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An aniline dication-like transition state in the Bamberger rearrangement
A Bamberger rearrangement of N-phenylhydroxylamine, Ph–N(OH)H, to p-aminophenol was investigated by DFT calculations for the first time. The nitrenium ion, C(6)H(5)–NH(+), suggested and seemingly established as an intermediate was calculated to be absent owing to the high nucleophilicity of the wate...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Beilstein-Institut
2013
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3678851/ https://www.ncbi.nlm.nih.gov/pubmed/23766821 http://dx.doi.org/10.3762/bjoc.9.119 |
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author | Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi |
author_facet | Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi |
author_sort | Yamabe, Shinichi |
collection | PubMed |
description | A Bamberger rearrangement of N-phenylhydroxylamine, Ph–N(OH)H, to p-aminophenol was investigated by DFT calculations for the first time. The nitrenium ion, C(6)H(5)–NH(+), suggested and seemingly established as an intermediate was calculated to be absent owing to the high nucleophilicity of the water cluster around it. First, a reaction of the monoprotonated system, Ph–N(OH)H + H(3)O(+)(H(2)O)(n) (n = 4 and 14) was examined. However, the rate-determining transition states involving proton transfers were calculated to have much larger activation energies than the experimental one. Second, a reaction of the diprotonated system, Ph–N(OH)H + (H(3)O(+))(2)(H(2)O)(13), was traced. An activation energy similar to the experimental one was obtained. A new mechanism of the rearrangement including the aniline dication-like transition state was proposed. |
format | Online Article Text |
id | pubmed-3678851 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2013 |
publisher | Beilstein-Institut |
record_format | MEDLINE/PubMed |
spelling | pubmed-36788512013-06-13 An aniline dication-like transition state in the Bamberger rearrangement Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi Beilstein J Org Chem Full Research Paper A Bamberger rearrangement of N-phenylhydroxylamine, Ph–N(OH)H, to p-aminophenol was investigated by DFT calculations for the first time. The nitrenium ion, C(6)H(5)–NH(+), suggested and seemingly established as an intermediate was calculated to be absent owing to the high nucleophilicity of the water cluster around it. First, a reaction of the monoprotonated system, Ph–N(OH)H + H(3)O(+)(H(2)O)(n) (n = 4 and 14) was examined. However, the rate-determining transition states involving proton transfers were calculated to have much larger activation energies than the experimental one. Second, a reaction of the diprotonated system, Ph–N(OH)H + (H(3)O(+))(2)(H(2)O)(13), was traced. An activation energy similar to the experimental one was obtained. A new mechanism of the rearrangement including the aniline dication-like transition state was proposed. Beilstein-Institut 2013-06-03 /pmc/articles/PMC3678851/ /pubmed/23766821 http://dx.doi.org/10.3762/bjoc.9.119 Text en Copyright © 2013, Yamabe et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms) |
spellingShingle | Full Research Paper Yamabe, Shinichi Zeng, Guixiang Guan, Wei Sakaki, Shigeyoshi An aniline dication-like transition state in the Bamberger rearrangement |
title | An aniline dication-like transition state in the Bamberger rearrangement |
title_full | An aniline dication-like transition state in the Bamberger rearrangement |
title_fullStr | An aniline dication-like transition state in the Bamberger rearrangement |
title_full_unstemmed | An aniline dication-like transition state in the Bamberger rearrangement |
title_short | An aniline dication-like transition state in the Bamberger rearrangement |
title_sort | aniline dication-like transition state in the bamberger rearrangement |
topic | Full Research Paper |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3678851/ https://www.ncbi.nlm.nih.gov/pubmed/23766821 http://dx.doi.org/10.3762/bjoc.9.119 |
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