有机-无机杂化钨(钼)过氧配合物催化合成己二酸

Synthesis of Adipic Acid Catalyzed by Hybrid Organic-Inorganic Peroxotungsten and Peroxomolybdenum Compounds

以1,10-菲啰啉(Phen)作N,N配体制备了双核同多钨(钼)杂化过氧配合物H2M2O3(O2)4.2Phen(M:W、Mo),为己二酸的绿色合成提供了一类双功能催化剂。通过元素分析、重量法、化学滴定法、TG/DSC、IR和UV-Vis测试技术对其组成和结构进行了表征。在不使用有机溶剂和相转移催化剂的条件下,考察了它们催化30%的H2O2氧化环己烯、环己醇和环己酮合成己二酸的催化活性。实验结果表明,钨过氧配合物的催化活性较好,钼过氧配合物的催化活性差;以H2W2O3(O2)4.2Phen.H2O作催化剂,反应条件为n(底物)∶n(催化剂)∶n(H2O2)=100∶1.2∶440,反应温度为90℃,反应12 h,从环己烯、环己醇和环己酮到己二酸的收率分别为89.9%、53.5%和64.8%。

Hybrid peroxotungsten and peroxomolybdenum with 1,10-phenanthroline （Phen） H2M2O3（O2）4.2Phen（M = W, Mo） were synthesized and characterized by elemental analysis, gravimetry, titration, TG/DSC, IR and UV-Vis spectroscopy, which supplied new catalysts for the green synthesis of adipic acid. Their catalytic activities for the oxidation of cyclohexene, cyclohexanol and cyclohexanone by H2O2 to adipic acid were evaluated in the absence of organic solvent and phase-transfer agent. It was found that peroxotungsten catalyst exhibited a high activity, while peroxomolybdenum was not active. In the case of H2W2O3 （O2）4.2Phen.H2O, the isolated yield of adipic acid could reach 89. 9%, 53.5% and 64. 8% using cyclohexene, cyclohexanol or cyclohexanone as the substrate respectively when the reaction was carried out at 90℃ for 12h and the ratio of substrate： catalyst： H2O2 was 100：1.2：440.