氯苄双羰化合成苯丙酮酸新型催化剂吡啶—2—羧酸钴研究

Study on Double Carbonylation of Benzyl Chloride to Phenyl Pyruvic Acid by a Novel Cobalt Pyridine- 2- carboxylate Catalyst

实验发现吡啶-2-羧酸钴是氯苄双羰化合成苯丙酮酸的新颖催化剂.在水和1,4-二氧六环混合溶剂中,当T=353 K,p=2.4 mPa,V(H2O):V(dioxane)=1:1.1,氧化钙与氯苄克分子比为1.00,氯苄与吡啶-2-羰酸钴的摩尔比为1:0.05时,氯苄转化率为74.5%,选择性达99%,苯丙酮酸产率为73.8%.研究了反应条件对苯丙酮酸产率和选择性的影响,并使用IR,UV,GC-MS等对产物进行了测定.

It is found that the cobalt pyridine-2-carboxylate tetrahydrate [Co(Pyca)(2)(H2O)(2)]. 2H(2)O has a very good catalytic activity and selectivity for the double carbonylation of benzyl chloride to phenyl pyruvic acid in CaO/dioxane/H2O reaction system. The catalyst is also unsensitive to H2O and O-2 in the system, which is very convenient to handle in the reaction. The conversion of benzyl chloride is 74.5% with a selectivity of 99%, and the yield of the phenyl pyruvic acid is above 73.8% after running 10 h in 2.4 mPa and 353 K with the PhCH2Cl/CaO ratio of 1.00 and the catalyst of 5.5 mmol in the solvent. The only by-product in the reaction is phenyl acetic acid. It has also been found that the solvents used in the reaction have critical effect on the distribution of products in,the reaction. The less polar solvent dioxane is more favourable to the formation of phenyl pyruvic acid than the more polar solvent CH3OH. The products is characterized by IR, UV and GC-Ms.