Beilstein J. Org. Chem.2014,10, 1765–1774, doi:10.3762/bjoc.10.184
= 12) and +15.6 (n = 16) were obtained, where the experimental Ea is + 14.6 kcal/mol. Also, in the Bambergerrearrangement Ph-NH(OH) + (H3O+)2(H2O)13 → para-HO-C6H4-NH3+ + H3O+(H2O)14 [26], Ea = +26.3 kcal/mol was calculated, where the experimental Ea is +24.8 kcal/mol.
Our proposed reaction pathways
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Graphical Abstract
Scheme 1:
The general form of the Strecker reaction. The reaction (b) is taken from [2].
Beilstein J. Org. Chem.2013,9, 1073–1082, doi:10.3762/bjoc.9.119
Shinichi Yamabe Guixiang Zeng Wei Guan Shigeyoshi Sakaki Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, JAPAN. Phone: +81-075-711-7907 10.3762/bjoc.9.119 Abstract A Bambergerrearrangement of N-phenylhydroxylamine, Ph–N(OH)H, to
activation energy similar to the experimental one was obtained. A new mechanism of the rearrangement including the aniline dication-like transition state was proposed.
Keywords: Bambergerrearrangement; DFT calculations; N-phenylhydroxylamine; proton transfer; reactive intermediates; transition states
; Introduction
The fundamental Bambergerrearrangement is defined in Scheme 1 [1][2].
In the aqueous sulfuric acid, 4-aminophenol was afforded exclusively by the rearrangement. On the other hand, the 2- and 4-chloro-amino derivatives were afforded when hydrochloric acid was used. In spite of the classic and well
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Graphical Abstract
Scheme 1:
The Bamberger rearrangement. In the square bracket, the apparent exchange of H and OH is shown.