762-72-1

Basic information

• Product Name: Allyltrimethylsilane
• Synonyms: Allyltrimethylisilane;trimethyl-prop-2-enyl-silane;Allyltrimethylsilane(3-trimethylsilyl-1-propene)99%available;Allyltrimethylsilane, 98+%;Allyltrimethylsilane,99%;Allyltrimethylsilane,97%;Allyltrimethylsilane,3-(Trimethylsilyl)propene;triMethyl(prop-2-en-1-yl)silane
• CAS NO: 762-72-1
• Molecular Formula: C₆H₁₄Si
• Molecular Weight: 114.26
• EINECS: 212-104-5
• Product Categories: Industrial/Fine Chemicals;API intermediates;Si-(C)4 Compounds;Silicon Compounds (for Synthesis);Vinylsilanes, Allylsilanes;Si (Classes of Silicon Compounds);Synthetic Organic Chemistry
• Mol File: 762-72-1.mol
• Article Data: 30

Chemical Properties

• Boiling Point: 84-88 °C(lit.)
• Flash Point: 45 °F
• Appearance: Clear colorless/Liquid
• Density: 0.719 g/mL at 25 °C(lit.)
• Vapor Pressure: 79.2mmHg at 25°C
• Refractive Index: n20/D 1.407(lit.)
• Storage Temp.: 0-6°C
• Solubility: freely sol all organic solvents.
• Water Solubility: insoluble
• BRN: 906755
• CAS DataBase Reference: Allyltrimethylsilane(CAS DataBase Reference)
• NIST Chemistry Reference: Allyltrimethylsilane(762-72-1)
• EPA Substance Registry System: Allyltrimethylsilane(762-72-1)

Safety Data

• Hazard Codes: F,Xi
• Statements: 11-36/37/38
• Safety Statements: 16-26-36-23-33-7/9
• RIDADR: UN 1993 3/PG 2
• WGK Germany: 3
• TSCA: Yes
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 762-72-1(Hazardous Substances Data)

Usage

Chemical Properties

clear colourless liquid

Uses

Allyltrimethylsilane is a general reagent to introduce allyl groups across acid chlorides, aldehydes, ketones, iminium ions, enones, and for cross-coupling with other carbon electrophiles. It is used as a reagent in Hosomi?Sakurai reaction.

Preparation

Allyltrimethylsilane is synthesized by the reaction of trimethylchlorosilane and allylmagnesium bromide.

Application

Allyltrimethylsilane is used in the allylation of aldehydes, imines, allylic and benzylic alcohols, and chiral α-keto-amides that are derived from (S)-proline esters.

Reactions

Allyltrimethylsilane is involved as a reactant in Hosomi Sakurai reaction for allylation in the presence of Lewis acid. For example, it reacts with cyclohexanone to get 1-allylcyclohexanol. It acts as a nucleophile and is involved in Carbon-Ferrier rearrangement.As a Carbon Nucleophile in Lewis Acid-Catalyzed Reactions.Allyltrimethylsilane is an alkene some 10 times more nucleophilic than propene, as judged by its reactions with diarylmethyl cations.It reacts with a variety of cationic carbon electrophiles, usually prepared by coordination of a Lewis acid to a functional group, but also by chemical or electrochemical oxidation,or by irradiation in the presence of 9,10- dicyanoanthracene.carbon to give an intermediate cation, and the silyl group is lost to create a double bond at the other terminus. Among the more straightforward electrophiles are acid chlorides (eq 1).As a Carbon Nucleophile in Fluoride Ion-Catalyzed Reactions.The reactions with aldehydes, ketones (eq 23),54 and α,β-unsaturated esters (eq 24)55 can also be catalyzed by fluoride ion, usually introduced as tetra-n-butylammonium fluoride (TBAF), or other silicophilic ions such as alkoxide. These reactions produce silyl ether intermediates, which are usually hydrolyzed before workup. The stereochemistry of attack on chiral ketones can sometimes be different for the Lewis acid- and fluoride ion-catalyzed reactions.Other Reactions.Allyltrimethylsilane reacts with some highly electrophilic alkenes, carbonyl compounds, azo compounds, and singlet oxygen to a greater or lesser extent in ene reactions that do not involve the loss of the silyl group, and hence give vinylsilanes in a solvent-dependent reaction.

Flammability and Explosibility

Flammable

Purification Methods

Fractionate it through an efficient column at atmospheric pressure. If impure, dissolve it in THF, shake it with H2O (2x), dry (Na2SO4), filter and fractionate it. [Cudlin & Chvalovsky′ Collect Czech Chem Commun 27 1658 1962, Beilstein 4 IV 3927.]

InChI:InChI=1/C6H14Si/c1-5-6-7(2,3)4/h5H,1,6H2,2-4H3

Upstream product

• 2295-05-8 1,3-bis(trimethylsilyl)propane 
• 763-13-3 but-3-en-1-yltrimethylsilane 
• 75-77-4 chloro-trimethyl-silane 
• 107-05-1 3-chloroprop-1-ene 
• 17680-01-2 1-(trimethylsilyl)-1-propene 
• 103216-80-4 3-trimethylsilyl-1-pyrazoline 
• 103216-81-5 1-trimethylsilyl-2-pyrazoline 
• 91899-54-6 (Trimethylsilyl)copper 
• 101347-38-0 2,2-bis(allyloxy)hexamethyltrisilane 
• 106-95-6 allyl bromide 
• 18000-27-6 trimethylsilyllithium 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 98228-72-9 1,1-dichloro-1,3-dibromo-3-trimethylsilylpropane 
• 78334-82-4 1-dimethyl(phenyl)silyl-3-trimethylsilylpropene 

Downstream Products

• 61077-65-4 1-phenylpent-4-en-2-ol 
• 70243-63-9 3-(1-Hydroxy-propyl)-4-phenyl-hept-6-en-2-one 
• 70243-73-1 3-Allyl-2-(1-hydroxy-propyl)-cyclohexanone 
• 3314-65-6 5-Trimethylsilylmethyl-3-phenyl-4,5-dihydro-1,2-oxazole 
• 25203-83-2 (E)/(Z)-buta-1,3-dien-1-ylcyclohexane 
• 120869-63-8 (1R,2S)-1-Methyl-2-((E)-3-trimethylsilanyl-allyl)-cyclohexanol 
• 20849-87-0 2-allylthiophene 
• 33934-92-8 3-(2-propenyl)thiophene 
• 591-50-4 iodobenzene 
• 107686-21-5 5-Phenyl-oct-7-en-1-ol 
• 110382-93-9 C₁₆H₁₅NO₂ 
• 110382-92-8 C₁₆H₁₅NO₂ 
• 77234-00-5 dimethyl 4-phenyl-2,6-dimethyl-3,5-pyridinedicarboxylate 
• 105335-61-3 dimethyl 1α,3-dimethyl-5β-phenyl-8-<(trimethylsilyl)methyl>-2-azabicyclo<2.2.2>oct-2-ene-4,6α-dicarboxylate 

Relevant articles and documents

Synthesis of trans-mono(silyl)palladium(ii) bromide complexes

The stoichiometric reaction of cis-[Pd(ITMe)2(SiR3)2], where (SiR3 = SiMe3 and SiMe2Ph and ITMe = 1,3,4,5-tetramethylimidazol-2-ylidene) with allyl bromide affords the corresponding allylsilanes along with complexes of the type trans-[Pd(ITMe)2(SiR3)(Br)]. The structure of trans- [Pd(ITMe)2(SiMe2Ph)Br] 2b has been determined in the solid state and displays a slightly distorted square-planar geometry with the two N-heterocyclic carbene ligands in a trans-configuration.

Isomeric C5H11Si+ ions from the trimethylsilylation of acetylene: An experimental and theoretical study

The gas phase offers a unique medium to conduct the electrophilic addition reaction of (CH3)3Si+ (trimethylsilylium ion) to acetylene. However, this deceptively simple reaction displays a remarkable dependence on the gas phase pressure, revealing the interplay of competitive pathways. In FT-ICR mass spectrometry at ca 10-8 mbar, the nascent (CH3)3Si+-acetylene complex undergoes a rearrangement process yielding the CH2C(CH3)Si(CH 3)2+ ion. This structure has been assigned on the basis of the ion-molecule reactivity displayed by the sampled C 5H11Si+ adducts, matching the one of the model ion obtained from 2-(trimethylsilyl)propene. Whereas the absolute values of kinetic rate constants could not discriminate between isomeric species, the branching ratios for competitive addition-elimination channels in the reaction with i-C3H7OH and t-C4H9OCH 3 were found to be diagnostic of different structures. The pathways leading from the (CH3)3Si+-acetylene complex primarily formed to the candidate C5H11Si+ isomers have been investigated by ab initio quantum chemical calculations at CCSD(T)/6-311 ++G(2d,2p)//B3LYP/6-311G(2d,p) level. The energy profiles show that the path to the CH2C(CH3)Si(CH3) 2+ isomer is associated to the lowest activation energy barrier, below the reactants energy level. The energy released in the (CH 3)3Si+-acetylene association process, remaining stored in the complex formed at low pressure, thus allows the isomerization to a species holding the positive charge on electropositive silicon. Interestingly, the most stable of the conceivable isomers, (E)-(CH3)CHCHSi(CH 3)2+, is not accessed because of an activation energy barrier protruding above the reactants energy level. The combined information of ion-molecule reactivity and ab initio calculations of potential isomers and rearrangement pathways has thus afforded a comprehensive view of the (CH3)3Si+ addition reaction to acetylene under various pressure regimes.

Insight into cis-to-trans olefin isomerisation catalysed by group 4 and 6 cyclopentadienyl compounds

Intramolecular isomerisation of the pendant allyl unit present in the model compound [MoH(eta;5-C5H4SiMe 2CH2CH=CH2)- (CO)3] reported before was investigated by DFT calculations.