Access to ortho-Hydroxyphenyl Ketimines via Imine Anion-Mediated Smiles Rearrangement
Shunki Jinno1, Takahiro Senoo1, Keiji Mori1
1Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japan.
Abstract:
We have achieved a facile access to N-(2-halophenyl)-2-hydroxyphenylimine derivatives via imine anion-mediated Smiles rearrangement. When 2-(2-halophenoxy)benzonitriles were treated with 1.2-1.4 equiv of organolithium reagents, nucleophilic addition to the nitrile group followed by Smiles rearrangement occurred to give various N-(2-halophenyl)-2-hydroxyphenylimine derivatives, which are sometimes difficult to synthesize by the conventional acid-promoted condensation reaction between carbonyl compounds and aniline derivatives, in good to excellent chemical yields (up to 91%).
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Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...

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