Synthesis utilizing reducing ability of carbon monoxide: a new method for selective synthesis of diorgano selenides and diselenides using selenium-carbon monoxide-water reaction system
A new approach to the synthesis of diorganyl selenides and diselenides is described. Selective generation of tertiary amine salts of hydrogen selenide ([HSe-].[R3NH+]) and hydrogen diselenide ([HSe2-].[R3NH+]) has been achieved by controlling the reaction conditions for the reduction of elemental selenium with carbon monoxide and water in the presence of tertiary amine. Subsequent alkylation provided a wide variety of symmetrical dialkyl selenides (R2Se) and diselenides (R2Se2) with a high degree of selectivity. Acylation of the amine salt of hydrogen selenide by equimolar amounts of acid chlorides led to the formation of tertiary amine salt of selenocarboxylates [R3NH+].[RCOSe-] in excellent yields. Further acylation and alkylation of this salt yielded bis(acyl) selenides [(RCO)2Se] and Se-alkyl selenocarboxylates (RCOSeR'), respectively. Moreover, oxidation of the amine salt of selenocarboxylates gave rise to bis(acyl) diselenides [(RCO)2Se2].
NISHIYAMA, YUTAKA;KATSUURA, AKIO;NEGORO, ATSUHITO;HAMANAKA, SAWAKO, J. ORG. CHEM., 56,(1991) N2, C. 3776-3780