Use of carbon dioxide in industrial organic syntheses

Abstract

Although carbon dioxide is important as an abundant carbonaceous raw material, so far, its utilization in chemical processes has been rather limited. This review covers the reactions of CO, employed in industry, such as the production of urea, the Kolbe-Schmitt reaction, the synthesis of cyclic organic carbonates and the use of COz in methanol synthesis. Interesting recent developments in COZ chemistry, such as the reactions catalyzed by transition metals, are also described. Apart from the synthesis of polymers and hydrocarbons, the production of oxygen-containing substances appears to be very profitable and attractive for future industrial applications. Not only can derivatives of formic and carbonic acids be produced but also longer-chain carboxylic acids and their derivatives by reactions of carbon dioxide with hydrocarbons such as alkynes, alkenes and I ,3-dienes.

Synthesis of cyclic carbonates catalysed by aluminium heteroscorpionate complexes

“…Bimetallic complex 21 was found to be a highly active catalyst, giving complete conversion of epoxide 1c into styrene carbonate 2c under the reaction conditions (Table 1, entry 13). Comparison of the results obtained for complexes 10-12 and 21 (Table 1, entries [2][3][4]13) shows the added benefit of using a bimetallic complex. However, in this case the nature of the group attached to the enamine nitrogen atom was critical as changing this from a large alkyl group to a flat aryl group (complex 22) resulted in a significant decrease in catalytic activity of the resulting complex (Table 1, entry 14), to a level below that seen for monometallic complexes 10-12.…”

“…Obtained as a colourless liquid (163.7 mg, 85%). δ H (CDCl 3 ) 1.00 (3H, t J 7.1 Hz, CH 3 ), 1.6-1.9 (2H, m, CH 2 ), 4.05 (1H, dd J 6.3, 5.3 2,22.7,24.5,29.2,29.2,29.4,31.9,34.0,69.5,77.1,. Obtained as a white solid (276.8 mg, 84%).…”

The teraton challenge. A review of fixation and transformation of carbon dioxide

“…Heterogeneous catalysts of nickel, ruthenium and rhodium have proven to provide the best results for the Sabatier process. 112 Hydrogen needed for these reactions has to be produced, which is, as mentioned above, highly energy demanding. The fact is that none of these transformations are favorable for CO 2 mitigation unless the energy needed comes from renewable energy.…”

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

“…Carbon dioxide represents a renewable C1 building block for organic synthesis and industrial applications as an alternative to other common feedstocks which are based on natural gas, petroleum oil, or coal [1]. Apart from the advantages associated with the nontoxicity and abundance of CO 2 , its utilization further enables the reduction in its atmospheric content, which contributes significantly to the greenhouse effect.…”