Benzeneperoxyseleninic Acid

[62885-97-6]  · C6H6O3Se  · Benzeneperoxyseleninic Acid  · (MW 205.07)

(reagent for Baeyer-Villiger reaction and oxidizing agent for many functional groups)

Physical Data: mp 52 °C (with explosion).

Solubility: sparingly sol water, chloroform, and acetonitrile.

Form Supplied in: white powder.

Analysis of Reagent Purity: determination of active oxygen iodometrically (19.5%).1

Preparative Methods: the method of preparation involves oxidation of Benzeneseleninic Acid or Diphenyl Diselenide with 30% Hydrogen Peroxide used in excess at -10 °C. In a similar way, 2-nitro- and 2,4-dinitrobenzeneperoxyseleninic acids are obtained with 90% H2O2.1 Peroxyseleninic acids are postulated as active intermediates when organic substrates are treated with H2O2 or t-Butyl Hydroperoxide in the presence of areneseleninic acids or aryl diselenides.2-8

Handling, Storage, and Precautions: caution: explosion hazard! Benzeneperoxyseleninic acid decomposes when dried in vacuo. It may be stored in a refrigerator for 1 week. Left to stand in air at rt for 3-4 days, it rearranges to benzeneseleninic acid. In the presence of water, it decomposes to benzeneseleninic acid and H2O2. This compound should be handled in a fume hood.

Baeyer-Villiger Oxidation.

The treatment of aromatic aldehydes or aryl methyl ketones with benzeneperoxyseleninic acid gives formates or acetates.1 Similar results are achieved when H2O2 is used as a stoichiometric oxidant in the presence of catalytic amounts of bis(2,4-dinitrophenyl) diselenide (DNPDS), which forms 2,4-dinitrobenzeneperoxyseleninic acid in situ. The crude formate or acetate is hydrolyzed to phenol. This method is suitable for the synthesis of phenols substituted with electron-donating groups (eq 1).7 In a similar manner, a,b-unsaturated aldehydes are oxidized with H2O2 in the presence of 2-nitrophenyl diselenide (NPDS) to a mixture of products containing mainly the vinyl formates; hydrolysis then leads to saturated aldehydes or ketones having the carbon chain shortened by one carbon atom (eq 2).8

Oxidation of cyclic ketones (eq 3)5 and epoxidation of alkenes and allylic alcohols is achieved through the intermediate formation of (nonisolated) peroxyseleninic acids.2-4 Styrene and its analogs are efficiently epoxidized with H2O2 in the presence of 2-nitrobenzeneseleninic acid.6

Other Oxidations.

Immobilized benzeneperoxyseleninic acid is a possible intermediate when polymer-bound benzeneseleninic acid (in catalytic amounts) and H2O2 or t-BuOOH are used for oxidations such as epoxidation, diol synthesis, oxidation of benzylic alcohols to carbonyl species, the Baeyer-Villiger oxidation, and the conversion of phenols into quinones.9

Aromatic aldehyde N,N-dimethylhydrazones are oxidized to nitriles (eq 4)10 with 2-nitrobenzeneperoxyseleninic acid formed in situ from o-Nitrobenzeneseleninic Acid (NBSA), while aromatic and aliphatic aldoximes in the presence of primary or secondary alcohols are converted into carboxylic esters (eq 5).11

1. Syper, L.; Mlochowski, J. T 1987, 43, 207.
2. Grieco, P. A.; Yokoyama, Y.; Gilman, S.; Nishizawa, M. JOC 1977, 42, 2034.
3. Hori, T.; Sharpless, K. B. JOC 1978, 43, 1689.
4. Reich, H. J.; Chow, F.; Peake, S. L. S 1978, 299.
5. Grieco, P. A.; Yokoyama, Y.; Gilman, S.; Ohfune, Y. CC 1977, 870.
6. Kubicz, E.; Mlochowski, J.; Syper, L. JPR 1991, 333, 243.
7. Syper, L. S 1989, 167.
8. Syper, L. T 1987, 43, 2853.
9. Taylor, R. T.; Flood, L. A. JOC 1983, 48, 5160.
10. Said, S. B.; Skarżewski, J.; Mlochowski, J. S 1989, 223.
11. Said, S. B.; Skarżewski, J.; Mlochowski, J. SC 1992, 22, 1851.

Jacek Mlochowski & Ludwik Syper

Technical University of Wroclaw, Poland

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