Alkoxysilanes silanes, synthesis

Either alkoxy- or chlorosilanes are used as a starting material. Alkoxysilane gel synthesis may proceed via a base catalysed or an acid-base route. The effectiveness of each route is dictated by the functionality of the starting silane. The acid-base route is most generally preferred.61,62... 

The incorporation of organofunctional groups on the silica surface may be effectuated during the synthesis of the silica material. The addition of organofunctional alkoxysilanes to the TEOS solution in the sol-gel process, produces functionalized silica gels. This procedure does not allow a careful control of the obtained surface morphology. Since the relative amounts of silane and TEOS is the only variable parameter, neither layer thickness, nor modification density can be precisely tuned. This results in an irreproducible functionalization of the surface. 

Catalytic alcoholysis of silanes by a variety of transition metal based catalysts is a useful method to form silyl ethers under mild conditions (Scheme 19). The process is atom-economical hydrogen gas is the only byproduct. This mild method has not been fully exploited for the preparation of unsymmetrical bis-alkoxysilanes. A catalytic synthesis using silicon alcoholysis would circumvent the need of bases (and the attendant formation of protic byproducts), and eliminate the need for excess silicon dichlorides in the first silyl ether formation. We sought catalytic methods that would ultimately allow formation of chiral tethers that are asymmetric at the silicon center (Scheme 20). Our method, once developed, should be easily transferable for use with high-value synthetic intermediates in a complex target-oriented synthesis therefore, it will be necessary to evaluate the scope and limitation of our new method. 

Silane- and siloxanediols are important intermediates in silicone synthesis. During the technical chloro- or alkoxysilane hydrolysis the primary-formed silanols and siloxanols react preferably in the aqueous phase due to their considerable water solubility. To get more information on these reactions in water we investigated some silane- and siloxanediols using a method already described [1]. 

Sol-gel synthesis is the process of formation of porous, three-dimensional, integrated solid network (gel) of either discrete particles or network potymers from the conversion of monomers into stable suspension of colloidal solid particles or pol miers (sol) in a continuous liquid phase. Most popular precursors for the synthesis of colloids are metal alkoxides and alkoxysilanes. Tetramethoxysilane (TMOS) and Tetraethoxysilane (TEOS) are commonly used alkojq silanes, which form silica gel. The remarkable property of these silanes is that they readity react with water in the presence of shorter chain alcohol such as ethanol and ammonia to form monodispersed silica particles [7]. The size of silica particles formed is between 50 and 200 nm and depends on the silica ester used, type of alcohol, and molar ratios of water and alkoxysilane [32]. In this process, alcohol acts as a homogenizing solvent between alkoxides and water as both are immiscible but can be easily dissolved in alcohol. With the presence of this homogenizing agent, hydrolysis can be facilitated [33] due to the complete miscibility. However, aluminates borates and titanates often mixed with TEOS or TMOS are commonly used in sol-gel process. The hydrolysis of alkoxysilane proceeds according to Stober s process (Fig. 18.6). 

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