Chlorodimethylsilane

The synthesis of T8[OSiMe2H]8 was first reported by Hoebbel et al. from the reaction between TgLONMeJs and chlorodimethylsilane in dimethylformamide (DMF)/heptane (Table 18, entry 1). Other authors have modified the procedure by changing the solvents to tetrahydrofuran (THF) or hexane, or by using TslONMes (C2H40H)]g as the silicate anion source, but without significant improvement in the yield (Table 18). 

A combination of Friedel-Crafts alkylation and reduction can be achieved using InCl3 and chlorodimethylsilane. The Lewis acid presumably promotes both the Friedel-Craft reaction and the subsequent reduction.179... 

Scheme 9.4 shows some representative reactions of allylic and alkenyl silanes. Entry 1 involves 3-trimethylsilylcyclopentene, which can be made by hydrosilylation of cyclopentadiene by chlorodimethylsilane, followed by reaction with methylmagnesium bromide. 

Combining two different hydrosilylation catalysts in sequence with chlorodimethylsilane has allowed the construction of complex dye assemblies and conducting polymers. In the example shown (Scheme 8), Karstedt s catalyst was chosen after a brief screen for the hydrosilylation of an aromatic diyne with chlorodimethylsilane. After reduction of the chlorosilane, an equimolar mixture of disilane B and diyne A was treated with a catalytic amount of Wilkinson s catalyst, resulting in the formation of polymer C.42 Hydrosilylation of alkynes has also been studied as a means of synthesizing oligo(phenylenevinylene) units with pendant alkoxysilanes to create curable, hole-transporting films.43,43 ... 

Recently, Quirk and Mathers [264] performed LASIP of isoprene on silicon wafers. A chlorodimethylsilane-functionalized diphenylefhene (DPE) was coupled onto the surface and lithiated with n-BuLi to form the initiating species. The living poly(isoprene) (PI) was end- functionalized with ethylene oxide. A brush thickness of 5 nm after two days of polymerization (9.5 nm after four days) was obtained in contrast to a polymer layer thickness of 1.9 nm by the grafting onto method using a telechelic silane functionahzed PI. 

The first surface-initiated enzymatic polymerization reported was the synthesis of amylose brushes on planar and spherical surfaces [145]. For this, silica or silicone surfaces were modified with self-assembled monolayers of (3 amino-propyl)trimethoxysilane or chlorodimethylsilane, respectively. To these functionalities, oligosaccharides were added via (a) reductive amidation of the oligosaccharides to surface-bound amines, (b) conversion of the oiigosaccharide to the according aldonic acid lactone and reaction with surface bound amines, and (c) incorporation... 

Use of the related dimethylsilyl ethers, obtained from (3-hydroxy ketones using commercially available chlorodimethylsilane, affords 4 with only slightly less dia-stereoselectivity. Other Lewis acids can be used in place of SnCLj.1... 

Silylation (see also Protection of alcohols) (Bromomethyl)chlorodimethylsilane, 316 /-Butyldimethylchlorosilane, 92 Chloromethyldiphenylsilane, 74 Chloromethyltrimethylsilane, 76 Di-/-butylmethylsilyl trifluoromethanesul-fonate, 95... 

Cesium fluoride-Tetraalkoxysilanes, 69 Chlorodiisopropylsilane, 72 Chlorodimethylsilane, 73 Chlorodimethylthexylsilane, 74 Chlorodiphenylsilane, polymeric, 74 Chloromethyldiphenylsilane, 74 Chloromethyltrimethylsilane, 76 Chlorotriethylsilane, 165, 323 Chlorotrimethylsilane, 165, 168 Chlorotrimethylsilane-Lithium, 81 Chlorotrimethylsilane-Sodium iodide, 81... 

Derivatization of this salt with a series of organic halides, chlorodimethylsilane and chlorotrimethylsilane gives the 1,1-disubstituted-l-germacyclopentadienes in high yields. Furthermore, XH and 13C NMR studies give evidence of a high degree of --delocalization. 

The employment of system B (taking chlorodimethylsilane (8) instead of 142) to 1,3-cyclohexadiene (171) and 1,3-cyclooctadiene (175) afford 3,6-dimethylsilyl-cyclohexene (172) and 3,8-dimethylsilylcyclooctene (176) respectively. 

Attachment of a suitable branch to the C-3 position125 was achieved by applying known methods resorting to 1,2-dibromoethyl ethyl ether204 and (bromomethyl)-chlorodimethylsilane.205,206 In this way, 1,5-anhydro-3- O-(2-bromo-1 -ethoxy-ethyl)-2-deoxy-4,6- O-isopropylidene-D-araWno-hex-1 -enitol (67), 1,5-anhydro-... 

Magnesium-induced dimerization of (l-bromovinyl)-chlorodimethylsilane has been used to prepare 1,1,3,3-tri-methyl-2,4-dimethylene-l,3-disilacyclobutane (Equation 35) <1995JA11695>. 

C-glycosides or C-furanosides (2), but without stereoselectivity. However, the reaction with a chlorodimethylsilane shows considerable selectivity. The difference... 

Vinylchlorodimethylsilane has been recently reported as a product of dehydrogenative silylation of ethylene by chlorodimethylsilane with the same catalyst precursor. The product is obtained with 46-92% selectivity of unsatu-rated-to-saturated (ethyldimethylchlorosilane) products [23]. 

A combination of chlorodimethylsilane and allyltrimethylsilane effectively promotes the deoxygenative allylation of aromatic ketones to terminal alkenes in the presence of a catalytic amount of InCl3 (Equation (94)). The choice of solvent is important the reaction of acetophenone proceeds only in dichloromethane or 1,2-dichloroethane. Aldehydes and aliphatic ketones give complicated mixtures. 

Vinyltrimethylsilane (97%), trimethylchlorosilane (98%), chlorodimethylsilane (97%), bromoform (96%), 5-bromo-l-pentene (95%), nBuLi (2.5M solution in hexanes), MeLi (1.6M solution in diethyl ether), n-decane (puriss. p.a., standard for GC, > 99.8%) and hexachloroplatinic(lV) acid hydrate were purchased from Aldrich. Platinum divinyltetramethyldisiloxane complex (Karstedt s catalyst, 3% solution in xylenes), hexamethyl-cyclotrisiloxane (95%), vinylmethyldichlorosilane (97%) and 1,1,3,3-tetramethyldisiloxane (97%) were bought from ABCR. Bromine (puriss) was bought from Eluka. Triethylamine (pure for analysis) and zinc oxide (pure) was purchased from Chempur. Solvents (tetrahydrofurane, diethyl ether, methylene chloride, pentane, ethyl acetate) were supplied by POCh (Polish Chemical Reagents). 

In the final step for this large scale preparation, the hydroxyl group is silylated with chlorodimethylsilane and triethylamine to effect introduction ot the dimethylsilyl group. Alternatively, (diethylamino)dimethylsilane (HMe2SiNEt2) or 1,1,3,3-tetra... 

A reaction vessel equipped with a Dean-Stark decanter was charged with 10 parts of the condensation polymer of 2,2-bis(hydroxymethyl)propionic acid having a Mn of 2920 daltons, a Mw of4280 daltons, and a PDI of 1.47. This mixture was then treated with tin(di(chloro-dimethylsiloxy)-tin chlorodimethylsilane) (0.25 parts), ethyl acrylate (100 parts), and hydroquinone (0.05 parts). The mixture was then heated to between 92°C and 95°C so that the amount of distillate to the decanter was 15 to 20 parts per hour. Fresh ethyl acrylate was added to the reaction vessel as needed while the reaction continued for 20 hours. 

The high selectivity of olefin metathesis with (2a) was key in the formation of diverse nonracemic vinyl cyclopropanes from chiral homoaUyhc alcohols and allyl chlorodimethylsilane in three steps, or allyl trimethylsilane in two steps, giving diastereomerically pnre cis or trans... 

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