芳香族ニトリルの接触合成反応に関する研究　Ｖ　　酸化剤としてＢｒ?S２?Tを用いる芳香族アンモ酸化反応

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書誌事項

タイトル別名
  • Studies on the Catalytic Synthesis of Aromatic Nitriles (Part 5)
  • 酸化剤としてBr<sub>2</sub>を用いる芳香族アンモ酸化反応

抄録

In order to confirm the reaction mechanism for the previously reported ammoxidation reaction using SO2, ammoxidation reaction of toluene and ethylbenzene using Br2 as an oxidizing agent was investigated.<br>C6H5CH3+NH3+3Br2→C6H5CN+6HBr+25.0kcal/mol<br>(1) Activated alumina (γ-Al2O3), diatomaceous earth and fused alumina (Alundum; α-Al2O3) catalyzed the reaction at lower temperatures by 130-140°C than that in the case of SO2, and particularly γ-Al2O3 and diatomaceous earth were very active, but the activity of these catalysts rapidly decreased in the course of reaction, and benzylbromide instead of benzonitrile was formed over the decayed catalyst or at lower temperatures. The rapid decay of catalyst activity resulted from the deposit of NH4Br crystal and carbonaceous matter over the catalyst surface. In the case of ethylbenzene benzylcyanide was produced together with styrene and benzonitrile. It was inferred that the formation of benzylcyanide in this case was due to far lower reaction temperatures than those in the case of SO2.<br>(2) From the above experimental results and the theory of radical reaction by Semenov, the reaction mechanism was inferred as follows;<br>C6H5CH3→Br•→HBrC6H5CH2→Br2→Br•C6H5CH2Br→NH3γ-Al2O3C6H5CH2NH2→Br•γ-Al2O3→HBrC6H5CN<br>NH3→γ-Al2O3NH3(ads.)→Br•→NH2(ads.)→HBr→γ-Al2O3<br>where the route (1) is probably a main process. This mechanism is similar to that of the reaction using SO2.

収録刊行物

  • 石油学会誌

    石油学会誌 18 (1), 13-18, 1975

    公益社団法人 石油学会

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