6,6-二烷基富烯与有机锂的反应-双(取代环戊二烯基)钛, 锆衍生物的合成

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C5H4=C(CH2)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, 与正丙基俚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^1HNMR证明了化合物的结构。

Reaction of 6,6-dialkylfulvene with organolithium-syntheses of substituted titanocene and zirconocene derivatives

The steric effects on the reaction of 6,6-dialkylfulvene with organolithium have been studied. Reaction of EtLi with 6,6-dialkylfulvone readily results in the formation of reduction product. The addition products were formed by the reaction of BuLi with 6,6-dialkylfulvene. The analogous reaction of 6,6-polymethylenefulvene with organolithium was also examined Reaction of tetramethylenefulvene with aryllithium only leads to a-hydrogen elimination and in the case of penta and hexamethylenefulvene addition reaction takes place. A series of sec- and tert-alkyl and cycloalkenyl substituted titanocene and zirconocene derivatives have been prepared