Some derivatives of trithiatriazine

Abstract

This thesis can be conveniently divided into two parts (a) the reactions of trimeric sulphanuric chlorides and fluorides, and (b) the investigation of reactions of trithiazyltrichloride, thiodithiazyldichloride and their derivatives with epoxides and with nitriles and other unsaturated systems. (a) Reactions of Sulphanuric Halides The replacement of chlorine and fluorine in the sulphanuric halides (NSOCl)(_3) and (NSOF)(_3) by aliphatic, aromatic, amino and thioalkoxy groups has been investigated. The bromination and iodination of (NSOCl)(_3) was attempted, and the following new compounds were identified: (NS0)(_3)Cl(_2)Me, (NS0)(_3)Cl(C(_6)H(_3)Cl(_2))(_2), (NS0)(_3)F(Net(_2))(_2), (NSO)(_3)F(NC(_8)H(_18))(_2). Evidence was found for the existence of (NSONMe(_2))(_3), (NSO)(_3)(SEt)(_n)Cl(_3-n), (NSOBr) (_n), (NSOl)(_n) and (NSO)(_3)Ph(_2)(o-C(_6)H(_2)Cl(_3). The mass spectral fragmentation pattern of (NS0)(_3)Ph(_2)F was investigated. (b) Reactions of (NSCl)(_3), S(_3)N(_2)Cl(_2) and their derivatives The investigation of the reactions of (NSCl)(_3) with epoxides and nitriles commenced by Dr. G.G. Alange (Ph.D. Thesis, University of Durham, August 1969) was continued, and extended to other strained and unsaturated systems, namely episulphides and isocyanates. The reaction with nitriles yielded products of the type S(_2)N(_2)CClR where R is phenyl, t-butyl and trichloromethyl. This system, S(_2)N(_2)CClR is compared with that of 1,2,5-thiadiazoles and S(_3)N(_2)Cl(_2). A study of the reaction of S(_3)N(_2)C1(_2) with sulphuryl chloride led to a convenient new synthesis of trithiazyl trichloride. The reactions of S(_3)N(_2)C1(_2) with thionyl chloride and trichloromethylacetonitrile were also investigated. The reaction of epichlorohydrin with "(NSC1)(_3)" - prepared by rapid chlorination by chlorine gas of S(_4)N(_4) - was investigated. Results of both sections are generally discussed and an appendix covers the use of the chlorine isotope pattern for identifying fragments in the mass spectrum.