- Organic carbonate synthesis from CO2 and alcohol over CeO 2 with 2-cyanopyridine: Scope and mechanistic studies
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The combination system of CeO2-catalyzed carboxylation and 2-cyanopyridine hydration (CeO2 + 2-cyanopyridine system) is effective for the direct synthesis of organic carbonates from CO2 and alcohols. This catalyst system can be applied to various alcohols to afford the corresponding carbonates in high alcohol-based yields. The hydration of 2-cyanopyridine over CeO2 rapidly proceeds under the low concentration of water, which can remove the water from the reaction media. Since the reaction is limited by the chemical equilibrium, the removal of water remarkably shifts the chemical equilibrium to the carbonate side, leading to high carbonate yields. In addition, 2-picolinamide that is produced by hydration of 2-cyanopyridine forms an intramolecular hydrogen bonding between H atom of the amide group and N atom of the pyridine ring, which weakens the adsorption of 2-picolinamide on CeO2 by reduction of the acidity. The reaction mechanism of DMC formation in CeO2 + 2-cyanopyridine system is also proposed.
- Honda, Masayoshi,Tamura, Masazumi,Nakagawa, Yoshinao,Nakao, Kenji,Suzuki, Kimihito,Tomishige, Keiichi
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- Acetals of N,N-dimethylformamides: Ambiphilic behavior in converting carbon dioxide to dialkyl carbonates
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Carbon dioxide is immobilized into dialkyl carbonate using acetals of N,N-dimethylformamide under atmospheric pressure. No special treatment with tailor-made catalysts is needed. Use of dimethyl sulfoxide as a solvent is critical. An ambiphilic mechanism is proposed for the direct synthesis of dialkyl carbonates from acetals and carbon dioxide.
- Takada, Yuki,Matsuoka, Aki,Du, Ya,Naka, Hiroshi,Saito, Susumu
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supporting information
p. 146 - 147
(2013/04/10)
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- Synthesis of carbonates directly from 1 atm CO2 and alcohols using CH2Cl2
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We introduced here a new one-pot, general procedure for the preparation of dialkyl carbonates from alcohols in a straightforward fashion under 1 atm pressure of CO2 using Cs2CO3 and CH 2Cl2 as key reagents.
- Yamazaki, Yusuke,Kakuma, Kasumi,Du, Ya,Saito, Susumu
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experimental part
p. 9675 - 9680
(2011/02/24)
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