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

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

• 18163-02-5 (3-butenyl)dimethylsilane 
• 17887-33-1 bis-1,3-trimethylsilyl-2-hydroxypropane 
• 18387-42-3 1-(trimethylsilyl)-3-(methyldichlorosilyl)propane 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 106-95-6 allyl bromide 
• 17680-01-2 1-(trimethylsilyl)-1-propene 
• 2550-04-1 allyltriethoxysilane 
• 107-37-9 allyltrichlorosilane 
• 75-77-4 chloro-trimethyl-silane 
• 556-56-9 allyl iodid 
• 107-05-1 3-chloroprop-1-ene 
• 103216-80-4 3-trimethylsilyl-1-pyrazoline 
• 103216-81-5 1-trimethylsilyl-2-pyrazoline 
• 91899-54-6 (Trimethylsilyl)copper 

Downstream Products

• 1123-34-8 1-allyl-1-cyclohexanol 
• 5664-10-8 allylidenecyclohexane 
• 70243-64-0 3-(Hydroxy-phenyl-methyl)-4-phenyl-hept-6-en-2-one 
• 139284-72-3 4-trimethylsiloxy-4-phenyl-1-butene 
• 84110-23-6 (E)-1-Phenyl-4-trimethylsilanyl-but-3-en-1-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 
• 21889-88-3 hept-6-en-2-one 
• 21136-48-1 1,3-diphenylhex-5-en-1-one 
• 25203-83-2 (E)/(Z)-buta-1,3-dien-1-ylcyclohexane 
• 60340-28-5 1-phenylhex-5-en-3-ol 
• 20978-66-9 ethyl 2-hydroxy-2-phenyl-4-pentanoate 
• 20498-05-9 3-allylcyclohexanone 
• 62394-27-8 3-(2-propenyl)-3,5,5-trimethylcyclohexanone 

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.

Diastereoselective protonation on a radical anion in the photoallylation and photoreduction of 1,1-dicyano-2-methyl-3-phenyl-1-butene by allyltrimethylsilane

Diastereoselectivity in the photoallylation and photoreduction of 1,1-dicyano-2-methyl-3-phenyl-1-butene by allyltrimethylsilane in the presence of phenanthrene was dependent on the structures and stoichiometry of the added carboxylic acids. Diastereoselectivity increased up to 72% by the addition of equimolar amount of L-lactic acid based on the alkene. Springer Science+Business Media B.V. 2010.

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.

Selective mono- and di-allylation and allenylation of chlorosilanes using indium

Allyl and allenyl groups have been introduced into silicon systems by the allylation and allenylation of chlorosilanes using allyl bromide or propargyl bromide with indium. The allylation of chlorosilanes afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. By applying this method, the reactions of 1-bromo-3-methylbut-2-ene, 3-bromo-2-methylprop-1-ene and 3-bromobut-1-ene with chlorosilanes also proceed smoothly to give regioselectively allylic rearrangement products in good yields. Mediated by indium, dichlorosilanes (R2SiCl2) and trichlorosilanes (RSiCl3) can either afford monoallylated silanes or diallylated silanes depending on the amount of allyl bromide and indium used.

Polymer supported naphthalene-catalysed sodium reactions

Arene-catalysed sodium reactions have been utilised in the generation of organosodium complexes, from a variety of organochloride complexes, in high yield. Phenyltrimethylsilane, benzene and 2-methyl-1-phenyl-1-propanol were prepared in yields >80%, using polymer supported naphthalene-catalysed sodium reactions, whereby phenylsodium, prepared from the reaction of chlorobenzene, sodium powder and polymer-supported naphthalene (5-100%), was quenched with chlorotrimethylsilane, water or PriCHO respectively. The Royal Society of Chemistry.

Controlled introduction of allylic group to chlorosilanes

Allylation of chlorosilanes has been achieved with allylsamarium bromide, especially in a controlled manner. Thus allylation of trisubstituted chlorosilanes (R3SiCl) afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. Dichlorosilanes (R2SiCl2) can either afford monoallylated silanes or diallylated silanes depending on the amount of allylsamarium bromide used. Similarly, trichlorosilanes (RSiCl3) can selectively afford mono-, di-, and tri-allylation products. Finally, perchlorosilane (SiCl4) was allylated stepwise and the corresponding silanes containing one, two, three or four allylic groups, respectively, were obtained in satisfactory yields.

Evaluation of β- and γ-Effects of Group 14 Elements Using Intramolecular Competition

To evaluate β-effects and γ-effects of group 14 elements, we have devised a system in which the intramolecular competition between γ-elimination of tin and β-elimination of silicon, germanium, and tin can be examined. Thus, the reactions of α-acetoxy(arylmethyl)stannanes with allylmetals (metal = Si, Ge, Sn) in the presence of BF3·OEt2 were carried out. The reactions seem to proceed by the initial formation of an α-stannyl-substituted carbocation, which adds to an allylmetal to give the carbocation that is β to the metal and γ to tin. The β-elimination of the metal gives the corresponding allylated product, and the γ-elimination of tin gives the cyclopropane derivative. In the case of allylsilane, the cyclopropane derivative was formed as a major product, whereas in the case of allylgermane the allylated product was formed predominantly. In the case of the allystannane the allylated product was formed exclusively. These results indicate that the y-elimination of tin is faster than the β-elimination of silicon, but slower than the β-elimination of germanium and tin. The theoretical studies using ab initio molecular orbital calculations of the carbocation intermediates are consistent with the experimental results. The effect of substituents on silicon was also studied. The introduction of sterically demanding substituents on silicon disfavored the β-elimination of silicon probably because of the retardation of nucleophilic attack on silicon to cleave the carbon-silicon bond.

Infrared and nuclear magnetic resonance spectroscopic studies of the structure and dynamics of allylic magnesium compounds

The infrared spectra of allyl- and methallyl-d2-magnesium bromides have two double bond stretching bands, corresponding to C=CH2 and C=CD2 groups in equilibrating allylic isomers. The methylene resonances in the 13C NMR spectra of allylmagnesium bromide and chloride and methallylmagnesium bromide are broadened at low temperatures by an exchange process which appears to be the interconversion between the classical unsymmetrical allylic structures. Analogous changes are seen in the spectrum of 1,3-dimethylallylmagnesium chloride and in the proton NMR spectrum of allylmagnesium bromide. Rate constants and activation parameters for the exchange have been determined from the line broadenings. Unlike the Grignard reagent, the methylene resonances of diallylmagnesium in tetrahydrofuran are not significantly broadened at reduced temperature, and the deuterated reagent does not have two distinct double bond stretching bands in the IR spectrum.