13735-81-4

Basic information

• Product Name: 1-PHENYL-1-TRIMETHYLSILOXYETHYLENE
• Synonyms: 1-(Trimethylsilyloxy)-1-phenylethene;1-Phenyl-1-trimethylsiloxyethene;1-Phenylvinyl trimethylsilyl ether;(1-Phenylethenyloxy)trimethylsilane;[(1-Phenylethenyl)oxy]trimethylsilane;1-Phenyl-1-(trimethylsilyloxy)ethene;Trimethyl(α-methylenebenzyloxy)silane;Trimethyl[(1-phenylethenyl)oxy]silane
• CAS NO: 13735-81-4
• Molecular Formula: C11H16OSi
• Molecular Weight: 192.33
• EINECS: 237-308-1
• Product Categories: Building Blocks;Chemical Synthesis;Enol Ethers;Organic Building Blocks;Oxygen Compounds;Monoalkoxysilanes;Si (Classes of Silicon Compounds);Silicon Compounds (for Synthesis);Si-O Compounds;Synthetic Organic Chemistry
• Mol File: 13735-81-4.mol
• Article Data: 136

Chemical Properties

• Melting Point: 122-123 °C
• Boiling Point: 88-89 °C11 mm Hg(lit.)
• Flash Point: 174 °F
• Appearance: /
• Density: 0.938 g/mL at 25 °C(lit.)
• Vapor Density: >1 (vs air)
• Vapor Pressure: 0.239mmHg at 25°C
• Refractive Index: n20/D 1.502(lit.)
• Storage Temp.: −20°C
• Water Solubility: Reacts with water.
• Sensitive: Moisture Sensitive
• BRN: 1306914
• CAS DataBase Reference: 1-PHENYL-1-TRIMETHYLSILOXYETHYLENE(CAS DataBase Reference)
• NIST Chemistry Reference: 1-PHENYL-1-TRIMETHYLSILOXYETHYLENE(13735-81-4)
• EPA Substance Registry System: 1-PHENYL-1-TRIMETHYLSILOXYETHYLENE(13735-81-4)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• F: 10-21
• TSCA: No
• Hazardous Substances Data: 13735-81-4(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 13735-81-4 differently. You can refer to the following data:
1. 1-Phenyl-1-trimethylsiloxyethylene has been used in the synthesis of β-amino ketones in water via Mannich-type reaction and cis-2,6-disubstituted dihydropyrans via three-component, one-pot cascade reaction. It is also used as chemical additives and intermediates.
2. 1-Phenyl-1-trimethylsiloxyethylene has been used in the synthesis of:β-amino ketones in water via Mannich-type reactioncis-2,6-disubstituted dihydropyrans via three-component, one-pot cascade reaction

General Description

1-Phenyl-1-trimethylsiloxyethylene is a styrene type silyl enol ether, reacts with formaldehyde and 2,4-pentanedione to yield the corresponding dihydropyran. It also undergoes Mukaiyama aldol reaction with aldehydes in water in the presence of amphiphilic calix[6]arene derivatives as surfactants.

InChI:InChI=1/C11H16OSi/c1-10(12-13(2,3)4)11-8-6-5-7-9-11/h5-9H,1H2,2-4H3

Upstream product

• 4071-88-9 trimethylsilanyl-acetic acid ethyl ester 
• 98-86-2 acetophenone 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 1206-46-8 trimethyl(pentafluorophenyl)silane 
• 105623-17-4 (Z)-N-(2-methylpropylidene)benzylamine N-oxide 
• 16029-98-4 trimethylsilyl iodide 
• 532-27-4 1-chloroacetophenone 
• 75-77-4 chloro-trimethyl-silane 
• 43112-38-5 3-(trimethylsilyl)-2-oxazolidinone 
• 70-11-1 α-bromoacetophenone 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 934-72-5 Methyl p-tolyl sulfoxide 
• 5908-41-8 benzoyltrimethylsilane 
• 17903-72-9 N-Trimethylsilyl-N'-p-tolyl-diazen 

Downstream Products

• 451-40-1 phenyl benzyl ketone 
• 59137-68-7 1-phenyl-2-(tetrahydrofuran-2-yl)ethan-1-one 
• 89374-88-9 2-Methyl-1-butenyl Phenyl Ketone 
• 495-41-0 1-phenylbut-2-en-1-one 
• 89318-26-3 4-(2-Oxo-2-phenyl-ethyl)-4H-pyridine-1-carboxylic acid 2,2,2-trichloro-ethyl ester 
• 89318-27-4 2-(2-Oxo-2-phenyl-ethyl)-2H-pyridine-1-carboxylic acid 2,2,2-trichloro-ethyl ester 
• 717-21-5 3-(furan-1-yl)-1-phenyl-prop-2-en-1-one 
• 141054-35-5 1-(2-furyl)-3-phenyl-3-<(trimethylsilyl)oxy>propan-1-one 
• 145624-52-8 (R)-3-(2-furyl)-3-hydroxy-1-phenylpropan-1-one 
• 1144528-47-1 (S)-3-(2-furyl)-3-hydroxy-1-phenylpropan-1-one 
• 97039-68-4 1-phenyl-3-ethynyl-7-methyloctane-1,5-dione 
• 97039-70-8 1-(1-adamantyl)-3-ethynyl-5-phenylpentane-1,5-dione 
• 105426-60-6 1-phenyl-3-ethynyl-5-cyclobutylpentane-1,5-dione 
• 135419-07-7 (E)-2-tert-Butyl-5-oxo-5-phenyl-3-trimethylsilanyloxy-pent-2-enenitrile 

Relevant articles and documents

The Chemistry of O-Silylated Ketene Acetals; A Mild and Facile Preparation of Trimethylsilyl Enol Ethers and of Cyclic O,O-, O,S-, and S,S-Acetals from Enolizable Carbonyl Compounds

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Reactions of 1,1-dimethyl-2,2-bis(trimethylsilyl)hydrazine with alcohols and ketones: A new route to trimethylsilyl enol ethers [2]

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A Convenient Regioselective Synthesis of Mannich Bases

A new, convenient regioselective process for aminomethylation of ketones is reported, involving the in situ formation of silyl enol ethers and iminium salts.

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C?O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non-Rubottom Oxidation

Malonyl peroxides act both as oxidants and reagents for C?O coupling in reactions with methyl and silyl enol ethers. In the proposed conditions, the oxidative C?O coupling of malonyl peroxides with enol ethers selectively proceeds, bypassing the traditional Rubottom hydroxylation of enol ethers by peroxides. It was observed that the oxidative [5+2] cycloaddition of malonyl peroxides and enol ethers is the key stage of the discovered process. Oxidative C?O coupling of silyl enol ethers leads to the formation of α-acyloxyketones with a free carboxylic acid group. A specially developed preparative one-pot procedure transforms ketones via silyl enol ethers formation and the following coupling into α-acyloxyketones with yields 35–88%. The acid-catalyzed coupling with methyl enol ethers gives remarkable products while retaining the easily oxidizable enol fragment. Furthermore, these molecules contain a free carboxylic acid group, thus these nontrivial products contain two usually incompatible acid and enol ether groups. (Figure presented.).

Palladium Catalyzed Reaction of Trimethylsilyltributyltin with α-Halo Ketones. Preparation of Enol Silyl Ethers

The reaction of trimethylsilyltributyltin with α-halo ketone in the presence of a catalytic amount of palladium chloride plus twice molar amounts of trimethyl phosphite gave enol silyl ethers in good yields.

THE MANNICH REACTION OF CARBONYL COMPOUNDS VIA SILYL ENOL ETHERS BY A COMBINATION OF CHLOROIODOMETHANE AND N,N,N',N'-TETRAMETHYLDIAMINOMETHANE

The Mannich dimethylaminomethylation of carbonyl compounds is conveniently carried out via trimethylsilyl enol ethers by a combination of chloroiodomethane and N,N,N',N'-tetramethyldiaminomethane in DMSO or DMF as the solvent at ambient temperature.

Regioselective one-pot synthesis of 2,3-diaryl-2H-1-benzopyrans via Br?nsted acid-catalyzed [4+2] cycloaddition of salicylaldehydes with diarylacetylenes

A regioselective one-pot synthesis of 2,3-diaryl-2H-1-benzopyrans from easily available various diarylacetylenes and salicylaldehydes via Br?nsted acid-catalyzed [4+2] cycloaddition has been developed. High regioselectivity was observed in the reaction to afford 2-(electron-rich aryl)-3-(electron-poor aryl)-2H-1-benzopyrans in good yields. The present reaction provides versatile access to functionalized 2,3-diaryl-2H-1-benzopyrans, which would be useful as key intermediates for the synthesis of biologically and photochemically active molecules.

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Latent Nucleophilic Carbenes

Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which the lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, and trifluoromethane proceeded via insertion into sp, sp2, and spCH bonds. The carbene also reacted with the functional groups, such as CHO, COR, and CN at double or triple bonds, displaying high mobility of the trimethylsilyl group. The obtained silylformamidine can be considered as a latent nucleophilic carbene. It can be prepared in bulk quantities, stored, and used when the need arises. Calculation results predict similar behavior for some other silylated formamidines and related compounds.

Boron Trifluoride-Mediated Cycloaddition of 3-Bromotetrazine and Silyl Enol Ethers: Synthesis of 3-Bromo-pyridazines

Pyridazines are important scaffolds for medicinal chemistry or crop protection agents, yet the selective preparation of 3-bromo-pyridazines with high regiocontrol remains difficult. We achieved the Lewis acid-mediated inverse electron demand Diels-Alder reaction between 3-monosubstituted s-tetrazine and silyl enol ethers and obtained functionalized pyridazines. In the case of 1-monosubstituted silyl enol ethers, exclusive regioselectivity was observed. Downstream functionalization of the resulting 3-bromo-pyridazines was demonstrated utilizing several cross-coupling protocols to synthesize 3,4-disubstituted pyridazines with excellent control over the substitution pattern.

β-Diazocarbonyl Compounds: Synthesis and their Rh(II)-Catalyzed 1,3 C?H Insertions

Herein, we describe the first electrophilic diazomethylation of ketone silyl enol ethers with diazomethyl-substituted hypervalent iodine reagents that gives access to unusual β-diazocarbonyl compounds. The potential of this unexplored class of diazo compounds for the development of new reactions was demonstrated by the discovery of a rare Rh-catalyzed intramolecular 1,3 C?H carbene insertion that led to complex cyclopropanes with excellent stereocontrol.