Dimethyl carbonate

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 more recently as a solvent that is exempt from the restrictions placed on most volatile organic compounds (VOCs) in the US. Dimethyl carbonate is often considered to be a green reagent.

Production

World production in 1997 was estimated at 1000 barrels a day. 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⁺:
:: 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.

Reactions and potential applications

Methylating agent

Dimethyl carbonate methylates

aniline

s, carboxylic acids, and phenols. Sometimes these reactions require the use of an

autoclave

.

:

Dimethyl carbonate's main benefit over other methylating reagents such as

iodomethane

and

dimethyl sulfate

is its low toxicity. Additionally, it is biodegradable. 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. 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. 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. 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, the resulting product being recyclable by reversing the process and transesterifying the polycarbonate with phenol to yield diphenyl carbonate and bisphenol A.

Alternative fuel additive

There is also interest in using this compound as a fuel oxygenate additive.{{cite journal , doi = 10.1021/ef9600974 , journal = Energy & Fuels , title = Review of Dimethyl Carbonate (DMC) Manufacture and Its Characteristics as a Fuel Additive , year = 1997 , last1 = Pacheco , first1 = Michael A. , last2 = Marshall , first2 = Christopher L. , volume = 11 , pages = 2–29

Safety

DMC is a flammable liquid with a flash point of 17 Â°C (63 Â°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. DMC has a recommended exposure limit (REL) limit of 100 ppm by inhalation over an 8-hour work day, which is similar to that of a number of common industrial solvents (

toluene

, methyl ethyl ketone). 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.

See also

* Dimethyl dicarbonate

References

Methylating agents
Carbonate esters
Methyl esters