STUDIES IN SILICO-ORGANIC COMPOUNDS. (II). THE REACTIONS OF SILICOORTHOESTERS WITH CERTAIN ACID ANHYDRIDES<sup>1</sup>

Post, Howard W.; Hofrichter, Charles H.

doi:10.1021/jo01210a012

Cited by 19 publications

(5 citation statements)

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“…Formation of the siloxane bond through condensation between acetoxysilane and alkoxysilane has been known since 1940. [64,65] The by-product is ethyl acetate in which R = Et. However, this condensation reaction is not frequently reported.…”

Section: Synthesis Of 3d Siloxane Polymers Using Lewis Acid Catalystsmentioning

confidence: 99%

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

Wakabayashi

Kuroda

2013

ChemPlusChem

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Siloxane formation reactions of both the nonhydrolytic sol–gel process and Piers–Rubinsztajn reaction can be integrated as Lewis acid promoted siloxane syntheses without involving silanol groups. The former was developed in the field of inorganic materials chemistry and the latter was initiated in polymer chemistry. We have realized both reactions are quite similar, in terms of 1) the nonhydrolytic reaction, 2) the use of alkoxysilanes, 3) the group‐exchange reactions competing with the siloxane formation, and 4) the proposed reaction mechanisms. This Minireview focuses on the above two reactions. The evolution of both reactions should realize a more sophisticated molecular design of siloxane compounds, which surely contributes to the development of advanced functional materials.

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Section: Synthesis Of 3d Siloxane Polymers Using Lewis Acid Catalystsmentioning

confidence: 99%

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

Wakabayashi

Kuroda

2013

ChemPlusChem

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“…The latter reaction was reported in 1940 to proceed at an elevated temperature to yield a high-molar-mass product, [32] however, no structural analysis was given. We describe a detailed structural characterization, i.e., the degree of branching and the extent of internal crosslinking via MALDI-ToF MS (matrix-assisted laser-desorption ionization time-of-flight mass spectrometry) and NMR spectroscopy, and analysis of the molar mass distribution via size exclusion chromatography (SEC), viscosity, and light scattering experiments.…”

Section: Introductionmentioning

confidence: 99%

Hyperbranched Polyalkoxysiloxanes via AB₃‐Type Monomers

Jaumann

Rebrov

Kazakova

et al. 2003

Macro Chemistry & Physics

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We have synthesized polyethoxysiloxanes starting from the AB3‐type monomers triethoxysilanol and acetoxytriethoxysilane. The polymers are liquid and soluble in organic solvents. 29Si NMR spectroscopy and MALDI‐ToF mass spectrometry analyses show that the polymers have a hyperbranched structure with additional internal cyclization. 29Si NMR spectroscopy indicates that the polymer synthesized from acetoxytriethoxysilane is less branched than the polymer synthesized from triethoxysilanol. Analysis of the molar mass and mass distribution of the polymers via size exclusion chromatography (calibrated via MALDI‐ToF MS and viscosimetry) yields a molar mass of Mn ≈ 2 kg · mol−1 and Mw ≈ 8 kg · mol−1 for polymers synthesized from triethoxysilanol. The molar mass of the polymers synthesized from acetoxytriethoxysilane can be controlled by variation of the polymerization time in the range of Mn ≈ 1.8–12 kg · mol−1 and Mw ≈ 2.1–2 200 kg · mol−1. Photograph of a vial containing polyethoxysiloxane obtained from triethoxysilanol and a schematic drawing of the proposed molecular structure of the polymer.magnified imagePhotograph of a vial containing polyethoxysiloxane obtained from triethoxysilanol and a schematic drawing of the proposed molecular structure of the polymer.

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“…Si(OC2HB)4 + (CH3C0)20 CH3COOSi(OC2H6)3 + CH3COOC2H6 Acetic anhydride also reacts with trimethyl-y3-chloroethoxysilane (7) and with triethylethoxysilane (5). Ethyltriethoxysilane has, more recently, been found to react as well (8).…”

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confidence: 99%

STUDIES IN SILICO-ORGANIC COMPOUNDS. XIII. ADDITIONAL CHEMICAL PROPERTIES OF TRIALKOXYSILANES^{1, 2}

Reilly¹,

Post²

1951

J. Org. Chem.

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STUDIES IN SILICO-ORGANIC COMPOUNDS. (II). THE REACTIONS OF SILICOORTHOESTERS WITH CERTAIN ACID ANHYDRIDES¹

Abstract: The purpose of this investigation was to study the acylation of silicoorthoesters, including the alkyl orthosilicates.As far back as 1866, Friedel and Crafts reported that ethyl orthosilicate reacted with acetic anhydride (1), to give triethoxysilicomethyl acetate

Cited by 19 publications

References 4 publications

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

Hyperbranched Polyalkoxysiloxanes via AB₃‐Type Monomers

STUDIES IN SILICO-ORGANIC COMPOUNDS. XIII. ADDITIONAL CHEMICAL PROPERTIES OF TRIALKOXYSILANES^{1, 2}

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STUDIES IN SILICO-ORGANIC COMPOUNDS. (II). THE REACTIONS OF SILICOORTHOESTERS WITH CERTAIN ACID ANHYDRIDES1

Abstract: The purpose of this investigation was to study the acylation of silicoorthoesters, including the alkyl orthosilicates.As far back as 1866, Friedel and Crafts reported that ethyl orthosilicate reacted with acetic anhydride (1), to give triethoxysilicomethyl acetate

Cited by 19 publications

References 4 publications

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

Hyperbranched Polyalkoxysiloxanes via AB3‐Type Monomers

STUDIES IN SILICO-ORGANIC COMPOUNDS. XIII. ADDITIONAL CHEMICAL PROPERTIES OF TRIALKOXYSILANES1, 2

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STUDIES IN SILICO-ORGANIC COMPOUNDS. (II). THE REACTIONS OF SILICOORTHOESTERS WITH CERTAIN ACID ANHYDRIDES¹

Hyperbranched Polyalkoxysiloxanes via AB₃‐Type Monomers

STUDIES IN SILICO-ORGANIC COMPOUNDS. XIII. ADDITIONAL CHEMICAL PROPERTIES OF TRIALKOXYSILANES^{1, 2}