2916-76-9

Usage

Uses

Used in Organic Synthesis:
METHYL (TRIMETHYLSILYL)ACETATE is used as a key compound in organic synthesis for its ability to undergo specific reactions that yield desired products. It is particularly useful in the formation of steroid 17β-side chain methyl acrylates, which are essential components in the pharmaceutical industry.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, METHYL (TRIMETHYLSILYL)ACETATE is used as an intermediate in the synthesis of various drugs. Its ability to participate in reactions such as Peterson olefination, which primarily yields Z-isomers, makes it a valuable asset in the development of new medications.
Used in Chemical Research:
METHYL (TRIMETHYLSILYL)ACETATE is also employed in chemical research as a reagent for studying the properties and behavior of various organic compounds. Its unique chemical properties allow researchers to explore new reaction pathways and develop innovative synthetic methods.
Overall, METHYL (TRIMETHYLSILYL)ACETATE is a multifaceted compound with applications in organic synthesis, pharmaceuticals, and chemical research, making it an essential tool in the development of new drugs and the advancement of scientific knowledge.

Purification Methods

Methyl trimethylsilylacetate [2916-76-9] M 146.3, b 65-68o/50mm, d 4 0.89. Dissolve it in Et2O, shaken with 1M HCl, wash with H2O, aqueous saturated NaHCO3, H2O again, and dry it (a precipitate may be formed in the NaHCO3 solution and should be drawn off and discarded). The solvent is distilled off, and the residue is fractionated through a good column. IR (CHCl3) max 1728cm
1 . [Fessenden & Fessenden J Org Chem 32 3535 1967, Matsuda et al. J Org Chem 45 237 1980, Beilstein 4 III 1855, 4 IV 3974 for Et ester.]

InChI:InChI=1/C6H14O2Si/c1-8-6(7)5-9(2,3)4/h5H2,1-4H3

Upstream product

• 67-56-1 methanol 
• 4071-85-6 trimetylsilylketene 
• 16029-98-4 trimethylsilyl iodide 
• 75-77-4 chloro-trimethyl-silane 
• 79-20-9 acetic acid methyl ester 
• 922-69-0 1,1-dimethoxyethylene 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 96-32-2 bromoacetic acid methyl ester 
• 155402-41-8 dimethoxyboryl trimethylsilyl ketene 
• 94363-48-1 (dibromoboryl)(trimethylsily)ketene 
• 6990-27-8 bromobis(dimethylamino)borane 
• 32278-79-8 (ethoxyethynyl)trimethylgermane 
• 36850-80-3 [(1-methoxyvinyl)oxy]trimethylsilane 
• 1000-62-0 trimethylsilylethoxyacetylene 

Downstream Products

• 74080-58-3 methyl 3α-hydroxy-2β-(benzyloxymethyl)-5-(carbomethoxymethylene)cyclopentane-1α-acetate 3-tetrahydropyran-2-yl ether 
• 82259-28-7 [(4S,5R)-4-Benzyloxymethyl-2-oxo-5-(tetrahydro-pyran-2-yloxy)-hexahydro-cyclopenta[b]furan-6a-yl]-trimethylsilanyl-acetic acid methyl ester 
• 118533-11-2 benzyl 2-deoxy-3,4-O-isopropylidene-2C<(E)-methoxycarbonylmethylene>-β-L-erythro-pentopyranoside 
• 118533-09-8 benzyl 2-deoxy-3,4-O-isopropylidene-2C<(Z)-methoxycarbonylmethylene>-β-L-erythro-pentopyranoside 
• 97522-09-3 methyl 2-(2-chloro-6-nitrophenyl)acetate 
• 177956-75-1 Methyl (Z)-2-(carboxyethyl)cyclohexylideneacetate 
• 6717-72-2 17β-((Trimethysilyl)oxy)estr-4-en-3-one 
• 139042-23-2 17β-((Trimethylsilyl)oxy)estr-1-en-3-one 
• 72049-87-7 ((S)-3-Oxo-cyclohexyl)-trimethylsilanyl-acetic acid methyl ester 
• 135253-30-4 Methyl <(R),(Z)-2-(t-butyldiphenylsiloxy)methyl-1-cyclobutylidene>acetate 
• 463-51-4 Ketene 
• 1825-61-2 Trimethylmethoxysilane 
• 3219-63-4 (trimethylsilyl)methanol 
• 128059-56-3 methyl 3-phenyl-2-(trimethylsilyl)propanoate 

Relevant academic research and scientific papers

Novel tocopherol compounds XI. Synthesis, bromination and oxidation reactions of 3-(5-tocopheryl)propionic acid

3-(5-Tocopheryl)propionic acid (γ-tocopherol-5-propionic acid, 13) has been synthesized by a multi-step sequence involving the hetero-Diels-Alder reaction between O-methyl-C,O-bis-(trimethylsilyl)ketene acetal (10) and the ortho-quinone methide of α-tocopherol (5) as the key step. The title compound is the first 5a-substituted tocopherol that shows an oxidation behavior largely similar to α-tocopherol.

Synthesis of a heterocyclic amine and acid receptor

The synthesis of a molecule able to bind both with an amine and a carboxylic acid is described. This new host consists in a pyrroloisoquinoline structure possessing a side ann with an acetamidopyridine moiety. The pyrroloisoquinoline part was obtained after improvement of the previously published route involving regioselective reduction of appropriate 3-arylalkylaminosuccinimides followed by ring closure using iminium chemistry. The tricyclic structure was then functionalized by cross-coupling reaction under Pd0 catalysis of its triflate derivative with the trimethylsilyl ketene acetal of methyl acetate. The so-obtained ester was then reacted with 2-amino-4,6-dimethylpyridine leading, to the targeted host. The association constants of this latter compound with some carboxylic acids and amines were determined by H NMR titration. NOESY experiments and molecular modeling calculations were performed in order to precise the actual host-guest interactions. (C) 2000 Elsevier Science Ltd.

Dialkylamino- and alkoxytrialkylstannanes as reagent for synthesis of organoboryl (trialkylsilyl) ketenes

Dialkylamino- and alkoxytrialkylstannanes have been studied as N- and O-nucleophilic reagents in substitution reactions at the B-Br bond.The previously unknown bis(dialkylamino)- and dialkoxyboryl trialkylsilyl ketenes were synthesized.Some peculiarities of the reactivity of these compounds have been studied. - Key words: dialkylaminotrialkylstannane, alkoxytrialkylstannane, synthesis; borylsilyl ketene, methanolysis, aminolysis.

Preparation and reactivity of persistent and stable silyl-substituted bisketenes

2,3-Bis(trimethylsilyl)-1,3-butadiene-1,4-dione (1) is formed as the only product on thermolysis of 3,4-bis(trimethylsilyl)cyclobut-3-ene-1,2-dione (2), and the rate of ring opening of 2 is comparable to that of substituted cyclobutenes and cyclobutenones. Photolysis of 2 also forms 1, which reacts with ethanol in a stepwise fashion with faster addition of one ethanol molecule to give an isolable monoketene 18, which reacts in a further slower step to give succinate diesters, accompanied by desilylation. 2,3-Bis(tert-butyldimethylsilyl)-1,3-butadiene-1,4-dione (3), prepared analogously to 1, similarly adds one molecule of methanol to give the isolable monoketene 20, which then reacts to give dimethyl 2,3-bis(tert-butyldimethylsilyl)succinate (21) as the major product. The reaction of 1 with H2O is faster than with alcohols and forms (E)- and (Z)-2,3-bis(trimethylsilyl)succinic anhydrides (13) as the first observed products. The reactivity of 1 with different nucleophilic solvents is correlated by the Winstein-Grunwald equation and increases with both solvent ionizing power and solvent nucleophilicity.

Z-ISOMERS OF STEROID 17β-SIDE CHAIN METHYL ACRYLATES

THP-Protected androstan-3-ol 17β-carboxaldehydes I - III with 3β,5-ene, 3β,5α, and 3α,5α respective arrangements, were transformed into corresponding methyl Z- and E-acrylates IVa - IXa.Peterson olefination by methyl trimethylsilylacetate gave mainly Z-isomers, whereas under conditions of Wittig-Horner reaction with trimethyl phosphonoacetate E-isomers were obtained in more stereoselective manner.THP-Ethers of methyl Z-acrylates IVa, VIa, and VIIIa were deprotected and from resulting 3-hydroxy derivatives IVb, VIb, and VIIIb the hemisuccinates IVd, VId, and VIIId and β-D-glucopyranosides IVf, VIf, and VIIIf were prepared.

The Structure and Function of Oestrogens. IX Synthesis of the trans Isomer of 5,5,10b-Trimethyl-4b,5,6,10b,11,12-hexahydrochrysene-2,8-diol

Alkylation of ketene methyl trimethylsilyl acetal (10) with 1ξ-acetoxy-6-methoxy-2-(p-methoxyphenyl)-2-methyl-1,2,3,4-tetrahydronaphthalene (9) in the presence of zinc iodide gave 84percent of methyl (1'RS,2'RS)-2-ethanoate (11a).Cyclization of the derived acid (11b) with methanesulfonic acid gave 89percent of 2,8-dimethoxy-10b-methyl-cis-4b,10b,11,12-tetrahydrochrysen-6(5H)-one (12a), Clemmensen reduction of which afforded 52percent of 2,8-dimethoxy-4b-methyl-cis-4b,5,6,10b,11,12-hexahydrochrysene (12b).Oxidation of (12b) with dichlorodicyanobenzoquinone gave 70percent of the conjugated enone (4), which upon hydrogenation over 10percent palladium/charcoal gave a 5:1 ratio of 2,8-dimethoxy-10b-methyl-trans-4b,10b,11,12-tetrahydrochrysen-6(5H)-one (14) and the cis isomer (12a).Exhaustive methylation of the trans ketone (14) yielded 49percent of 2,8-dimethoxy-5,5,10b-trimethyl-trans-4b,10b,11,12-tetrahydrochrysen-6(5H)-one (16), which upon Clemmensen reduction followed by O-demethylation afforded 5,5,10b-trimethyl-trans-4b,5,6,10b,11,12-hexahydrochrysene-2,8-diol (2).

Reactions of Trialkylsilyl Trifluoromethanesulfonates, II. - Synthesis of O-Alkyl-O-(trialkylsilyl)ketene Acetals and 2-(Trialkylsilyl)carboxylates

Alkyl carboxylates 2 are silylated by trialkylsilyl triflates 1 in the presence of triethylamine (3) to yield ketene acetals 4.In reactions of the esters 6 mixtures of ketene acetals 7 and at the α-carbon silylated esters 8 are obtained.Ethanoic acid esters and lactones are doubly silylated to give the products 11, 12, and 15, respectively.Under suitable conditions silylation of the esters 10 gives rise to the 2-trimethylsilylethanoic acid esters 13.The thermodynamically more stable products are obtained.Product distributions depend on the structure of the esters and the silylating agents 1.