By Michele Aresta and Rudi van Eldik (Eds.)
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9O2 provides the highest DMC yield, at 443 K, which correlates with the higher number of acid and basic sites. 5PMo12O40 are active at temperatures as low as 313–333 K under an atmospheric pressure of CO2 (114). Unfortunately, DMC selectivity does not exceed 23%; DME, formaldehyde, and methyl formate are the other products analyzed. A much higher selectivity close to 85% is reached also at atmospheric pressure under UV irradiation of a Cu-doped Ni-V mixed oxide supported on silica. At 403 K, DMC yield is practically twice that without irradiation (115).
Synthesis of cyclic carbonates from propargyl alcohols Cyclic carbonates have also been synthesized from propargyl alcohol derivatives and CO2 as the starting materials. 28) is based on the cyclization of the propargyl carbonate moiety (HC^CCH2OCO2–) into the corresponding a-alkylidene cyclic carbonate in the presence of a suitable catalyst such as ruthenium (268), cobalt (269), palladium (270, 271), copper (272–277), or phosphine (278–280). 55 Synthesis of Organic Carbonates R2 R1 R2 R2 + CO2 R1 cat.
4 kJ molÀ1). This means that the use of carbon dioxide requires the development of an “ad hoc” catalyst able to activate the process. 1 Linear (A) and cyclic (B) organic carbonates. Synthesis of Organic Carbonates 27 2. MARKET AND PRODUCTION Organic carbonates find utilization in several fields as intermediates for pharmaceuticals, (2) agrochemicals, engineered polymers, (3) as lubricants (the first commercial application of dialkyl carbonates as lubricant was in 1987 when AgipPetroli introduced dialkyl carbonates as a new synthetic base fluid in the formulated semisynthetic, gasoline engine oil components) (4), electrolytes for lithium-ion batteries (5, 6), solvents for coating (7), varnish (8), and chemical reactions (1, 9–11).
CO Chemistry by Michele Aresta and Rudi van Eldik (Eds.)