双锂试剂与6,6-二烷基富烯的反应——取代茂钛、锆有机化合物的合成  

Reactions between Dilithium-Organo Reagent and 6, 6-Dialkylfulvenes——Syntheses of Substituted Titanocene and Zirconocenes Derivatives

作　　者：刘玉龙[1] 陈寿山[2] 

机构地区：[1]安徽大学应用化学研究所,合肥230039 [2]南开大学元素有机化学研究所,天津300071

出　　处：《化学学报》1993年第11期1118-1124,共7页Acta Chimica Sinica

摘　　要：研究了双锂试剂与6,6-二烷基富烯反应的立体、结构效应。1,4_丁基二锂、1,6-己基二锂同6,6-二甲基、6-甲基-6-乙基、6-甲基-6-正丙基和6,6-五甲基富烯发生加成反应。对苯基二锂与6,6-二甲基、6-甲基-6-乙基、6-甲基-6-正丁基和6,6-四甲基、五甲基、六甲基富烯均进行α-攫氢反应,但使6-甲基-6-正丙基富烯还原偶联。1,2,3-正四苯基-1,4-二锂丁二烯-1,3同6-甲基-6-正丙基、6,6-五甲基富烯发生α-攫氢反应。讨论了上述反应的机理。由上述形成的取代环戊二烯基阴离子同CpTiCl_3,(GpTiCl_2)_2O,TiCI_4和ZrCl_4反应,制得亚甲基桥联和烯基茂钛、锆化合物。The steric Stracture effect of 6, 6-dialkylfulvenes in reaction with 1, 4-dilithiobutane(L-A), 1, 6 dilithlohexane (L-B), 1, 4-dilithiobenzene (L-C) and 1, 2, 3, 4-teora phenyl-1, 4-dilithio-1, 3-butediene(L-D)are studied. Dilithium reagent L-A and L-B adds on the exo-cyclic double bound on 6, 6-dimethyl-, 6-methyl-6-ethyl-,6-methyl-6-n-propylfulvehes and 6, 6-penta-methylene-fulvene. The a hydrogen abstraction reaction takes place when dilithium reagent L-C reacts with 6, 6-dimethyl-, 6-methyl-6-ethyl-, 6-methyl-6-n-butyl-fulvenes and 6, 6-tetramethylene-, pentamethylenehexamethylene-fulvenes, except that the 6-methyl-6-n-propylfulvene undergoes reductive coupling reaction. With larger steric dilithium reagent L-D 6-methyl-6-n-propyl-, 6, 6-pentamethylene-fulvenes give rise to α-hydrogen abstraction reaction. Besides, a series of methylene-bridged and alkenyl substituted titanocenes and zurconocenes derivatives are prepared.

关 键 词：双锂试剂 钛 二烷基富烯 锆 

分 类 号：O623.12[理学—有机化学]