NATURAL SCIENCES

Journal of fundamental
and
applied researches

Chemistry of N,NN-dialkoxycarbonyl derivatives of benzoquinonediimines

2013. №4, pp. 148-168

Melenteva Ekaterina A. - post-graduate student, Astrakhan State University, 1 Shaumyan Sq., Astrakhan, 414000, Russian Federation, morfei199077@rambler.ru

The results of study of N,NN-dialkoxycarbonyl derivatives of ortho- and para-benzoquinonediimine chemistry are summarized in the mini-review. Some reactions of C-, O-, S-and N-nucleophiles are analyzed. It is shown that depending on the nature of the nucleophile, reaction can proceed by mechanism of 1,4-addition or 1,6-addition on system of conjugated double bonds of quinonediimine. Reaction of N,N’-dimethoxycarbonyl-p-benzoquinonediimine and 2-chloro-N,N’-dimethoxycarbonyl-p-benzoquinonediimine with thioacetic acid in methylene chloride at room temperature proceeds as reaction of 1,4-addition on system of conjugated N=C C=C bonds of quinonediimine with formation of aromatic structure products, which at heating in concentrated hydrochloric acid are exposed of heterocyclization with preparation of 1,3-benthothiazol-2(3Н)-ones with methoxycarbonylamino group at the С6 atom. It was discovered that reaction of N,NN-dimethoxycarbonyl-o-benzoquinonediimine with cyclopentadiene, cyclohexene and styrene in situ proceeds as Diels-Alder reaction with reversed electronic requirements and produces corresponding tetrahydroquinoxaline derivatives and its p-substituted analogue by reaction with dienes acts as normal dienophile. It was detected regularities of reactions of dialkoxycarbonylquinonediimine derivatives with 1,3-dipolar compounds that are generating inaccessible by other trends carbamate derivatives of indazole, benzimidazole, bicyclic[4.1.0]hept-3-ene and other compounds. The efficiency of use of Michael adducts to symmetric and asymmetric N-alkoxycarbonyl-p-benzoquinonediimine of variety CH acids in the synthesis of indoles was demonstrated by concrete examples. As against of dimedone reaction of quinonediimine with alkylidenemalonates in similar conditions results instead of expected Michael 1,4-addition adducts in reception of corresponding substituted N,N’-dimethoxycarbonyl-p-benzoquinonediimines. It was exposed regularities reactions of N,NN-dimethoxycarbonyl-p-benzoquinonediimine reactions with enamines. It was demonstrated main directions of indole modification with the introduction of new pharmacophore groups.

Key words: N,NN-dimethoxycarbonyl-p-benzoquinonediimine,N,NN-dimethoxycarbonyl-o-benzoquinonediimine,N1-benzyloxycarbonyl,N4-benzoyl-p-benzoquinonediimine,1,4- and 1,6-addition reactions of a nucleophilic reagents,Meldrumds acid and its analogs,Diels-Alder reaction