Pd(OAc)_2/HQ/FePc、Pd(OAc)_2/FePc 催化烯烃氧化合成酮的研究

Study of Oxidation of Olefins Catalyzed by Pd(OAc) 2/HQ/FePc and Pd(OAc) 2/FePc for the Synthesis of Ketones

考察了在乙腈酸性水溶液中Ｐｄ（ＯＡｃ）２／氢醌（ＨＱ）／酞青铁（ＦｅＰｃ）和Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对环己烯、环戊烯、苯乙烯、正癸烯氧化合成相应酮的催化活性．实验结果表明，两类催化体系对环戊烯的酮基化均呈现出较高的催化活性，环戊酮收率可达９８％．在其它烯烃的氧化反应中，三元催化体系Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ的催化活性高于二元的Ｐｄ（ＯＡｃ）２／ＦｅＰｃ．这表明，在Ｗａｃｋｅｒ类催化体系中，电子传递体的作用是很重要的．对催化体系中各组分的作用进行了讨论，并给出了可能的催化作用机理．

The catalytic activities of Pa(OAc) 2/HQ/FePc and Pd(OAc) 2/FePc in the oxidation of cyclohexene, cyclopentene, styrene and decene to the corresponding ketones in the acidic aqueous solution of MeCN were examined respectively. The experimental results indicated that both the two catalytic systems showed high catalytic acitivites for the ketonization of cyclopentene, with the yield of cyclopentanone up to 98%. For the ketonization of other olefins, however, the catalytic activity of Pd(OAc) 2/HQ/FePc system was higher than that of Pd(OAc) 2/FePc. It is shown that the electron transfer played an important role in the ketonization of olefins catalyzed by wacker like catalyst system. At the same time, the role played by each component of the catalyst system in the oxidation of olefins was discussed, and a possible reaction mechanism was proposed.