The reactions of oximes with covalent halides. Part I. Dimethylglyoxime, diphenylglyoxime, and the benzil monoximes with titanium tetrachloride

Abstract

A suspension of dimethylglyoxime, DMGH₂(n mol.) in light petroleum or chloroform at 20° gave with titanium tetrachloride the adducts TiCl₄,nDMGH₂(n= 1 or 2). At 40°, however, there was loss of hydrogen chloride and the compound TiCl₃,DMGH was obtained. The analogous TiCl₃,DPGH was formed at 20° from diphenylglyoxime, DPGH₂. The two isomers of benzil monoxime, BMOH (1 mol.) with titanium tetrachloride (1 mol.) each gave the adducts, TiCl₄,BMOH. With benzil monoxime (2 mol.) in chloroform the adducts TiCl₄,2BMOH,0·5CHCl₃ were obtained. The dimethylglyoxime adducts decomposed violently on heating, but the benzil monoxime adducts underwent a Beckmann fragmentation at ca. 120° to give phenyl cyanide.