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Syntheses and Reactivities of Stable Halosilylenoids,(Tsi)X_2SiLi (Tsi=C(SiMe_3)_3,X=Br,Cl)

机译:(Tsi)X_2SiLi(Tsi = C(SiMe_3)_3,X = Br,Cl)的合成和反应性

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摘要

Halosilylenoids,stable at room temperature (Tsi)X_2SiLi (Tsi=C(SiMe_3)_3,X=Br,Cl),were synthesized from the reaction of TsiSiX_3 with lithium naphthalenoide.Bromosilylenoid reacted with tBuOH and MeI both at -78 deg C and at room temperature to give (Tsi)HSiBr_2 and (Tsi)MeSiBr_2,respecitvely,in high yields;this clearly shows its nucleophilicity.In the reaction of bromosilylenoid with methanol,2-propanol,and 2,3-dimethyl-1,3-butadiene,the corresponding products,(Tsi)HSi(OMe)_2,(Tsi)Hsi(OiPr)Br,and bromo(Tsi)silacyclopent-3-ene,were obtained in high yields;this demonstrates its amphiphilic property,as if bromosilylene would be trapped.Chlorosilylenoid also exhibited both nucleophilic and amphiphilic properties.The ~(29)Si chemical shifts for (Tsi)Br_2SiLi,(Tsi)Br_2SiK,and (Tsi)Cl_2SiLi were 106,70,and 87 ppm,respectively.
机译:由TsiSiX_3与萘二甲酰亚胺锂反应合成了在室温(Tsi)X_2SiLi(Tsi = C(SiMe_3)_3,X = Br,Cl)稳定的卤代亚硒基类化合物。在室温下以高收率分别得到(Tsi)HSiBr_2和(Tsi)MeSiBr_2;这清楚地表明了它的亲核性。在溴烯基烯酮与甲醇,2-丙醇和2,3-二甲基-1,3-的反应中丁二烯及其相应的产物(Tsi)HSi(OMe)_2,(Tsi)Hsi(OiPr)Br和溴(Tsi)硅环戊3-烯的收率高;这表明它具有两亲性,就像溴代甲硅烷基一样(Tsi)Br_2SiLi,(Tsi)Br_2SiK和(Tsi)Cl_2SiLi的〜(29)Si化学位移分别为106,70和87 ppm。

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