AZIDES AND AMINES FROM GRIGNARD REAGENTS AND TOSYL AZIDE

Grignard reagents react with tosyl azide to form salts of tosyltriazenes, which can be reduced to amines by Raney nickel alloy and aqueous base. Fragmentation of the triazene salts to form aryl or alkyl azides takes place best in aqueous sodium pyrophosphate at 0-20°. Yields are moderate to good with aromatic reagents, poor with aliphatic. o-Tolyl and o-t-butylphenyl Grignard reagents react with tosyl azide under some conditions to give the azobenzene and toluenesulfonamide instead. © 1969, American Chemical Society. All rights reserved.