13950-57-7

Basic information

• Product Name: ETHYL (DIPHENYLMETHYLSILYL)ACETATE
• Synonyms: ETHYL (DIPHENYLMETHYLSILYL)ACETATE;ethyl (methyldiphenylsilyl)acetate;2-(Methyldiphenylsilyl)acetic acid ethyl ester
• CAS NO: 13950-57-7
• Molecular Formula: C₁₇H₂₀O₂Si
• Molecular Weight: 284.425
• Mol File: 13950-57-7.mol
• Article Data: 6

Chemical Properties

• Boiling Point: 352.4°Cat760mmHg
• Flash Point: 142.8°C
• Appearance: /
• Density: 1.04g/cm³
• Vapor Pressure: 3.84E-05mmHg at 25°C
• Refractive Index: 1.541
• CAS DataBase Reference: ETHYL (DIPHENYLMETHYLSILYL)ACETATE(CAS DataBase Reference)
• NIST Chemistry Reference: ETHYL (DIPHENYLMETHYLSILYL)ACETATE(13950-57-7)
• EPA Substance Registry System: ETHYL (DIPHENYLMETHYLSILYL)ACETATE(13950-57-7)

Safety Data

• Hazardous Substances Data: 13950-57-7(Hazardous Substances Data)

Usage

Physical properties

clear to light yellow liquids.

Uses

vinyl 1,1-dication synthetic equivalent in reactions with Grignard reagents; reagent for Peterson synthesis of α,β-un saturated esters.

Preparation

whereas the direct silylation of the lithium enolate of an ester normally results in the formation of a mixture of the α-silyl ester and the corresponding silyl ketene acetal, the same reaction with methyldiphenylchlorosilane gives exclusively the α-methyldiphenylsilyl ester. This direct C-silylation is the best general route to α-silyl esters.

InChI:InChI=1/C17H20O2Si/c1-3-19-17(18)14-20(2,15-10-6-4-7-11-15)16-12-8-5-9-13-16/h4-13H,3,14H2,1-2H3

Upstream product

• 144-79-6 chloromethyldiphenylsilane 
• 141-78-6 ethyl acetate 
• 623-73-4 diazoacetic acid ethyl ester 
• 776-76-1 methyldiphenylsilane 
• 105-36-2 ethyl bromoacetate 

Downstream Products

• 159826-47-8 ethyl 3,7,11-trimethyl-4-(phenylthio)dodeca-2Z,6Z,10-trienoate 
• 20085-73-8 ethyl (2Z,6Z)-3,7,11-trimethyl-2,6,10-dodecatrienoate 
• 20085-72-7 ethyl (2E,6Z)-3,7,11-trimethyl-2,6,10-dodecatrienoate 
• 15790-85-9 (Z)-ethyl 4-methyl-2-pentenoate 
• 15790-86-0 ethyl-4-methyl-2-(E)-penteneoate 
• 2351-97-5 ethyl 4-methylpent-2-enoate 
• 463-51-4 Ketene 
• 1825-59-8 ethoxy(methyl)(diphenyl)silane 

Relevant articles and documents

Lewis Acid-Activated Reactions of Silyl Ketenes for the Preparation of α-Silyl Carbonyl Compounds

Silyl-substituted ketenes are attractive molecular building blocks due to their stability and ease of storage, as opposed to unstable alkyl and aryl ketenes. To better understand the reactivity of silyl ketenes and, in turn, their use in the preparation o

Silver-catalyzed silicon-hydrogen bond functionalization by carbene insertion

The catalytic functionalization of silicon-hydrogen bonds by means of the insertion of carbene units:CHCO2Et from ethyl diazoacetate (EDA) has been achieved using a silver-based catalyst, constituting the first example of this metal to promote this transformation. Competition experiments have revealed that the relative reactivity of substituted silanes depends on the bond dissociation energy of the Si-H bond (tertiary > secondary > primary for ethyl substituted). In the presence of bulky substituents such order reverts to secondary > primary ≈ tertiary (for phenyl substituted). Screening with other diazo compounds has shown that N2C(Ph)CO2Et displays similar reactivity to that of EDA, whereas other N2C(R)CO 2Et (R = Me, CO2Et) gave lower conversions. The Royal Society of Chemistry 2013.

Selective γ-Substitution of α,β-Unsaturated Esters via α-Trimethylsilyl β,γ-Unsaturated Esters

In order to achieve selective γ-substitution of α,β-unsaturated esters, we investigated the directive effect of silicon in the reaction of various electrophiles with α-trimethylsilyl β,γ-unsaturated esters.These esters were prepared by nickel-catalyzed vinylation reactions of the lithium enolate of ethyl α-(trimethylsilyl)acetate.The α-silyl β,γ-unsaturated esters reacted with a variety of electrophiles (aldehydes, ketones, acetals, ketals, acid chlorides, and chloro thioethers) in the presence of Lewis acids (titanium tetrachloride and trimethylsilyl trifluoromethanesulfonate) to give exclusively the γ-substituted product in moderate to good yields.In some cases, the primary substitution products underwent additional conversions under the reaction conditions, such as the cyclization of the δ-hydroxyl or δ-keto enoates to dihydropyrones or pyrones, respectively.These α-silyl β,γ-unsaturated esters are effective reagents for achieving complete γ-selective substitution of α,β-unsaturated ester systems.