Condensed Heterotricycles: dibenz[6,f][I,4]oxazepin-II(10H)-thiones II-substituted dibenz[b,f][I,4]oxazepines & dibenz[b,f][I,4]thiazepine analogues

Abstract

The reaction of iminochloride 4, obtained from 2-nitrodibenzoxazepinone (2), phosphorus oxychloride and dimethylaniline, with cyclic secondary bases, affords 11-amino derivatives 5, and with γ-dimethylaminopropanol, the amino-alkoxy derivative 23, isomeric with SintamilJ (i). Aluminium chloride-catalysed cyclizations of o-isothiocyanatodiphenyl ethers and diphenyl sulphides 8-11 yield dibenzoxazepine and thiazepinethiones 13-16, which are converted to ll-amlno derivatives of the types 6 and 7 by reaction with amines and to 11-aminoalkylmercapto derivatives of type .20 by reaction with aminoalkylchlorides. Amidoxime 21 and azine 22 are obtained from thiones 15 and 13, by reaction with hydroxylamine and hydrazine respectively. 11-Dimethylaminomethyldibenzoxazepine (28) is obtained along with the ring-cleaved product 30, by cyclization of the amide 25 with. PPA and POGl3 mixture or by the conversion of the chloracetamide 24 to 27, followed by reaction with dimethylamine. Phenanthridinethione (19) is readily obtained by the cyclization. of the isothiocyanate 18.