A novel route to pentacoordinated organylsilanes and -germanes
摘要:
New convenient methods of sila- and germatranes synthesis from ethoxy-and tetraorganylsilanes and -germanes have been elaborated. The reaction of ethoxysilanes with boratrane in the presence of catalytic amounts of metal alcoholates has been investigated. Dimethylformamide (DMF) as a solvent and NaOEt as a catalyst used instead of xylene and Al(O-i-Pr)(3) were found to give better yields. The possibility of using alkoxy-, aminosilanes, tetraethoxygermane and even tetraorganylsilanes in this reaction leading to the corresponding atranes with good yields has been demonstrated. Triethanolamine in the presence of catalytic amounts of base or CsF easily substitutes furyl-, dihydrofuryl-, dihydropyranyl- and thienyl groups in tris-and tetraheterylsilanes, leading to organylsilatranes with good to excellent yields. (C) 1997 Elsevier Science S.A.
New 1-organyl-2-azasilatran-3-ones have been synthesized via the reaction of trifunctional silanes RSiX3 (R = Et, Pr, Ph, CH2=CH, or ClCH2; X = Cl or Me2N) with N,N-bis(2-hydroxyethyl)glycinamides (HOCH2CH2)(2)NCH2C(O)NHR (R = H or Me) and their N',O-trimethylsilyl derivatives. The obtained products can be hydrolyzed to give the corresponding organylsilanetriols. Lithiation of 1-methyl- and 1-phenyl-2-azasilatran-3-ones with n-butyllithium or their reduction with lithium aluminum hydride leads to the products of splitting of the atrane backbone RSiBu3 and RSiH3 (R = Me or Ph), respectively.
Lukevits,E. et al., Journal of general chemistry of the USSR, 1977, vol. 47, p. 98 - 101
作者:Lukevits,E. et al.
DOI:——
日期:——
Chloraminosilanes II. Preparation and spectroscopic studies on alkyl-(dimethylamino)chlorosilanes
作者:S.S. Washburne、W.R. Peterson
DOI:10.1016/s0022-328x(00)90592-8
日期:1970.1
Several new compounds containing both chloro and dimethylaminogroups linked to silicon have been prepared. The general method involved reacting a solution of the appropriate polychlorosilane in ether at ca. - 50° with a chilled ethereal solution of dimethylamine. Prepared in this fashion were CH3Si(NMe2)Cl2, CH3Si(NMe2)2-Cl, PhSi(NMe2)Cl2, PhSi(NMe2)2Cl, CH3(H)Si(NMe2)Cl, (CH3)2Si(NMe2)Cl, CH2CH(CH3)Si(NMe2)Cl
New convenient methods of sila- and germatranes synthesis from ethoxy-and tetraorganylsilanes and -germanes have been elaborated. The reaction of ethoxysilanes with boratrane in the presence of catalytic amounts of metal alcoholates has been investigated. Dimethylformamide (DMF) as a solvent and NaOEt as a catalyst used instead of xylene and Al(O-i-Pr)(3) were found to give better yields. The possibility of using alkoxy-, aminosilanes, tetraethoxygermane and even tetraorganylsilanes in this reaction leading to the corresponding atranes with good yields has been demonstrated. Triethanolamine in the presence of catalytic amounts of base or CsF easily substitutes furyl-, dihydrofuryl-, dihydropyranyl- and thienyl groups in tris-and tetraheterylsilanes, leading to organylsilatranes with good to excellent yields. (C) 1997 Elsevier Science S.A.