Emmanouil A. Theodorakis

A convenient and high yielding procedure for the preparation of isoselenocyanates. Synthesis and reactivity of O-alkylselenocarbamates.

Abstract A high yielding one pot procedure for the preparation of isoselenocyanate from the corresponding formamide is reported. Various aromatic and aliphatic primary amines were employed in order to prepare the isoselenocyanates to establish the generality of the procedure. O-Alkylselenocarbamates of various primary, secondary and tertiary alcohols were synthesized and their stability and comparative reactivity were studied. Radical deoxygenation of the selenocarbamate of a secondary and a tertiary alcohol was accomplished under various conditions.

The invention of radical reactions part xxiii. new reactions nitrile and thiocyanate transfer to carbon radicals from sulfonyl cyanides and sulfonyl isothiocyanates

Abstract Reaction of p-toluenesulphonyl cyanide or methanesulfonyl cyanide with carbon radicals, generated from the corresponding O-acyl-N-hydroxy-2-thiopyridone derivatives by visible light photolysis gives nitriles in good yield. The homolysis products of these sulfonyl nitriles can also be trapped by electron rich olefins. We have also found that carbon radicals react easily with mesyl or tosyl isothiocyanate producing thiocyanates.

Radical nitrile transfer with methanesulfonyl cyanide or p-toluenesulfonyl cyanide to carbon radicals generated from the acyl derivatives of N-hydroxy-2-thiopyridone

Abstract Reaction of methanesulfonyl cyanide or p-toluenesulfonyl cyanide with carbon radicals generated from the acyl derivatives of N-hydroxy-2-thiopyridone gives the corresponding nitriles in high yield. A mechanistic scheme is suggested.

O-Sulfinylation of alcohols with methanesulfonyl cyanide or p-toluenesulfonyl cyanide.

Abstract Reaction of p-toluenesulfonyl cyanide or methanesulfonyl cyanide with alcohols in the presence of 1,8-diazabicyclo[5.4.0]under-7-ene (DBU) or 1,4-diazabicyclo[2.2.2]octane (DABCO) gives sulfinates in good yield. A mechanistic scheme involving sulfinyl cyanates 9 and 21 is suggested.

O-Sulfinylation with methanesulfonyl cyanide or p-toluenesulfonyl cyanide and DBU

Abstract Reaction of methanesulfonyl cyanide or p-toluenesulfonyl cyanide with alcohols in the presence of 1,8-diazabicyclop[5.4.0]undec-7-ene (DBU) gives sulfinates in good yield. A mechanistic scheme involving sulfinyl cyanates is suggested.