Doklady Chemistry

This review summarizes the results of the authors' study of chemical transformations of basic N-substituted methyl 4H-thieno[3,2-b]pyrrolecarboxylate in two main directions concerning the synthesis of new polymers and heterocycles (isoquinolines). In the first part presents data on the synthesis of a series of polyheterofunctionalized polymers based on the first developed from monomeric starting 4N-substituted bis-4H-thieno[3,2-b]-pyrrolomethanes and structurally similar products of cross-coupling (1H-pyrrol-3-ylmethyl)-4H-thieno[3,2-b]-pyrroles, their physicochemical properties were studied, possible step-by-step routes of formation and examples of practical use were proposed. In the second part the results obtained in the course of studying the AlCl₃-promoted acylation reactions of N-benzyl- and N-2,3-dimethoxybenzyl-substituted methyl 4H-thieno[3,2-b]-pyrrole carboxylates with acid chlorides of the above-mentioned acids with the isolation of a new topology isoquinolines fused with 4H-thieno[3,2-b]pyrrole and benzene rings are discussed.

A convenient method for the synthesis of optically pure secondary heteroaromatic S-alcohols by asymmetric reduction of prochiral heteroaromatic ketones catalyzed by D. carota or P. crispum cells has been developed. Using o-, m-, p-bromophenylethanone as an example, we studied the effect of the substituent position in the aromatic ring of acetophenone on the efficiency and stereoselectivity of carbonyl group bioreduction by D. carota and P. crispum catalysts.

The catalytic properties of FAU zeolites with different porosity (microporous Na-X and granulated micro-me-so-macroporous Na-X_h, K-Na-X_h and CuO/Na-X_h) in the synthesis of aniline by the reaction of nitrobenzene with 2-propanol were studied for the first time. It was found that the maximum yield of aniline of 94% with almost complete conversion of nitrobenzene is observed on the CuO/Na-X_h catalyst (300°C, 20 wt. % catalyst, nitrobenzene : alcohol = 1 : 16 mol/mol, 5 h). The high activity and selectivity of the CuO/Na-X_h zeolite are due to its hierarchical porous structure, as well as the presence of the maximum number of "weak" and "medium" acid sites. Zeolite K-Na-X_h demonstrates the lowest selectivity for aniline and an increase in side reactions of acetone condensation, which is apparently associated with a decrease in the number of acidic sites and the appearance of basic sites.

The chromogenic effect in molecular systems capable of existing in two isomeric forms, caused by the inversion of the thermodynamic stability of isomers during the transition from the condensed state to the gas phase at low residual pressure and defined as barochromism, was discovered in a series of benzothiazole spiropyrans. This, along with what was described earlier for indoline spiropyrans, allows us to assume the universal nature of the discovered phenomenon.