Author Topic: 4-Me-3-OH-phenylacetone from o-cresol in two steps  (Read 1624 times)

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  • Guest
4-Me-3-OH-phenylacetone from o-cresol in two steps
« on: February 09, 2004, 05:09:00 PM »
As requested in

Post 486912

(silenziox: "For Antoncho", Novel Discourse)
, the literal transcription (this notion is essential since the original text is cryptic enough by itself :)  - so don't ask me for more details :) ):

Stage 1.

Russ. J. Chem. 1958:¹17,57383

A method of oxidizing phenols to the corresponding quinolacetates is described, using minimal qtties of AcOH (sufficient for forming a paste) and Pb(AcO)4, by adding a phenol solution in a small volume of AcOH at temp <50 C; the Pb salt is filtered and from the filtrate, quinolacetates are gotten using usual methods. Thus, upon oxidation 86g ortho-cresol, there was obtained 30g 1,2-dihydro-1-methyl-2-oxophenylacetate.

Now, I understand that this part doesn’t make much sense, unfortunately, that’ all Potter provided us with – maybee we should look at the original text, which he probably hadn’t.

Stage 2.

Variant 1.

 Monatsh. Chem. 1957,88,¹3, 298-306

A variety of compounds was synthesized by condensation of 1,2-dihydro-1-Me-2-oxophenylacetate with compounds containig an active methylene group.
Thus, upon reaction of 1,2-dihydro-1-Me-2-oxophenylacetate with acetoacetic ester in presence of piperidine at 20 C, t=48h (1-2 hrs at 80-90 C), there’s formed C6H3-1-HO-2CH3-5-CH(COCH3)COOC2H5, the product is distilled at 130-140 C/0,05 mmHg.

This product was heated at 100 Ñ in 25mls 1N NaOH, yield 36%.

Variant 2.

Upon reaction of 1,2-dihydro-1-Me-2-oxophenylacetate with acetylacetone in presence of piperidine at 20 Ñ the rxn proceeds for 16 hrs (10mins at 100 C). The product, C6H3-1-HO-2CH3-5-CH(COCH3)2 is distilled at 115-120/0,05 mmHg. Yield = 89%

0,55 g of the above product was heated in 5mls 10% aq. NaOH for 2hrs at 100 C. Yeild of 4-Me-3-OH-P2P comprised 71%. B.p. – 110-120 Ñ (èôåð temperature) at 0,05 mmHg.

So…. here goes  :)  The chemistry is absolutely weird for us, the Hive Bees, and there’s not much details.

Anyway, I hope you found it interesting, although there’s very little hope that someone here will ever embark onto this synthetic route :)

I think it’d bee much more useful if someone could get those refs, won’t it? ;)




  • Guest
For similar reaction see also:
« Reply #1 on: February 09, 2004, 10:50:00 PM »

This has been brought up previously on the Hive:


Post 309640

(java: "easy ketone.ArCH2COCH3", Chemistry Discourse)

It'd be interresting if one could proceed from p-Dimethoxybenzene to 2,5-Dimethoxyphenylacetone this way:

1. p-dMeOB --> 2,5-dMeO-Phenyllead triacetate
2. acetoacetic ester
3. decarboxylation --> 2,5-dMe-P2P  :)

BTW, Pb(OAc)4 can be made ala

or simply by gassing a solution of Pb(OAc)2 * 3H2O in GAA w/ Cl2 ...

Of course led compounds are toxic, so this synt wouldnt be the safest or enviromentally frendly. :P


  • Guest
The refs. requested (in German)
« Reply #2 on: February 10, 2004, 04:20:00 PM »
Here are the articles mentioned in

Post 419906 (missing)

(Potter: "3-HO-4-Me-P2P èç î-êðåçîëà", Russian HyperLab)

Über die Michael-Reaktion mit Chinolacetaten I.
F. Langer, F. Wessely



Über die Einwirkung von Bleitetraacetat auf Phenole VI.
W. Metlesics, E. Schinzel, H. Vilcsec, F. Wessely




  • Guest
more articles by F. Wessely
« Reply #3 on: October 11, 2004, 01:56:00 PM »
< 3-Hydroxy-4-methylbenzaldehyde from 2,5-dimethylphenol in 2 steps >

originally found by Potter (

Post 414525 (missing)

(Potter: "3-ãèäðîêñè-4ìåòèëáåíçàëüäåãèä", Russian HyperLab)

Die Reaktion von 5-Methyl-o-chinolacetaten mit Nucleophilen
J. Leitich, F. Wessely
Monatsh. Chem., 1964, 95, 116-128.

   Lead tetraacetate reacts with 2,5-xylenol to give 2,5-dimethyl-o-quinol acetate. The latter can be rearranged into 3-hydroxy-4-methylbenzyl acetate, which hydrolyses to 3-hydroxy-4-methylbenzyl alcohol.

Reaktion von Chinolacetaten mit Dimethylsulfoxyd
J. Leitich, F. Wessely
Monatsh. Chem., 1964, 95, 129-146.

   The action of dimethyl sulfoxide on 5-methyl-o-quinol acetates results in m-hydroxybenzaldehydes. If the 5-methyl group is replaced by a primary alkyl group, it is possible to obtain ketones. The reaction is also applicable to p-quinol acetates.