Tsyhankov O. The influence of the substituents nature on the structure characteristics and chemical properties of N-сhloro-N-alkoxyamides, N,N-dialkoxyamides and derivatives of N-alkoxyhydrazines

The dissertation is devoted to the the development of new synthetic methods, study of the structure and chemical properties of different kinds of O-N-N, O-N-O, O-N-Cl geminal systems. The structure of N-alkoxyureas derivatives of overall formula H2NC(O)N(X)OMe (X=H, Cl, OMe, OAc, N+C5H5) and ArHNC(O)N(X)OMe (X=H, Cl, OMe) has been studied and the dominance of the anomeric effect nO(Me)--*N-X in O-N-X geminal systems has been confirmed by the experimental data. The investigation of the structure of N-Х-N-methoxy-4-nitrobenzamides (X=H, Cl, OAc) revealed the high degree of pyramidality of nitrogen atom in the geminal system O-N-Cl, the dominance of the actions of the anomeric effect nO(Me)--*N-Х has been confirmed. The convenient method of the synthesis of sterically hindered and nonaccessible N,N-dialkoxyureas and N,N-dialkoxycarbamates by N-chloro-N-alkoxy derivatives of ureas and carbamates alcoholysis in the presence of silver trifluoroacetate has been developed. The chlorides of N-alkoxy-N-[1-(4-dimethylamino)pyridinium]derivatives of ureas, benzamides and N-tert-alkylamines form in the reactions of the proper N-chloro-N-alkoxyamino compounds with 4-dimethylaminopyridine. The XRD study of N-alkoxy-N-[1-(4-dimethylamino)pyridinium]ureas salts has revealed the high pyramidality degree of the central nitrogen atom in O-N-N+ geminal system. The new kinds of 1,1,1-trialkyl-2-alkoxyhydrazines chlorides, 1-N-alkoxyamino-1,4-diaza[2.2.2]bicyclooctanes and N-alkoxyhydrazines form in the reactions of N-chloro-N-alkoxyureas with trimethylamine or 1,4-diaza[2.2.2]bicyclooctane and in the reaction of methyl N-chloro-N-methoxycarbamate with K-salt N-acetylbenzenesulphonylamide. The XRD studies of N,N'-dicarbomethoxy-N,N'-dimethoxyhydrazine, N'-methoxy-N'-carbomethoxy-N-acetylbenzensulphonylhydrazide, 1,1,1-trimethyl-2-alkoxyhydrazine perchlorate had revealed the pyramidal configuration of the central nitrogen atoms in O-N-N geminal system and the unusual elongation of N-N+ bond and the shortening of N-OMe bond of 1,1,1-trimethyl-2-methoxyhydrazine perchlorate.