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Synthesis of Organic Carbonates - ResearchGate

N2 - Bifunctional ZnII porphyrin catalysts bearing tributylammonium bromide groups at the meta positions of the meso-phenyl groups showed high catalytic activity for the synthesis of cyclic carbonates from epoxides and CO2. Herein, several substituents with different electronic properties were introduced at the para positions. Introduction of electron-donating groups decreased the catalytic activity, whereas the introduction of electron-withdrawing groups increased the activity. The substituents modulated the Lewis acidity of the zinc center, which was confirmed by binding constant experiments. The bifunctional catalyst bearing cyano groups showed the highest catalytic activity with a turnover frequency of up to 42 000 h−1.

AB - Bifunctional ZnII porphyrin catalysts bearing tributylammonium bromide groups at the meta positions of the meso-phenyl groups showed high catalytic activity for the synthesis of cyclic carbonates from epoxides and CO2. Herein, several substituents with different electronic properties were introduced at the para positions. Introduction of electron-donating groups decreased the catalytic activity, whereas the introduction of electron-withdrawing groups increased the activity. The substituents modulated the Lewis acidity of the zinc center, which was confirmed by binding constant experiments. The bifunctional catalyst bearing cyano groups showed the highest catalytic activity with a turnover frequency of up to 42 000 h−1.

Synthesis of Organic Carbonates

Synthesis of Carbonate Compounds Using Carbon Dioxide …

Direct synthesis of organic carbonates from the ..

The goal of this project is to develop efficient ceria catalysts for recycling two categories of waste chemicals: CO2 from fossil fuel combustion, and bio-derived alcohols such as methanol (wood alcohol) and glycerol (a byproduct of biodiesel refining). Conventionally, organic carbonates are produced indirectly using toxic and corrosive chemicals such as phosgene. This was necessitated because the direct conversion of dimethyl carbonate (DMC) from methanol and CO2, as shown above, is only product favored as a low temperature process while the activation barrier for this reaction is very high on existing catalysts. We are currently measuring the activation barrier for this reaction on ceria, a known catalyst for this process, as well as on modified ceria surfaces. We are using information gained from reaction kinetics from our modified ceria surfaces to improve our understanding of the reaction mechanisms, while using computational studies of reaction mechanisms to inform our surface modification experiments. Current heterogeneous catalysts used for this reaction provide conversion efficiency of only around 1%. Improvements of catalytic conversion to around 10% is believed to be enough to make this reaction pathway industrially viable for the production of carbonates from carbon dioxide and waste alcohols.

Bifunctional ZnII porphyrin catalysts bearing tributylammonium bromide groups at the meta positions of the meso-phenyl groups showed high catalytic activity for the synthesis of cyclic carbonates from epoxides and CO2. Herein, several substituents with different electronic properties were introduced at the para positions. Introduction of electron-donating groups decreased the catalytic activity, whereas the introduction of electron-withdrawing groups increased the activity. The substituents modulated the Lewis acidity of the zinc center, which was confirmed by binding constant experiments. The bifunctional catalyst bearing cyano groups showed the highest catalytic activity with a turnover frequency of up to 42 000 h−1.

Synthesis of cyclic carbonates with carbon dioxide and ..

Conversion of Carbon Dioxide into Organic Carbonates for Polymer Synthesis

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metal-free synthesis of organic cyclic carbonates from ..


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