Bayer-Villiger Oxidation of Aldehydes and Ketones

[Rhodium]

The Bayer-Villiger Oxidation of Aldehydes and Ketones
C. H. Hassall

Organic Reactions, Vol. 9, Ch. 3, pp. 73-106 (1957)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bayer-villiger.or-a.pdf)

Contents

Introduction
Mechanism of the Reaction
Scope of the Reaction
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Saturated Aliphatic Ketones Alicyclic Ketones
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Aromatic Ketones
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif" title="View this image">,https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_feqa.gif" title="View this image">-Unsaturated Ketones
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Polycarbonyl Compounds
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Aldehydes
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Side Reactions
Selection of Experimental Conditions
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Peroxides
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Hydrogen Peroxide
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Persulfuric Acid
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Perbenzoic Acid
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Monoperphthalic Acid
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Peracetic Acid
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Solvents and Catalysts
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Temperature and Time
Experimental Procedures
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Catechol
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">3,4-Dihydroxyphenanthrene
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Phenyl p-Nitrobenzoate
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Etiocholan-3https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif" title="View this image">,12https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif" title="View this image">,17https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_feqa.gif" title="View this image">-triol
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Diphenic Acid
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">2-Acetoxyindan-1,3-dione
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Lactone C₂₁H₃₂O₄ from Isoandrosterone Acetate
Tabular Survey of the Baeyer-Villiger Reaction
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Table I. Oxidation of Saturated Aliphatic Ketones
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Table II. Oxidation of Alicyclic Ketones
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Table III. Oxidation of Aliphatic, Aromatic, Alicyclic Aromatic, Aromatic, and Heterocyclic Ketones
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Table IV. Oxidation of https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif" title="View this image">,https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_feqa.gif" title="View this image">-Unsaturated Carbonyl Compounds
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Table V. Oxidation of Polycarbonyl Compounds
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif" title="View this image">Table VI. Oxidation of Aldehydes

This review should come in handy for the procedures discussed in the following threads:

Post 432975

(Aurelius: "Baeyer-Villiger Oxid. --> Methoxybenzaldehydes", Methods Discourse)

Post 472943

(bio: "Benzaldehyde + MEK acid catalyzed aldol", Methods Discourse)

Post 477679

(Rhodium: "Syntheses of Dillapiole & its 4-Methylthio analog", Chemistry Discourse)

Post 446838

(GC_MS: "SPC/SPB", Novel Discourse)

Post 397551

(demorol: "Phenols from aldehydes", Novel Discourse)

[bio]

Very helpful Rhodium, thank you for posting that article. It improves my understanding of the reaction. Reference 77 Boeseken and Jacobs, Rec. trav. chim. 55, 804 (1936) for phenylacetone may have some tips that could be used to improve this procedure. I believe they used HCl in the hydrolysis step. The hydrolysis should be near quatitative, is that correct? Because I have noticed a lot of clean high boiling golden/red residue after the distillaton and wonder how much could be the unconverted enol ester. If any bee has access to this journal please post it. No library in my vicinity. There are also several references in the catalyst section that could improve the yield. The sulfuric or toluenesulfonic acids might work and if anyone can find some of these I will try it and post the results. As much as possible I want to avoid exotic catalysts.