Synthesis and pyrolysis of (cyclobutylmethyl)trimethylsilane

Russian Chemical Bulletin -     

The selective chlorination of organohydridesilanes

Conclusions A convenient method of preparing organochlorohydridesilanes by selective chlorination of organohydridesilanes with stannic chloride was proposed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2114–2117, September, 1967.     

Mass spectra of methylsubstituted monosila- and monogermacyclobutanes, 1,2- disila- and 1,2-digermacyclopentanes. Some correlations with thermal decomposition

The mass spectra of 1,1-dimethyl-1-silacyclobutane (I—as reported by Cherniak et al.),⁶, 1,1-dimethyl-1-germacyclobutane (II), 1,1,2,2-tetramethyl-1,2-disilacyclopentane (III) and 1,1,2,2-tetramethyl-1,2-digermacyclopentane (IV) are compared and some correlations between electron-impact fragmentation and thermal decomposition are derived. The mass spectra of the germanium compounds with respect to the silicone compounds are enriched by light fragment ions and exhibit lower intensities of odd-electron ions. The composition of some ions and apparently of neutral fragments coincides with that of the unstable intermediates which are suggested in the thermal decomposition mechanism of some related compounds. The loss of C₂H₄ is more characteristic under electron-impact as well as in thermal decomposition of Si-compounds, while C₃H₆ is preferable eliminated by the Ge-compounds.     

Electronic interaction between the nitrogen,oxygen, and silicon atoms in the molecules of α-aziridin-1-ylalkoxy(triethyl)silanes

By the PMR method we have established the existence of a high frequency of the inversion of the nitrogen atom in the molecules of -aziridin-1-ylalkoxysilanes. This is due to the fact that the high (because of p-d bonding with the silicon atom) electronegativity of the oxygen atom in the Si-O-C-N system makes possible an interaction between the unshared electron pair of the nitrogen atom and the antibonding orbital of the C-O bond. The latter, in its turn, increases the degree of p-d bonding between the oxygen and silicon atoms (in these compounds the order of the Si-O bond is greater than in the alkoxysilanes).     

Transsilylation of disilazanes with 1-chloro-1-methyl-1-silacyclobutane and other triorganylchlorosilanes

The first stage of the reaction of hexamethyldisilazane with 1-chloro-1-methyl-1-silacyclotmtane gives 1,3,3,3-tetramethyl-1,1-trimethylenedisilazane, and after that 1,3-dimethyl-1,3-bis(trimethylene)disilazane is formed. The latter reacts with 1-chloro-1-methyl-1-silacyclobutane to give tris[methyl(trimethylene)silyl] amine. From a large number of examples it is shown that transsilylation of disilazanes with chlorosilanes is a general reaction.