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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...

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Autores principales: Yamabe, Shinichi, Zeng, Guixiang, Guan, Wei, Sakaki, Shigeyoshi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2013
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.
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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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