光照下非贵金属催化环己烯的转移加氢反应

Catalytic Transfer Hydrogenation of Cyclohexene with Non-precious Metal under Irradiation

研究了光照下,甲醇为氢源,非贵金属镍盐、钴盐催化环己烯的转移加氢反应。结果表明,以CoCl_2、Co(OAc)_2或NiCl_2、Ni(OAc)_2为催化剂,环己烯可以发生催化转移加氢反应,得到环己烷,综合催化剂的加氢活性和产物环己烷的选择性,CoCl_2的催化效果是最好的,在293K光照24h,环己烷的产率和选择性分别为20%和46%,其次为NiCl_2。在环己烯/CoCl_2体系中添加三正丁胺或升高温度,对催化转移加氢反应不利;而在环己烯/NiCl_2催化体系中添加三正丁胺或升高温度,可以提高催化转移加氢反应的活性。在甲醇、乙醇和异丙醇中,甲醇为氢源的环己烯转移加氢反应效果最好。

The catalytic transfer hydrogenation of cyclohexene,using methanol as hydrogen donor,was carried out with cobalt and nickel salts catalysts under irradiation.The results indicated that cyclohexane was obtained with four salt catalysts,i.e. NiCl_2,Ni(OAc)_2 and CoCl_2,Co(OAc)_2.Among these catalysts,CoCl_2 was the most efficient in terms of octane yield and selectivity. the yield of cyclohexane was 20%and the selectivity of cyclohexane was 46%with CoCl_2 as catalyst at 293K after 24h.Second is NiCl_2.The catalytic activity of NiCl_2 increased with increasing temperature and addition of tri-n-butylamine.However,the catalytic activity of CoCl_2 decreased with increasing temperature and addition of tri-n-butylamine.In addition,it was shown that the activity of the hydrogenation decresed with ethanol and 2-propanol in place of methanol as hydrogen donor.