- Sustainable Catalytic Synthesis of Diethyl Carbonate
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New sustainable approaches should be developed to overcome equilibrium limitation of dialkyl carbonate synthesis from CO2 and alcohols. Using tetraethyl orthosilicate (TEOS) and CO2 with Zr catalysts, we report the first example of sustainable catalytic synthesis of diethyl carbonate (DEC). The disiloxane byproduct can be reverted to TEOS. Under the same conditions, DEC can be synthesized using a wide range of alkoxysilane substrates by investigating the effects of the number of ethoxy substituent in alkoxysilane substrates, alkyl chain, and unsaturated moiety on the fundamental property of this reaction. Mechanistic insights obtained by kinetic studies, labeling experiments, and spectroscopic investigations reveal that DEC is generated via nucleophilic ethoxylation of a CO2-inserted Zr catalyst and catalyst regeneration by TEOS. The unprecedented transformation offers a new approach toward a cleaner route for DEC synthesis using recyclable alkoxysilane.
- Putro, Wahyu S.,Ikeda, Akira,Shigeyasu, Shinji,Hamura, Satoshi,Matsumoto, Seiji,Lee, Vladimir Ya.,Choi, Jun-Chul,Fukaya, Norihisa
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p. 842 - 846
(2020/12/07)
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- Interaction of organodialkoxysilanolates with carbon dioxide
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A series of organo(alkoxy)disiloxanes was obtained by the reaction of carbon dioxide with sodium alkoxy(organo)silanolates under high pressure as well as by bubbling CO2 through the reaction mixture. It has been suggested that the reaction involves the intermediate formation of carbonate derivatives of sodium alkoxy(organo)silanolates.
- Temnikov,Cherkun,Boldyrev,Zimovets,Kononova,Elmanovich,Gallyamov,Muzafarov
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p. 105161 - 105165
(2016/11/18)
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- PREPARATION OF ALKOXYSILANES BY ETHERIFICATION OF CHLOROSILANES WITH REMOVAL OF HYDROGEN CHLORIDE BY VAPOR OF THE BOILING SOLVENT.
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Etherification of chlorosilanes with alcohols is the usual method of obtaining alkoxysilanes. Hydrogen chloride formed as a byproduct must be removed so as to avoid side reactions and increase the yield. The vapor of boiling solvent was used as an agent to remove hydrogen chloride from the reaction zone. Various solvents were tried and their effect on yield was studied. Removal of hydrogen chloride with the vapor of the boiling solvent during etherification of chlorosilanes makes it possible to obtain alkoxysilanes in 80-90% yield as the result of strong suppression of side reactions.
- Belyakova,Pomerantseva,Efimova,Chernyshev
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p. 426 - 427
(2007/10/02)
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