4-Me-3-OH-phenylacetone from o-cresol in two steps

[Antoncho]

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?


Yours,

Antoncho

[dioulasso]

http://orgsyn.org/orgsyn/prep.asp?prep=cv7p0229

This has been brought up previously on the Hive:

e.g.

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

https://www.thevespiary.org/rhodium/Rhodium/chemistry/lead.tetraacetate.html

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.

[azole]

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

None

(http://hyperlab.0catch.com/Monatsh1957_88_298.djvu)

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

None

(http://hyperlab.0catch.com/Monatsh1957_88_1069.djvu)

[azole]

< 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.
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000487486-MonatshChem1964_95_116.djvu" target="_blank" title="Download this file">

   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.

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000487486-xylenol1.gif" target="_blank" title="View this image">
Reaktion von Chinolacetaten mit Dimethylsulfoxyd
J. Leitich, F. Wessely
Monatsh. Chem., 1964, 95, 129-146.
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000487486-MonatshChem1964_95_129.djvu" target="_blank" title="Download this file">

   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.
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000487486-xylenol2.gif" target="_blank" title="View this image">