Mechanism of Direct Electrophilic Aromatic Amination: an Electrophile is Found by Quantum?Chemical Study; ChemistrySelect; Vol. 4, iss. 10

Mechanism of Direct Electrophilic Aromatic Amination: an Electrophile is Found by Quantum?Chemical Study; ChemistrySelect; Vol. 4, iss. 10

Detalles Bibliográficos
Parent link:ChemistrySelect
Vol. 4, iss. 10.— 2019.— [P. 2933-2940]
Autor Corporativo: Национальный исследовательский Томский политехнический университет Инженерная школа новых производственных технологий Научно-образовательный центр Н. М. Кижнера
Otros Autores: Stankevich K. S. Ksenia Sergeevna, Bondarev A. A. Aleksandr Aleksandrovich, Lavrinenko A. K. Anastasiya Konstantinovna, Filimonov V. D. Viktor Dmitrievich
Sumario:Title screen
Direct amination is an extremely valuable reaction, allowing for the one‐step preparation of aromatic amines. However, its mechanism was poorly studied. Here, for the first time, using quantum chemical calculations, we have shown that direct amination of arenes by hydrazoic acid follows the classical SEAr mechanism with aminodiazonium cation H2N3+as electrophile. The peculiarity of H2N3+ electronic structure has been described using our novel method for tracing the molecular orbitals. The located stationary points and transition states allowed us to define direct amination as SEAr reaction, which rate is determined by early transition state between π‐ and σ‐complexes. Considering the calculated reaction constant ρ and an early transition state, we placed direct amination of arenes by HN3 somewhere in between nitration and halogenations. Our results explain the accumulated experimental data and open a prospect for the development of the new aminating agents working in milder conditions.
Режим доступа: по договору с организацией-держателем ресурса
Lenguaje:inglés
Publicado: 2019
Materias:
электронный ресурс
труды учёных ТПУ
amination
density functional theory
electrophilic substitution
hydrazoic acid
tracing the molecular orbitals
аминирование
теория функционала плотности
замещение
молекулярные орбитали
Acceso en línea:https://doi.org/10.1002/slct.201803911
Formato: Electrónico Capítulo de libro
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=659881

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