Yakymenko I. Reactions of arylsulfonyl derivatives of quinonymines with nucleophiles

The dissertation is devoted to the study of reactions of N-substituted quinone monoimines with nucleophilic agents and to the study of the influence of the structure of the starting compounds and the conditions of synthesis on their course. It was found that the nucleophilic attachment of 2,3-dimethylindole is possible only if the electrophilic center is available in the ortho position to the carbonyl group of N-substituted 1,4-benzoquinone monoimines. As the redox potential of N-substituted 1,4-benzoquinone monoimines increases, the direction of the reaction from the nucleophilic addition of 2,3-dimethylindole to the reduction of quinonymine to the corresponding aminophenol is changed. It is established that the interaction of N-chloramides of carboxylic acids with N-arylsulfonyl-1,4-benzoquinone monoimines is possible only under the condition of full openness of the electrophilic center in the ortho position to the carbonyl oxygen atom. The paper shows the possibility of using O-acylbenzhydroxamic acids in the acylamination reactions of N-arylsulfonyl-1,4-benzoquinone monoimines in the presence of a catalytic amount of potassium acetate. It is proved that the nature of the acyl group of O-acylbenzhydroxamic acids does not have a significant effect on the course of the reaction. For the first time, the possibility of acylamination of 1,4-benzoquinone with a low redox potential compared to N-arylsulfonyl-1,4-benzoquinone monoimines has been shown. The presence of benzoylamino groups in the N-arylsulfonyl-1,4-benzoquinone monoimines in the ortho position to the carbonyl oxygen atom promotes the introduction of nucleophiles into the para- or meta-position to it, even in the case of partial blocking of these positions by an adjacent methyl group. The substitution of arylsulfonyloxyimino group in the reactions of aryl (alkyl) sulfonyloxy-1,4-benzoquinone monoimines with phenylhydrazine and hydrazides of aromatic carboxylic and arylsulfonic acids is greatly influenced by steric blocking of the carbonyl group of quinoneimine, its redox potential and nucleophile basicity. With even partial availability of the carbonyl group of aryl(alkyl)sulfonyloxy-1,4-benzoquinone monoimines, their reduction to the corresponding aminophenols is observed.