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 wa...

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Bibliographic Details
Published inBeilstein journal of organic chemistry Vol. 9; no. 1; pp. 1073 - 1082
Main Authors Yamabe, Shinichi, Zeng, Guixiang, Guan, Wei, Sakaki, Shigeyoshi
Format Journal Article
LanguageEnglish
Published Germany Beilstein-Institut 03.06.2013
Subjects
Bamberger rearrangement
Chemistry
DFT calculations
Full Research Paper
N-phenylhydroxylamine
proton transfer
reactive intermediates
transition states
proton transfer
transition states
Bamberger rearrangement
reactive intermediates
N-phenylhydroxylamine
DFT calculations
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Summary: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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ISSN:1860-5397
1860-5397
DOI:10.3762/bjoc.9.119