Electrophilic amination of methylbenzenes with the system NaN3-AlCl3-HCl.: Effects of the solvent, crown ether, and substrate structure

被引：6

作者：

Borodkin, GI ^{[1
]}

Elanov, IR ^{[1
]}

Popov, SA ^{[1
]}

Pokrovskii, LM ^{[1
]}

Shubin, VG ^{[1
]}

机构：

[1] Russian Acad Sci, Siberian Div, Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia

来源：

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 39卷 / 05期

关键词：

D O I：

10.1023/A:1026057212359

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：672 / 679

页数：8

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