The conversion of 2-(4-chloro-5H-1,2,3-dithiazolylideneamino)benzonitriles into 3-aminoindole-2-carbonitriles using triphenylphosphine

Abstract

2-(4-Chloro-5H-1,2,3-dithiazolylideneamino)benzonitrile 1a reacts with triphenylphosphine (4 equiv) in the presence of water (2 equiv) to afford anthranilonitrile 2a, 3-aminoindole-2-carbonitrile 3a and (2-cyanoindol-3-yl)iminotriphenylphosphorane 4a, together with triphenylphosphine sulfide and oxide. The use of polymer bound triphenylphosphine provides cleaner reaction mixtures. 2-(4-Chloro-5H-1,2,3-dithiazolylideneamino)-4,5-dimethoxybenzonitrile 1h does not give the corresponding indole on treatment with triphenylphosphine but gives 6,7-dimethoxyquinazoline-2-carbonitrile 5 (15%) and 2-cyano-4,5-dimethoxy cyanothioformanilide 6 (36%). A total of seven new 3-aminoindole-2-carbonitriles 3a-g are prepared and fully characterised. © 2009 Elsevier Ltd. All rights reserved.