Carbonate ester

A carbonate ester (organic carbonate or organocarbonate) is an ester of carbonic acid. This functional group consists of a carbonyl group flanked by two alkoxy groups. The general structure of these carbonates is R1O(C=O)OR2 and they are related to esters R1O(C=O)R, ethers R1OR2 and also to the inorganic carbonates.

Chemical structure of the carbonate ester group

Monomers of polycarbonate (e.g. Lexan) are linked by carbonate groups. These polycarbonates are used in eyeglass lenses, compact discs, and bulletproof glass. Small carbonate esters like dimethyl carbonate, ethylene carbonate, propylene carbonate are used as solvents, dimethyl carbonate is also a mild methylating agent.

Structures
Structure of dicarbonate (PhOC(O)OC6H4)2CMe2 derived from bis(phenol-A) and two equivalents of phenol.[1]

Carbonate esters have planar OC(OC)2 cores, which confers rigidity. The unique O=C bond is short (1.173 Å in the depicted example), while the C-O bonds are more ether-like (the bond distances of 1.326 Å for the example depicted).[1]

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(propylene carbonate) and poly(bisphenol A carbonate) (Lexan).

Preparation

Organic carbonates are not prepared from inorganic carbonate salts. Two main routes to carbonate esters are practiced: the reaction of an alcohol (or phenol) with phosgene (phosgenation), and the reaction of an alcohol with carbon monoxide and an oxidizer (oxidative carbonylation). Other carbonate esters may subsequently be prepared by transesterification.[2][3]

In principle carbonate esters can be prepared by direct condensation of methanol and carbon dioxide. The reaction is however thermodynamically unfavorable.[4] A selective membrane can be used to separate the water from the reaction mixture and increase the yield.[5][6][7][8]

  • Dimethyl carbonate, a representative acyclic carbonate ester
  • Diphenyl carbonate, another representative acyclic carbonate ester
  • Ethylene carbonate, a cyclic carbonate ester
  • Trimethylene carbonate, another cyclic carbonate ester
  • Poly(propylene carbonate)
  • Poly(bisphenol A carbonate), a commercially important plastic (Lexan)

Phosgenation

Alcohols react with phosgene to yield carbonate esters according to the following reaction:

2 ROH + COCl2 → RO(CO)OR + 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 (e.g. pyridine) are required to neutralize the hydrogen chloride that is cogenerated.[2][3] 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:[3]

PhOH + COCl2 → PhO(CO)Cl + HCl
2 PhO(CO)Cl → PhO(CO)OPh + COCl2

Overall reaction is:

2 PhOH + COCl2 → PhO(CO)OPh + 2 HCl

Oxidative carbonylation

Oxidative carbonylation is an alternative to phosgenation. The advantage is the avoidance of phosgene. Using copper catalysts, dimethylcarbonate is prepared in this way:[3][9]

2 MeOH + CO + 1/2 O2 → MeO(CO)OMe + H2O

Diphenyl carbonate is also prepared similarly, but using palladium catalysts. The Pd-catalyzed process requires a cocatalyst to reconvert the Pd(0) to Pd(II). Manganese(III) acetylacetonate has been used commercially.[10]

Reaction of carbon dioxide with epoxides

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.[11] Industrially, ethylene and propylene oxides readily react with carbon dioxide to give ethylene and propylene carbonates (with an appropriate catalyst).[2][3] For example:

C2H4O + CO2 → C2H4O2CO

Catalysts for this reaction have been reviewed, as have non-epoxide routes to these cyclic carbonates.[11]

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.[2][3]

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 (the latter from the reaction between dimethyl carbonate and methyl carbamate). This process is not an economical.[12]

Uses

Organic carbonates are used as solvents.[13] 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.[14]

In Grignard reaction carbonate esters might be used to create tertiary alcohols.

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.

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References
  1. Perez, Serge; Scaringe, Raymond P. (1987). "Crystalline features of 4,4'-isopropylidenediphenylbis(phenyl carbonate) and conformational analysis of the polycarbonate of 2,2-bis(4-hydroxyphenyl)propane". Macromolecules. 20 (1): 68–77. Bibcode:1987MaMol..20...68P. doi:10.1021/ma00167a014.
  2. Shaikh, Abbas-Alli G.; Swaminathan Sivaram (1996). "Organic Carbonates". Chemical Reviews. 96 (3): 951–976. doi:10.1021/cr950067i. PMID 11848777.
  3. Buysch, Hans-Josef (2012). "Carbonic Esters". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_197.
  4. Zhang, Zhi-Fang (2011). "Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol over CexZr1-xO2and [EMIM]Br/Ce0.5Zr0.5O2". Industrial & Engineering Chemistry Research. 50 (4): 1981–1988. doi:10.1021/ie102017j.
  5. Li, Chuan-Feng (2003). "Study on application of membrane reactor in direct synthesis DMC from CO2 and CH3OH over Cu–KF/MgSiO catalyst". Catalysis Today. 82 (1–4): 83–90. doi:10.1016/S0920-5861(03)00205-0.
  6. http://alexandria.tue.nl/extra1/afstversl/st/vermerris2005.pdf
  7. Aouissi, Ahmed; Al-Othman, Zeid Abdullah; Al-Amro, Amro (2010). "Gas-Phase Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide over Co1.5PW12O40 Keggin-Type Heteropolyanion". International Journal of Molecular Sciences. 11 (4): 1343–1351. doi:10.3390/ijms11041343. PMC 2871119. PMID 20480023.
  8. Bian, Jun (2009). "Highly effective synthesis of dimethyl carbonate from methanol and carbon dioxide using a novel copper–nickel/graphite bimetallic nanocomposite catalyst". Chemical Engineering Journal. 147 (2–3): 287–296. doi:10.1016/j.cej.2008.11.006.
  9. Shaikh, Abbas-Alli G.; Sivaram, Swaminathan (1996-01-01). "Organic Carbonates". Chemical Reviews. 96 (3): 951–976. doi:10.1021/cr950067i. ISSN 0009-2665. PMID 11848777.
  10. Grigorii L. Soloveichik1 (2016). "Oxidative Carbonylation: Diphenyl Carbonate". In Shannon S. Stahl; Paul L. Alsters (eds.). Liquid Phase Aerobic Oxidation Catalysis: Industrial Applications and Academic Perspectives. Title Liquid Phase Aerobic Oxidation Catalysis: Industrial Applications and Academic Perspectives: Industrial Applications and Academic Perspectives. Wiley-VCH. pp. 189–208. doi:10.1002/9783527690121.ch12. ISBN 9783527337811.
  11. North, Michael; Pasquale, Riccardo; Young, Carl (2010). "Synthesis of cyclic carbonates from epoxides and CO2". Green Chem. 12 (9): 1514. doi:10.1039/c0gc00065e.
  12. "Archived copy" (PDF). Archived from the original (PDF) on 2013-10-05. Retrieved 2013-10-04.CS1 maint: archived copy as title (link)
  13. Schäffner, B.; Schäffner, F.; Verevkin, S. P.; Börner, A. (2010). "Organic Carbonates as Solvents in Synthesis and Catalysis". Chemical Reviews. 110 (8): 4554–4581. doi:10.1021/cr900393d. PMID 20345182.
  14. Sibiya, Mike Sbonelo. Catalytic transformation of propylene carbonate into dimethyl carbonate and propylene glycol
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