754-05-2

Basic information

• Product Name: Vinyltrimethylsilane
• Synonyms: CH2=CHSi(CH3)3;ethenyltrimethyl-silan;Silane, trimethylvinyl-;silane,trimethylvinyl-;Vinyltrimethysilane;VINYLTRIMETHYLSILANE;(TRIMETHYLSILYL)ETHYLENE;TRIMETHYLVINYLSILANE
• CAS NO: 754-05-2
• Molecular Formula: C₅H₁₂Si
• Molecular Weight: 100.23
• EINECS: 212-042-9
• Product Categories: Si (Classes of Silicon Compounds);Si-(C)4 Compounds;Vinylsilanes, Allylsilanes;Amides;Amines;and Other Vinyl Monomers;Chemical Synthesis;Materials Science;Monomers;Organometallic Reagents;Organosilicon;Others;Polymer Science;Vinyl Halides
• Mol File: 754-05-2.mol

Chemical Properties

• Melting Point: -132°C
• Boiling Point: 55 °C(lit.)
• Flash Point: <-30 °C
• Appearance: /liquid
• Density: 0.684 g/mL at 25 °C(lit.)
• Vapor Pressure: 4.44 psi ( 20 °C)
• Refractive Index: n20/D 1.391(lit.)
• Storage Temp.: Flammables area
• Solubility: Miscible with tetrahydrofuran, diethyl ether, benzene and dichlo
• BRN: 956572
• CAS DataBase Reference: Vinyltrimethylsilane(CAS DataBase Reference)
• NIST Chemistry Reference: Vinyltrimethylsilane(754-05-2)
• EPA Substance Registry System: Vinyltrimethylsilane(754-05-2)

Safety Data

• Hazard Codes: F,Xn
• Statements: 11-22-36/37/38-40
• Safety Statements: 16-26-33-36-36/37/39-36/37
• RIDADR: UN 1993 3/PG 1
• WGK Germany: 1
• TSCA: Yes
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 754-05-2(Hazardous Substances Data)

Usage

Uses

1. Used in Semiconductor Processing:
Vinyltrimethylsilane is used as a precursor in semiconductor processing, particularly in the preparation of silyl-ethers by Rh(I) catalysis. It plays a crucial role in the development of advanced semiconductor materials and devices.
2. Used in Organic Synthesis:
Vinyltrimethylsilane is used as an ethylene equivalent in electrophilic substitution reactions. It serves as a versatile building block for the synthesis of various organic compounds, including:
a. 3-Trimethylsilyl-3-buten-2-one, a methyl vinyl ketone surrogate for Robinson annulations.
b. α,β-Unsaturated aldehydes through the homologation of aldehydes.
c. Vinyl aryl sulfides.
d. 3-Triethylsilyl-3-buten-2-one.
e. α,β-Unsaturated primary amides.
f. Bicyclopentenones.
g. 1-Chlorocyclopropene.
3. Used in Radical Addition Reactions:
Vinyltrimethylsilane is employed in radical addition reactions, such as the addition of α-iodo-α,α-difluoroketones and α-iodosulfones to the compound, leading to the formation of various organic products.
4. Used in Cycloaddition Reactions:
Vinyltrimethylsilane is utilized in 3 + 2 cycloaddition reactions with nitrones, resulting in the formation of diverse heterocyclic compounds.
5. Used in the Formation of Trimethylsilylcyclopropanes:
Vinyltrimethylsilane is used in titanium-mediated reactions to form trimethylsilylcyclopropanes, which are valuable intermediates in organic synthesis.
6. Used as a Hydrogen Acceptor Catalyst:
Vinyltrimethylsilane acts as a hydrogen acceptor catalyst in the conversion of alcohols to hydrogenated Wittig adducts, facilitating the synthesis of various organic compounds.
7. Used in the Synthesis of Trimethylsilylaziridines and Sulfonyl Chlorides:
Vinyltrimethylsilane is employed in the formation of 2-trimethylsilylaziridines and sulfonyl chlorides, which are important building blocks in organic chemistry.
8. Used in the Synthesis of 2-Trimethylsilylethylsulfonyl Chloride:
Vinyltrimethylsilane is used in the improved synthesis of 2-trimethylsilylethylsulfonyl chloride, a valuable reagent in organic synthesis.
9. Used in the Formation of Iron Carbonyl Trienone Complexes:
Vinyltrimethylsilane is utilized in the formation of an iron carbonyl trienone complex, which has potential applications in catalysis and materials science.
10. Used in the Synthesis of 2-Phenyl-2-Trimethylsilylethanol and 2-Vinylanilines:
Vinyltrimethylsilane is employed in the synthesis of 2-phenyl-2-trimethylsilylethanol and 2-vinylanilines, which are important intermediates in the pharmaceutical and agrochemical industries.
11. Used in Decarbonylative Vinylation of Aromatic Esters:
Vinyltrimethylsilane is used in the decarbonylative vinylation of aromatic esters, a key reaction in the synthesis of various organic compounds.
12. Used in Asymmetric Epoxidation:
Vinyltrimethylsilane is employed in asymmetric epoxidation reactions, which are essential for the synthesis of enantiomerically pure compounds.
13. Used in Direct Silylation of Heteroarylcarbonyl Compounds:
Vinyltrimethylsilane is used in the direct silylation of heteroarylcarbonyl compounds, providing a convenient route to various organosilicon heterocycles.
14. Used in Trimethylsilylation of Vinylboronates:
Vinyltrimethylsilane is utilized in the trimethylsilylation of vinylboronates, which are important intermediates in the synthesis of organosilicon compounds.

Preparation

Prepared in 67–91% yield from vinylmagnesium bromide and chlorotrimethylsilane in THF.

Flammability and Explosibility

Flammable

Purification Methods

If the 1H NMR spectrum shows impurities, then dissolve it in Et2O, wash it with aqueous NH4Cl solution, dry over CaCl2, filter, evaporate and distil it at atmospheric pressure in an inert atmosphere. It is used as a co-polymer and may polymerise in the presence of free radicals. It is soluble in CH2Cl2. [Nagel & Post J Org Chem 17 1379 1952, Beilstein 4 IV 3922.]

InChI:InChI=1/C5H12Si/c1-5-6(2,3)4/h5H,1H2,2-4H3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 75-01-4 chloroethylene 
• 1826-67-1 vinyl magnesium bromide 
• 75-94-5 trichlorovinylsilane 
• 75-16-1 methylmagnesium bromide 
• 593-60-2 Vinyl bromide 
• 763-13-3 but-3-en-1-yltrimethylsilane 
• 7677-24-9 trimethylsilyl cyanide 
• 18140-32-4 1-(trimethylsilyl)-2-(methyldichlorosilyl)ethane 
• 5796-98-5 bis-trimethylsilanyl peroxide 
• 917-57-7 vinyllithium 
• 35802-68-7 β-chlorovinyltrimethylsilane 
• 18135-34-7 O,O-dimethyl dithiophosphoric acid S-trimethylsilyl ester 
• 754-06-3 vinyltrimethyltin 

Downstream Products

• 18269-42-6 6,6-dimethyl-3-thia-6-sila-heptanoic acid 
• 772-64-5 (phenylethyl)silane 
• 16722-09-1 trimethylsilyloxirane 
• 18156-67-7 (2-bromoethyl)trimethylsilane 
• 13506-99-5 1-phenyl-3-trimethylsilanyl-propan-1-one 
• 17988-59-9 phenyl 2-(trimethylsilyl)ethyl sulfide 
• 41773-65-3 3-(4-nitro-phenyl)-5-trimethylsilanyl-4,5-dihydro-isoxazole 
• 18053-55-9 benzyl 2-(trimethylsilyl)ethyl sulfide 
• 64489-03-8 1-benzenesulfonyl-2-chloro-2-trimethylsilylethane 
• 27840-95-5 trimethylsilylethyl diphenyl phosphine 
• 312-81-2 (2,2,3,3-tetrafluorocyclobutyl)trimethylsilane 
• 1115-16-8 4,4-dimethyl-2-(trimethylsilyl)pentanoic acid 
• 57340-38-2 1-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-2-trimethylsilanyl-benzene 
• 60366-58-7 3-[2-(dimethyl-phenyl-silanyl)-1-trimethylsilanyl-ethyl]-1,1-dimethyl-1H-silepine 

Relevant articles and documents

Radiolytic silylation of alkenes and alkynes by gaseous R3Si+ ions. Stereochemical evidence for the β-silyl effect

Carbocation intermediate stabilized by a β silyl group have been characterized using the silylation of alkenes by R3Si+ ions as a route of formation. Neutral silylated products have been obtained from the reaction of R3Si+ ions, generated in a gaseous medium at atmospheric pressure by a radiolytic technique, with selected alkenes, alkynes, and allene, thereby indicating the occurrence of electrophilic silylation. Notable fectures of the charged silylated intermediates emerge from the isomeric product distribution. The silylation of cis- and trans-2-butene shows a high degree of retention of configuration, as expected if a bridged species (I) were the reaction intermediate. Alternatively, the intermediacy of an open structure (II), whereby C-C bond rotation is inhibited by the hyperconjugative interaction between the β silyl group and the vacant up orbital, should be inferred. The charged intermediates from the silylation of alkenes and alkynes are found to be unreactive toward conceivable isomerizations to more stable species, such as the ones bearing the positive charge of silicon. Stereoelectronic factors affect the deprotonation of the silylated intermediates, which may involves loss of the proton either the α or the γ position with respect to the silylated carbon. A comparison of the reactivity of alkenes and alkynes in the cationic silylation reaction is presented.

KINETICS AND MECHANISM OF THE PYROLYSIS OF ALLYLTRIMETHYLSILANE.

The gas-phase thermal decomposition of allyltrimethylsilane has been reinvestigated by using deuterium labeling and kinetic studies of variable pressure. Trimethylvinylsilane, the major product at high pressures, is found not to be a primary product of unimolecular decomposition. Silyl radical trapping allowed kinetic separation of the two competitive primary processes of decomposition: a concerted retroene elimination of propene to directly produce a silene and Si-C bond homolysis.

Trimethylsilylacetylene synthesis process

The invention discloses a process route for synthesizing trimethylsilylacetylene, which comprises the following steps of: generating trimethylchlorosilylethylene by taking ethylene bromide and trimethylchlorosilane as initial raw materials through a Grignard method, and forming 1-bromo trimethylchlorosilylethylene under the action of alkali through a bromination reagent; and removing monomolecularhydrogen bromide under the action of strong alkali to generate trimethylsilylacetylene. Compared with the traditional process, the process route has the advantages that the use of gas acetylene is avoided, the risk is reduced, the safety is improved, the used raw materials are easily available, the operation is easy, the safety and the environmental protection are realized, and the industrial production can be realized.

Platinum(II) Di-ω-alkenyl Complexes as slow-Release Precatalysts for Heat-Triggered Olefin Hydrosilylation

We describe the synthesis, characterization, and catalytic hydrosilylation activity of platinum(II) di-ω-alkenyl compounds of stoichiometry PtR2, where R = CH2SiMe2(vinyl) (1) or CH2SiMe2(allyl) (2), and their adducts with 1,5-cyclooctadiene (COD), dibenzo[a,e]cyclooctatetraene (DBCOT), and norbornadiene (NBD), which can be considered as slow-release sources of the reactive compounds 1 and 2. At loadings of 0.5 × 10-6-5 × 10-6 mol %, 1-COD is an active hydrosilylation catalyst that exhibits heat-triggered latency: no hydrosilylation activity occurs toward many olefin substrates even after several hours at 20 °C, but turnover numbers as high as 200000 are seen after 4 h at 50 °C, with excellent selectivity for formation of the anti-Markovnikov product. Activation of the PtII precatalyst occurs via three steps: slow dissociation of COD from 1-COD to form 1, rapid reaction of 1 with silane, and elimination of both ω-alkenyl ligands to form Pt0 species. The latent catalytic behavior, the high turnover number, and the high anti-Markovnikov selectivity are a result of the slow release of 1 from 1-COD at room temperature, so that the concentration of Pt0 during the initial stages of the catalysis is negligible. As a result, formation of colloidal Pt, which is known to cause side reactions, is minimized, and the amounts of side products are very small and comparable to those seen for platinum(0) carbene catalysts. The latent reaction kinetics and high turnover numbers seen for 1-COD after thermal triggering make this compound a potentially useful precatalyst for injection molding or solvent-free hydrosilylation applications.

Bench-Stable Cobalt Pre-Catalysts for Mild Hydrosilative Reduction of Tertiary Amides to Amines and Beyond

The readily synthesized and bench-stable cobalt dichloride complex (dpephos)CoCl2 is employed as a pre-catalyst for a diversity of silane additions to unsaturated organic molecules, including the normally challenging reduction of amides to amines. With regard to hydrosilative reduction of amides even more effective and activator free catalytic systems can be generated from the bench-stable, commercially available Co(acac)2 and Co(OAc)2 with dpephos and PPh3 ligands. These systems operate under mild conditions (100 °C), with many examples of room temperature transformations, presenting a first example of mild cobalt-catalyzed hydrosilylation of amides.

Vanadium-Catalyzed Cross Metathesis: Limitations and Implications for Future Catalyst Design

Self-metathesis of terminal olefins using vanadium(V) alkylidenes is presented. Under various reaction conditions, incomplete conversion is observed due to decomposition of the metallocyclobutane intermediate via β-hydride elimination. The activity was observed to decline when a more electron withdrawing, less sterically bulky ligand was used, in contrast to trends observed in ring-opening metathesis polymerization with vanadium catalysts. These results provide insight into the current limitations of olefin metathesis with vanadium catalysts, as well as guidance for catalyst development.

Cobalt-catalyzed hydrosilation/hydrogen-transfer cascade reaction: A new route to silyl enol ethers

Capitalizing on cobalt: A new route to silyl enol ethers employing a Co-catalyzed cascade reaction featuring a tandem hydrosilation/hydrogen-transfer reaction is reported. The low catalyst loading, mild reaction conditions, and unique η2-silane resting state showcase the impressive utility of this seldom used transition-metal catalyst in C-H activation reactions (see scheme; VTMS = vinyltrimethylsilane; Cp* = 1,2,3,4,5- pentamethylcyclopentadiene). Copyright

Enantio- and diastereoselective synthesis of syn-β-hydroxyallylsilanes via a chiral (Z)-γ-silylallylboronate

syn-β-Hydroxyallylsilanes of general structure 11 and 28 are prepared in 50-86% yield and 91-95% ee (for aliphatic aldehydes; 50% ee for benzaldehyde) via the BF3-Et2O-promoted γ-silylallylboration reactions, using reagents 14 and 15.

Titanocene-mediated homolytic opening of epoxysilanes

The titanocene(III) chloride mediated opening of silyloxiranes has been examined. Electron transfer from the metal leads to α-silyl radicals with total regiocontrol. The radicals could be trapped by various olefins, and the corresponding adducts were obtained in good yields (Table). Further substitution of the oxirane by alkyl groups proved detrimental to the reactions, but ring opening remained essentially regioselective.

Catalytic asymmetric Claisen rearrangement in natural product synthesis: Synthetic studies toward (-)-xeniolide F

(Chemical Equation Presented) The catalytic asymmetric Claisen rearrangement (CAC) of a highly substituted and functionalized α-alkoxycarbonyl-substituted allyl vinyl ether has been exploited to gain access to an advanced building block for the projected total synthesis of (-)-xeniolide F, the enantiomer of a xenicane diterpene isolated from a coral of the genus Xenia.