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Dimethyl carbonate

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Not to be confused with dimethyl carbate.
Dimethyl carbonate
Dimethyl carbonate
Ball-and-stick model of dimethyl carbonate
Names
Preferred IUPAC name
Dimethyl carbonate
Other names
DMC
Methyl carbonate, di-
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.009.527 Edit this at Wikidata
UNII
  • InChI=1S/C3H6O3/c1-5-3(4)6-2/h1-2H3 checkY
    Key: IEJIGPNLZYLLBP-UHFFFAOYSA-N checkY
  • InChI=1/C3H6O3/c1-5-3(4)6-2/h1-2H3
    Key: IEJIGPNLZYLLBP-UHFFFAOYAC
  • COC(=O)OC
Properties
C3H6O3
Molar mass 90.078 g·mol−1
Appearance colorless liquid
Density 1.069-1.073 g/mL
Melting point 2 to 4 °C (36 to 39 °F; 275 to 277 K)
Boiling point 90 °C (194 °F; 363 K)
13.9 g/100 mL
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Flammable
Flash point 17 °C (63 °F; 290 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Dimethyl carbonate (DMC) is an organic compound with the formula OC(OCH3)2. It is a colourless, flammable liquid. It is classified as a carbonate ester. This compound has found use as a methylating agent and as a co-solvent in lithium-ion batteries.[1] Notably, dimethyl carbonate is a weak methylating agent, and is not considered as a carcinogen.[2] Instead, dimethyl carbonate is often considered to be a green reagent,[3][4] and it is exempt from the restrictions placed on most volatile organic compounds (VOCs) in the United States.[5]

Production

World production in 1997 was estimated at 1000 barrels a day.[6] Production of dimethyl carbonate worldwide is limited to Asia, the Middle East, and Europe.

Dimethyl carbonate is traditionally prepared by the reaction of phosgene and methanol. Methyl chloroformate is produced as an intermediate:

COCl2 + CH3OH → CH3OCOCl + HCl
CH3OCOCl + CH3OH → CH3OCO2CH3 + HCl

This synthesis route has been largely replaced by oxidative carbonylation. In this process, carbon monoxide and an oxidizer provide the equivalent of CO2+:[7][8]

CO + 1/2 O2 + 2 CH3OH → (CH3O)2CO + H2O

It can also be produced industrially by a transesterification of ethylene carbonate or propylene carbonate and methanol, which also affords respectively ethylene glycol or propylene glycol. This route is complicated by the methanol-DMC azeotrope, which requires azeotropic distillation or other techniques.[9]

Reactions and potential applications

Methylating agent

Dimethyl carbonate methylates anilines, carboxylic acids, and phenols, albeit usually slowly.[10][11][12] Sometimes these reactions require the use of an autoclave.

Methylation of phenylacetic acid by dimethyl carbonate promoted by DBU

Dimethyl carbonate's main benefit over other methylating reagents such as iodomethane and dimethyl sulfate is its low toxicity. Additionally, it is biodegradable.[7] Unfortunately, it is a relatively weak methylating agent compared to these traditional reagents.

Solvent

In the US, dimethyl carbonate was exempted under the definition of volatile organic compounds (VOCs) by the U.S. EPA in 2009.[13] Due to its classification as VOC exempt, dimethyl carbonate has grown in popularity and applications as a replacement for methyl ethyl ketone (MEK) and parachlorobenzotrifluoride, as well as tert-butyl acetate until it too was exempted.[14] Dimethyl carbonate has an ester- or alcohol-like odor, which is more favorable to users than most hydrocarbon solvents it replaces. Dimethyl carbonate has an evaporation rate of 3.22 (butyl acetate = 1.0), which slightly slower than MEK (3.8) and ethyl acetate (4.1), and faster than toluene (2.0) and isopropanol (1.7). Dimethyl carbonate has solubility profile similar to common glycol ethers, meaning dimethyl carbonate can dissolve most common coating resins except perhaps rubber based resins. Hildebrand solubility parameter is 20.3 MPa and Hansen solubility parameters are: dispersion = 15.5, polar = 3.9, H bonding = 9.7.[15] Dimethyl carbonate is partially soluble in water up to 13%, however it is hydrolyzed in water-based systems over time to methanol and CO2 unless properly buffered. Dimethyl carbonate can freeze at same temperatures as water, it can be thawed out with no loss of properties to itself or coatings based on dimethyl carbonate.

Intermediate in polycarbonate synthesis

A large captive use of dimethyl carbonate is for the production of diphenyl carbonate through transesterification with phenol. Diphenyl carbonate is a widely used raw material for the synthesis of bisphenol-A-polycarbonate in a melt polycondensation process,[16] the resulting product being recyclable by reversing the process and transesterifying the polycarbonate with phenol to yield diphenyl carbonate and bisphenol A.[17]

Alternative fuel additive

There is also interest in using this compound as a fuel oxygenate additive.[6]

In lithium-ion and lithium-metal batteries

Similar to ethylene carbonate, dimethyl carbonate forms an electronically-insulating Li+-conducting film at negative electrode potentials. However, the film in dry DMC solutions is not as effective in passivating the negative electrode as the film in wet solutions.[18] For this reason dimethyl carbonate is rarely used in lithium batteries without a co-solvent.[19]

Safety

DMC is a flammable liquid with a flash point of 17 °C (63 °F), which limits its use in consumer and indoor applications. DMC is still safer than acetone, methyl acetate and methyl ethyl ketone from a flammability point of view. The National Center for Sustainable Transportation recommends limiting exposure by inhalation to less than 100 ppm over an 8-hour work day, which is similar to that of a number of common industrial solvents (toluene, methyl ethyl ketone).[20] Workers should wear protective organic vapor respirators when using DMC indoors or in other conditions where concentrations exceed the REL. DMC is metabolized by the body to methanol and carbon dioxide, so accidental ingestion should be treated in the same manner as methanol poisoning.[citation needed]

See also

References

  1. ^ Köntje, M.; Memm, M.; Axmann, P.; Wohlfahrt-Mehrens, M. (December 2014). "Substituted transition metal phospho olivines LiMM′PO4 (M = Mn, M′ = Fe, Co, Mg): Optimisation routes for LiMnPO4". Progress in Solid State Chemistry. 42 (4): 106–117. doi:10.1016/j.progsolidstchem.2014.04.005.
  2. ^ https://www.fsc.go.jp/fsciis/attachedFile/download?retrievalId=kya20180111146&fileId=202[full citation needed]
  3. ^ Kreutzberger, Charles B. (2001). "Chloroformates and Carbonates". Kirk-Othmer Encyclopedia of Chemical Technology. New York: John Wiley. doi:10.1002/0471238961.0301180204011312.a01.pub2. ISBN 9780471238966.
  4. ^ Seo, Dongseok (16 June 2021). "Toxicity assessment of dimethyl carbonate following 28 days repeated inhalation exposure". Environmental Analysis, Health and Toxicology. 36 (2): e2021012-0. doi:10.5620/eaht.2021012. PMC 8421751. PMID 34130377.
  5. ^ "Update: U.S. EPA Exempt Volatile Organic Compounds". American Coatings Association. 2018-01-30. Archived from the original on 2021-02-08. Retrieved 2019-03-20.
  6. ^ a b Pacheco, Michael A.; Marshall, Christopher L. (1997). "Review of Dimethyl Carbonate (DMC) Manufacture and Its Characteristics as a Fuel Additive". Energy & Fuels. 11: 2–29. doi:10.1021/ef9600974.
  7. ^ a b Pietro Tundo & Maurizio Selva (2002). "The Chemistry of Dimethyl Carbonate". Acc. Chem. Res. 35 (9): 706–16. doi:10.1021/ar010076f. PMID 12234200.
  8. ^ Hans-Josef Buysch. "Carbonic Esters". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_197. ISBN 978-3527306732.
  9. ^ Patraşcu, Iulian; Bîldea, Costin S.; Kiss, Anton A. (2022-02-01). "Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea". Frontiers of Chemical Science and Engineering. 16 (2): 316–331. doi:10.1007/s11705-021-2047-9. ISSN 2095-0187.
  10. ^ Lee, Youngmin; Shimizu, Isao (1998). "Convenient O-Methylation of Phenols with Dimethyl Carbonate". Synlett. 1998 (10): 1063–1064. doi:10.1055/s-1998-1893. S2CID 196807122.
  11. ^ Shieh, Wen-Chung; Dell, Stephen; Repič, Oljan (2002). "Nucleophilic Catalysis with 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) for the Esterification of Carboxylic Acids with Dimethyl Carbonate". J. Org. Chem. 67 (7): 2188–2191. doi:10.1021/jo011036s. PMID 11925227.
  12. ^ Shieh, Wen-Chung; Dell, Steven; Repič, Oljan (2001). "1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) and Microwave-Accelerated Green Chemistry in Methylation of Phenols, Indoles, and Benzimidazoles with Dimethyl Carbonate". Organic Letters. 3 (26): 4279–81. doi:10.1021/ol016949n. PMID 11784197.
  13. ^ http://www.epa.gov/ttn/oarpg/t1/fact_sheets/voc_exemp01011309.pdf[dead link‍][full citation needed] Information about the EPA's action on exempting dimethyl carbonate as a VOC and petitioner's background information, public comments and other references are available electronically at http://www.regulations.gov, EPA's electronic public docket and comment system. The docket number for this action is Docket ID No. EPA-HQ-OAR-2006-0948. See http://www.epa.gov/ttn/oarpg/t1pfpr.html[dead link‍][full citation needed] and scroll down to Jan 13, 2009 pdf for the rule.
  14. ^ "Update: U.S. EPA Exempt Volatile Organic Compounds". American Coatings Association. 2018-01-30. Archived from the original on 2019-03-20. Retrieved June 23, 2020.
  15. ^ Kanegsberg, Barbara; Kanegsberg, Edward (2011-04-04). Handbook for Critical Cleaning: Cleaning Agents and Systems, Second Edition (Second ed.). CRC Press. p. 16. ISBN 9781439828281.
  16. ^ Fukuoka, Shinsuke (2012). Non-Phosgene Polycarbonate from CO2 - Industrialization of Green Chemical Process. Nova Science Publishers. ISBN 9781614708773.
  17. ^ Buysch, Hans-Josef (2000). "Carbonic Esters". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_197. ISBN 978-3527306732.
  18. ^ Aurbach, Doron; Ein‐Eli, Yair (June 1995). "The Study of Li‐Graphite Intercalation Processes in Several Electrolyte Systems Using In Situ X‐Ray Diffraction". Journal of the Electrochemical Society. 142 (6): 1746–1752. Bibcode:1995JElS..142.1746A. doi:10.1149/1.2044188.
  19. ^ Aurbach, D.; Markovsky, B.; Shechter, A.; Ein‐Eli, Y.; Cohen, H. (December 1996). "A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate‐Dimethyl Carbonate Mixtures". Journal of the Electrochemical Society. 143 (12): 3809–3820. Bibcode:1996JElS..143.3809A. doi:10.1149/1.1837300.
  20. ^ Durbin, Thomas D.; Karavalakis, Georgios; Johnson, Kent C.; Cocker, David; Yang, Jiacheng; Jiang, Yu; Kumar, Sachin (June 2017). Evaluating the viability of dimethyl carbonate as an alternative fuel for the transportation sector.
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