TRI CHLOROSILANE

To prepare multifunctionalized symmetric organosilicon compounds by the polyalkylation of benzene. (2-chloroethyi)trichlorosilane and (3-chloropropyl)tri-chlorosilane were reacted with benzene. Polyalkylations of benzene with (2-chloroethyl)silane and (3-chloropropyl)silane were carried out in the presence of aluminum chloride catalyst at a reaction temperature of 80 C. The reaction of benzene with excess (2-chloroethyI )trichlorosilanes afforded pcralkylated product, hexakis(2-(trichlorosilyl)ethyl)benzene in good yield (70%). ... 

As shown in Table XIV, the reactivity of (trichloromethyl)silanes varied depending upon the substituent on silicon. The reactivity and yields of (trichloromethyl)-methyldichlorosilanes were slightly higher than those of (trichloroinethyl)tri-chlorosilanes in the aluminum chloride-catalyzed alkylation as similarly observed in the alkylations with (ai-chloroalkyl)silanes and (dichloroalkyl)silanes. The electron-donating methyl group on the silicon facilitates the alkylation more than the electron-withdrawing chlorine. The minor products, (diphenylmethyl)chloro-silanes, were presumably derived from the decomposition of (triphenylmethyl)-chlorosilanes. 

Reduction of 1-benzyl-3,4-dibromophospholan oxide (125) with tri-chlorosilane, followed by debromination, gave 1-benzylphosphole. Determination of the molecular structure by X-ray analysis showed slight puckering of the ring with retention of pyramidal configuration at phosphorus. ... 

The only known example of this type of compound is a i74-trichlorosi-lylcyclohexadienetricarbonyliron complex, prepared (89% yield) by the reaction of cyclohexadienyltricarbonyliron tetrafluoroborate with tri-chlorosilane-triethylamine adduct in acetonitrile at 40° (117) ... 

The hydrolytic condensation of tert-butyltrichlorosilane ISu SiC l, in water was performed in a 25-fold up-scaling of the HTE synthesis. Bu SiCh is a solid at room temperature since the HTE workstation employed can only handle liquids, the tri-chlorosilane was dissolved in a minimum of acetonitrile. The same procedure was used for the up-scaled synthesis. After 18 h of reaction at 50 °C, the reaction mixture contained a white precipitate, which was isolated by filtration (fraction A). 

Another approach in generating molecular insulating layers without the need of chemical conversion after deposition is the use of preliminarily modified molecules which can form dense self-assembled monolayers. To create dense self-assembled monolayers with sufficient robustness and insulating properties, a modified alkyltrichlorosilane with an aromatic end-group (18-phenoxyoctadecyl)tri-chlorosilane (PhO-OTS chemical structure Fig. 6.15a) was synthesized and tested [50]. The SAMs were created in a one-step process from vapor phase or solution. On self-assembly on a natively oxidized silicon surface the n-n interaction between the phenoxy end-groups of adjacent molecules creates an intermolecular top-link, leading to a more closely packed surface compared to monolayer than when linear end groups are used. 

Morino, Y., and E. Hirota Molecular Structure and Internal Rotation of Hexachloroethane, Hexachlorodisilane, and Trichloromethyl-Tri-chlorosilane. J. chem. Physics 28, 185—197 (1958). 

As in other preparative methods for organosilicon compounds, the direct synthesis produces a mixture of methylchlorosilanes rather than the single compound shown in equation 3. Besides dimethyl-dichlorosilane, the mixture usually contains silicon tetrachloride, tri-chlorosilane, methyltrichlorosilane, methyldichlorosilane, trimethyl-chlorosilane, and even silicon tetramethyl. Under proper conditions, dimethyldichlorosilane is the principal product. Of the other compounds, methyltrichlorosilane usually is next in abundance this substance finds use in the cross-linked methyl silicone resins, or it can be methylated further by the Grignard method to increase the yield of dimethyldichlorosilane. There is no way of recycling it in the direct process, and so supplemental operations are required for the conversion. The interconversion of this and the other minor products of the direct synthesis, involving the exchange of methyl and chlorine groups as desired, has been a special study in itself.10... 

Pd(PPh3)4] (103) catalyzes the hydrosilylation of both ethylene and propylene by tri-chlorosilane. The same complex also catalyzes reaction (170). ... 

Another approach to molecular assembly involves siloxane chemistry [61]. In dais method, die electrically or optically active oligomers are terminated with tri-chlorosilane. Layers are built up by successive cycles of dip, rinse, and cure to form hole transport, emissive, and electron transport layers of the desired thicknesses. Similar methods have also been used to deposit just a molecular mono-layer on the electrode surface, in order to modify its injection properties. 

An apparatus has been developed392 for the analysis of a mixture containing tri-chlorosilane, methyldichlorosilane, silicon tetrachloride, trimethylchlorosilane, di-methyldichlorosilane and methyltrichlorosilane by gas-liquid chromatography on a column of nitrobenzene supported on Celite 545. The column is eluted with nitrogen and the emergent gas is absorbed in flowing 0.01 N potassium ohloride. Hydrolysis of the silanes yields hydrochloric acid which alters the electrical resistance of the potassium chloride solution and this permits quantitative analysis of the silane mixture. 

Some of the enantiopure phospholane oxides 116 were used for further transformations. For example, they could be isomerised by treatment with base for several hours in a protic solvent to afford 117 or subjected to a second deprotonation to produce 118 as a single isomer. Attempts to prepare Z)w(phospholanes) by double nucleophilic attack of the anions derived from 116 were unsuccessful. Some of the phospholane oxides were reduced with tri-chlorosilane/pyridine to afford the free phospholane with retention of configuration. The same strategy was applied to 1-phenylphospholane oxide but low yields of racemic products were obtained. This suggests that substrate 115 is probably a special case due to the formation of a more stable benzylic carbanion. ... 

In addition, the asymmetric reduction of A7-aryl ketimines with tri-chlorosilane could be achieved on polymer-supported organocatalysts by Kocovsky et alP Indeed, 7V-methylvaline-derived formamide anchored to a polymeric support, used at a catalyst loading of 15 mol %, allowed good enantioselectivities of up to 82% ee combined with good yields to be obtained for the formed chiral amines (Scheme 8.3). This novel methodology simplified the recovery of the catalyst, which could be reused at least five times without any loss of the activity. The best results were obtained with the catalysts directly attached to the polymer or via a suitable spacer. A strong influence of the solvents on the catalytic performance was observed with chloroform giving the... 

Stationary phase Tri chlorosilane Silicon tetrachloride Trimethyl- chlorosilane Methyltri- chlorosilane Dimethyldi- chlorosilane... 

Preparative Methods (1) reaction of 2,3-dibromopropene with lithium (trimethylsilyl)cuprate in HMPA at 0°C (63-90%) (2) reaction of 2,3-dibromopropene with tri-chlorosilane in the presence of trichlorosilane and cop-per(l) chloride, followed by treatment with methylmagnesium bromide (63-71%).i 3- ... 

A mixture of styrene, tri-chlorosilane, and nickel tetracarbonyl stirred 1 hr. under argon -> 1-trichloro-silyl-l-phenylethane. 

Reduction.—a)8-Unsaturated nitriles have been reduced efficiently and selectively at the double bond by several boron reagents, namely sodium cyanoborohydride, sodium borohydride, and copper methyltrialkyl borates reduction is accompanied by hydrosilylation when ajS-unsaturated nitriles are treated with tri-chlorosilane in the presence of tris(triphenylphosphine)chlororhodium (Scheme 19). 

P-ligands (67) obtained after double deojygenation by silanes, e.g., tri-chlorosilane, that could be used for the synthesis of cyclic platinum complexes (66) by reaction with half an equivalent of dichlorodibenzoni-triloplatinum (Scheme 32). Cyclic Pt-complexes are special heterocycles that may be regarded potential catalysts in homogeneous catalysis. ... 

The synthesis of phosphorous-functionalized click ligands also requires special conditions. Phosphine building blocks need be protected as either the corresponding borane complex (l-2a and 4-5a) or oxide (l-2b and 4—5b) in order to prevent an undesirable Staudinger reaction with the azide synthons (Scheme 1). A range of bi-and tridentate P,N click ligands have been synthesized, and the free clickphines (3 and 6) are liberated by a final deprotection of the phosphine group with either DABCO in the case of the borane complexes [86-90] or reduction with tri-chlorosilane [88-92] in the case of the phosphine oxides. 

Guizzetti S, BenagUa M, Cozzi F, Rossi S, Celentano G. Enantioselective catalytic reduction of ketoimines with tri-chlorosilane promoted by readily available chiral Lewis bases. Chirality 2009 21 233 238. 

After our report of all-cis cyclic silanols, Shchegolikhina s group reported the synthesis of cyclic silanols via sodium or potassium cyclic silanolates from substituted trialkoxysilanes (1). Overall yields are better than those by hydrolytic condensation of tri-chlorosilanes. Kawakami s group applied this method and reported the synthesis of phenyl and isobutyl cyclic silanols (2). We slightly modified Kawakami s method and obtained all-cis-[/-PrSi 0H)0]4 in 74% yield. 

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