Determination of the Direction of Reactions of Dienone Derivatives of Cyclohexane with Polynucleophilic Nitrogen-Containing Reagents by Spectral and Computational Methods
Daniil A. Puzanov, Danila A. Rogov, Natalia O. Vasilkova, Adel P. Krivenko. Saratov State University, Saratov, Russia
Abstract
Dienone derivatives of cyclohexane are the object of study of fundamental issues of theoretical organic chemistry (regeodirection, reactivity), since are ambident electrophiles, due to the presence of two reaction centers, and are widely used as multifunctional substrates for the construction of biologically active azoheterocyclic systems. When studying the reactions of 2,6-diarylmethylidenecyclohexanones with polynucleophilic nitrogen-containing reagents (2-nitro- and 2,4-dinitrophenylhydrazine, 3-amino-1,2,4-triazole, cyanoguanidine), we found that, depending on the nature of the nucleophile, the reaction proceeds as nucleophilic substitution of carbonyl groups (with the formation of hydrazones, using hard nucleophiles) or as 1,4-addition with the formation of cyanoimino- or -triazolquinazolines, using soft nucleophiles. The structure of the obtained compounds is confirmed by spectral methods (IR, 1Н, 13С NMR, HSQC, HMBC).
The reactivity of substrates and reagents, in accordance with Pearson's GMKO theory, was estimated from local and global reserve capacity descriptors obtained using the calculation method [B3LYP/6-31G(2p,2d)].
Speaker
Daniil A. Puzanov
Saratov State University
Россия
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