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

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

methylating agent
compared to these traditional reagents.

Solvent

In the US, dimethyl carbonate was exempted under the definition of

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

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

methanol poisoning.[citation needed
]

See also

References

  1. 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. ISBN 9780471238966
    .
  4. 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. ^
    doi:10.1021/ef9600974
    .
  7. ^
    PMID 12234200
    .
  8. ISBN 978-3527306732
    .
  9. ISSN 2095-0187
    .
  10. S2CID 196807122
    .
  11. PMID 11925227
    .
  12. PMID 11784197
    .
  13. ^ http://www.epa.gov/ttn/oarpg/t1/fact_sheets/voc_exemp01011309.pdf Archived 2021-02-08 at the Wayback Machine[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 Archived 2012-01-07 at the Wayback Machine[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. ISBN 9781439828281
    .
  16. ISBN 9781614708773
    .
  17. ISBN 978-3527306732
    .
  18. doi:10.1149/1.2044188
    .
  19. 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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