31469-15-5

Basic information

• Product Name: DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL
• Synonyms: MTDA;DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL;METHYL TRIMETHYLSILYL DIMETHYLKETENE ACETAL;[(1-METHOXY-2-METHYL-1-PROPENYL)OXY]TRIMETHYLSILANE;1-METHOXY-2-METHYL-1-(TRIMETHYLSILOXY)PROPENE;1-METHOXY-1-(TRIMETHYLSILOXY)-2-METHYL-1-PROPENE;1-METHOXY-1-TRIMETHYLSILOXY-2-METHYLPROPENE;1-Methoxy-1-trimethylsiloxy-2-methyl-1-propene~Methyl trimethylsilyl dimethylketene acetal~MTDA
• CAS NO: 31469-15-5
• Molecular Formula: C₈H₁₈O₂Si
• Molecular Weight: 174.31
• EINECS: -0
• Product Categories: Monoalkoxysilanes;Si (Classes of Silicon Compounds);Silicon Compounds (for Synthesis);Si-O Compounds;Synthetic Organic Chemistry;Vinylsilanes, Allylsilanes
• Mol File: 31469-15-5.mol
• Article Data: 27

Chemical Properties

• Boiling Point: 35 °C15 mm Hg(lit.)
• Flash Point: 58 °F
• Appearance: /
• Density: 0.858 g/mL at 25 °C(lit.)
• Vapor Pressure: 8.76mmHg at 25°C
• Refractive Index: n20/D 1.415(lit.)
• Storage Temp.: 2-8°C
• Solubility: freely sol organic solvents.
• Water Solubility: Hydrolyzes in water.
• Sensitive: Moisture Sensitive
• Stability: Moisture and Acid Sensitive
• BRN: 1362893
• CAS DataBase Reference: DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL(CAS DataBase Reference)
• NIST Chemistry Reference: DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL(31469-15-5)
• EPA Substance Registry System: DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL(31469-15-5)

Safety Data

• Hazard Codes: Xi
• Statements: 10-36/37/38
• Safety Statements: 16-26-36
• RIDADR: UN 3271 3/PG 3
• WGK Germany: 3
• F: 10-21
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 31469-15-5(Hazardous Substances Data)

Usage

Description

DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL, also known as 1-Methoxy-2-methyl-1-(trimethylsiloxy)propene, is a versatile reagent and catalyst in organic synthesis. It is a clear colorless liquid with a boiling point of 35 °C at 15 mmHg and a density of 0.858 g/cm3.

Uses

Used in Organic Synthesis:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as a functional equivalent of enolate of methyl isobutyrate in various electrophilic reactions, such as alkylation, aldol reaction, and Michael reaction. It serves as an ester enolate surrogate, enabling the formation of carbon-carbon bonds and the synthesis of complex organic molecules.
Used in Polymer Synthesis:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as an initiator for group-transfer polymerization of acrylates. It facilitates the controlled polymerization process, leading to the formation of polymers with specific properties and structures.
Used in Conjugate Addition and Aldol Reactions:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as a versatile reagent in conjugate addition and aldol reactions, enabling the formation of carbonyl compounds and the synthesis of various organic compounds.
Used in the Synthesis of Chiral β-Lactams:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used in the synthesis of chiral β-lactams by reacting with (S)-alkylidene(1-arylethyl)amines in the presence of titanium tetrachloride. It acts as a catalyst or initiator in this reaction, enabling the formation of biologically active compounds.
Used in Nitroarylation, Oxidation, Dimerization, and Cycloadditions:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as a reagent in various other organic reactions, such as nitroarylation, oxidation, dimerization, and cycloadditions. It contributes to the formation of diverse organic compounds and the development of novel synthetic routes.

Preparation

The title compound is a prototypical ketene silyl acetal (KSA) that can been prepared by either of the two most commonly employed methods: (a) deprotonation of the α-hydrogen of an ester followed by silylation (1),16 and (b) metal-catalyzed hydrosilylation of α,β-unsaturated esters(2).

Purification Methods

Add Et2O, wash with cold H2O, dry (Na2SO4), filter, evaporate Et2O, and distil the oily residue in a vacuum. [Ainsworth et al. J Organometal Chem 46 59 1972.]

InChI:InChI=1/C8H18O2Si/c1-7(2)8(9-3)10-11(4,5)6/h1-6H3

Upstream product

• 547-63-7 Methyl isobutyrate 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 75-77-4 chloro-trimethyl-silane 
• 187809-34-3 C₅H₁₀O₂ 
• 993-07-7 trimethylsilan 
• 80-62-6 methacrylic acid methyl ester 
• 67-64-1 acetone 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 22421-97-2 methyl 2-chloroisobutyrate 
• 23426-63-3 2-bromo-2-methylpropionic acid methyl ester 
• 6065-54-9 dimethyl dimethylmalonate 

Downstream Products

• 79388-25-3 methyl 2,2-dimethyl-3-(phenylamino)-3-(2-pyridyl)propanoate 
• 86000-11-5 methyl 2,2-dimethyl-3-(benzylamino)propionate 
• 92268-71-8 2-Methyl-2-(1-trimethylsilanyloxy-cyclohexyl)-propionic acid methyl ester 
• 101499-38-1 dimethyl 2,2-dimethyl-3-phenylpentane-1,5-dioate 
• 109323-51-5 6-Chloro-cyclohepta-1,3-diene 
• 109323-55-9 methyl-2-(2,6-cycloheptadienyl)-2-methyl-propanoate 
• 59115-08-1 methyl 2-methyl-2-(4-nitrophenyl)propanoate 
• 97522-00-4 2-{4-[4-(1-Methoxycarbonyl-1-methyl-ethyl)-phenyl-NNO-azoxy]-phenyl}-2-methyl-propionic acid methyl ester 
• 92671-32-4 2-(5-Chloro-2-nitro-phenyl)-2-methyl-propionic acid methyl ester 
• 97522-27-5 methyl α,α-dimethyl-6-bromo-5-chloro-2-nitro-2,4-cyclohexadiene-1-acetate 
• 145473-82-1 2,2-Dimethyl-5-oxo-3-phenyl-hexanoic acid methyl ester 
• 144741-42-4 methyl 3-cyclohexyl-2,2-dimethyl-3-(trimethylsiloxy)propionate 
• 86000-14-8 methyl 2,2-dimethyl-3-(N-phenylamino)propionate 
• 126415-71-2 methyl 2,2-dimethyl-3-phenyl-3-(N-tert-butylamino)propanoate 

Relevant articles and documents

Addition of ketene silyl acetals to the triplet excited state of C60 via photoinduced electron transfer leading to the fullereneacetates

The photochemical carbon-carbon bond formation of C60 with ketene silyl acetals is described to give a new way for fullerene functionalization chemistry. The photoaddition of ketene silyl acetals to C60 occurs efficiently under irradiation of the visible light in benzene as well as benzonitrile to yield the fullereneacetates. The comparison of the observed rate constants determined from the dependence of the quantum yields on the concentrations of ketene silyl acetals as well as the quenching of triplet excited state of C60 by ketene silyl acetals with those predicted for the electron transfer processes indicates that the photoaddition proceeds via photoinduced electron transfer from ketene silyl acetals to the triplet excited state of C60. The negative shift in the one-electron reduction potentials by the adduct formation of C60 is examined by the cyclic voltammetry measurements. The factors to control the formation of mono- and bisadducts of C60 are clarified based on the rates of photoinduced electron transfer from ketene silyl acetals to the triplet excited states of C60 and the adducts.

Chiral Modification of the Tetrakis(pentafluorophenyl)borate Anion with Myrtanyl Groups

The synthesis and characterization of chiral [B(C6F5)4]– derivatives bearing a myrtanyl group instead of a fluoro substituent in the para position are described. These new chiral borates were isolated as their bench-stable lithium, sodium, and cesium salts. The corresponding trityl salts were prepared and tested as catalysts in representative counteranion-directed Diels–Alder reactions and Mukaiyama aldol additions but no enantioselectivity was obtained. Preformation of a chalcone-derived silylcarboxonium ion with the chiral borate as counteranion did not lead to any asymmetric induction in a reaction with cyclohexa-1,3-diene.

Silanediol versus chlorosilanol: Hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

Biphenyl-2,2’-bisfenchyloxydichlorosilane (7, BIFOXSiCl2) is synthesized and employed as precursor for the new silanols biphenyl-2,2’-bisfenchyloxychlorosilanol (8, BIFOXSiCl(OH)) and biphenyl-2,2’-bisfenchyloxysilanediol (9, BIFOXSi(OH)2

The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with α,β-Unsaturated Methyl Esters

α,β-Unsaturated esters are readily available but challenging substrates to activate in asymmetric catalysis. We now describe an efficient, general, and highly enantioselective Mukaiyama–Michael reaction of silyl ketene acetals with α,β-unsaturated methyl esters that is catalyzed by a silylium imidodiphosphorimidate (IDPi) Lewis acid.