775-12-2

Usage

Chemical Properties

clear colorless liquid

Uses

Thiocarbonyl derivatives of secondary alcohols are readily reduced by diphenylsilane in a radical chain process at room temperature using triethylborane-air as an initiator. An improved radical chain procedure for the deoxygenation of secondary and primary alcohols using diphenylsilane as hydrogen atom donor and triethylborane-air as initiator. Diphenylsilane is a reagent in the invention of radical reactions for deoxygenation of alcohols via their thiocarbonyl derivatives, deamination via isonitriles, and dehalogenation of bromo- and iodo- compounds by radical chain chemistry. Fluorescent film sensor for vapor-phase nitroaromatic explosives via monolayer assembly of oligo(diphenylsilane) on glass plate surfaces. Reductions of carboxylic acid derivatives by silanes in the presence of rhodium complexes were studied. Carboxylic esters were reduced to alcohols by diphenylsilane catalyzed by [RhCl (cod)] 2/4PPh 3 or [RhCl (PPh 3) 3] at room temperature in up to 99% yields. Sequential C- Si bond formations from diphenylsilane and its application to silanediol peptide isostere precursors.

Application

Used in the preparation of silyl-substituted alkylidene complexes of tantalum. Used in the ionic reduction of enones to saturated ketones. Used in the reductive cyclization of unsaturated ketones. Reduces esters in the presence of zinc hydride catalyst. Reduces α-halo ketones in presence of Mo(0). Reduces thio esters to ethers. Reduces esters to alcohols with Rh catalysis. Employed in the asymmetric reduction of methyl ketones and other ketones. Reductively cleaves allyl acetates.

Purification Methods

Dissolve it in Et2O, mix slowly with ice-cold 10% AcOH. The Et2O layer is then shaken with H2O until the washings are neutral to litmus. Dry over Na2SO4, evaporate the Et2O and distil the residual oil under reduced pressure using a Claisen flask with the take-off head modified into a short column. Ph2SiH2 boils at 257o/760mm, but it cannot be distilled at this temperature because exposure to air leads to flashing, decomposition and formation of silica. It is a colourless, odourless oil, miscible with organic solvents but not H2O. A possible impurity is Ph3SiH which has m 43-45o and would be found in the residue. [West & Rochow J Org Chem 18 303 1953, Benkhesser et al. J Am Chem Soc 74 648 1952, Gilman & Zuech J Am Chem Soc 81 5925 1959, Beilstein 16 IV 1366.]

InChI:InChI=1/C12H12Si/c1-3-7-11(8-4-1)13-12-9-5-2-6-10-12/h1-10H,13H2

Upstream product

• 2553-19-7 diethoxydiphenylsilane 
• 694-53-1 phenylsilane 
• 1631-90-9 bromo-phenyl-silane 
• 80-10-4 diphenylsilyl dichloride 
• 1631-83-0 diphenylsilyl chloride 
• 6843-66-9 dimethoxy(diphenyl)silane 
• 4206-75-1 phenylchlorosilane 
• 16343-18-3 1,1,2,2-tetraphenyldisilane 
• 693-02-7 hex-1-yne 
• 2170-06-1 1-Phenyl-2-(trimethylsilyl)acetylene 
• 109-72-8 n-butyllithium 
• 931-88-4 cis-Cyclooctene 
• 53490-50-9 1-Methyl-1,2,2-triphenyl-disilane 
• 71-43-2 benzene 

Downstream Products

• 76-51-7 5-ethyl-5,10-dihydro-10,10-diphenylphenazasiline 
• 101-81-5 Diphenylmethane 
• 18858-68-9 (benzhydryloxy)diphenylsilane 
• 3508-62-1 10,10-diphenyl-5,10-dihydrodibenzo[b,e][1,4]azasiline 
• 18754-81-9 decyl-diphenyl-silane 
• 18768-74-6 bis-decyl-diphenyl-silane 
• 1829-58-9 (prop-2-enyl)diphenylsilane 
• 10519-88-7 diallyldiphenylsilane 
• 789-25-3 HSiPh₃ 
• 17995-01-6 bromo-diphenyl-silane 
• 4072-00-8 Diphenyldibromsilan 
• 694-53-1 phenylsilane 
• 4206-75-1 phenylchlorosilane 
• 18755-09-4 bis-cyclohexyloxy-diphenyl-silane 

Relevant academic research and scientific papers

Interconversion of silylphenyl and phenylsilyl cations in the reaction with benzene

The possibility for positive charge migration in SiC6H 7 + cation from carbon to silicon (or vice versa) was studied by the radiochemical method. Silylphenyl cation with initial charge localization on the carbon atom is transformed into phenylsilylium ion where the positive charge is localized on the silicon atom. No migration of positive charge from the silicon atom to carbon occurs. 2005 Pleiades Publishing, Inc.

A systematic analysis of the structure-reactivity trends for some 'cation-like' early transition metal catalysts for dehydropolymerization of silanes

The use of 'cation-like' metallocene combination catalysts (Cp′2MCl2-2BuLi-B(C6F5)3; Cp′ = η5-cyclopentadienyl, or substituted η5-cyclopentadienyl; M = Ti, Zr, Hf, U) for dehydropolymerization of silanes significantly improves the polymer molecular weight. For example, under the same conditions a Cp(C5Me5)ZrCl2-2BuLi catalyst gives Mn = 1890, while a Cp(C5Me5)ZrCl2-2BuLi-B(C6F5)3 gives Mn = 7270. The influence of various factors (steric and electronic effects of the cyclopentadienyl ligands, the nature of the metal, temperature, solvent, concentration and structure of silane) on the build-up of polysilane chains are systematically analyzed.

Palladium(II) catalysed silicon-oxygen bond formation versus rearrangement reactions

Phenylsilane and diphenylsilane undergoes rearrangement reactions by palladium catalysts such as Pd(TMEDA)Cl2, Pd(TEEDA)Cl2, [Pd(PPh3)]2Cl2 (where TMEDA = tetramethylethylenediamine, TEEDA = tetraethylethylenediamine) at room temperature. However, the reductive Si-O bond forming reaction can be performed on hydrosilanes through competitive paths. The reactions of phenylsilane and quinonic compounds are catlaysed by Pd(TMEDA)Cl2 (such as 1,4-benzoquinone, 1,4-napthoquinone) to give siloxanes, backbone of these siloxanes which contains rearranged phenylsilane units. The thin films of such oligomers has plot of resistance vs temperature profile resembling semiconductor.

Nickel-catalyzed cyclopolymerization of hexyl- and phenylsilanes

[Ni(dmpe)2] (dmpe = 1,2-bis(dimethylphosphino)ethane) catalyzed the dehydrogenative polymerization of hexylsilane in toluene at room temperature to produce a mixture of acyclic and cyclic poly(hexylsilanes). A simlar reaction at 70 C resulted in selective cyclopolymerization of hexylsilane to yield a cyclic polymer with an average molecular weight of Mn = 1450 (Mw/Mn = 1.01, GPC polystyrene standard). The 1H NMR, 29Si{1H} DEPT NMR, and IR spectroscopic data indicated the presence or absence of the -SiH2R end groups of the polymer and its acyclic or cyclic structure. Addition of hexylsilane to the solution of the poly(hexylsilanes) containing the acyclic polymer (Mn = 1330) and heating the mixture in the presence of 5 mol % of [Ni(dmpe) 2] catalyst formed a polymer composed of the cyclic molecules without a change in the average molecular weight. The polymerization of phenylsilane catalyzed by [Ni(dmpe)2] also yielded the cyclic poly(phenylsilane). The reaction using a mixture of [Ni(cod)2] (cod = 1,5-cyclooctadiene) and PMe3 as the catalyst produced acyclic and/or cyclic poly(phenylsilanes) depending on the conditions. 9,9-Dihydrosilafluorene reacted with [PdMe2(dmpe)] to afford a persilylated palladacyclopentane, [Pd(SiC12H8)4(dmpe)], with four 1,1-silafluorene units.

An effective total synthesis of four angiotensin-converting enzymes containing silanediols

Four angiotensin-converting enzymes (ACE) containing silanediols 1 have been synthesized successfully in 8% overall yield in 8 steps from inexpensive starting materials such as diphenyldichlorosilane 5, β-methylallylic alcohol 7 and Ellman sulfinimine 9.

CATALYTIC REDUCTION OF HALOGENATED CARBOSILANES AND HALOGENATED CARBODISILANES

Selective reduction methods for halogenated carbosilanes and carbodisilanes are disclosed. More particularly, high yields of the desired carbosilanes and carbodisilanes are obtained by reduction of their halogenated counterparts using a reducing agent and tetrabutylphosphonium chloride (TBPC) as a catalyst.

Method for preparing of cyclic amidine compounds using borane catalyst and cyclic amidine compounds prepared therefrom

The present invention is in the presence of an organoboron catalyst. Silane compoundsN-The present invention relates to a process for preparing (Z)- cyclic amidine compounds available as source materials and intermediates of a heteroaromatic ring compound and subsequent sulfonyl azid compounds, and (Z)- cyclic amidine compounds prepared therefrom.

PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS

The invention relates to a process for the stepwise synthesis of silahydrocarbons bearing up to four different organyl substituents at the silicon atom, wherein the process includes at least one step a) of producing a bifunctional hydridochlorosilane by a redistribution reaction, selective chlorination of hydridosilanes with an ether/HCI reagent, or by selective chlorination of hydridosilanes with SiCI4, at least one step b) of submitting a bifunctional hydridochloromonosilane to a hydrosilylation reaction, at least one step c) of hydrogenation of a chloromonosilane, and a step d) in which a silahydrocarbon compound is obtained in a hydrosilylation reaction.

Metal-free hydrogen evolution cross-coupling enabled by synergistic photoredox and polarity reversal catalysis

A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si-H and O-H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cationviavisible-light photoredox catalysis.

Selective homo- And cross-desilacoupling of aryl and benzyl primary silanes catalyzed by a barium complex

Under mild conditions (25 °C, 5 mol% cat.), highly selective homo- and cross-desilacoupling of aryl and benzyl primary silanes to secondary silanes was achieved by the use of the heteroleptic barium aminobenzyl complex [(TpAd,iPr)Ba(CH2C6H4NMe2-o)] (TpAd,iPr = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) (1) as a catalyst. Dihydrosilanes originating from catalytic redistribution and cross-desilacoupling reactions were isolated in fine yields, which demonstrates the feasible application of the barium complex in the syntheses of secondary aryl- and benzylsilanes. This journal is