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Title: The effect of pressure on the rate of the benzidine rearrangement : II. O, o'-hydrazotoluene
Authors: Osugi, Jiro
Sasaki, Muneo
Onishi, Ichiro
Issue Date: 30-Apr-1967
Publisher: The Physico-Chemical Society of Japan
Journal title: The Review of Physical Chemistry of Japan
Volume: 36
Issue: 2
Start page: 100
End page: 110
Abstract: The rates of the acid-catalysed rearrangement and of the oxidation of o, o'-hydrazotoluene in aqueous ethanol (96vol. % EtOH) have been measured at pressures up to 3000kg/cm^2. The rates of the rearrangements of one-proton and two-proton mechanisms were increased by pressure. In the two-proton mechanism, as a small negative volume of activation and a positive entropy of activation are observed, it seems likely that the second proton transfer is a pre-equilibrium. The oxidation accompanied with the rearrangement in acidic solution includes two concurrent reactions : one is independent of [H^+] and the other is inversely proportional to [H^+], both being strongly accelerated by pressure. Because of the large negative volumes of activation, it is implied that each reaction goes through an ionic activated complex.
Appears in Collections:Vol.36 No.2

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