Amino-derivatives of metals and metalloids. Part IV. Aminosilylation and aminophosphination of some unsaturated substrates
作者:R. H. Cragg、M. F. Lappert
DOI:10.1039/j19660000082
日期:——
The aminometallation of carbon dioxide and disulphide, and phenyl iso- and isothio-cyanate are described, using Me2Si(NEt2)2, Me2Si(NHEt)2, PhP(NMe2)2, and PhP(NMe2)Cl. The results are correlated with data on other systems. Structures are suggested for the new carbamato-, dithiocarbamato-, ureido-, and thioureido-silanes and -phosphines, on the basis of alcoholyses, infrared spectra, and analogy with
Double insertion of carbondioxide into the Si–N bonds of diaminosilanes of the type Me2Si(NRR′)2 gives di(carbamoyloxy)silanes Me2Si[(OCO)NRR′]2. The reactions proceed exothermically and quantitatively in most cases. A comprehensive analysis of the CO2-insertion products including single-crystal X-ray structure analyses was carried out. Quantum chemical calculations indicate an activation energy of
将二氧化碳双重插入Me 2 Si(NRR')2型二氨基硅烷的Si-N键中可得到二(氨基甲酰氧基)硅烷Me 2 Si [(OCO)NRR'] 2。在大多数情况下,反应放热且定量地进行。对插入CO 2的产物进行了综合分析,包括单晶X射线结构分析。量子化学计算表明,第一次和第二次插入的活化能均为约124 kJ / mol,并支持了反应的放热性质。二(氨基甲酰氧基)硅烷Me 2 Si [(OCO)NRR'] 2的热分解研究揭示了低聚硅氧烷和聚硅氧烷的形成。取决于热解参数,除了硅氧烷之外,还形成异氰酸酯,胺和/或脲。应用了各种方法来研究分解过程并鉴定和量化产物,包括热分析,质谱以及FTIR和NMR(溶液和固态)光谱学。整个反应方案为使用二氧化碳作为氧源的聚硅氧烷提供了一条新颖的途径。
Interaction of hydrosilanes with carbon dioxide and secondary amines or silylamines
作者:A. D. Kirilin、A. A. Dokuchaev、I. N. Menchaikina、E. V. Semenova、N. B. Sokova、E. A. Chernyshev
DOI:10.1007/bf01430738
日期:1996.9
The reaction of hydrosilanes with carbondioxide and secondary amines or silylamines was studied for the first time. The dependence of the composition and the structure of the products obtained on the nature of the reagents and on the reaction conditions was found. The hydrosilane-carbon dioxide system, unknown previously, can be used as anN-siloxycarbonylating reagent in the synthesis ofO-silylurethanes
Sheludyakov,V.D. et al., Journal of general chemistry of the USSR, 1977, vol. 47, p. 1391 - 1394
作者:Sheludyakov,V.D. et al.
DOI:——
日期:——
The Reaction of Tin Tetracarbamates with Organyl Chlorosilanes: A Novel Synthetic Route Towards O-Silylurethanes
作者:D. S. Buryi、A. S. Levashov
DOI:10.1134/s1070363219050116
日期:2019.5
O-Silylurethanes have been synthesized in up to 87% yield via the reaction of tin tetracarbamates with organyl chlorosilanes in the presence of tertiary amines.