Abstract: Using mesitylene and o-xylene as examples, it was shown that the solvent nature strongly affects the conversion of methylbenzenes in electrophilic amination with the system NaN3-AlCl3-HCl. Two-parameter correlations were found between the substrate conversion, on the one hand, and dielectric constant and number of heavy atoms in the solvent, on the other. A considerable solvent effect on the regioselectivity of amination of o-xylene was observed. The presence of 18-crown-6 weakly affects the ratio of isomeric amines, but the conversion of o-xylene sharply decreases. Solid aromatic substrates, such as durene and pentamethylbenzene can also be involved in electrophilic amination with the system NaN3-AlCl3-HCl. On the basis of the experimental data and the results of quantum-chemical calculations, participation of a nitrenium intermediate in this reaction was postulated.

Cite: Borodkin G. , Elanov I. , Popov S. , Pokrovskii L. , Shubin V.
Electrophilic amination of methylbenzenes with the system NaN3-AlCl3-HCl. Effects of the solvent, crown ether, and substrate structure
Russian Journal of Organic Chemistry. 2003. V.39. N5. P.672-679. DOI: 10.1023/A:1026057212359 WOS Scopus РИНЦ

ArticleLinkType.TRANSLATED_TO_ORIGINAL: Бородкин Г.И. , Еланов И.Р. , Попов С.А. , Покровский Л.М. , Шубин В.Г.
Электрофильное аминирование метилбензолов системой nan 3-alcl 3-hcl. эффекты структуры, растворителя и краун-эфира
Журнал органической химии (RUSS J ORG CHEM+). 2003. Т.39. №5. С.718-724. РИНЦ

Identifiers:

Web of science	WOS:000185779100011
Scopus	2-s2.0-1642491910
Elibrary	13431070
OpenAlex	W349867138

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