18293-99-7

Basic information

• Product Name: 3,3-DIMETHYLALLYLTRIMETHYLSILANE
• Synonyms: 4-TRIMETHYLSILYL-2-METHYL-2-BUTENE;3,3-DIMETHYLALLYLTRIMETHYLSILANE;3-METHYL-1-TRIMETHYLSILYL-2-BUTENE;4-TRIMETHYLSILYL-2-METHYL-2-BUTENE 97%;trimethyl(3-methyl-2-butenyl)silane;1-(Trimethylsilyl)-3-methyl-2-butene;2-Methyl-4-(trimethylsilyl)-2-butene;3-Methyl-2-butenyltrimethylsilane
• CAS NO: 18293-99-7
• Molecular Formula: C₈H₁₈Si
• Molecular Weight: 142.31
• Mol File: 18293-99-7.mol

Chemical Properties

• Boiling Point: 138°C at 760 mmHg
• Flash Point: 10.6°C
• Appearance: /
• Density: 0.75g/cm³
• Vapor Pressure: 8.54mmHg at 25°C
• Refractive Index: 1.417
• CAS DataBase Reference: 3,3-DIMETHYLALLYLTRIMETHYLSILANE(CAS DataBase Reference)
• NIST Chemistry Reference: 3,3-DIMETHYLALLYLTRIMETHYLSILANE(18293-99-7)
• EPA Substance Registry System: 3,3-DIMETHYLALLYLTRIMETHYLSILANE(18293-99-7)

Safety Data

• RIDADR: 1993
• HazardClass: 3.1
• PackingGroup: II
• Hazardous Substances Data: 18293-99-7(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
3,3-Dimethylallyltrimethylsilane is used as a reagent for introducing the 1,1-dimethylallyl group into various organic compounds, facilitating the synthesis of complex organic molecules and enhancing the efficiency of chemical reactions.
Used as a Protecting Group for Alcohols:
In the synthesis of alcohols, 3,3-Dimethylallyltrimethylsilane is employed as a protecting agent to prevent unwanted side reactions, ensuring the selective formation of the desired alcohol products.
Used in the Production of Organosilicon Compounds:
3,3-Dimethylallyltrimethylsilane serves as a precursor in the synthesis of other organosilicon compounds, contributing to the development of new materials with unique properties and applications.
Used in Catalytic Reactions:
3,3-Dimethylallyltrimethylsilane is utilized in various catalytic processes, where it aids in the acceleration of chemical reactions, improving the overall yield and selectivity of the products. This makes it an indispensable tool in the field of catalysis and organic chemistry.

InChI:InChI=1/C8H18Si/c1-8(2)6-7-9(3,4)5/h6H,7H2,1-5H3

Upstream product

• 3017-69-4 2-methyl-1-propenylbromide 
• 2344-80-1 Chloromethyltrimethylsilane 
• 67707-64-6 (α,α-dimethylallyl)trimethylsilane 
• 75-77-4 chloro-trimethyl-silane 
• 503-60-6 3,3-dimethyl-allyl chloride 
• 993-07-7 trimethylsilan 
• 78-79-5 isoprene 
• 870-63-3 prenyl bromide 
• 22093-99-8 methyl-(3-methyl-but-2-enyl)-ether 
• 40426-44-6 3-methoxy-3-methyl-1-butene 
• 32264-50-9 1,1-dibromo-2,2-dimethylcyclopropane 
• 19916-99-5 (3-methyl-but-1-en-3-yl)trimethylsilylether 
• 71821-61-9 3-methyl-1-(trimethylsilyloxy)but-2-ene 
• 99966-30-0 10-trimethylsilylmethyl-9-oxa-10-borabicyclo<3.3.2>decane 

Downstream Products

• 7677-24-9 trimethylsilyl cyanide 
• 90433-15-1 4-(1,1-dimethyl-2-propenyl)benzonitrile 
• 90433-29-7 4-(3-methylbut-2-en-1-yl)benzonitrile 
• 92912-11-3 methyl (E)-7,7-dimethyl-4,8-nonadienoate 
• 75-77-4 chloro-trimethyl-silane 
• 546-49-6 artemisia ketone 
• 87143-68-8 ethyl 3,3-dimethyl-2-(phenylthio)pent-4-enoate 
• 100696-97-7 (3-Methoxy-4,4-dimethyl-hex-5-enyl)-benzene 
• 108733-07-9 3,3-dimethyl-4,4-bis(4-methylphenyl)-1-butene 
• 119752-25-9 2-[1-(4-Cyano-phenyl)-4-methyl-pent-3-enyl]-malononitrile 
• 119752-26-0 2-[1-(4-Cyano-phenyl)-2,2-dimethyl-but-3-enyl]-malononitrile 
• 87143-67-7 4,4-dimethyl-3-phenylthiohex-5-en-2-one 
• 98-52-2 4-(1,1-dimethylethyl)-cyclohexanol 
• 124494-15-1 1-(2,2-Dimethyl-1-phenyl-but-3-enyl)-4-methoxy-benzene 

Relevant articles and documents

Photochemical Organocatalytic Regio- and Enantioselective Conjugate Addition of Allyl Groups to Enals

We report the first catalytic enantioselective conjugate addition of allyl groups to α,β-unsaturated aldehydes. The chemistry exploits the visible-light-excitation of chiral iminium ions to activate allyl silanes towards the formation of allylic radicals, which are then intercepted stereoselectively. The underlying radical mechanism of this process overcomes the poor regio- and chemoselectivity that traditionally affects the conjugate allylation of enals proceeding via polar pathways. We also demonstrate how this organocatalytic strategy could selectively install a valuable prenyl fragment at the β-carbon of enals.

Catalysis and chemodivergence in the interrupted, formal homo-nazarov cyclization using allylsilanes

A chemodivergent, Lewis acid catalyzed allylsilane interrupted formal homo-Nazarov cyclization is disclosed. With catalytic amounts of SnCl4 and in the presence of allyltrimethylsilane, a formal Hosomi-Sakurai-type allylation of the oxyallyl cation intermediate is observed. A variety of functionalized donor-acceptor cyclopropanes and allylsilanes were shown to be amenable to the reaction transformation and the allyl products were formed in up to 92% yield. Under dilute reaction conditions with stoichiometric SnCl4 and at reduced temperatures, an unusual formal [3 + 2]-cycloaddition between the allylsilane and the oxyallyl cation occurred to give hexahydrobenzofuran products in up to 69% yield.

Amide formation in one pot from carboxylic acids and amines via carboxyl and sulfinyl mixed anhydrides

An efficient method has been developed for the preparation of yet unknown acyclic mixed anhydrides of carboxylic and sulfinic acids. Sterically hindered 2-methylbut-3-ene-2-sulfinyl carboxylates add primary and secondary amines preferentially onto the carbonyl moieties realizing a new method for the one-pot preparation of carboxamides. It uses 1:1 mixtures of carboxylic acids and amines without a base, requires no excess of reagents, and liberates only volatile coproducts. Protected di- and tripeptides have been prepared in solution without epimerization by application of this method.

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.

γ-Silyl-stabilized tertiary ions? Solvolysis of 4-(trimethylsilyl)-2-chloro-2-methylbutane

Rate constant, isotope-effect, and product studies of the solvolysis of 4-(trimethylsilyl)-2-chloro-2-methylbutane, 11, and its carbon analog, 2-chloro-2,5,5-trimethylhexane, 10, in aqueous ethanol and aqueous 2,2,2-trifluoroethanol (TFE) indicate very little participation of the γ-silyl substituent. These results are in sharp contrast to earlier reports on secondary γ-silyl substituted systems, in which the back lobe of the silicon-carbon bond has been shown to overlap with the carbocation p-orbital to form a so-called 'percaudally' stabilized intermediate. While the solvolytic behaviors of 11 and 10 are nearly identical in ethanol, differences in the TFE lead to the conclusion that there is a minor amount of participation by the silyl substituent in that solvent. Interestingly, this observation lends credence to an earlier suggestion that TFE is better than ethanol at stabilizing more highly delocalized ions. Copyright

The γ-silicon effect. I. Solvent effects on the solvolyses of 2,2- dimethyl-3-(trimethylsilyl)propyl and 3-(aryldimethylsilyl)-2,2- dimethylpropyl p-toluenesulfonates

The solvolysis rates of 2,2-dimethyl-3-(trimethylsilyl)propyl and 3- (aryldimethylsilyl)-2,2-dimethylpropyl p-toluenesulfonates were measured in a wide variety of solvents at 45 °C. The solvent effects were analyzed by using the Winstein-Grunwald equation. The solvent effects observed did not give simple linear correlations with the 2-adamantyl Y(OTs) parameter, but showed dispersion behavior in a series of binary solvents. The m values of 0.59-.67 were remarkably lower than unity for the limiting k(c) solvolysis of 2-adamantyl p-toluenesulfonate. The deviation patterns could not be interpreted in terms of nucleophilic assistance by the solvent. The dispersion behavior with reduced m values was found to be more significant for the 3-(aryldimethylsilyl) than for the 3-(trimethylsilyl) derivatives and was compatible with the delocalization of the incipient cationic charge by participation of the Si-Cγ bond in the rate-determining step. An extended dual-parameter treatment, log (k/k(80E)) = m(c)Y(OTs) + m(Δ)Y(Δ), successfully correlated such γ-silyl assisted solvolyses. The M(Δ) values of 0.24-0.49 so obtained, where M(Δ) = 0.51 m(Δ)/(m(c) +0.51 m(Δ)), are a measure of the extent of charge delocalization, suggesting that the γ-silyl group in the percaudal interaction is more effective in delocalizing the cationic charge than the alkyl group in C-C σ-participation, but less so than σ-assisted interaction by the β-aryl group.

Allyl, benzyl and propargyl silanes via the Suzuki reaction

The clean, efficient Pd-catalyzed cross-coupling of vinyl, alkynyl and aryl bromides with the air-stable organoborane, 10-trimethylsilylmethyl-9-oxa-10-borabicyclo[3.3.2]decane (2) gives excellent yields of the corresponding silylmethylated products, proceeding with complete retention of configuration in the first case.

THE SILYL-CUPRATION AND STANNYL-CUPRATION OF ALLENES

The stoichiometric silyl-cupration of allene 7, followed directly by treating the intermediate cuprate with a proton, with a range of carbon electrophiles, and with chlorine gives the vinylsilanes 8-13.Alternatively, when iodine is the electrophile, the product is the vinyl iodide 16.This can then be metallated and treated with a proton or a range of carbon electrophiles to give the allylsilanes 18-21.More-substituted allenes also undergo silyl-cupration followed by protonation, phenylallenes giving vinylsilanes, and alkylallenes giving, on the whole, allylsilanes.Stoichiometric stannyl-cupration of allenes takes place, with similar but less reliable regiocontrol to that of the corresponding silyl-cupration.

ELECTROPHILIC REACTION OF ALLYLTRIMETHYLSILANE WITH NITRILES IN THE PRESENCE OF BORON TRICHLORIDE

Allyltrimethylsilane reacted with various nitriles in the presence of boron trichloride, giving after hydrolysis β,γ-unsaturated ketones in high yields.The reactions of substituted allyltrimethylsilanes and intramolecular reaction of allylic trimethylsilane with nitrile were also studied.