Palladium(II) sulfate-heteropoly acid-catalyzed oxidation of cycloolefins in liquid phase.

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概要

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• Heteropoly acid (HPA) was used as an oxidant in the Wacker catalyst system. Among the catalyst systems examined, the PdSO<SUB>4</SUB>–H<SUB>3</SUB>PMo<SUB>6</SUB>W<SUB>6</SUB>O<SUB>40</SUB> catalyst system showed the highest activity with regard to the oxidation of cycloolefins, particularly cyclopentene and cyclohexene, to the corresponding cyclic ketones. The largest total turnover number with respect to Pd<SUP>2+</SUP> was found to be 85 in water containing 20% <I>N</I>-methylformamide by volume. The initial rate of cyclohexene oxidation was expressed as<BR><I>V</I><SUB>o</SUB>=<I>k</I>[Cyclohexene]<SUP>1.0</SUP>[PdSO<SUB>4</SUB>]<SUP>1.0</SUP>[HPA]<SUP>0</SUP>[O<SUB>2</SUB>]<SUP>0</SUP>.<BR>The rate-determining step was suggested as being where cyclohexene was oxidized to cyclohexanone by Pd(II) salt. The apparent activation energy was 7.8 kcal mol<SUP>−1</SUP> (1 cal=4.18 J). In the catalytic oxidation of cycloolefins (C<I><SUB>n</SUB></I>H<SUB>2<I>n</I>−2</SUB>: <I>n</I>=5, 6, 7, and 8), the yield of alicyclic ketone decreased as the carbon number n increased. Methyl-substituted cyclohexenes exhibited lower reactivities than cyclohexene.

• 公益社団法人 日本化学会の論文

著者

• Ogawa Haruo

  Department Of Chemistry Faculty Of Education Tokyo Gakugei University

• Teratani Shousuke

  The Institute of Physical and Chemical Research

• Fujinami Hideharu

  Department of Chemistry, Tokyo Gakugei University

• Taya Kazuo

  Department of Chemistry, Tokyo Gakugei University

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