Carbonate esters have planar OC2 cores, which confers rigidity. The unique O=C bond is short, while the C-O bonds are more ether-like. Carbonate esters can be divided into three structural classes: acyclic, cyclic, and polymeric. The first and general case is the acyclic carbonate group. Organic substituents can be identical or not. Both aliphatic or aromatic substituents are known, they are called dialkyl or diaryl carbonates, respectively. The simplest members of these classes are dimethyl carbonate and diphenyl carbonate. Alternatively, the carbonate groups can be linked by a 2- or 3-carbon bridge, forming cyclic compounds such as ethylene carbonate and trimethylene carbonate. The bridging compound can also have substituents, e.g. CH3 for propylene carbonate. Instead of terminal alkyl or aryl groups, two carbonate groups can be linked by an aliphatic or aromatic bifunctional group. A third family of carbonates are the polymers, such as poly and poly.
Preparation
Organic carbonates are not prepared from inorganic carbonate salts. Two main routes to carbonate esters are practiced: the reaction of an alcohol with phosgene, and the reaction of an alcohol with carbon monoxide and an oxidizer. Other carbonate esters may subsequently be prepared by transesterification. In principle carbonate esters can be prepared by direct condensation of methanol and carbon dioxide. The reaction is however thermodynamically unfavorable. A selective membrane can be used to separate the water from the reaction mixture and increase the yield.
Phosgenation
Alcohols react with phosgene to yield carbonate esters according to the following reaction: 2 ROH + COCl2 → ROOR + 2 HCl Phenols react similarly. Polycarbonate derived from bisphenol A is produced in this manner. This process is high yielding. However, toxic phosgene is used, and stoichiometric quantities of base are required to neutralize the hydrogen chloride that is cogenerated. Chloroformate esters are intermediates in this process. Rather than reacting with additional alcohol, they may disproportionate to give the desired carbonate diesters and one equivalent of phosgene: Overall reaction is:
Oxidative carbonylation is an alternative to phosgenation. The advantage is the avoidance of phosgene. Using copper catalysts, dimethylcarbonate is prepared in this way: Diphenyl carbonate is also prepared similarly, but using palladium catalysts. The Pd-catalyzed process requires a cocatalyst to reconvert the Pd to Pd. Manganese acetylacetonate has been used commercially.
The reaction of carbon dioxide with epoxides is a general route to the preparation of cyclic 5-membered carbonates. Annual production of cyclic carbonates was estimated at 100,000 tonnes per year in 2010. Industrially, ethylene and propylene oxides readily react with carbon dioxide to give ethylene and propylene carbonates. For example: Catalysts for this reaction have been reviewed, as have non-epoxide routes to these cyclic carbonates.
Carbonate transesterification
Carbonate esters can be converted to other carbonates by transesterification. A more nucleophilic alcohol will displace a less nucleophilic alcohol. In other words, aliphatic alcohols will displace phenols from aryl carbonates. If the departing alcohol is more volatile, the equilibrium may be driven by distilling that off.
From urea with alcohols
Dimethyl carbonate can be made from the reaction of methanol with urea. Ammonia that is produced can be recycled. Effectively ammonia serves as a catalyst for the synthesis of dimethyl carbonate. The byproducts are methyl- and N-methylcarbamate. This process is not an economical.
Uses
Organic carbonates are used as solvents. They are classified as polar solvents and have a wide liquid temperature range. One example is propylene carbonate with melting point −55 °C and boiling point 240 °C. Other advantages are low ecotoxicity and good biodegradability. Many industrial production pathways for carbonates are not green because they rely on phosgene or propylene oxide. Organic carbonates are used as a solvent in lithium batteries. Due to their high polarity, they dissolve lithium salts. The problem of high viscosity is circumvented by using mixtures for example of dimethyl carbonate, diethyl carbonate, and dimethoxyethane. Cyclic carbonates are susceptible to polymerization.
