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The Hive => Methods Discourse => Topic started by: Rhodium on February 01, 2004, 10:03:00 AM

Title: Bayer-Villiger Oxidation of Aldehydes and Ketones
Post by: Rhodium on February 01, 2004, 10:03:00 AM
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)

(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)Saturated Aliphatic Ketones Alicyclic Ketones
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Aromatic Ketones
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif),(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_feqa.gif)-Unsaturated Ketones
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Polycarbonyl Compounds
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Aldehydes
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Side Reactions
Selection of Experimental Conditions
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Peroxides
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Hydrogen Peroxide
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Persulfuric Acid
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Perbenzoic Acid
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Monoperphthalic Acid
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Peracetic Acid
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Solvents and Catalysts
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Temperature and Time
Experimental Procedures
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Catechol
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)3,4-Dihydroxyphenanthrene
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Phenyl p-Nitrobenzoate
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Etiocholan-3(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif),12(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif),17(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_feqa.gif)-triol
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Diphenic Acid
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)2-Acetoxyindan-1,3-dione
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)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)Table I. Oxidation of Saturated Aliphatic Ketones
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Table II. Oxidation of Alicyclic Ketones
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)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)Table IV. Oxidation of (https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_lwwo.gif),(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_feqa.gif)-Unsaturated Carbonyl Compounds
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Table V. Oxidation of Polycarbonyl Compounds
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000485811-file_fdlo.gif)Table VI. Oxidation of Aldehydes

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

Post 432975 (https://www.thevespiary.org/talk/index.php?topic=9872.msg43297500#msg43297500)

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

Post 472943 (https://www.thevespiary.org/talk/index.php?topic=9103.msg47294300#msg47294300)

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

Post 477679 (https://www.thevespiary.org/talk/index.php?topic=7720.msg47767900#msg47767900)

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

Post 446838 (https://www.thevespiary.org/talk/index.php?topic=12194.msg44683800#msg44683800)

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

Post 397551 (https://www.thevespiary.org/talk/index.php?topic=12195.msg39755100#msg39755100)

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

Title: Bayer-Villiger Oxidation
Post by: bio on February 01, 2004, 09:51:00 PM
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.
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