Peracetic acid selenides

The oxidation of 2-butene with selenium dioxide in acetic acid solution produces l-acetoxy-2-butene as the oxidation product of the olefin and bis(l-methyl-2-acetoxypropyl)-selenide (I) as the final reduced state of the oxidant instead of elemental selenium. Further, (I) may act as a catalyst for the oxidation of 2-butene with peracetic acid or oxygen to 3-acetoxy-1-butene. A mechanism is proposed to explain the formation of selenides in the oxidation of olefins with selenium dioxide and their catalytic activity in the oxidation of olefins with other oxidants. 

Purification of the Organoselenium Compounds. After the oxidation of 2-butene with selenium dioxide was completed, the acetic acid solvent and the volatile reaction products were distilled at reduced pressure (10 mm. HgA). The residue, a yellow oil, was purified by adsorption chromatography in a column packed with silica gel. n-Hexane and ethyl ether were used as eluents. The same procedure was applied to the fractionation and purification of the organoselenium compounds obtained from the oxidation of bis(l-methyl-2-acetoxypropyl) selenide with peracetic acid. 

Oxidation of Bis (1-methyl-2-acetoxypropyl) selenide with Peracetic Acid. The oxidation of the selenide was conducted in a 10 wt. % solution in glacial acetic acid at 5°C. Peracetic acid was added dropwise as a 1M solution in acetic acid. To prevent any potential overoxidation of the selenide, only 0.3 mole of peracetic acid per mole of selenide was used. 

Oxidation of Bis (1 -methyl-2-acetoxypropyl) selenide with Peracetic Acid. The reaction produced 0.75 mole of 3-acetoxy-l-butene per mole of peracetic acid consumed, and a new organoselenium compound was isolated from the reaction solution. NMR analysis of this compound led us to suggest that it was a substituted alkylselenenyl acetate of the following structure ... 

Oxidation of Bis (1-methyl-2-acetoxypropyl) selenide in the Presence of 2-Butene. The only product of the reaction was 3-acetoxy-l-butene. No epoxides and only traces of diols were detected in the reaction product. Approximately 0.85 mole of 3-acetoxy-l-butene was produced per mole of peracetic acid consumed, and approximately 90% of the original selenide was recovered unchanged. 

Oxidation of Bis (l-methyl-2-acetoxypropyl) selenide in the Presence of 2-Methyl-2-butene. The analysis of the solution near the beginning of the reaction showed that 3-acetoxy-l-butene was the only initial product of the oxidation, but after adding 0.5 mole of peracetic acid per mole of selenide, increasing amounts of the oxidation products of 2-methyl-2-butene, such as 2-methyl-3-acetoxy-l-butene, and 3-methyl-3-acetoxy-l-butene were detected. After adding 4 moles of peracetic acid per mole of selenide, the allylic products from the oxidation of 2-methyl-... 

Peracetic Acid Oxidation of 2-Butene Catalyzed by Bis (1-methyl-2-acetoxypropyl) selenide. Based upon the identification of an alkyl-selenenyl acetate among the products of the oxidation of bis(l-methyl-2-... 

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