Aryl derivatives primary alkylamines

Catalytic amounts of Co(OAc)2 or Mn(OAc)2 in combination with ferf-butyl hydrogen peroxide (1.2 equiv.) as oxidant proved to be effective for amination of benzoxazoles, benzothiazoles, and 2-phenyl-1,3,4-oxadiazole [95]. It is worth noting that in amination of benzoxazoles with secondary aliphatic amines the cobalt catalyst provides better results, while the manganese catalyst is more effective for a similar reaction with primary alkylamines and ammonia. Also the reactions of benzoxazoles with secondary aliphatic amines or formamides have been performed successfully with Cu(OAc)2 (20 mol.%) and oxygen as oxidant [96]. Other azoles do not react with primary alkylamines in the presence of this oxidant. In contrast, when FeCls was used in 0.25-1 equiv. amounts, amination of benzoxazoles and 2-aryl-1,3,4-oxadiazoles (with the exception of their nitro derivatives) proved to... 

A full paper detailing the conversion of primary alkylamines into the corresponding thiocyanates has appeared,and this important contribution to thiocyanate synthesis has now been extended to include aromatic derivatives. Thus, the readily prepared (56) reacts, in refluxing ethanol, with arylamines to give (57), which are smoothly pyrolysed to aryl thiocyanates in preparatively useful yields (Scheme 55). 

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