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
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.
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收藏
页码:672 / 679
页数:8
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