ChemInform Abstract: Synthesis, Structure and Properties of Compounds with a Chalcogen‐Nitrogen Bond. Part 11. Reaction of Selenium Imides with Thiols and Thioamides.

Abstract

ChemInform Abstract The oxidative power of chalcogen imides toward thiols and thioamides increases in the order S < Se < Te. This is due to the increasing polarity and, hence, decreasing stability of the chalcogen-nitrogen bond within this series. The aim of this investigation is to evaluate the influence exerted by electron-accepting or electron-donating substituents attached to the Se atom of selenium imides on the polarity of the Se-N bond. Diphenyl-and dibenzylselenium imides on reaction with the thiols (I) afford disulfides of type (II). The diphenylselenium imide and the dibenzylselenium imide differ in their behavior toward thiourea (Va), thiobenzamide (Vb) and N,N'-diphenylthiourea. The diphenyl derivative affords the 1,2,4-thiadiazoles (III) or (IV), whereas the dibenzyl derivative is found to be a stronger oxidant to give cyanamide (VIa), benzonitrile (VIb) or diphenylcarbodiimide (VII), thus demonstrating the enhanced Se-N polarity in the dibenzyl derivative.