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.
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Borodkin, G.I., Elanov, I.R., Popov, S.A. et al. Electrophilic Amination of Methylbenzenes with the System NaN3-AlCl3-HCl. Effects of the Solvent, Crown Ether, and Substrate Structure. Russian Journal of Organic Chemistry 39, 672–679 (2003). https://doi.org/10.1023/A:1026057212359
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DOI: https://doi.org/10.1023/A:1026057212359