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All 22 posts Subject: KMnO4/CuSO4 system for ketone synthesis Please login to post Down

Ziqquratu
(Stranger)
03-14-03 07:33
No 416888
      KMnO4/CuSO4 system for ketone synthesis

I was in the library the other day, killing some time between classes, when I came across an article relating to the use of a Permanganate/Copper Sulfate pentahydrate system for the formation of ketones and azobenzenes. It also dealt with the use of this reagent in the synthesis of ketones from alcohols. This led me to two ideas for novel syntheses.

First, the oxidation of a primary amine to a ketone could be used to convert MDA to MDP-2-P, probably (according to the article) in high yeild. If there is a simple, high yeilding synthesis of MDA from safrole (I dont know, I havent looked it up), this could be used to get ketone. The yeild from safrole to MDP-2-P would only have to be 50% or so to be comparable to the peracid routes. Also, it would be a useful synthesis when using piperonal and nitroethane to make MDA - a complete and reasonably easy synthesis for those who prefer MDMA without buying any sassy!
Second, there have been many reports of failed attempts at making MDP-2-P via MDP-2-Pol from safrole and sulfuric acid. It has been suggested that perhaps this is because of the choice of oxidant and not because of migration of the OH group to the 1-carbon. Perhaps this system could work - the paper reports 100% yeild of dacan-2-one from 2-decanol, and 90% yeilds of 1-phenylbut-1-en-3-one from 1-phenylbut-1-en-3-ol, indicating by the fact that it leaves the double bond alone that it is a mild reagent.
The preparation of this reagent is simple - potassium permanganate and copper sulfate pentahydrate (usually in slightly less than a 2:1 ratio) are ground together in a mortar until homogeneous. Then the oxidant and the amine are mixed in DCM under reflux for 24 to 48 hours, typically in high (even quantatative) yeild. Presumably oxidising the alcohols used the same procedure.

Reference: Noureldin, Nazih A.; Bellegarde, Jody W.:
A Novel Method. The Synthesis of Ketones and Azobenzenes Using Supported Permanganate, Synthesis 1999, No. 6, pp. 939-942.

Rhodium
(Chief Bee)
03-14-03 23:16
No 417128
User Picture       Isosafrole + DMSO + Heat = MDP2P

I am not aware of any method for making MDA from safrole which is easier or higher-yielding than making MDP2P from safrole.

According to Chemical Abstracts 97, 23367 (1982), heating isosafrole in DMSO to 100-120°C for an unspecified amount of time results in autooxidation of the isosafrole, forming MDP2P as the major product, but the precise yield is also unspecified in the abstract.

The details for this incredibly easy MDP2P synthesis has been published in Yukagaku 31(4), 222-225 (1982) (ISSN: 0513-398X), which unfortunately is a Japanese journal.

SPISSHAK
(Hive Addict)
03-15-03 03:33
No 417164
      Interesting

Damn those Japs are a slick breed, I know of a way that could be translated, there is an infrared pen you can buy at various computer retail outlets, it scans text like Japaneese, chineese and 140 other languanges you download the dictionary translations to your computer and plug this pen into usb port, it costs about $200.00, maybe one of the richer bees can go and buy one and translate all these invaluable texts.

foxy2
(Distinctive Doe)
03-15-03 06:34
No 417188
      I doubt such a device would translate ...

I doubt such a device would translate chemistry/technical info very well at all.

SPISSHAK
(Hive Addict)
03-15-03 06:49
No 417195
      I'm afraid your'e right

It's back to OCR software, this is in progress if anyone can get the article the software will be purchased to translate it.

pHarmacist
(Hive Addict)
03-15-03 09:32
No 417235
User Picture       Rhodium

Why not ask our japanese friend 6079_Smith_W_II from room 101 to translate it? If you can get the japanese article I know another japanese friend that can translate it... wink

That route to MDP2P is absolutely AWESOME! I've never heard about this route before but DMSO decomposes easy at higher temps so I should have had my hints.

Accept No Imitations, There Can Only Bee One; www.the-hive.ws

Rhodium
(Chief Bee)
03-15-03 16:11
No 417299
User Picture       Japanese

I don't have access to the journal, so the post above was a subtle "could somebody else please fetch the journal, scan it and make it available so that we can have it translated"... wink I only found the data above in CA yesterday.

Your friend can read scientific japanese? Ask him if he can decrypt this 4-Hydroxyindole synthesis: https://www.rhodium.ws/projects/translation/japanese/jp-a-h09-169725.pdf

hypo
(Hive Addict)
03-15-03 16:16
No 417302
      isosafrole + DMSO --> MDP2P ???

stupid question: where does the =O come from!?

Rhodium
(Chief Bee)
03-15-03 16:36
No 417313
User Picture       oxygen origin
(Rated as: good read)

As the reaction is labelled as an "auto-oxidation" I suppose that it comes from the air, or else they would label the DMSO as the oxidant (and dimethylsulfide would form). Another similar reaction I have seen mentioned bubbled dry air through the reaction mixture.

The full Abstract of the originally dicussed article:

Autoxidation of benzene and phenolic compounds containing isopropyl, isopropenyl, vinyl or allyl group in polar aprotic solvents.
Iwamuro, Hajime; Kanehiro, Masahiko; Matsubara, Yoshiharu. Fac. Sci. Technol., Kinki Univ., Higashiosaka, Japan.
Yukagaku 31(4), 222-5 (1982) CODEN: YKGKAM ISSN: 0513-398X. Journal written in Japanese. CAN 97:23367 AN 1982:423367

Abstract

Autoxidn. of cumene, m- and p-diisopropylbenzene, p-cymene, and 1-isopropenyl-4-methylbenzene in Me2SO at 100-20° gave AcPh, 3- and 4-Me2CHC6H4COMe, and 4-MeC6H4COMe in 100% selectivity, whereas similar oxidn. in DMF and 1,3-dimethyl-2-imidazolidinone (I) gave Me2C(OH)Ph, 3- and 4-Me2CHC6H4C(OH)Me2, 2-p-tolyl-2-propanol. Autoxidn. of styrene, isosafrole, anethole, and isoeugenol in Me2SO at 100-20° gave PhCHO, piperonylacetone, and (p-methoxyphenyl)acetone as major products, whereas in I, DMF, or AcNMe2 they gave PhCHO, 1-phenyl-1,2-epoxyethane, piperonal, p-anisaldehyde p-MeOC6H4CH2COMe, 1-p-anisyl-1,2-epoxypropane, and vanillin.

SPISSHAK
(Hive Addict)
03-15-03 17:03
No 417318
      yes that's correct

Rhodium is right the oxidant is air, I think the DMSO has properties like a high dielectric constant that make isosafrole more suseptible to oxidation.

Sunlight
(Pioneer Researcher)
03-16-03 01:53
No 417460
      Oxydation of tryptamine

Please post details of the procedure of oxydation of amines to ketones, it could be used to oxidize tryptamine into indol 3 acetaldehyde, then easily converted to DMT or other with NaBH4 reductive amination .

Ziqquratu
(Stranger)
03-16-03 03:29
No 417472
      Oxidation of Amines to Carbonyl Compounds
(Rated as: excellent)

The oxidant was prepared by grinding equal amounts, by weight, of KMnO4 and CuSO4.5H2O in a mortar until homogeneous.

Oxidation of Amines; General Procedure
The amine (2.0mmol) in CH2Cl2 (20mL) was placed in a 50mL round bottomed flask. The oxidant (2.0g) was added and the heterogeneous mixture stirred at ambient temperature or under reflux for 48 h. The progress of the reaction was followed by tlc or glc until no starting material could be detected. After cooling to ambient temperature, the product was then filtered through Celite and the residue washed thoroughly with CH2Cl2 (3 x 10mL) and Et2O (3 x 10mL). The product was isolated by flash evaporation and identified from spectroscopic analysis.

Ref: A Novel Method. The Synthesis of Ketones and Azobenzenes Using Supported Permanganate, Synthesis 1999, No. 6, pp. 939-942.

Sunlight
(Pioneer Researcher)
03-16-03 19:33
No 417646
User Picture       Thanks

Thank you. I wonder if the amine in teh indol ring will be affected.

SPISSHAK
(Hive Addict)
03-17-03 00:24
No 417772
      Aromaticity

THe indole nitrogen is more stable due to aromaticity.

pHarmacist
(Hive Addict)
03-17-03 12:26
No 418051
User Picture       japz

Your friend can read scientific japanese? Ask him if he can decrypt this 4-Hydroxyindole synthesis: https://www.rhodium.ws/projects/translation/japanese/jp-a-h09-169725.pdf

Done, now, it's just a matter of reply...

Accept No Imitations, There Can Only Bee One; www.the-hive.ws

codyboy
(Stranger)
06-30-03 21:28
No 443577
      Does it Work?

Dont talk much..... Read plenty....
Do we know if this is a viable route yet?
I shall wait.
Thanks,
codyboy

Rhodium
(Chief Bee)
08-05-03 02:21
No 451720
User Picture       Isosafrole to MDP2P by auto-oxidation!
(Rated as: excellent)

Autoxidation of benzene and phenolic compounds containing isopropyl, isopropenyl, vinyl or allyl group in polar aprotic solvents.
Iwamuro, Hajime; Kanehiro, Masahiko; Matsubara, Yoshiharu.
Yukagaku 31(4), 222-5 (1982) (https://www.rhodium.ws/pdf/isosafrole.dmso.oxidation.pdf) (Retrieved by PolytheneSam)

Here is Ref #1 from the article:

Autoxidation and Condensation Reactions of Carbanions in Dimethyl Sulfoxide Solution
Glen A. Russell, Edward G. Janzen, Hans-Dieter Becker, Frank J. Smentowski
J. Am. Chem. Soc. 84, 2652-2653 (1962) (https://www.rhodium.ws/pdf/dmso.autooxidation.pdf)

nitrous351
(Hive Bee)
09-10-03 16:32
No 458186
      Rhodium...

I'd bee more than happy to try the iso-safrole->mdp2p reaction and post results....however, I'm not so sure I can get any DMSO. Do you think that DMF would work (or another solvent with a high dielectric constant)?
I am looking for someone at my university to translate the Japanese journal article, but in the meantime, if you would care to think up a general procedure to get me started, that would bee great.
I don't have access to analytical equipment, but I could post yields based on how much (if any) mdp2p I was able to recover by distillation. Thanks

EDIT: After looking at the Japanese article's tables (which are in English...yay!) it appears that isosafrole refluxed with DMSO for 26 hours at 120C will yield 60% mdp2p... refluxing isosafrole with DMI for 8 hours at 120C results in 56% mdp2p... but this doesn't help with the procedure, so can anybee suggest a procedure/ratios to get me started? thanks

D.A.R.E. = Drugs Are Really Exciting

hester18
(Stranger)
09-16-03 19:52
No 459443
      KMnO4/CuSO4 for Methcathinone

Could this reaction be used for the synthesis of methcathinone by the oxidation of pseudoephedrine?
And would it be better to use the KMnO4/CuSO4 combination than to use a plain permangenate solution for the reaction?
If so why and is there a printed synthesis regarding this?

Rhodium
(Chief Bee)
09-17-03 00:12
No 459469
User Picture       Article: KMnO4 supported on CuSO4
(Rated as: good read)

Here is the full article mentioned in the first post in this thread:

A Novel Method. The Synthesis of Ketones and Azobenzenes Using Supported Permanganate
Noureldin, Nazih A.; Bellegarde, Jody W.
Synthesis 1999, No. 6, 939–942 (1999) (https://www.rhodium.ws/pdf/kmno4.on.cuso4-oxidation.system.pdf)

Abstract

The heterogeneous use of potassium permanganate, supported on copper(II) sulfate pentahydrate, provides a simple and effective means for oxidizing amines. Primary aliphatic amines, such as sec-butylamine, are oxidized to the corresponding carbonyl compounds in good to excellent yields. Primary aromatic amines, such as 4-chloroaniline, are converted quantitatively into the corresponding azo compounds. Carbon–carbon bond cleavage, which usually occurs when alkylbenzene side chains are oxidized by permanganate under homogeneous conditions, does not occur. Under appropriate reaction conditions carbon–hydrogen bond cleavage at the benzylic position, known to occur under heterogeneous permanganate conditions, is also eliminated. For example, a quantitative yield of bis(2,4,6-trimethylphenyl)diazene is obtained from the oxidation of 2,4,6-trimethylaniline using small amounts of permanganate and copper(II) sulfate pentahydrate.

GC_MS
(Hive Addict)
09-21-03 18:27
No 460253
User Picture       Olefin auto-oxidation

When thinking about the auto-oxidation of olefins as isosafrole, anethole and/or isoeugenol, you have to imagine some sort of intermediary complex between a molecule of O₂ and the olefin double bond. There will be an oxidative cleavage of your olefin, which in case of isosafrole will yield piperonal (anethole -> anisaldehyde, isoeugenol -> vanillin) and acetaldehyde.

In the past, I have tried some Na₂Cr₂O₇ and KMnO₄ mediated oxidations of isosafrole, isoeugenole, anethole and asaron. In case of isoeugenol and anethole, I have had performed a GC/MS analysis as well, and I found that in both cases, their corresponding benzaldehydes were present as the major substances. However, other concomitant substances were the original starting product and also their corresponding P2Ps! At the time, I was rather surprised as I didn't expect the latter to show up. However, I have no idea for how much their P2P analogues contributed to the composition of the final product: 5%? 10%? Anyway, not sufficient to isolate them for further synthetical needs. So, to summarize, auto-oxidation of anethole and isoeugenol does result in 4-methoxy-P2P and 4-hydroxy-3-methoxy-P2P, albeit in small amounts.

And all the sudden, there is a group of crazy Japanese writing a possibly interesting article in a language the majority of the Bees unfortunately doesn't understand. It seems that bubbling oxygen in a solution of olefin in DMSO results in the P2P analogue as the major product and the benzaldehyde as the minor one. This, however, does not fully agree with the theoretical principle of the olefin auto-oxidation. So, might there be something else going on?

No... and yes. At least, that is my theory. My theory goes as follows:

You dissolve for instance a certain amount of isosafrole in DMSO and introduce a stream of oxygen into the mixture. The oxygen will form an intermediary complex with isosafrole, which will decompose into piperonal and acetaldehyde. These two aldehydes, however, are subject to auto-oxidation as well! In Post 415088 (GC_MS: "The synthesis of peracids", Chemistry Discourse), I describe how perbenzoic acid can be formed by introducing oxygen in a solution of benzaldehyde in acetone. Acetaldehyde will result in peracetic acid while piperonal will yield 3,4-methylenedioxy perbenzoic acid. The actions of peracids on alkenes as isosafrole is (or should be) well known. No? Well, you might want to read some pages on Rh's site... (https://www.rhodium.ws/chemistry/peracid.html)
And this is where the fun starts laugh . The epoxide (formed by the reaction between isosafrole and peracid) can rearrange to a zwitterion (positive charge on C1 and negative charge on O of the side chain), which on itself is a substrate in a Pfitzner-Moffatt oxidation reaction.

And voila, there you have your MD-P2P. I must add that the zwitterion I just talked about can also rearrange to MD-P2P spontaneously.

So, how did I pull this theory out of my ass all the sudden? The abstract mentions the presence of epoxidated alkanes, benzaldehydes etc if they used DMI, DMAc or DMF as solvent. Only when they used DMSO, there was a major presence of the P2P analogue. To me, it seems that DMI, DMAc and DMF allow the auto-oxidation to happen "the normal way". DMSO "rearranges" the equilibria of the side-reactions and oxidizes an intermediary zwitterion, yielding the beloved MD-P2P.

Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".

Rhodium
(Chief Bee)
11-28-03 16:23
No 473645
User Picture       Oxidation of Isosafrole to Piperonal by Oxygen
(Rated as: good read)

Oxidation of Isosafrole to Piperonal by Oxygen Gas
N.M. Baranova & A.D. Yakusheva
J. Appl. Chem. USSR (Engl.Transl.), 47, 2840-2841 (1974) (https://www.rhodium.ws/pdf/isosafrole2piperonal.oxygen.pdf)
Zh. Prikl. Khim. 47(12), 2751-55 (1974)

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	All 22 posts		Subject: KMnO4/CuSO4 system for ketone synthesis		Please login to post		Down


		Ziqquratu (Stranger) 03-14-03 07:33 No 416888				KMnO4/CuSO4 system for ketone synthesis
						I was in the library the other day, killing some time between classes, when I came across an article relating to the use of a Permanganate/Copper Sulfate pentahydrate system for the formation of ketones and azobenzenes. It also dealt with the use of this reagent in the synthesis of ketones from alcohols. This led me to two ideas for novel syntheses. First, the oxidation of a primary amine to a ketone could be used to convert MDA to MDP-2-P, probably (according to the article) in high yeild. If there is a simple, high yeilding synthesis of MDA from safrole (I dont know, I havent looked it up), this could be used to get ketone. The yeild from safrole to MDP-2-P would only have to be 50% or so to be comparable to the peracid routes. Also, it would be a useful synthesis when using piperonal and nitroethane to make MDA - a complete and reasonably easy synthesis for those who prefer MDMA without buying any sassy! Second, there have been many reports of failed attempts at making MDP-2-P via MDP-2-Pol from safrole and sulfuric acid. It has been suggested that perhaps this is because of the choice of oxidant and not because of migration of the OH group to the 1-carbon. Perhaps this system could work - the paper reports 100% yeild of dacan-2-one from 2-decanol, and 90% yeilds of 1-phenylbut-1-en-3-one from 1-phenylbut-1-en-3-ol, indicating by the fact that it leaves the double bond alone that it is a mild reagent. The preparation of this reagent is simple - potassium permanganate and copper sulfate pentahydrate (usually in slightly less than a 2:1 ratio) are ground together in a mortar until homogeneous. Then the oxidant and the amine are mixed in DCM under reflux for 24 to 48 hours, typically in high (even quantatative) yeild. Presumably oxidising the alcohols used the same procedure. Reference: Noureldin, Nazih A.; Bellegarde, Jody W.: A Novel Method. The Synthesis of Ketones and Azobenzenes Using Supported Permanganate, Synthesis 1999, No. 6, pp. 939-942.



		Rhodium (Chief Bee) 03-14-03 23:16 No 417128				Isosafrole + DMSO + Heat = MDP2P
						I am not aware of any method for making MDA from safrole which is easier or higher-yielding than making MDP2P from safrole. According to Chemical Abstracts 97, 23367 (1982), heating isosafrole in DMSO to 100-120°C for an unspecified amount of time results in autooxidation of the isosafrole, forming MDP2P as the major product, but the precise yield is also unspecified in the abstract. The details for this incredibly easy MDP2P synthesis has been published in Yukagaku 31(4), 222-225 (1982) (ISSN: 0513-398X), which unfortunately is a Japanese journal.



		SPISSHAK (Hive Addict) 03-15-03 03:33 No 417164				Interesting
						Damn those Japs are a slick breed, I know of a way that could be translated, there is an infrared pen you can buy at various computer retail outlets, it scans text like Japaneese, chineese and 140 other languanges you download the dictionary translations to your computer and plug this pen into usb port, it costs about $200.00, maybe one of the richer bees can go and buy one and translate all these invaluable texts.



		foxy2 (Distinctive Doe) 03-15-03 06:34 No 417188				I doubt such a device would translate ...
						I doubt such a device would translate chemistry/technical info very well at all.



		SPISSHAK (Hive Addict) 03-15-03 06:49 No 417195				I'm afraid your'e right
						It's back to OCR software, this is in progress if anyone can get the article the software will be purchased to translate it.



		pHarmacist (Hive Addict) 03-15-03 09:32 No 417235				Rhodium
						Why not ask our japanese friend 6079_Smith_W_II from room 101 to translate it? If you can get the japanese article I know another japanese friend that can translate it... That route to MDP2P is absolutely AWESOME! I've never heard about this route before but DMSO decomposes easy at higher temps so I should have had my hints. Accept No Imitations, There Can Only Bee One; www.the-hive.ws



		Rhodium (Chief Bee) 03-15-03 16:11 No 417299				Japanese
						I don't have access to the journal, so the post above was a subtle "could somebody else please fetch the journal, scan it and make it available so that we can have it translated"... I only found the data above in CA yesterday. Your friend can read scientific japanese? Ask him if he can decrypt this 4-Hydroxyindole synthesis: https://www.rhodium.ws/projects/translation/japanese/jp-a-h09-169725.pdf



		hypo (Hive Addict) 03-15-03 16:16 No 417302				isosafrole + DMSO --> MDP2P ???
						stupid question: where does the =O come from!?



		Rhodium (Chief Bee) 03-15-03 16:36 No 417313				oxygen origin (Rated as: good read)
						As the reaction is labelled as an "auto-oxidation" I suppose that it comes from the air, or else they would label the DMSO as the oxidant (and dimethylsulfide would form). Another similar reaction I have seen mentioned bubbled dry air through the reaction mixture. The full Abstract of the originally dicussed article: Autoxidation of benzene and phenolic compounds containing isopropyl, isopropenyl, vinyl or allyl group in polar aprotic solvents. Iwamuro, Hajime; Kanehiro, Masahiko; Matsubara, Yoshiharu. Fac. Sci. Technol., Kinki Univ., Higashiosaka, Japan. Yukagaku 31(4), 222-5 (1982) CODEN: YKGKAM ISSN: 0513-398X. Journal written in Japanese. CAN 97:23367 AN 1982:423367 Abstract Autoxidn. of cumene, m- and p-diisopropylbenzene, p-cymene, and 1-isopropenyl-4-methylbenzene in Me2SO at 100-20° gave AcPh, 3- and 4-Me2CHC6H4COMe, and 4-MeC6H4COMe in 100% selectivity, whereas similar oxidn. in DMF and 1,3-dimethyl-2-imidazolidinone (I) gave Me2C(OH)Ph, 3- and 4-Me2CHC6H4C(OH)Me2, 2-p-tolyl-2-propanol. Autoxidn. of styrene, isosafrole, anethole, and isoeugenol in Me2SO at 100-20° gave PhCHO, piperonylacetone, and (p-methoxyphenyl)acetone as major products, whereas in I, DMF, or AcNMe2 they gave PhCHO, 1-phenyl-1,2-epoxyethane, piperonal, p-anisaldehyde p-MeOC6H4CH2COMe, 1-p-anisyl-1,2-epoxypropane, and vanillin.



		SPISSHAK (Hive Addict) 03-15-03 17:03 No 417318				yes that's correct
						Rhodium is right the oxidant is air, I think the DMSO has properties like a high dielectric constant that make isosafrole more suseptible to oxidation.



		Sunlight (Pioneer Researcher) 03-16-03 01:53 No 417460				Oxydation of tryptamine
						Please post details of the procedure of oxydation of amines to ketones, it could be used to oxidize tryptamine into indol 3 acetaldehyde, then easily converted to DMT or other with NaBH4 reductive amination .



		Ziqquratu (Stranger) 03-16-03 03:29 No 417472				Oxidation of Amines to Carbonyl Compounds (Rated as: excellent)
						The oxidant was prepared by grinding equal amounts, by weight, of KMnO4 and CuSO4.5H2O in a mortar until homogeneous. Oxidation of Amines; General Procedure The amine (2.0mmol) in CH2Cl2 (20mL) was placed in a 50mL round bottomed flask. The oxidant (2.0g) was added and the heterogeneous mixture stirred at ambient temperature or under reflux for 48 h. The progress of the reaction was followed by tlc or glc until no starting material could be detected. After cooling to ambient temperature, the product was then filtered through Celite and the residue washed thoroughly with CH2Cl2 (3 x 10mL) and Et2O (3 x 10mL). The product was isolated by flash evaporation and identified from spectroscopic analysis. Ref: A Novel Method. The Synthesis of Ketones and Azobenzenes Using Supported Permanganate, Synthesis 1999, No. 6, pp. 939-942.



		Sunlight (Pioneer Researcher) 03-16-03 19:33 No 417646				Thanks
						Thank you. I wonder if the amine in teh indol ring will be affected.



		SPISSHAK (Hive Addict) 03-17-03 00:24 No 417772				Aromaticity
						THe indole nitrogen is more stable due to aromaticity.



		pHarmacist (Hive Addict) 03-17-03 12:26 No 418051				japz
						Your friend can read scientific japanese? Ask him if he can decrypt this 4-Hydroxyindole synthesis: https://www.rhodium.ws/projects/translation/japanese/jp-a-h09-169725.pdf Done, now, it's just a matter of reply... Accept No Imitations, There Can Only Bee One; www.the-hive.ws



		codyboy (Stranger) 06-30-03 21:28 No 443577				Does it Work?
						Dont talk much..... Read plenty.... Do we know if this is a viable route yet? I shall wait. Thanks, codyboy



		Rhodium (Chief Bee) 08-05-03 02:21 No 451720				Isosafrole to MDP2P by auto-oxidation! (Rated as: excellent)
						Autoxidation of benzene and phenolic compounds containing isopropyl, isopropenyl, vinyl or allyl group in polar aprotic solvents. Iwamuro, Hajime; Kanehiro, Masahiko; Matsubara, Yoshiharu. Yukagaku 31(4), 222-5 (1982) (https://www.rhodium.ws/pdf/isosafrole.dmso.oxidation.pdf) (Retrieved by PolytheneSam) Here is Ref #1 from the article: Autoxidation and Condensation Reactions of Carbanions in Dimethyl Sulfoxide Solution Glen A. Russell, Edward G. Janzen, Hans-Dieter Becker, Frank J. Smentowski J. Am. Chem. Soc. 84, 2652-2653 (1962) (https://www.rhodium.ws/pdf/dmso.autooxidation.pdf)



		nitrous351 (Hive Bee) 09-10-03 16:32 No 458186				Rhodium...
						I'd bee more than happy to try the iso-safrole->mdp2p reaction and post results....however, I'm not so sure I can get any DMSO. Do you think that DMF would work (or another solvent with a high dielectric constant)? I am looking for someone at my university to translate the Japanese journal article, but in the meantime, if you would care to think up a general procedure to get me started, that would bee great. I don't have access to analytical equipment, but I could post yields based on how much (if any) mdp2p I was able to recover by distillation. Thanks EDIT: After looking at the Japanese article's tables (which are in English...yay!) it appears that isosafrole refluxed with DMSO for 26 hours at 120C will yield 60% mdp2p... refluxing isosafrole with DMI for 8 hours at 120C results in 56% mdp2p... but this doesn't help with the procedure, so can anybee suggest a procedure/ratios to get me started? thanks D.A.R.E. = Drugs Are Really Exciting



		hester18 (Stranger) 09-16-03 19:52 No 459443				KMnO4/CuSO4 for Methcathinone
						Could this reaction be used for the synthesis of methcathinone by the oxidation of pseudoephedrine? And would it be better to use the KMnO4/CuSO4 combination than to use a plain permangenate solution for the reaction? If so why and is there a printed synthesis regarding this?



		Rhodium (Chief Bee) 09-17-03 00:12 No 459469				Article: KMnO4 supported on CuSO4 (Rated as: good read)
						Here is the full article mentioned in the first post in this thread: A Novel Method. The Synthesis of Ketones and Azobenzenes Using Supported Permanganate Noureldin, Nazih A.; Bellegarde, Jody W. Synthesis 1999, No. 6, 939–942 (1999) (https://www.rhodium.ws/pdf/kmno4.on.cuso4-oxidation.system.pdf) Abstract The heterogeneous use of potassium permanganate, supported on copper(II) sulfate pentahydrate, provides a simple and effective means for oxidizing amines. Primary aliphatic amines, such as sec-butylamine, are oxidized to the corresponding carbonyl compounds in good to excellent yields. Primary aromatic amines, such as 4-chloroaniline, are converted quantitatively into the corresponding azo compounds. Carbon–carbon bond cleavage, which usually occurs when alkylbenzene side chains are oxidized by permanganate under homogeneous conditions, does not occur. Under appropriate reaction conditions carbon–hydrogen bond cleavage at the benzylic position, known to occur under heterogeneous permanganate conditions, is also eliminated. For example, a quantitative yield of bis(2,4,6-trimethylphenyl)diazene is obtained from the oxidation of 2,4,6-trimethylaniline using small amounts of permanganate and copper(II) sulfate pentahydrate.



		GC_MS (Hive Addict) 09-21-03 18:27 No 460253				Olefin auto-oxidation
						When thinking about the auto-oxidation of olefins as isosafrole, anethole and/or isoeugenol, you have to imagine some sort of intermediary complex between a molecule of O₂ and the olefin double bond. There will be an oxidative cleavage of your olefin, which in case of isosafrole will yield piperonal (anethole -> anisaldehyde, isoeugenol -> vanillin) and acetaldehyde. In the past, I have tried some Na₂Cr₂O₇ and KMnO₄ mediated oxidations of isosafrole, isoeugenole, anethole and asaron. In case of isoeugenol and anethole, I have had performed a GC/MS analysis as well, and I found that in both cases, their corresponding benzaldehydes were present as the major substances. However, other concomitant substances were the original starting product and also their corresponding P2Ps! At the time, I was rather surprised as I didn't expect the latter to show up. However, I have no idea for how much their P2P analogues contributed to the composition of the final product: 5%? 10%? Anyway, not sufficient to isolate them for further synthetical needs. So, to summarize, auto-oxidation of anethole and isoeugenol does result in 4-methoxy-P2P and 4-hydroxy-3-methoxy-P2P, albeit in small amounts. And all the sudden, there is a group of crazy Japanese writing a possibly interesting article in a language the majority of the Bees unfortunately doesn't understand. It seems that bubbling oxygen in a solution of olefin in DMSO results in the P2P analogue as the major product and the benzaldehyde as the minor one. This, however, does not fully agree with the theoretical principle of the olefin auto-oxidation. So, might there be something else going on? No... and yes. At least, that is my theory. My theory goes as follows: You dissolve for instance a certain amount of isosafrole in DMSO and introduce a stream of oxygen into the mixture. The oxygen will form an intermediary complex with isosafrole, which will decompose into piperonal and acetaldehyde. These two aldehydes, however, are subject to auto-oxidation as well! In Post 415088 (GC_MS: "The synthesis of peracids", Chemistry Discourse), I describe how perbenzoic acid can be formed by introducing oxygen in a solution of benzaldehyde in acetone. Acetaldehyde will result in peracetic acid while piperonal will yield 3,4-methylenedioxy perbenzoic acid. The actions of peracids on alkenes as isosafrole is (or should be) well known. No? Well, you might want to read some pages on Rh's site... (https://www.rhodium.ws/chemistry/peracid.html) And this is where the fun starts . The epoxide (formed by the reaction between isosafrole and peracid) can rearrange to a zwitterion (positive charge on C1 and negative charge on O of the side chain), which on itself is a substrate in a Pfitzner-Moffatt oxidation reaction. And voila, there you have your MD-P2P. I must add that the zwitterion I just talked about can also rearrange to MD-P2P spontaneously. So, how did I pull this theory out of my ass all the sudden? The abstract mentions the presence of epoxidated alkanes, benzaldehydes etc if they used DMI, DMAc or DMF as solvent. Only when they used DMSO, there was a major presence of the P2P analogue. To me, it seems that DMI, DMAc and DMF allow the auto-oxidation to happen "the normal way". DMSO "rearranges" the equilibria of the side-reactions and oxidizes an intermediary zwitterion, yielding the beloved MD-P2P. Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".



		Rhodium (Chief Bee) 11-28-03 16:23 No 473645				Oxidation of Isosafrole to Piperonal by Oxygen (Rated as: good read)
						Oxidation of Isosafrole to Piperonal by Oxygen Gas N.M. Baranova & A.D. Yakusheva J. Appl. Chem. USSR (Engl.Transl.), 47, 2840-2841 (1974) (https://www.rhodium.ws/pdf/isosafrole2piperonal.oxygen.pdf) Zh. Prikl. Khim. 47(12), 2751-55 (1974)

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