金属四羧酸酞菁对烯烃的催化环氧化

Epoxidation of Olefins Catalyzed by Metal Phthalocyanine Tetracarboxylic Acid

合成了4种金属的四羧酸酞菁金属(Metal Phthalocyanine Tetracarboxylic Acid,M-PTC)配合物,利用红外光谱、紫外光谱及X射线晶体衍射分析对配合物结构进行了表征。以其作为催化剂,开展了以分子氧为氧源的烯烃环氧化的研究。考察了反应体系中溶剂、温度、时间、溶剂用量、共还原剂用量以及催化剂用量对反应的影响。其中Fe-PTC催化活性最好,在n(环辛烯):n(催化剂):n(共还原剂)=4:0.002 5:16、溶剂(1,2-二氯乙烷)12 mL、温度45℃和反应时间5 h条件下,环辛烯转化率达到100%,环氧环辛烷的选择性为91.1%,催化剂活性TON值达到1 457。催化剂循环使用7次后,其结构和活性无明显变化。

Four metal phthalocyanine tetraboxylic acid complexes（M-PTC） were synthesized and characterized by the IR,UV spectrometry and XRD.The catalytic activities of these complexes were screened using the epoxidation of olefins with molecular oxygen as oxidant.The factors including the category and amount of solvents,reaction temperature,as well as the amounts of isobutyradehyde（IBA） and catalyst were evaluated.It was found that Fe-PTC was the best catalyst.Under optimized conditions（ClCH2 CH2 Cl as the solvent,n（cyclooctene） ∶ n（catalyst） ∶ n（IBA） = 4∶ 0.002 5∶ 16,45 ℃,5 h）,the epoxidation of cyclooctene can give 91.1% yield,91.1% selectivity and 1 457 turn over number（TON）.Fe-PTC could be reused for 7 times without loss of catalytic activity.The IR spectra of the fresh-prepared and recovered catalysts indicated that the structure of the catalyst remained unchanged before and after reaction.