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Dimethyl oxalate

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Dimethyl oxalate
Skeletal formula of dimethyl oxalate
Ball-and-stick model of the dimethyl oxalate molecule
Names
IUPAC name
Dimethyl oxalate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.008.231 Edit this at Wikidata
  • InChI=1S/C4H6O4/c1-7-3(5)4(6)8-2/h1-2H3
    Key: LOMVENUNSWAXEN-UHFFFAOYSA-N
  • InChI=1/C4H6O4/c1-7-3(5)4(6)8-2/h1-2H3
    Key: LOMVENUNSWAXEN-UHFFFAOYAF
  • O=C(OC)C(=O)OC
Properties
C4H6O4
Molar mass 118.088 g·mol−1
Appearance White crystals
Melting point 53 to 55 °C (127 to 131 °F; 326 to 328 K)[1]
Boiling point 166 to 167 °C (331 to 333 °F; 439 to 440 K)[1]
-55.7·10−6 cm3/mol
Related compounds
Related compounds
 Diphenyl oxalate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Dimethyl oxalate is a chemical compound from the group of oxalates (specifically, the dimethyl ester of oxalic acid).

Production

Dimethyl oxalate can be obtained by esterification of oxalic acid with methanol using sulfuric acid as a catalyst:

Also the preparation by oxidative carbonylation is possible.[2]

The oxidative carbonylation of methanol forms the C2 block dimethyl oxalate from traditional C1 blocks from synthesis gas, using a Pd2+-catalyzed reaction at relatively mild process conditions and with high yields.[3][4][5][6] The synthesis gas is mostly obtained from coal or biomass. The oxidation proceeds via dinitrogen trioxide, which is formed according to (1) of nitrogen monoxide and oxygen and then reacts according to (2) with methanol forming methyl nitrite:[7]

Methylnitrit-Synthese

In the next reaction step of dicarbonylation (3) carbon monoxide reacts with methyl nitrite to dimethyl oxalate in the vapor phase at atmospheric pressure and temperatures at 80-120 °C over a palladium catalyst:

DMO-Synthese zusammengefasst

The following sum equation shows that oxygen acts as the actual oxidizing agent dinitrogen trioxide on the reactants and methyl nitrite:

DMO from MeOH via oxidative carbonylation

This method is lossless with respect to methyl nitrite, which acts practically as an carrier of oxidation equivalents. However, the water formed must be removed, otherwise the formed dimethyl oxalate can be hydrolyzed.

Interestingly, according to X.-Z. Jiang[7] the course of the reaction depends crucially on the nature of the carrier material on which the palladium catalyst is applied. With 1% Pd/α-Al2O3 dimethyl oxalate is produced selectively in a dicarbonylation reaction, under the same conditions with 2% Pd/C dimethyl carbonate is produced by monocarbonylation:

Monocarbonylation of MeOH corr

Alternatively, the oxidative carbonylation of methanol can be carried out with high yield and selectivity with 1,4-benzoquinone as an oxidant in the system Pd(OAc)2/PPh3/benzoquinone with mass ratio 1/3/100 at 65 °C and 70 atm CO:[6]

Oxidative carbonylation with BQ corr

Properties

Dimethyl oxalate is a colorless solid, which is soluble in water.[8]

Use

Dimethyl oxalate is used for alkylation[9] and in the cosmetics industry as a chelating agent.[10]

For countries with low oil but large coal reserves (meaning countries with large potential for synthesis gas based chemistry, e.g. china), the oxidative carbonylation of methanol provides a promising approach to the important C2-basic chemical ethylene glycol.[11] Dimethyl oxalate can be converted into ethylene glycol in high yields (94.7%[12]) by hydrogenation at a copper-containing catalysts:[13]

MEG from DMO

The methanol formed is recycled in the process of oxidative carbonylation; therefore the only raw materials consumed in the overall process are carbon monoxide, hydrogen and oxygen. One plant following that coal-to-MEG process with a production capacity of 200,000 tons ethylene glycol per year is already operational in Inner Mongolia, a second plant with a capacity of 250,000 with tons/year was scheduled for 2012 in Henan.[14] Other plants with a total annual capacity of more than 1 million tons of ethylene glycol per year are planned.

Furthermore, dimethyl carbonate is accessible by decarbonylation from dimethyl oxalate at temperatures around 100 °C in the presence of alkali metal alcoholates, which is discussed as a fuel additive from biomass (so-called oxygenate):[15][16]

DMC from DMO

The formed carbon monoxide can be feed back to the reaction forming dimethyl oxalate (3).

Diphenyl oxalate is obtained by transesterification of dimethyl oxalate with phenol in the presence of titanium catalysts,[17] which is again decarbonylated to diphenyl carbonate in the liquid or gas phase. Diphenyl carbonate can be used as a replacement for the highly toxic phosgene for the production of polycarbonates.[18]

References

  1. ^ a b P. P. T. Sah and S-L. Chien, Journal of the American Chemical Society, 1931, 53, 3901-3903.
  2. ^ Hans-Jürgen Arpe: Industrielle Organische Chemie: Bedeutende Vor- und Zwischenprodukte, S. 168; ISBN 978-3-527-31540-6.
  3. ^ US 4467109, Susumu Tahara et al., "Process for continuous preparation of diester of oxalic acid", issued 1983-05-19, assigned to Ube Industries  and EP 108359, K. Masunaga et al., "Process for the preparation of a diester of oxalic acid", assigned to Ube Industries 
  4. ^ EP 425197, K. Nishihira & K. Mizutare, "Process for preparing diester of carbonic acid", published 1991-05-2, assigned to Ube Industries 
  5. ^ US 4451666, J.A. Sofranko, A.M. Gaffney, "Synthesis of oxalate esters by the oxidative carbonylation of alcohols", published 1984-05-29, assigned to Atlantic Richfield Co. 
  6. ^ a b E. Amadio: Oxidative Carbonylation of Alkanols Catalyzed by Pd(II)-Phosphine Complexes, PhD Thesis, Ca’Foscari University Venice, 2009.
  7. ^ a b X.-Z. Jiang, Palladium Supported Catalysts in CO + RONO Reactions, Platinum Metals Rev., 1990, 34, (4), 178–180
  8. ^ Entry for Oxalsäuredimethylester at ChemBlink; retrieved, 25 February 2011.
  9. ^ Alkylation with Oxalic Esters. Scope and Mechanism
  10. ^ Marina Bährle-Rapp: Springer Lexikon Kosmetik und Körperpflege, S. 130; ISBN 978-3-540-20416-9.
  11. ^ Nexant/Chemsystems, Coal to MEG, Changing the Rules of the Game at the Wayback Machine (archived July 14, 2011) (PDF; 5,4 MB), 2011 Prospectus
  12. ^ 983 EP 046 983, S. Tahara et al., "Process for continuously preparing ethylene glycol", assigned to Ube Industries  and H. T. Teunissen and C. J. Elsevier, Ruthenium catalyzed hydrogenation of dimethyl oxalate to ethylene glycol, J. Chem. Soc., Chem. Commun., 1997, 667-668), DOI:10.1039/A700862G.
  13. ^ S. Zhang et al., Highly-Dispersed Copper-Based Catalysts from Cu–Zn–Al Layered Double Hydroxide Precursor for Gas-Phase Hydrogenation of Dimethyl Oxalate to Ethylene Glycol, Catalysis Letters, Sept. 2012, 142 (9), 1121–1127, DOI:10.1007/s10562-012-0871-8.
  14. ^ http://www.icis.com/resources/news/2012/01/30/9527520/china-s-coal-based-chemicals-are-a-trade-off/
  15. ^ Fond der Chemischen Industrie – Informationsserie Nachwachsende Rohstoffe: Stammbaum Biomasse-Produkte (PDF; 99 kB)
  16. ^ US 4544507, P. Foley, "Production of carbonate diesters from oxalate diesters", assigned to Celanese Corp 
  17. ^ US 5834614, K. Nishihira et al., "Process for producing diaryl carbonate", assigned to Ube Industries, Ltd.  and X.B. Ma et al., Preparation of Diphenyl Oxalate from Transesterification of Dimethyl Oxalate with Phenol over TS-1 Catalyst, Chinese Chem. Lett., 14 (5), 461–464 (2003), DOI:10.1016/s0378-3820(03)00075-4.
  18. ^ JP 2011236146, "Method for Producing Diaryl Carbonate and Method for Producing Polycarbonate", assigned to Mitsubishi Chemical Corp. 
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