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タイトル: | The effect of pressure on the rate of the benzidine rearrangement III : 2,2'-dibromohydrazobenzene |
著者: | Osugi, Jiro Sasaki, Muneo Onishi, Ichiro |
著者名の別形: | オオスギ, ジロウ ササキ, ムネオ オオニシ, イチロウ |
発行日: | 10-Dec-1969 |
出版者: | The Physico-Chemical Society of Japan |
誌名: | The Review of Physical Chemistry of Japan |
巻: | 39 |
号: | 1 |
開始ページ: | 57 |
終了ページ: | 63 |
抄録: | The rates of the acid-catalysed rearrangement of 2, 2'-dibromohydrazobenzene in aqueous ethanol (85 vol% EtOH) have been measured at pressures up to 3, 000 kg/cm^2. It was observed that two different reaction: one is of first order with respect to [HCl] (one-proton mechanism), and the other is of second order (two-proton mechanism), occurred concurrently and the former was strongly accelerated by pressure. From the values of volumes, energies and entropies of activation ; ΔV_1≠=-10.7 cc/mole, E_1≠=16.3 kcal/mole, ΔS_1≠=-34 e.u. for the one-proton mechanism and ΔV_2≠=-0.4 cc/mole, E_2≠=29 kcal/mole, ΔS_2≠=7.3 e.u. for the two-proton mechanism, the transition states of the both mechanisms were discussed. |
URI: | http://hdl.handle.net/2433/46931 |
出現コレクション: | Vol.39 No.1 |
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