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以聚卟啉金属配合物PMTPP(M=Co(Ⅱ)、Mn(Ⅱ)和Zn(Ⅱ))为催化剂催化分子氧氧化环己烯,氧化产物以2-环己烯-1-醇(1)、2-环己烯-1-酮(2)和7-氧杂二环[4.1.0]环己烷(3)为主。配合物PCo(Ⅱ)TPP具有最好的催化活性,对影响该配合物活性的因素研究发现,反应温度在70℃,反应时间为8 h时,环己烯的转化率可达到90%,且产物1的选择性可达54%,催化剂使用3次后活性没有明显下降。在此基础上,还探讨了配合物PCo(Ⅱ)TPP氧化环己烯的可能反应机理,初步认为氧化反应的过程是链式自由基反应。
Catalytic oxidation of cyclohexene by molecular oxygen with PMTPP (M = Co (Ⅱ), Mn (Ⅱ) and Zn (Ⅱ)) as polyporphyrin and oxidation of 2-cyclohexen-1-ol ), 2-cyclohexen-1-one (2) and 7-oxabicyclo [4.1.0] cyclohexane (3). The results showed that the conversion rate of cyclohexene reached 90% when the reaction temperature was 70 ℃ and the reaction time was 8 h, and the activity of PCo (Ⅱ) complex was the best. The selectivity of product 1 was up to 54%, and the activity of the catalyst was not significantly reduced after 3 times. On this basis, the possible reaction mechanism of cyclohexene oxide with PCo (Ⅱ) complex was also discussed. It is preliminarily believed that the oxidation reaction is chain free radical reaction.