Steric Hindrance in Highly-Substituted Organosilicon Compounds. Iii. The Preparation and Properties of Some Triarylsilyl Ethers

Gilman, Henry; Smart, Graham

doi:10.1021/jo01368a025

Cited by 26 publications

(4 citation statements)

References 14 publications

(24 reference statements)

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“…Methoxysilane groups (3Si1OCH 3 ) are hydrolyzed into silanol groups (3Si1OH) by moisture in the presence of some acid or base catalyst. This silanol group undergoes self-condensation reactions to produce siloxane bonds 1,2) , or reacts with alcohol (R1C1OH) to form siloxy compounds through alkoxy exchange reaction [3][4][5] .…”

Section: Introductionmentioning

confidence: 99%

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Function and performance of silicone copolymers, 3. Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites

Hou

Kuo²

1999

Macromol. Chem. Phys.

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SUMMARY: A novel monomer that contains two secondary crosslinking sites (an active methoxysilane group and an epoxide group) was synthesized from an alkoxy exchange reaction between 2-hydroxyethyl methacrylate (2-HEMA) and 3-glycidoxypropyltrimethoxysilane (Z-6040). This monomer (MSA) was copolymerized with methyl methacrylate using 2,29-azoisobutyronitrile (AIBN) as an initiator, and its chemical structure was characterized by 1 H NMR. The temperature for 10% weight loss (T 10 ) determined from thermogravimetric analysis (TGA) decreases with increasing MSA content, while the residual weight at 800 8C (R 800 ) increases with increasing in MSA content. In addition, this monomer can be self-cured via reacting with the moisture in air in the presence of a tin catalyst. The curing reaction is very fast in the first 24 h and almost reaches a plateau value after 7 d. Finally, MSA was blended with trimethylolpropane triacrylate (TMPTA) to form a new UV-coating polymer whose critical surface tension is in the range of 24 -28 dyn/cm.

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Section: Introductionmentioning

confidence: 99%

“…This silanol group undergoes self-condensation reactions to produce siloxane bonds 1,2) , or reacts with alcohol (R1C1OH) to form siloxy compounds through alkoxy exchange reaction [3][4][5] . Tripropyl titanate (TPT) 6,7) is a very effective catalyst to accelerate the alkoxy exchange reactions without formation of the siloxane bonds.…”

Section: Introductionmentioning

confidence: 99%

Function and performance of silicone copolymers, 3. Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites

Hou

Kuo²

1999

Macromol. Chem. Phys.

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“…Silyl carboxylates (acyloxysilane) were first studied by Yur'ev and Belyakova in 1960 [14]. Previous reports suggested that the reaction of nucleophiles with silyl carboxylates followed two possible pathways, where alcohol attacks silicon or the carbonyl group in Scheme 1 [14][15][16][17][18]. Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

“…Organic cations, for example, imidazolium, ammonium, phosphonium, and pyridinium ions, can be combined with a variety of anions, for example, BF4 − , triflates, halides, (CF3SO2)2N − , or PF6 − which give rise to Scheme 1. Possible pathways for O-nucleophile attack (O-acetylation) [14][15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Mild and Efficient Tunable Brønsted Acidic Ionic Liquid Catalyzed O-Acetylation and O-Trimethylsilylation with Trimethylsilyl Acetate (TMSOAc) and Hexamethyldisilazane (HMDS)

et al. 2021

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This report discloses a mild and efficient O-acetylation using easily accessible TMSOAc as a novel acetyl reagent and O-trimethylsilylation using HMDS for various alcohols catalyzed by tunable Brønsted acidic ionic liquids (TBAILs). Imidazolium-based TBAILs were prepared by a two-step atom-economic reaction and acidities measured by using UV-visible spectroscopy. Both protections for alcohols were accomplished at room temperature with good to excellent yields, while the products and TBAILs were separated by simple work-up for O-silylation and column chromatography for O-acetylation. Notably, with the simple post-process, TBAILs catalyst in this solvent free method easily recovered and recycled several times without significant degradation.

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In Situ Generation of ArCu from CuF₂ Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient

delPozo

Casares

Espinet

2016

Chemistry A European J

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A bimetallic system Pd/CuF2, catalytic in Pd and stoichiometric in Cu, is very efficient and selective for the coupling of fairly hindered aryl silanes with aryl, anisyl, phenylaldehide, or pyridyl iodides of conventional size. The reaction involves the activation of the silane by Cu II followed by disproportionation and transmetalation from the Cu I (aryl) to Pd II , on which coupling takes place. The Cu III formed in the disproportionation is reduced to Cu I (aryl) by the aryl silane in excess, so that the CuF2 used is fully converted into Cu I (aryl) and used in the coupling. Moreover, no extra source of fluoride is needed. Interesting size selectivity towards coupling is found in competitive reactions of hindered aryl silanes. Easily accessible [PdCl2(IDM)(AsPh3)] is by far the best catalyst, and the isolated products are esentially free of As or Pd (< 1 ppm). The mechanistic aspects of the process are experimentally examined and discussed.

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Steric Hindrance in Highly-Substituted Organosilicon Compounds. Iii. The Preparation and Properties of Some Triarylsilyl Ethers

Cited by 26 publications

References 14 publications

Function and performance of silicone copolymers, 3. Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites

Function and performance of silicone copolymers, 3. Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites

Mild and Efficient Tunable Brønsted Acidic Ionic Liquid Catalyzed O-Acetylation and O-Trimethylsilylation with Trimethylsilyl Acetate (TMSOAc) and Hexamethyldisilazane (HMDS)

In Situ Generation of ArCu from CuF₂ Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient

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Steric Hindrance in Highly-Substituted Organosilicon Compounds. Iii. The Preparation and Properties of Some Triarylsilyl Ethers

Cited by 26 publications

References 14 publications

Function and performance of silicone copolymers, 3. Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites

Function and performance of silicone copolymers, 3. Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites

Mild and Efficient Tunable Brønsted Acidic Ionic Liquid Catalyzed O-Acetylation and O-Trimethylsilylation with Trimethylsilyl Acetate (TMSOAc) and Hexamethyldisilazane (HMDS)

In Situ Generation of ArCu from CuF2 Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient

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In Situ Generation of ArCu from CuF₂ Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient