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タイトル: | The effect of pressure on the rate of the benzidine rearrangement : II. O, o'-hydrazotoluene |
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: | 30-Apr-1967 |
出版者: | The Physico-Chemical Society of Japan |
誌名: | The Review of Physical Chemistry of Japan |
巻: | 36 |
号: | 2 |
開始ページ: | 100 |
終了ページ: | 110 |
抄録: | 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. |
URI: | http://hdl.handle.net/2433/46887 |
出現コレクション: | Vol.36 No.2 |
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