Syntheses and Reactivities of Stable Halosilylenoids, (Tsi)X2SiLi (Tsi=C(SiMe3)3, X=Br, Cl)
作者:Myong Euy Lee、Hyeon Mo Cho、Young Mook Lim、Jin Kyong Choi、Chang Hee Park、Seong Eun Jeong、Uk Lee
DOI:10.1002/chem.200305151
日期:2004.1.23
Halosilylenoids, stable at room temperature (Tsi)X(2)SiLi (Tsi=C(SiMe(3))(3), X=Br, Cl), were synthesized from the reaction of TsiSiX(3) with lithium naphthalenide. Bromosilylenoid reacted with tBuOH and MeI both at -78 degrees C and at room temperature to give (Tsi)HSiBr(2) and (Tsi)MeSiBr(2), respectively, in high yields; this clearly shows its nucleophilicity. In the reaction of bromosilylenoid
从TsiSiX(3)与萘锂的反应合成了在室温下稳定的卤化亚烯基(Tsi)X(2)SiLi(Tsi = C(SiMe(3))(3),X = Br,Cl)。溴化烯类化合物在-78摄氏度和室温下与tBuOH和MeI反应,分别以高收率分别得到(Tsi)HSiBr(2)和(Tsi)MeSiBr(2);这清楚地表明了它的亲核性。在溴化烯类化合物与甲醇,2-丙醇和2,3-二甲基-1,3-丁二烯的反应中,相应的产物(Tsi)HSi(OMe)(2),(Tsi)HSi(OiPr)Br和以高收率获得了溴(Tsi)silacyclopent-3-ene;这证明了其两亲性,好像会捕获溴亚甲硅烷基一样。绿皮烯类化合物还表现出亲核和两亲性质。(Tsi)Br(2)SiLi,(Tsi)Br(2)SiK和(Tsi)Cl(2)SiLi的(29)Si化学位移分别为106、70和87 ppm,