No 165780
Oxidation of Piperic Acid (Pepper to Piperonal)

Yeah, I know the plot was from Natural Products-A Lab Guide. Just thought y'all might be interested in just how easy & dirt fucking cheap this rxn might be. If anyone dreams in a manner similar to this one, pls post.. I wondered if there was a better solvent for the oxidation product, but I woke up before I could ask the announcer.
P.S. Total dream time was roughly 2hrs continous (Yeah I nap hard)



The Cook
(Member)
10-24-98 01:29
No 165781
Oxidation of Piperic Acid (Pepper to Piperonal)

Hey, if you're effieciency freaks, this sucks for you. My dream ended with >1g
And my roommate washed the plate it was on.



Rhodium
(Chief Bee)
04-24-04 19:24
No 502699
Alkenes to Aldehydes Using KMnO4
(Rated as: good read)

Article mentioned in Post 165774 (Cherrie Baby: "Oxidation of Piperic Acid (Pepper to Piperonal)", Chemistry Discourse)

Cleavage of Alkenes to Aldehydes Using Potassium Permanganate
P. Viski, Z. Szeverenyi, and L. I. Simandi
J. Org. Chem. 51, 3213-3214 (1986) (https://www.rhodium.ws/chemistry/alkene2aldehyde.kmno4-thf.h...)
The Hive - Clandestine Chemists Without Borders



starlight
(Hive Bee)
08-31-04 13:19
No 528471
inaccuracy/omission

The procedure described in the paper on Rhodium's page calls for dissolving 10g of potassium permanganate in 100ml of water.

The solubility of potassium permanaganate in water at 20C is 6.3g/100ml.

Either the volume of water is wrong or the permanganate solution needs to be prepared and kept at a higher temperature during the addition.

Do you think it is safe to add permanganate solution to THF and concentrate it afterwards? (thinking of peroxides here).,




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CherrieBaby
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[*] posted on 3-10-2005 at 08:11


I've edited my original reply a few times because I discovered that the topic has already been discussed, both at the hive and at synthetikal:

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

I posted some details from a hive post below.

I think alkaline copper sulphate is a cheaper option.

CuSO4 + 2NaOH -> CuO + H2O + Na2SO4

2CuO -> Cu2O + (O)

Unfortunately the precise reaction is unpublished.

Which one of these is it?:

(1) MDP-CH=CH-CH=CH-COOH + 2(O) -> MDP-CHO + HOC-CH=CH-COOH

(2) MDP-CH=CH-CH=CH-COOH + 3(O) -> MDP-CHO + HOOC-CH=CH-COOH

(3) MDP-CH=CH-CH=CH-COOH + 7(O) -> MDP-CHO + 2 HOOC-COOH

My vote goes for (2) and here's why. We know that the alkene ajacent to the aromatic is oxidised (see below). But we also know that Fehlings oxidises aliphatic aldehydes. Nothing suggests that Fehlings will oxidise butenedioic acid (aka Maleic acid) because Fehlings does not (normally) oxidise alkenes. We can also be fairly sure that piperonylic acid won't be produced if the oxidiser is not in excess because aromatic aldehydes are oxidised very slowly by Fehlings (compared to aliphatics).

So my recommendation is 1 part piperic acid, 12 parts sodium hydroxide and 6 parts copper sulphate to go with rxn. (2) above. That's all theoretical. How about someone with decent analytical gear give this a test and report back to us please?

Fehlings Solution is alkaline Copper Sulphate + tartrate. In Fehlings, tartrate works to complex the CuO thereby making it available in aqueouse media and possibly acting as a phase-transfer catalyst. There is no write up for this precise reaction in the literature [rxn. (2) above]. I think it has only been done with Syringaldehyde and substances mentioned in US2516412.

This is the only report I can find on the rxn and I can't even remember which forum I copied it from. I don't necessarily agree what the proportions given below are correct. My estimated ratios for Piperic acid:CuSO4.5H2O:NaOH are 1:6:12.
Code:
Substance - MWt. - ratio - weight1 - weight2 Piperic acid - 218.21 - 1 - 218.21 - 5 CuSO4.5H2O - 249.68 - 6 - 1498.08 - 34.33 NaOH - 40 - 12 - 480 - 11.00
weight1: based on 1 mole piperic acid
weight2: based on 5g piperic acid.

So rather than use MistaMiyagi's numbers I would go for 5g Piperic acid, 34.33g CuSO4.5H2O and 11g NaOH. Of course if MistaMiyagi's numbers give better yields than mine then I'm wrong and he's right. Whatever MistaMiyagi's yield of 4.5g of piperonal from 5g of piperic acid is impossible.
Quote:
MistaMiyagi (Dream Team)
Posted: Fri Feb 25, 2005 4:25 am
Subject: Piperonal from Piperic Acid, CuSO4*5H20, NaOH

This is a condensed version of a Hive post. Unfortunately, I never saved a copy of the thread before the Hive went down.
If there are any enterprising individuals out there, the thread was accessed by this url:
https://www.the-hive.ws/forum/showflat.pl?Cat=&Number=32...

Materials
5g piperic acid
16.9g NaOH
25.6g CuSO4 * 5H2O
150mL DCM
205mL H2O
suff. HCl(aq) to acidify

Procedure

1. Combine piperic acid, NaOH, CuSO4 * 5H2O, and H2O.
2. Reflux for 8 hours.
3. Collect liquid via suction filtration, discarding solids.
4. Acidify with HCl(aq).
5. Extract product with 3x50mL DCM.
6. Distill extract to recover DCM, if desired.

Yield: 4.5g piperonal

From the Hive.
Quote:
Antoncho
Date: 04-06-02 21:26
Post No 293365
Subject: Double bond ox. cleavage (to aldehyde) with CuO
(Rated as: excellent)

This is from the same source that the preparation of 3,5-diMeO-4-OH-propenylbenzene, which i recently posted into Methods discourse - see Antoncho: "2,6-diMeO-4-allylphenol" (Methods Discourse).

Edit: the original info comes from Patent US2516412

I'm not sure if this hasn't been discussed bee4 - i just couldn't construct an accurate query on TFSE. But i think it hasn't since - why then no one ever thought of possibility of applying this to piperic acid?

EXAMPLE VII: Syringaldehyde from the isolated intermediate

Syringaldehyde may also be prepared by oxidizing the isolated 3,5-dimethoxy-4-hydroxypropenylbenzene of Example V with nitrobenzene in alkali or other low potential oxidizing agents.
Thus 195 parts 3,5-dimethoxy-4-hydroxypropenylbenzene are added to a cupric oxide mixture freshly prepared from 1000 parts hydrated copper sulfate, 660 parts sodium hydroxide, and 8000 parts of water and the resulting mixture is heated to boiling under reflux for eight hours. The separated red cuprous oxide is filtered and washed with water. The alkaline filtrate and washings are acidified and extracted with ether.
Bisulfite purification of the ether extract should yield approximately 155 parts or 90% syringaldehyde.
Other alkaline copper oxidizing agents such as Fehling's Solution, Benedict’s Solution, may be used with the same results. An alkaline copper oxidizing agent is particularly advantageous for replacing the propenyl group with the aldehyde group because the strength of its action in changing from a cupric to a cuprous compound is definitely adequate to oxidize to the aldehyde, and at the same time insufficient to continue the oxidation to the acid further or to destruction. However, in large scale operation, it will be obvious that oxidizing agents having no such automatic action may be employed for reasons of economy, and the extent of the reaction controlled by controlling the amount of the reagent.

So... What do you think?

One thing that confuses me is - AFAIK, Fehling's liquid is a Cu++/NH3 complex - which will certainly decompose at 100 C, with all ammonia going out of solution. What could they mean?

Antoncho


[Edited on 3-10-2005 by CherrieBaby]
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[*] posted on 7-10-2005 at 12:19


1) Apart from using CuO (US Patent 2516412) there are at least another 3 simple possible ways to convert piperic acid to piperonal.

2) British Patent: 774,608 mentions the following oxidation using manganese dioxide.
Code:
O Ar-C=C< --> Ar-C=O + O=C< | |
3) The article from Rhodium "aldehyde.txt", in the archive below, describes an oxidative cleavage using NaHCO3/KMnO4

4) The article I uploaded, Arctander (below) describes large scale oxidative cleavage of piperic acid to piperonal using dichromate.

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

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

1) US Patent 2,516,412, "Method of Synthesizing Syringaldehyde"
2) British Patent 774608, 1957, "A Process for the Preparation of Aromatic Carbonyl Compounds from Aryl Ethylenes"
3) Oxidation of a Propenylbenzene (Asarone) to benzaldehyde (2,4,5-Trimethoxybenzaldehyde) using NaHCO3/KMnO4
4) Arctander, from "Perfume and Flavour Chemicals, 1969, Heliotropin, pp183-4
5) Cervený, Kozel & Marhoul, "Synthesis of Heliotropin", Perfumer & Flavorist 14, pp13-18, 1989
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[*] posted on 7-10-2005 at 12:48


Hi CherryBaby,

The thing about CuII oxidations is that they are selective and don't go further than piperonal. The other oxidising agents can go too far unless the reaction is tightly controlled.

Anyway, I don't like this board. I don't like the atmosphere. Bad manners, snotty fools - rationally ignorant, I believe is the correct term. I have started to run I2P and hang out there. There are only a couple of boards there so far - but the opportunity remains. The IRC is friendly.
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Epopteia
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[*] posted on 8-10-2005 at 08:37
possibilities


The CuO procedure does not work as published on substrates having no phenolic group in my experience. Maybe it is because you need the Phenolate anion in solution which is oxidised by the CuO.

The Manganese dioxide procedure may work on Piperic acid (I don't know) but the published procedure does not work on highly activated aromatics such as isodillapiole. You get a lot of brown tar with the reaction conditions specified in the patent. Perhaps a lower temperature may help in this case.

The dichromate is the way to go in my opinion, but then its toxic and an environmental toxin, so careful handling and responsible disposal are a must.
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[*] posted on 8-10-2005 at 10:09


Quote:
Originally posted by Epopteia
The CuO procedure does not work as published on substrates having no phenolic group in my experience. Maybe it is because you need the Phenolate anion in solution which is oxidised by the CuO.
Maybe the phenolate complexes with CuO in a similar way to how tartrate does - enabling CuO to be transported into solution? Perhaps Fehlings might work better than CuO alone.

[Edited on 8-10-2005 by CherrieBaby]
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[*] posted on 22-10-2005 at 00:33


Perhaps this may work to oxidise piperic acid to piperonal?

From, "The manufacture of chemicals by electrolysis", A. J. Hale, 1919, page 68.
http://www.sciencemadness.org/library/books/the_manufacture_...
Quote:
Vanillin can be formed by electrolytic oxidation of the sodium salt of iso-eugenol. According to the process of F. van Heyden Nchfg. a 15% alkaline solution of sodium iso-eugenol forms the anolyte, and the catholyte comparment is filled with caustic soda solution (10 to 20%). The temperature is kept at 60C, and the lead peroxide anode evidently acts as a catalyst, since with platinum the discharged oxygen is evolved without the oxidation:

CH3O(HO):C6H3.CH:CH.CH3 + 3(O) ==> CH3O(HO):C6H3.CHO + CH3.COOH

Refs:
DRP 92007 (1895)
Electrochem. Review, 1900, 1, 31.


[Edited on 22-10-2005 by CherrieBaby]
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[*] posted on 13-9-2006 at 09:10


Hello,

could anybody repost the article by Arctander (see below) or the whole Piperonal.zip synopsis, as rapidshare is no longer hosting the file. :-(



Quote:
Originally posted by CherrieBaby
1) Apart from using CuO (US Patent 2516412) there are at least another 3 simple possible ways to convert piperic acid to piperonal.

2) British Patent: 774,608 mentions the following oxidation using manganese dioxide.
Code:
O Ar-C=C< --> Ar-C=O + O=C< | |
3) The article from Rhodium "aldehyde.txt", in the archive below, describes an oxidative cleavage using NaHCO3/KMnO4

4) The article I uploaded, Arctander (below) describes large scale oxidative cleavage of piperic acid to piperonal using dichromate.

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

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

1) US Patent 2,516,412, "Method of Synthesizing Syringaldehyde"
2) British Patent 774608, 1957, "A Process for the Preparation of Aromatic Carbonyl Compounds from Aryl Ethylenes"
3) Oxidation of a Propenylbenzene (Asarone) to benzaldehyde (2,4,5-Trimethoxybenzaldehyde) using NaHCO3/KMnO4
4) Arctander, from "Perfume and Flavour Chemicals, 1969, Heliotropin, pp183-4
5) Cervený, Kozel & Marhoul, "Synthesis of Heliotropin", Perfumer & Flavorist 14, pp13-18, 1989
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[*] posted on 14-9-2006 at 15:01


Can anybody here suggest a microwave assisted variant of oxidising rxn? I just did a google search on 'microwave + oxidation', but I can find nothing more than the abstracts?

Gorrilla: I concur wholeheartedly with your appraisal of this forum.

ex-hive'r
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[*] posted on 14-9-2006 at 15:36


Anyway, after bitching (re.this board & lack of ref's), I found this...

http://www.pubmedcentral.gov/pagerender.fcgi?artid=1276483&a...

as these guys used H2O2 to oxidise the somewhat similar acid (piperonal + pyruvic acid) why couldn't it work for piperic acid (to piperonal)? Don't get me wrong, I am an ameteur (although I do try to learn;)).

PS. If I am wrong (and I am prone to being so), please provide constructive criticism not flames:(
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[*] posted on 14-9-2006 at 19:10


Quote:
Originally posted by 2bob
...
http://www.pubmedcentral.gov/pagerender.fcgi?artid=1276483&a...

as these guys used H2O2 to oxidise the somewhat similar acid (piperonal + pyruvic acid) why couldn't it work for piperic acid (to piperonal)? Don't get me wrong, I am an ameteur (although I do try to learn;)).

PS. If I am wrong (and I am prone to being so), please provide constructive criticism not flames:(


The H2O2 oxidation there is of an alpha-keto acid, chopping off the CO2 and oxidising the C=O to CO2H. Without the oxidation you'd get an aldehyde.

But that's an alpha-keto acid, and piperic acid is an alpha, beta unsaturated acid - not the same thing. Look closely at the structures in that article you found, and at the of piperic acid.

There are H2O2 oxidations that will give the aromatic aldehyde, one using a vanadium peroxo complex was posted on this site but while many substrates had benzaldehyde yields in the 90-98 percent range, the target here gave only about 50% yields.
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[*] posted on 14-9-2006 at 23:56


still, that is somewhat better than the yeilds to date with KMnO4 (by about 10-20x). In fact a 50% yeild would possibly make this attainable/feasible.:o

What about piperic acid and pyruvate?

Here is the Orgsyn file which demonstrates the difficulty in using KMnO4:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0538

The only clue I've yet found is that the solution must be neutral:

http://www.henriettesherbal.com/eclectic/kings/piper-nigr_pi...

(this file also suggests that white pepper may contain even more piperine than the black?)

b
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[*] posted on 15-9-2006 at 02:34


Quote:
Originally posted by 2bob
...

What about piperic acid and pyruvate?



Ummm, you've lost me - what about them?

Quote:

Here is the Orgsyn file which demonstrates the difficulty in using KMnO4:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0538

The only clue I've yet found is that the solution must be neutral:

http://www.henriettesherbal.com/eclectic/kings/piper-nigr_pi...

(this file also suggests that white pepper may contain even more piperine than the black?)



Stopping the oxidation at the aldehyde is tricky, but that was the proccess for some time.

There's enough variation whith pepper from different locals that going for the more expensive white pepper isn't likely to be worthwhile. Another thing that should be noted is that there are several of acids (as amides) in pepper, these are piperic acid except for the cis/trans orientation of the double bonds. Doing much purification of the piperic acid will remove these, which is a waste when making the aldehyde since the double bonds are chopped in the process.
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[*] posted on 18-9-2006 at 00:38


does piperonal form an addition product with sodium bisulfite (like benzaldehyde does)? If so, why not utilise a 10x excess of piperic acid, which is then neutralised with sodium bisulfite, to which 1 equiv of the oxidising agent is dripped in (along with a metallic tin catalyst to increase the oxidation rate)?

If this worked, what I envisage would be the almost immediate oxidation of the piperic acid to piperonal (which would then form the addition product with the bisulfite and precipitate out). The excess of piperic acid would of course be unaffected, and the next batch would simply replace 1 equiv of both piperic acid and sodium bisulfite, and the dripwise addition of the oxidant solution. Looking at the references for the procedure, one of the important requirements is that the solution be neutral when the oxidising reagent is added.
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[*] posted on 18-9-2006 at 19:29


(Sorry, this bee has trouble with the 'edit' system: I cannot post after editing).

The reason I suggest using NaHSO3 is because of its dual capacity to bind to the aldehyde (piperonal) and to neutralise excess KMnO4, etc:

http://en.wikipedia.org/wiki/Sodium_bisulfite
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[*] posted on 28-12-2006 at 00:11


dichromate and sulfuric acid mix with acid in mix then steam distill aldehyde out of mix has always given great results.



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[*] posted on 8-1-2007 at 04:15


Hi
Why dont you use solid catalyst? Cu-KMnO4, Ni-KMnO4, Ni-Co-KMnO4...and reaction done by helping of sonic or microwave.
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[*] posted on 9-1-2007 at 11:16


Look, I have an idea about protocatuchualdehyde syntheses starting from vanillin, converting it to 3,4-dihydroxibenzoic acid.
Here is the preparation published in orgsyn :
http://orgsyn.org/orgsyn/prep.asp?prep=cv3p0745
Easy to get materials. Then doing decarboxylation style like in plain Benzoic acid with NaOH/Ca(OH)2, but instead using hydroxides to use Mg/Ca(I was told by one chemist that those metals salts would work, but he wasn't sure about that) formate at high temperatures, aldehyde distills out at 180*C, so applying vacuum to lower boiling point and prevent oxidation of that again to benzoic acid. Nicodem ? Other experienced and smart chemists, please comment if that thing work or not, if not why not and maybe some references on that subject ? Thank you very much.

COOH + HCOOH -> COH + CO2 + H2O

P.S. I don't want to post new topic on that.

[Edited on 9-1-2007 by Maja]
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[*] posted on 9-1-2007 at 11:41


Well, from 3,4-dihydroxybenzoic acid (protocatechuic acid) you would first have to prepare 3,4-methlyenedioxybenzoic acid since protocatechuic acid can not be used in the ketonization methods with formic acid salts (its hydroxy groups are acidic and the product would get "caught" in the required base and thus pirolyze before distilling; not to even mention the oxidation sensitivity of catechols at the oxygen from air).
For doing this you might need to temporarily protect the –COOH group. Esterification with methanol should be OK. Some methylenation methods might even work without protection so it would certainly be worth trying without protection first.
As for the ketonization step (or should I say "aldehydation"?) I already posted some patents in the "toluene --> benzaldehyde" thread in reply to Drunkguy's question. Any method that works on benzoic acid should work, more or less efficiently, also on 3,4-methylenedioxybenzoic acid. But since we all know why all this interest in piperonal wouldn't it be wiser to ketonize with propanoic acid, thus obtaining 3,4-methylenedioxypropiophenone?




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[*] posted on 9-1-2007 at 12:04


I'm sorry for my lack of knowledge in organic chemistry, but maybe you can link me to methods protecting -COOH group and "some methylation methods". Thats just esterification with methanol in presence of conc sulfuric acid ? Or formaldehyde and H2SO4 ? Maybe you can tell me about that more ?

Quote:
wouldn't it be wiser to ketonize with propanoic acid, thus obtaining 3,4-methylenedioxypropiophenone?


What do you mean ? Using 3,4-methylendioxypropanoic acid instead benzoic and converting it to propiophenone ? Patents or some more info. PLEASE. THANK YOU VERY MUCH FOR SPOON FEEDING ME :)
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[*] posted on 9-1-2007 at 12:34


Quote:
Originally posted by Maja
I'm sorry for my lack of knowledge in organic chemistry, but maybe you can link me to methods protecting -COOH group and "some methylation methods".

I would certainly try the methylenation on the unprotected acid before trying to use any protection. It should/might work with some methods. As for the various reagents and methods for the methylenation of various catecholes all you need to do is search the Rhodium archive. There are more or less all of the best references already compiled.

Quote:
What do you mean ? Using 3,4-methylendioxypropanoic acid instead benzoic and converting it to propiophenone ? Patents or some more info.

No. I was insinuating that most people interested in piperonal are actually interested in 3,4-methylenedioxyamhetamines anyway. So why piperonal from 3,4-methylenedioxybenzoic acid when you can make 3,4-methylenedioxypropiophenone by the ketonization of 3,4-methylenedioxybenzoic acid with propanoic acid? This way you need no nitroethane, 2-bromopropanoic esters or whatever you would otherwise require if starting from piperonal. Instead you start by the usual propiophenone routes. In addition, the ketonizations with propanoic acid are way more likely to work than with formic acid. Not to mention that one can then use 3,4-methylenedioxypropiophenone also for "methylone" which is at least legal in many countries (unlike the other target compounds). No other special reason.




…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)

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[*] posted on 9-1-2007 at 13:09


Quote:
I would certainly try the methylenation on the unprotected acid before trying to use any protection. It should/might work with some methods. As for the various reagents and methods for the methylenation of various catecholes all you need to do is search the Rhodium archive. There are more or less all of the best references already compiled.
TOTTALY FORGOT ABOUT RHODIUM ARCHIVES, THANKS.

OK, one more time sorry .... Can you give me some syntheses for example using ketonization ? I was unable to find them in www.orgsyn.org maybe thats due that my English isn't native language so I don't know maybe reaction name :/

Quote:
No. I was insinuating that most people interested in piperonal are actually interested in 3,4-methylenedioxyamhetamines anyway. So why piperonal from 3,4-methylenedioxybenzoic acid when you can make 3,4-methylenedioxypropiophenone by the ketonization of 3,4-methylenedioxybenzoic acid with propanoic acid? This way you need no nitroethane, 2-bromopropanoic esters or whatever you would otherwise require if starting from piperonal. Instead you start by the usual propiophenone routes. In addition, the ketonizations with propanoic acid are way more likely to work than with formic acid. Not to mention that one can then use 3,4-methylenedioxypropiophenone also for "methylone" which is at least legal in many countries (unlike the other target compounds). No other special reason.]



[Edited on 9-1-2007 by Maja]
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[*] posted on 9-1-2007 at 16:31


Some things are best not said.



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[*] posted on 12-1-2007 at 14:03


Quote:
Originally posted by MargaretThatcher
Some things are best not said.


some things are best not sold

but one hand washes the other
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