Mikhailichenko O. Synthesis, structure and reactivity of N-sulfonylsubtituted 1,4-quinoneimines

The object of investigation is the influence of donor-acceptor characteristics of the substituent at sulfur atom on structure, spectral characteristics and reactivity in regard to the nucleophiles. The aim of investigation is to determine the influence of steric and donor-acceptor characteristics of the S-substituent in the N-alkyl(trifluoromethyl)sulfonyl-1,4-benzoquinoneimines on their spectral, structural characteristics and reactivity in regard to the nucleophiles. The methods – the organic synthesis, chromatography (thin-layer and columnar), the element analysis, X-ray, the IR, NMR 1H, 13С, 19F spectroscopy. The newness - the new N-alkyl(trifluoromethyl)sulfonyl-1,4-benzoquinoneimines have been synthesized, mechanism of Z,E-isomerisation and structure features of these compounds have been investigated. For the first time the presence of the (p-d) pi coupling in the N-sulfonylsubtituted quinoneimines has been confirmed. The reaction ability of the N-sulfonylderivatives of quinoneimines in regard to the S-, N-, О- and С-nucleophiles has been analyzed. For the first time the dependence of the reaction's direction from the polarization of the quinoneimine has been demonstrated. It has been posited, that in the row of the quinoneimines with the N-substituent PhCO < PhSO2 < MeSO2 < CF3SO2 the regioselectivity of the nucleophilic 1,4-addition increases. It has been demonstrated, that the N-sulfonylsubstituted 1,4-quinoneimines react with the nucleophil-anions as neutral molecules. For the first time the general mechanism of the reaction of the N-sulfonylsubstituted 1,4-quinoneimines with enamines has been formulated.