Carbonate ester

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Chemical structure of the carbonate ester group.

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 and ethers R1OR2 and also to the inorganic carbonates.

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, and ethylene and propylene carbonate are used as solvents. Dimethyl carbonate is a mild methylating agent as well.

The chemistry of carbonate esters has been reviewed.[1]

Types[edit]

Carbonate esters can be divided into three categories by their structures. The first and general case is the dialkyl or diaryl carbonate that comprises a carbonate group with two R substituents. The simplest members of this class include dimethyl carbonate and diphenyl carbonate:

Instead of terminal alkyl or aryl R-groups, two carbonate groups can be linked by an aliphatic or aromatic bifunctional group. For example, poly(propylene carbonate) and poly(bisphenol A carbonate) (Lexan):

Alternatively, the carbonate groups can be linked by a 2- or 3-carbon bridge, such as ethylene carbonate and trimethylene carbonate; substituents, e.g. CH3 for propylene carbonate are possible too:

Oleochemical carbonates[edit]

Carbonates (esters of carbonic acid, H2CO3) are well known to chemists as they represent an important class of organic compounds and among them oleochemical carbonates have interesting characteristics which make them candidates for many industrial applications.

The most common carbonates have the following structure: RO—CO—OR. R is a linear chain with 8 to 18 carbon atoms, saturated or with one double bond (dioleyl carbonate), or a branched chain (ethylhexyl, butyloctyl, or hexyldecyl).

They are miscible in organic solvents but insoluble in water. Unsaturation or branching on the alkyl chain lowers their melting point.[2] The condensation of phosgene (ClCOCl) with an alcohol appears the most commonly used procedure to synthesize oleochemical carbonates.

The polar nature of the carbonate moiety enables it to adhere strongly to metal surfaces. Thus, they are used as lubricant components which have a protective property for metal corrosion. Some C8 to C18 carbonates have been exploited in personal-care products (sunscreen, cosmetics), dioctyl carbonate being also used as emollient or solvent in UV-filter solutions. Extraction of metal ions (gold, silver, platinum) is improved by the use of the chelating properties of oleochemical carbonates when mixed with the metal-containing aqueous phase. Future developments will ensure a growing interest in these molecules.

Preparation[edit]

There are two main industrial ways of preparing carbonate esters: 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.[1][3]

Phosgenation[edit]

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

2 ROH + COCl2 → ROCO2R + 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.[1][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 → PhOCOCl + HCl
2 PhOCOCl → PhOCO2Ph + COCl2

Oxidative carbonylation[edit]

With an appropriate catalyst, alcohols can react with carbon monoxide and an oxidant (e.g. oxygen gas):[1][3]

2 CH3OH + CO + [O] → CH3OCO2CH3 + H2O

Reaction of carbon dioxide with epoxides[edit]

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.[4] Industrially, ethylene and propylene oxides readily react with carbon dioxide to give ethylene and propylene carbonates (with an appropriate catalyst).[1][3] For example:

C2H4O + CO2 → C2H4O2CO

Catalysts for this reaction have been reviewed, as have non-epoxide routes to these cyclic carbonates.[4]

Carbonate transesterification[edit]

Once the initial carbonate has been produced, it may 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.[1][3]

Experimental routes[edit]

From carbon dioxide and alcohols[edit]

In principle carbonate esters can be prepared the direct condensation of methanol and carbon dioxide.[5][6] The reaction is thermodynamically unfavorable, due to the buildup of water byproduct.[7] A selective membrane can be used to separate the water from the reaction mixture and increase the yield.[8][9]

From urea with alcohols[edit]

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). The yield of dimethyl carbonate is only 30%, so unless the byproducts are recycled or commercially realized this is not an economic method.[10]

Organic synthesis[edit]

Laboratory methods for the synthesis of carbonate ester in the laboratory are from the corresponding diols, or by reaction of an epoxide with carbon dioxide catalysed by a zinc halide.[11]

Use as solvents[edit]

A large number of organic carbonates are used as solvents.[12] 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.[13]

Use in batteries[edit]

Organic carbonates are used as a solvent in lithium batteries; due to their high polarity they can dissolve lithium salts. The problem of high viscosity is circumvented by using carbonate mixtures for example mixtures of dimethyl carbonate, diethyl carbonate and dimethoxy ethane.

References[edit]

  1. ^ a b c d e f Shaikh, Abbas-Alli G.; Swaminathan Sivaram (1996). "Organic Carbonates". Chemical Reviews. 96 (3): 951–976. doi:10.1021/cr950067i. PMID 11848777. 
  2. ^ Kenar JA, Inform 2004, 15, 580
  3. ^ a b c d e f Hans-Josef Buysch (2005), "Carbonic Esters", Ullmann's Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, doi:10.1002/14356007.a05_197 
  4. ^ a b North, Michael; Pasquale, Riccardo; Young, Carl (2010). "Synthesis of cyclic carbonates from epoxides and CO2". Green Chem. 12 (9): 1514. doi:10.1039/c0gc00065e. 
  5. ^ http://www.mdpi.com/1422-0067/11/4/1343
  6. ^ "Highly effective synthesis of dimethyl carbonate from methanol and carbon dioxide using a novel copper–nickel/graphite bimetallic nanocomposite catalyst". Chemical Engineering Journal. 147: 287–296. doi:10.1016/j.cej.2008.11.006. 
  7. ^ http://pubs.acs.org/doi/full/10.1021/ie102017j
  8. ^ "Study on application of membrane reactor in direct synthesis DMC from CO2 and CH3OH over Cu–KF/MgSiO catalyst". Catalysis Today. 82: 83–90. doi:10.1016/S0920-5861(03)00205-0. 
  9. ^ http://alexandria.tue.nl/extra1/afstversl/st/vermerris2005.pdf
  10. ^ http://ir.sxicc.ac.cn/bitstream/0/1655/1/7596-7599.pdf
  11. ^ Zinc(II)-pyridine-2-carboxylate / 1-methyl-imidazole: a binary catalytic system for in the synthesis of cyclic carbonates from carbon dioxide and epoxides Arkivoc 2007 (iii) 151-163 (EA-2262DP) Thomas A. Zevaco, Annette Janssen, and Eckhard Dinjus Link
  12. ^ 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. 
  13. ^ Sibiya, Mike Sbonelo. Catalytic transformation of propylene carbonate into dimethyl carbonate and propylene glycol