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本文研究了6,6-二烷基富烯与有机锂反应的立体效应。6,6-二甲基、甲基乙基、二乙基、甲基苯基富烯与乙基锂易发生环外双键的还原反应。6-甲基-6-正丙基、异丁基富烯同正丁基锂则发生环外双键的加成反应。6,6-多亚甲基富烯[C_5H-4=C(CH_2)_n]与有机锂的反应随n值不同而异,n=4的富烯同正丙基锂和正丁基锂进行α-攫氢和环外双键还原的竞争反应;n=5,6的富烯与乙基锂、异丙基锂和异丁基锂发生还原反应,与正丙基锂和正丁基锂则进行加成与还原的竞争反应。n=4的富烯与芳基锂发生α-攫氢反应,随n值增大则倾向于加成反应。通过上述反应所得的锂化合物合成了一系列新的仲、叔烷基和烯基取代的环戊二烯基钛、锆衍生物。应用~1H NMR证明了化合物的结构。
In this paper, we studied the stereoscopic effect of 6,6-dialkylfulvene with organolithium. 6,6-dimethyl, methyl ethyl, diethyl, methyl phenyl fulvene and ethyl lithium susceptible to the occurrence of exocyclic double bond reduction. 6-methyl-6-n-propyl, isobutyl fulvene with n-butyl lithium is the occurrence of exocyclic double bond addition reaction. The reaction of 6,6-polymethylene fulvene [C_5H-4 = C (CH_2) _n] with organolithium varies depending on the value of n, the fulvene with n = 4 is reacted with n-propyllithium and n-butyllithium for α - a competition reaction between hydrogen capture and reduction of exocyclic double bonds; a fulvene with n = 5, 6 and a reduction reaction of lithium, isopropyllithium and isobutylithium with n-butyllithium and n-butyllithium Addition and reduction of the competitive reaction. The fullerene with n = 4 undergoes α-snap-off hydrogenation with aryllithium and tends to undergo addition reaction as n increases. A series of new secondary, tertiary and alkenyl substituted cyclopentadienyl titanium and zirconium derivatives were synthesized from the lithium compounds obtained by the above reaction. 1H NMR confirmed the structure of the compound.