合成了新颖的双功能水溶性金属卟啉催化剂M(TTMAPP)I_4(X)(M=Co,Fe,Mn和Cr;X=Oae,CF_3COO,CCl_3COO,Ots,Cl,Br和I),研究了它们催化CO_2与末端环氧化合物合成环碳酸酯的偶联反应.分别考察了反应温度、不同金属的Lewis酸中心、抗衡离子和催化剂重复使用次数对反应性能的影响.当以Co(Ⅲ)(TTMAPP)I_4(OAc)为催化剂,底物与催化剂摩尔比为1 000,温度为353K,CO_2压力为667kPa和无溶剂条件下,反应5h时丙烯环碳酸酯收率为95.4%.在298K,底物与催化剂之比为2 000时,加入1 ml甲醇,反应24h丙烯环碳酸酯收率为19.4%.催化剂可以用乙醚同收,循环使用5次后催化剂活性没有明显降低.
New catalysts of water soluble bifunctional metalloporphyrins M(TTMAPP)I_4(X) (M = Co, Fe, Mn, and Cr; X =OAc, CF_3COO, CCl_3COO, OTs, Cl, Br, and I) were synthesized and used to catalyze the synthesis of cyclic carbonate through the coupling reaction of ter-minal epoxides and CO_2. The effects of reaction temperature, various metals as the Lewis acidic center, counterions, and recycling of the catalysts were studied. 5,10,15,20-Tetra-(p-N,N,N-trimethylphenyl ammonium iodide)porphyrinium cobalt(Ⅲ) acetate [Co(Ⅲ)-(TTMAPP)I_4(OAc)] was efficient in the coupling reaction of various terminal epoxides and CO_2 at 353 K under 667 kPa of CO_2 pressure without solvent and molar ratio of epoxide:catalyst = 1000. It gave a propylene carbonate yield of 95.4% within 5 h. At 298 K in the presence of 1 ml methanol with the molar ratio of epoxide:catalyst = 2000, it gave a propylene carbonate yield of 19.4% within 24 h. The catalyst could be recovered with diethyl ether and reused five times without significant loss of catalytic activity.
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