Silane addition method

Figure 13.6 Effect of silane addition method on properties of 40wt% kaolin-filled nylon 6,6.

A number of additional methods involve the addition of alkynylsilanes to electrophiles with concomitant 1,3-isomerization to afford allenylsilanes geminally substituted with the electrophile moiety. The first of these methods employed a trimethyl-silyl-substituted propargylic silane as the alkynylsilane and various acetals as the electrophile precursors (Table 9.29) [53], The allenylsilanes are formed without contamination by alkynyl isomers. 

As a further test of the etched open tubular approach for the analysis of optical isomers, another column was fabricated based on the selector naphthylethylamine that had been attached to porous silica by the silanization/hydrosilation method for use in HPLC [70]. As in the HPLC experiments, this column was best suited for the resolution of the optical isomers of dinitrobenzoyl methyl esters of amino acids. The best separation (a = 1.14) was obtained for the alanine derivative. In addition, the peak symmetry and efficiency for the naphthylethylamine column was significantly better than that obtained on the cyclodextrin column. However, as shown in HPLC experiments, changes in the amino acid moiety (replacing alanine with valine, etc.) often results in a loss of chiral resolution. In the case of optical isomers, the separation mechanism in HPLC and CEC modes is identical since only interaction between the solute and the bonded phase can result in resolution of the enantiomers. 

Over the past year, two additional methods were reported to reduce pyridine A-oxides to the corresponding pyridines. Sandhu and co-workers have presented an efficient and general method for the deoxygenation of A-oxides using Zn(OTf)2 and CuCOTf) <06SL395>. Similarly, Fernandes et al. have developed a novel reduction method, with wide functional group tolerance, using a silane (PhSiHj) in the presence of a catalytic amount of MoO Cl to produce pyridines in excellent yield. 

Special methods of incorporation carbon fiber was added at the end of mixing to limit breakage " silane addition stage was varied to improve properties of silica-filled composite ... 

Sr may be obtained by a similar procedure [see Ref but a quicker, more reliable method is as follows. A single silane addition [F, = 0.125 X fF[Pg.398]

The creation of an asymmetric center by C-H bond formation is a very common process which can involve several types of reactions. Hydrogenation of prochiral olefins is often used with the rhodium catalysts of the Wilkinson type (5). These catalysts were shown to be inactive for ketone or imine reduction except in some cases (15), It was then interesting to develop an alternate method for asymmetric synthesis of chiral alcohols or amines. Since it was found that RhCl(PPh3)3 was able to catalyze silane additions to ketones (16,17) or imines (18), preparation of chiral alcohols or amines by asymmetric hydrosilylation could be envisaged (Figure 2). The 1,4-addition of silanes to conjugated... 

Compared to the Grignard and direct processes, the addition method has the advantage of yielding one principal product rather than a mixture. The process is also economically attractive since olefins are low-cost materials and suitable Si—H containing compounds (trichlorosilane and methyldichlorosilane) are by-products of the direct process. The addition process is versatile but cannot, of course, be used to prepare methylchlorosilanes. It is particularly suitable for the production of silanes with organofunctional groups useful reactions of this type include the following ... 

Several new syntheses of vinylsilanes have been described. Tris(trimethyl-silyl)aluminium undergoes 5yn-addition to alkynes alternatively the same -isomers can be obtained by photochemical isomerisation of Z-1-alkenyl-silanes. Other methods described involve treatment of the lithium salts of hydrazones with trimethylsilyl chloride, Wurtz-type coupling with vinyl bromides, and reaction of acetylenes with a silyl-copper reagent followed by an electrophile. Using the hydrazone method, a route has been devised for 1,2-carbonyl transposition within ketones (Scheme 17). ... 

Silicon cluster reactions are an example of a newly emerging field of research which is very amenable to study with electronic structure methods. This exercise will examine the potential surface for silicon cation reacting with silane (SiH4). Such reactions are central to the growth of large silicon clusters, which occurs by sequential additions of -SiHj ... 

The oxidative addition of silanes (with silicon-hydrogen bonds) to coordinatively unsaturated metal complexes is one of the most elegant methods for the formation of metal-silicon bonds. Under this heading normally reactions are considered which yield stable silyl metal hydrides. However, in some cases the oxidative addition is accompanied by a subsequent reductive elimination of, e.g., hydrogen, and only the products of the elimination step can be isolated. Such reactions are considered in this section as well. 

This excellent method of oxidative cleavage (/) of carbon-silicon bonds requires that the silane carry an electronegative substituent (2), such as alkoxy or fluoro. Either hydrogen peroxide or mcpba may be used as oxidant, and the alcohol is produced with retention of configuration (3). Fluoride ion is normally a mandatory additive in what is believed to be a fluoride ion-assisted rearrangement of a silyl peroxide, as shown below ... 

An external magnetic field has also been used to confine the plasma [143]. An arrangement where electromagnets are located under the cathode is known as the controlled plasma magnetron method [144]. The diffusion of electrons to the walls is prevented by the magnetic field between cathode and anode. This results in an increase in electron density, and consequently in a faster decomposition of silane and a higher deposition rate. At a deposition rate of 1 nm/s, device quality material is obtained [144]. In addition, a mesh is located near the anode, and the anode can by biased externally, both in order to confine the plasma and in order to control ion bombardment. 

This method of silanation, which uses organic solvent without the addition of water, is suitable for highly reactive silane derivatives, such as chlorosilanes, aminosilanes, and methoxysilanes. This procedure will not work for ethoxysilanes, as these compounds are not reactive enough without prior hydrolysis to create the silanol. This method is convenient to use for silica particle modification and for the functionalization of metallic nanoparticles having the requisite—OH groups present (see Chapter 14, Section 5). 

The following protocol for modification of silica nanoparticles is based on the method of Zhao et al. (2004), which describes the addition of amine functionalities using trimethoxysilyl-propyldiethylenetriamine. Other functional silane modifications may be done similarly. 

The method of competitive reactions was used (38) to measure the relative rates of addition of Et3 ClnSiH (n = 0-3) to 1-heptene with Co2(CO)8 and RhCl(PPh3)3 as catalysts. With the rhodium catalyst at 80°C no hydrosilation took place at 120°C only that silane with a greater number of Si—Cl bonds yielded products. 

The preference for the /3-silyl isomer product complements methods available for hydrostannation of alkynes, for which the a-stannyl regioisomer is formed preferentially.70 7011 70c In addition, the /3-silyl products serve as the platform for a tertiary alcohol synthesis (Scheme 15). Upon treatment of vinylsilanes such as B with tetrabutylam-monium fluoride (TBAF) in DMF at 0 °C, a 1,2 carbon-to-silicon migration occurs, affording the tertiary heterosilane E. Oxidation of the C-Si bond then provides the tertiary alcohol. Good 1,2-diastereocontrol has been demonstrated for y-alkoxy substrates, as in the example shown. The studies suggest that the oxidation of the sterically demanding silane intermediate is facilitated by the intramolecular formation of a silyl hemiketal or silyllactone for ketone or ester substrates, respectively.71... 

---