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Title: The effect of pressure on the rate of the benzidine rearrangement V : 2-chloro-2'-methylhydrazobenzene
Authors: Osugi, Jiro
Onishi, Ichiro
Issue Date: 31-Mar-1972
Publisher: The Physico-Chemical Society of Japan
Journal title: The Review of Physical Chemistry of Japan
Volume: 41
Issue: 1/2
Start page: 32
End page: 41
Abstract: The effect of pressure on the rate of the acid-catalyzed rearrangement of 2-chloro-2'-methylhydrazobenzene in 85 vol% aqueous ethanolic solution was studied under the conditions of 15~30℃ and 1~1, 500kg/cm^2. As a result, it was observed that two different reactions concurred ; one was of first order with respect to [HCl] (one-proton mechanism) and the other was of second order (two-proton mechanism), and the former was fairly, while the latter was slightly accelerated by pressure. Based on the activation parameters obtained, i.e. E≠=22.2kcal/mole, ΔS≠=-1.6 e.u., ΔV≠=-6.8cm^3/mole for one-proton mechanism and E≠=18.0kcal/mole, ΔS≠=-12.4 e.u., ΔV≠=-3.2cm^3/mole for two-proton mechanism, the reaction mechanisms and the transition states were discussed. The existence of a linear relationship between the logarithms of the rate constants of the rearrangement and pKa values of ortho-substituted anilinium ions was suggested, by correcting pKa, for the steric effect of ortho-substituents.
Appears in Collections:Vol.41 No.1 & 2

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