Some reactions of 1,3-Dichloro-2-azoniaallene Salts with heteronucleophiles

Abstract

1,3-Dichloro-2-azoniaallene hexachloroantimonates (1) reacted with H2S to give 1,2,4-dithiazolium salts 2. With hydrazines 1,2,4-triazolium salts (3, 4) were formed. 1,3-Dimethylurea, respectively 1,3-dimethylthiourea or ethyl allophanate, reacted with 1 to afford 2-oxo- or 2-thioxo-1,3,5-triazinium salts (5–7). With diphenylmethaneimines imino substituted 2-azoniaallene salts 8 were produced. From chloroacetonitrile dichloropyrimidines 9, and from the tricyanomethyl anion a hexatriene 10 and a triazine 11 could be prepared. The 1,5-dichloro substituted 2-azoniaallene salts 12 reacted as bifunctional electrophiles with nucleophiles such as benzophenone hydrazone or anilines, to furnish 1,3,5-triazinium salts 14. Against benzohydrazide the allene 12j behaved as trivalent electrophile giving the bicyclic 1,3,5-oxadiazinium salt 13j, the constitution of which has been secured by a crystal structural analysis. The vinyl-2-azoniaallene salt 1i cyclized on heating to the 1,3-thiazinium salts 16, 17. From 17 the triazinium salts 18 were prepared with alcohols.