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タイトル: | The effect of pressure on the rate of the benzidine rearrangement V : 2-chloro-2'-methylhydrazobenzene |
著者: | Osugi, Jiro Onishi, Ichiro |
著者名の別形: | オオスギ, ジロウ オオニシ, イチロウ |
発行日: | 31-Mar-1972 |
出版者: | The Physico-Chemical Society of Japan |
誌名: | The Review of Physical Chemistry of Japan |
巻: | 41 |
号: | 1/2 |
開始ページ: | 32 |
終了ページ: | 41 |
抄録: | 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. |
URI: | http://hdl.handle.net/2433/46960 |
出現コレクション: | Vol.41 No.1 & 2 |
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