Mechanism of Direct Electrophilic Aromatic Amination: an Electrophile is Found by Quantum?Chemical Study; ChemistrySelect; Vol. 4, iss. 10
| Parent link: | ChemistrySelect Vol. 4, iss. 10.— 2019.— [P. 2933-2940] |
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| Institution som forfatter: | |
| Andre forfattere: | , , , |
| Summary: | 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 |
| Sprog: | engelsk |
| Udgivet: |
2019
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| Fag: | |
| Online adgang: | https://doi.org/10.1002/slct.201803911 |
| Format: | Electronisk Book Chapter |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=659881 |
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| 200 | 1 | |a Mechanism of Direct Electrophilic Aromatic Amination: an Electrophile is Found by Quantum?Chemical Study |f K. S. Stankevich [et al.] | |
| 203 | |a Text |c electronic | ||
| 300 | |a Title screen | ||
| 320 | |a [References: 39 tit.] | ||
| 330 | |a 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. | ||
| 333 | |a Режим доступа: по договору с организацией-держателем ресурса | ||
| 461 | |t ChemistrySelect | ||
| 463 | |t Vol. 4, iss. 10 |v [P. 2933-2940] |d 2019 | ||
| 610 | 1 | |a электронный ресурс | |
| 610 | 1 | |a труды учёных ТПУ | |
| 610 | 1 | |a amination | |
| 610 | 1 | |a density functional theory | |
| 610 | 1 | |a electrophilic substitution | |
| 610 | 1 | |a hydrazoic acid | |
| 610 | 1 | |a tracing the molecular orbitals | |
| 610 | 1 | |a аминирование | |
| 610 | 1 | |a теория функционала плотности | |
| 610 | 1 | |a замещение | |
| 610 | 1 | |a молекулярные орбитали | |
| 701 | 1 | |a Stankevich |b K. S. |c Physicist |c Engineer Tomsk Polytechnic University |f 1992- |g Ksenia Sergeevna |3 (RuTPU)RU\TPU\pers\37546 | |
| 701 | 1 | |a Bondarev |b A. A. |g Aleksandr Aleksandrovich | |
| 701 | 1 | |a Lavrinenko |b A. K. |g Anastasiya Konstantinovna | |
| 701 | 1 | |a Filimonov |b V. D. |c Russian chemist |c Professor of the TPU |f 1945- |g Viktor Dmitrievich |3 (RuTPU)RU\TPU\pers\26423 |9 12127 | |
| 712 | 0 | 2 | |a Национальный исследовательский Томский политехнический университет |b Инженерная школа новых производственных технологий |b Научно-образовательный центр Н. М. Кижнера |3 (RuTPU)RU\TPU\col\23556 |
| 801 | 2 | |a RU |b 63413507 |c 20190403 |g RCR | |
| 856 | 4 | |u https://doi.org/10.1002/slct.201803911 | |
| 942 | |c CF | ||