Liedienova O. Synthesis, structure and reactivity of N-acyl- and N-[aryl-sulfonylimino(methyl, phenyl)methyl]-1,4-benzoquinonemonoimines

In this thesis the structural features, Z,E-isomerization, and reaction ability of N-acyl- and N-[arylsulfonylimino(methyl, phenyl)methyl]-1,4-benzoquinonemonoimines have been studied. It has been synthesized the new N-acetyl- and N-[arylsulfonylimino-(methyl)methyl]-1,4-benzoquinonemonoimines alkylsubstituted in the quinoid ring and the products of their reactions with potassium thiocyanate, sodium arylsulfinite, hydrogen halides and halogens. It was found the presence of ArSO2N group in N-[arylsulfonylimino(methyl)-methyl]-1,4-benzoquinonemonoimines leads to increase of electron-acceptor properties of substituent near nitrogen atom of quinoid ring and to increase in LUMO energy. That leads to growth of role of charge control in the reaction with potassium thiocyanate and of nucleophilic 1,4-addition in reaction with sodium arylsulfinite in comparison with N-acyl-1,4-benzoquinonemonoimines In halogenation of N-[arylsulfonylimino(methyl)methyl]-1,4-benzoquinonemonoimines the halogenation of methyl group of imidoyl fragment was first revealed, and in bromine action on N-acyl-1,4-benzoquinonemonoimines the derivatives of 1,3-benzoxazol-6-ol. The presence of Z,E-isomerizations relative to quinoneimine С=N bond, exocyclic С=N2 bond and rotation around =N1-С= bond in solutions of N-[arylsulfonylimino(methyl, phenyl)methyl]-1,4-benzoquinonemonoimines have been revealed. The theoretical barriers of these processes have been found. The experimental barriers of Z,E-isomerization relative to exocyclic С=N2 bond for N-[arylsulfonylimino(methyl)methyl]-1,4-benzoquinonemonoimines and rotation around =N1-С= bond for N-[arylsulfonylimino(phenyl)methyl]-1,4-benzoquinonemonoimines have been determined.