Silanes, alkoxy derivates

Alkoxysilane. An alkoxy derivative of a silane a compound of silicon having at least one Si-OR linkage, where R represents an aliphatic group. 

The silanes are almost always tri-alkoxy derivatives. While the alkoxy group is lost during the filler treating process, it s nature plays an important role and needs to be carefully selected. It controls volatility and flash point, affects toxicity, and plays an important role in determining the rate of hydrolysis. The most common groups used are, methoxy-, ethoxy-, and methoxy-ethoxy. 

Silanes - The general chemical structure of organosilanes is RS1X3, where X is a hydrolyzable group, such as methoxy, ethoxy, acetoxy, or chloride, and R is a nonhydrolyzable organofimctional group. Most commercial silanes are alkoxy derivates, RSi(OR )3, the most common of which follow. 

Orthosilicates are derivatives of orthosilicic acid Si(OH)4. The most common is tetraethyl orthosilicate Si(OC2H04, often called TEOS, an acronym that also fits the alternative way of naming such a compound, tetraethoxysilane. Thus orthosilicates are actually a sub-set of the larger class of XRSi(OR )3 silanes, where the XR group is also an alkoxy group. The XR and OR groups do not have to be the... 

A chiral bis(oxazolinyl)phenylrhodium complex was found to catalyze the asymmetric hydrosilylation of styrenes with hydro(alkoxy)silanes such as HSiMe(OEt)2 (Scheme 7).47 Although the regioselectivity in forming branched product 27 is modest, the enantiomeric purity of the branched product 27 is excellent for styrene and its derivatives substituted on the phenyl group. The hydrosilylation products were readily converted into the corresponding benzylic alcohols 29 (up to 95% ee) by the Tamao oxidation. 

The very different reactivity toward allylation of a,P-unsaturated esters and acyl-silanes [132] is due to stabilization of the allyl cation intermediates by the alkoxy group in the former class of substances, in contrast to those derived from acylsilanes which are expected to be less stable than 3-monooxyallyl cations. In the 1,1-dioxy substituted cations two donor atoms are bonded to the acceptor site, but in the 1-oxy-3 -silyl congeners a rf,a-antagonism (captodative) exists. 

Reductive cleavage of the carbon-silicon bond of acyl silanes, including a-alkoxy and t/./i-dialkoxy derivatives, to give aldehydes may be accomplished by palladium-catalysed hydrogenolysis at ambient temperature and pressure212. 

However, the reaction rate is also increased by using silanes with R groups such as fluoro or alkoxy instead of alkyl. In fact, there are only a few successful examples of coupling reactions using trimethylsilane derivatives. 

Ethers of orthosilicon acid and their derivatives, tetraalkoxy(aroxy)silanes and alkyl(aryl)alkoxy(aroxy)silanes are a rather extensive class of silicone compounds. They are independently applied in various spheres of technology, but are particularly valuable as semi-products for preparing important silicone oligomers and polymers. 

Chlorosilanes are also converted to siloxanes by reactions not involving hydrolysis. Most are highly exothermic, and appropriate measures for heat dissipation are recommended for safety. Thus chlorosilanes can be converted to siloxanes by reaction with DMSO or with NajCOj or ZnO in suitable solvents such as ethyl acetate or dioxane. Siloxanes can also be obtained by the reaction of alcohols with chlorosilanes, but this is really a kind of hydrolysis in which the water is generated in situ as a by-product of the formation of alkyl chloride from the alcohol and HCl. Siloxanes can of course be prepared from the reaction of HjO with many other kinds of hydrolyzable silanes (e.g., sulfato, iodo, bromo, fluoro, alkoxy, aryloxy, acyloxy, amino, amido, ketoximo) but such intermediates are themselves derived from chlorosilane precursors. Acetoxysilanes undergo thermolysis to yield siloxane bonds. 

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