<I>N</I>-Alkylideneanilines. IV. Kinetics and Mechanism for Site-Exchange of the Methyl Groups in <I>N</I>-Isopropylideneanilines
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概要
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The kinetics of the site-exchange of the methyl groups in twelve <I>N</I>-isopropylideneanilines have been studied by the coalescence point analysis of their proton NMR spectra. The free energies of activation at the coalescence temperature were found to be in the range 16.5 (at 53.5 °C for <I>p</I>-nitro) ∼22.4 (at 161 °C for <I>p</I>-amino derivative) kcal/mol. They give a Hammett σ<SUP>−</SUP>ρ plot with ρ=2.83 (r=0.976). The results are interpreted in terms of an in-plane inversion about the imine nitrogen for the site-exchange. Noticeable deviation of the points representing <I>p</I>-chloro and <I>p</I>-bromo compounds from the linearity indicates the destabilization of the transition state by the electron-releasing resonance effect of the substituents and is consistent with the inversion mechanism.
- 公益社団法人 日本化学会の論文
著者
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Iwamura Hiizu
Department Of Chemistry Faculty Of Science The University Of Tokyo
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Nishimura Shigeo
Department Of Applid Chemistry For Resources Tokyo University Of Agriculture And Technology
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Tsuchimoto Michiko
Department of Industrial Chemistry, Tokyo University of Agriculture and Technology
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