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本文研究了6,6-二烷基富烯与α-萘基锂反应的立体结构和溶剂效应。首次发现了富烯与有机锂的还原偶联反应。在乙醚-THF中α-萘基锂与6,6-二甲基、二乙基和甲基乙基富烯发生环外双键的加成、α-氢攫取、还原和还原偶联的竞争反应。与6-甲基-6-正丙基,正丁基,异丁基富烯发生还原偶联反应.与n=4,5,6的6,6-n亚甲基富烯分别进行α-氢攫取、还原和还原偶联反应.在1:1的乙醚-石油醚中,除6,6-四亚甲基富烯发生α-氢攫取外,其他所有富烯主要进行加成反应。利用上述反应合成一些新的取代和桥联双(环戊二烯基)钛、锆衍生物。
In this paper, we studied the stereostructure and solvent effect of 6,6-dialkylfulvene reacted with α-naphthyl lithium. The reductive coupling reaction of fulvene with organolithium was first discovered. The α-naphthyllithium in ether-THF undergoes exocyclic double bond addition, α-hydrogen snap, reduction and reductive coupling competition with 6,6-dimethyl, diethyl and methyl ethylfulvene reaction. With 6-methyl-6-n-propyl, n-butyl, isobutyl fulvene reductive coupling reaction with n = 4,5,6 6,6-n methylene fulvene α- Hydrogen capture, reduction and reductive coupling reactions were carried out in a 1: 1 mixture of ether and petroleum ether except for the α-hydrogen of 6,6-tetramethylenefulvene. Some new substituted and bridged bis (cyclopentadienyl) titanium and zirconium derivatives were synthesized using the above reaction.