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タイトル: An aniline dication-like transition state in the Bamberger rearrangement.
著者: Yamabe, Shinichi
Zeng, Guixiang
Guan, Wei
Sakaki, Shigeyoshi
著者名の別形: 山邊, 信一
キーワード: Bamberger rearrangement
DFT calculations
N-phenylhydroxylamine
proton transfer
reactive intermediates
transition states
発行日: Jun-2013
出版者: Beilstein-Institut.
誌名: Beilstein journal of organic chemistry
巻: 9
開始ページ: 1073
終了ページ: 1082
抄録: 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.
著作権等: © 2013 Yamabe et al; licensee Beilstein-Institut.
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)
URI: http://hdl.handle.net/2433/175391
DOI(出版社版): 10.3762/bjoc.9.119
PubMed ID: 23766821
出現コレクション:学術雑誌掲載論文等

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