768-33-2

Usage

Chemical Description

Chlorodimethylphenylsilane is an organosilicon compound used as a reagent in organic synthesis.

Uses

Used in the Synthesis of Enantioenriched Allenylsilanes:
Chlorodimethylphenylsilane is used as a reagent in the synthesis of enantioenriched allenylsilanes through an ortho-ester Claisen rearrangement of chiral and silylpropargylic alcohols. This process allows for the preparation of valuable chiral building blocks, which are essential in the development of pharmaceuticals, agrochemicals, and other specialty chemicals.
In the chemical industry, Chlorodimethylphenylsilane is used as a precursor for the production of various organosilicon compounds, such as silyl ethers, silyl enol ethers, and silyl ketene acetals. These compounds are widely used in organic synthesis, particularly in the formation of carbon-carbon and carbon-heteroatom bonds.
Additionally, Chlorodimethylphenylsilane can be employed as a coupling agent in the formation of silicon-containing polymers and materials, which have potential applications in the electronics, automotive, and aerospace industries due to their unique properties, such as thermal stability, hydrophobicity, and biocompatibility.

Purification Methods

Fractionate it through a 1.5 x 18inch column packed with stainless steel helices, or a spinning band column. [Daudt & Hyde J Am Chem Soc 74 386 1952, Lewis et al. J Am Chem Soc 70 1115 1948, Eaborn J Chem Soc 494 1953.] It is used for standardising MeLi or MeMgBr which form Me3PhSi which is estimated by GC. [Maienthal et al. J Am Chem Soc 76 6392 1954, House & Respess J Organomet Chem 4 95 1965, Beilstein 16 IV 1475.] TOXIC and MOISTURE SENSITIVE.

InChI:InChI=1/C8H11ClSi/c1-10(2,9)8-6-4-3-5-7-8/h3-7H,1-2H3

Upstream product

• 676-58-4 methylmagnesium chloride 
• 75-78-5 dimethylsilicon dichloride 
• 108-86-1 bromobenzene 
• 1558-25-4 (chloromethyl)trichlorosilane 
• 766-77-8 Dimethylphenylsilane 
• 5272-18-4 dimethylphenylsilanol 
• 778-24-5 Dimethyldiphenylsilane 
• 37865-47-7 dimethylphenyl(trimethylgermyl)silane 
• 76-83-5 trityl chloride 
• 4342-61-4 1,2-dichlorotetramethylsilane 
• 98-88-4 benzoyl chloride 
• 121949-41-5 dimethyl-2,2,3,3-tetrafluoropropoxychlorosilane 
• 100-58-3 phenylmagnesium bromide 
• 108-90-7 chlorobenzene 

Downstream Products

• 75-78-5 dimethylsilicon dichloride 
• 75-77-4 chloro-trimethyl-silane 
• 18057-04-0 phenyldimethyl(t-butylperoxy)silane 
• 14920-92-4 pentamethyl(phenyl)disiloxane 
• 17909-06-7 benzoyloxy-dimethyl-phenoxy-silane 
• 1825-58-7 dimethyl(ethoxy)phenylsilane 
• 1125-26-4 dimethylphenylvinylsilane 
• 18405-80-6 Si-ethoxy-Si,Si,Si',Si'-tetramethyl-Si'-phenyl-Si,Si'-methanediyl-bis-silane 
• 18848-27-6 Si,Si,Si',Si'-tetramethyl-Si,Si'-diphenyl-Si,Si'-biphenyl-4,4'-diyl-bis-silane 
• 18858-61-2 bis-{4-(dimethylphenylsilyl)-phenyl}-ether 
• 18055-58-8 Si-ethoxy-Si,Si',Si'-trimethyl-Si,Si'-diphenyl-Si,Si'-methanediyl-bis-silane 
• 18752-89-1 1,1,3,3-tetramethyl-1-(4-phenoxy-phenyl)-3-phenyl-disiloxane 
• 1450-20-0 2,2-Dimethyl-1,1,1,2-tetraphenyldisilan 
• 17887-60-4 (acetoxy)dimethyl(phenyl)silane 

Relevant academic research and scientific papers

A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes

Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.

METHOD FOR PRODUCING ARYLSILANE COMPOUND CONTAINING HALOSILANE COMPOUND AS RAW MATERIAL

PROBLEM TO BE SOLVED: To provide a method for producing an arylsilane compound with low production cost. SOLUTION: A method for producing an arylsilane compound includes a reaction step for the cross-coupling reaction of a halosilane compound represented by general formula (A-1), (A-2), or (A-3) and an arylboronic acid pinacol ester in the presence of a nickel catalyst, a Lewis acid catalyst, and an organic base (R independently represent an aromatic hydrocarbon group, a heteroaromatic ring group, or a C1-20 hydrocarbon group; X independently represent a halogeno group or a trifluoromethanesulfonyloxy group). SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT

Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane

Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Y as a hydrogen-atom-transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di- and trihydrosilanes was achieved in a highly selective fashion assisted by continuous-flow micro-tubing reactors. The ability to access silyl radicals using photocatalytic Si?H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.

Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents

Nickel-catalyzed cross-coupling reactions of chlorosilanes with organoaluminum reagents were developed. An electron-rich Ni(0)/PCy3 complex was found to be an effective catalyst for the desired transformation. The reaction of dichlorosilanes 1 proceeded to give the corresponding monosubstituted products 2. Trichlorosilanes 4 underwent selective double substitution to furnish the corresponding monochlorosilanes 2. Overall, the selective synthesis of a series of alkylmonochlorosilanes 2 from di- and trichlorosilanes was achieved using the present catalytic systems.

METHOD FOR PRODUCING HALOSILANE

PROBLEM TO BE SOLVED: To provide a method for producing halosilane that can efficiently produce halosilane. SOLUTION: Alkoxy halomethane is used as a halogenating agent and reacted with oxysilane having a structure represented by formula (a), to efficiently produce halosilane having a structure represented by formula (b) (In the formula (b), X is a chlorine atom, a bromine atom, or an iodine atom). SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT

Rh(iii)-Catalysed solvent-free hydrodehalogenation of alkyl halides by tertiary silanes

Efficient catalytic reduction of CDCl3 and other alkyl halides, including persistent organic pollutants, by different tertiary silanes using the unsaturated silyl-hydrido-Rh(iii) complex {Rh(H)[SiMe2(o-C6H4SMe)](PPh3)2}[BArF4] as a pre-catalyst is accomplished. The reactions are performed in a solvent-free manner. On account of experimental evidence, a simplified catalytic cycle is suggested for the hydrodehalogenation of CDCl3.

DMF-activated chlorosilane chemistry: Molybdenum-catalyzed reactions of R3SiH, DMF and R′3SiCl to initially form R′3SiOSiR′3 and R3SiCl

The room temperature reactions between R3SiH (R3?=?Et3, PhMe2, Ph2Me) and R′3SiCl (R′3?=?Me3, PhMe2, Ph2Me), with an excess of dimethylformamide (DMF) in the presence of (Me3N)Mo(CO)5 as a catalyst, result in the initial formation of R3SiCl, R′3SiOSiR′3 and Me3N as detected by 29Si, 13C, 1H NMR spectroscopy and GC/MS. As the reaction proceeds, the more so if the reaction temperature is raised, mixed disiloxanes R3SiOSiR′3 and ultimately lesser amounts of R3SiOSiR3 may be detected. A mechanism involving the activation of chlorosilanes by the nucleophilic DMF is proposed to produce transient imminium siloxy ion pairs, [Me2N[dbnd]CHCl]+[R′3SiO]? ? [Me2N[dbnd]CH(OSiR′3)]+Cl? which react with R3SiH to form Me2NCH2OSiR′3 and R3SiCl. A secondary reaction of Me2NCH2OSiR′3 with R′3SiCl produces the symmetrical disiloxane R′3SiOSiR′3 and ClCH2NMe2. The final stage of the reaction is the reduction of ClCH2NMe2 by R3SiH, a reaction which is reported for the first time. The newly created chlorosilane R3SiCl can become involved in the initial DMF activation chemistry thereby forming the other disiloxanes observed as the reaction proceeds.

Method of preparation of phenyl dimethylchlorosilane

The invention discloses a method for preparing phenyl dimethylchlorosilane. The method for preparing phenyl dimethylchlorosilane comprises the following steps of: carrying out a Grignard reaction on chlorobenzene and magnesium so as to generate a Grignard reagent, and carrying out condensation reaction on the obtained Grignard reagent and dimethyl dichlorosilane under a novel catalyst so as to generate the phenyl dimethylchlorosilane; and carrying out the Grignard reaction and the condensation reaction respectively in a solvent system formed by methyl tertiary butyl ether and/or 2-methyltetrahydrofuran. Through adopting the solvent formed by methyl tertiary butyl ether and/or 2-methyltetrahydrofuran for reaction, when the Grignard reaction and the condensation reaction are carried out, the side reaction is less, and the reaction is much slow and is easy to control; the productivity of phenyl dimethylchlorosilane is improved; and the waste liquid amount during the production process is reduced.

Direct evidence for intermolecular oxidative addition of σ(Si-Si) bonds to gold

Oxidative addition plays a major role in transition-metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl3, phosphine gold chlorides promote the oxidative addition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative 31P and 29Si NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of σ(Si-Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(Si-Si) bonds to gold and open promising perspectives for the development of new gold-catalyzed redox transformations. Oxidative addition is the most elusive elementary step in reactions with gold. Now, evidence for the intermolecular oxidative addition of σ(Si-Si) bonds is reported. Phosphine gold chlorides readily reacted with disilanes at low temperature in the presence of GaCl3. The ensuing bis(silyl) gold(III) complexes were characterized by 31P and 29Si NMR spectroscopy, and their structures were analyzed by DFT calculations. Copyright

Chemo- and regioselective catalytic reduction of N-heterocycles by silane

The ruthenium complex [Cp(iPr3P)Ru(NCCH3) 2]+ (1) catalyzes the regioselective hydrosilylation of pyridines to 1,4-dihydropyridines. Substitution in the 3- and 5-positions is tolerated, whereas pyridines with substituents in the 2-, 4-, and 6-positions are not reduced. Reduction of functionalized pyridines having keto and ester substituents results in a mixture of products. N-Silyl-1,4-dihydropyridine reacts with ketones and aldehydes to give products of N-Si addition across the C=O bond. Hydrosilylation of pyridine in acetone results quantitatively in the addition product PhMe2SiO-CMe2-NC5H 6, which decomposes in hexane to give the parent dihydropyridine HNC5H6. The phenanthroline complex [Cp(phen)Ru(NCCH 3)2]+ (10) catalyzes regioselective 1,4-reduction of phenanthroline by a 3-4-fold excess of silane/water or silane/alcohol mixtures. The Cp* analogue [Cp*(ph n)Ru(NCCH 3)2]+ (9) catalyzes 1,4-regioselective monohydrosilylation of phenanthroline, quinoline, acridine, and 1,3,5-triazine and the 1,2-reduction of isoquinoline. In contrast, 2-substituted phenanthroline, pyrazine, 2-ethylpyridine, 2,6-lutidine, 2,4-lutidine, and pyrimidine are not reduced under these conditions by either of the catalysts studied.