An aniline dication-like transition state in the Bamberger rearrangement

作者：Yamabe Shinichi^*; Zeng Guixiang; Guan Wei; Sakaki Shigeyoshi

来源：Beilstein Journal of Organic Chemistry, 2013, 9: 1073-1082.

DOI：10.3762/bjoc.9.119

• Bamberger rearrangement
• DFT calculations
• N-phenylhydroxylamine
• proton transfer
• reactive intermediates
• transition states

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, C6H5-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 + H3O+(H2O)(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 + (H3O+)(2)(H2O)(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.

• 出版日期2013-6-3