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dc.contributor.author | Yamabe, Shinichi | en |
dc.contributor.author | Zeng, Guixiang | en |
dc.contributor.author | Guan, Wei | en |
dc.contributor.author | Sakaki, Shigeyoshi | en |
dc.contributor.alternative | 山邊, 信一 | ja |
dc.date.accessioned | 2013-07-02T07:30:16Z | - |
dc.date.available | 2013-07-02T07:30:16Z | - |
dc.date.issued | 2013-06 | - |
dc.identifier.issn | 1860-5397 | - |
dc.identifier.uri | http://hdl.handle.net/2433/175391 | - |
dc.description.abstract | A amberger rearrangement of N-phenylhydroxylamine, Ph–N(OH)H, to p-aminophenol was investigated by DFT calculations for the first time. The nitrenium ion, C_6H_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_3O^+(H_2O)_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_3O^+)_2(H_2O)_{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. | en |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | - |
dc.publisher | Beilstein-Institut. | en |
dc.rights | © 2013 Yamabe et al; licensee Beilstein-Institut. | en |
dc.rights | This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. he license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc) | en |
dc.subject | Bamberger rearrangement | en |
dc.subject | DFT calculations | en |
dc.subject | N-phenylhydroxylamine | en |
dc.subject | proton transfer | en |
dc.subject | reactive intermediates | en |
dc.subject | transition states | en |
dc.title | An aniline dication-like transition state in the Bamberger rearrangement. | en |
dc.type | journal article | - |
dc.type.niitype | Journal Article | - |
dc.identifier.jtitle | Beilstein journal of organic chemistry | en |
dc.identifier.volume | 9 | - |
dc.identifier.spage | 1073 | - |
dc.identifier.epage | 1082 | - |
dc.relation.doi | 10.3762/bjoc.9.119 | - |
dc.textversion | publisher | - |
dc.identifier.pmid | 23766821 | - |
dcterms.accessRights | open access | - |
出現コレクション: | 学術雑誌掲載論文等 |
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