Reaction of Dibenzyl Selenides with Nitric Acid

Abstract

Action of nitric acid (d=1.5) upon bis(pentamethylbenzyl) selenide in cold dichloromethane results in a reductive cleavage of the carbon-selenium bond, giving pentamethylbenzyl nitrate and elemental selenium in nearly quantitative yield. By similar treatment, bis (p-chloro- and p-nitrobenzyl) selenides suffer no bond cleavage but are easily oxidized to the corresponding selenoxides; no ring nitration is observed. Reaction of unsubstituted dibenzyl selenide with nitric acid affords a nitrate of the expected selenoxide as a water-soluble crystalline solid. A marked effect of ring substituents on the reaction∗ modes of dibenzyl selenides has been investigated and a possible mechanism is suggested for the reductive cleavage with nitric acid of bis (polymethylated benzyl) selenides. © 1981, The Chemical Society of Japan. All rights reserved.