Dimethyl oxalate

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Dimethyl oxalate
Dimethyle-oxalate.svg
Dimethyl oxalate 3D ball.png
Names
Preferred IUPAC name
Dimethyl oxalate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.008.231 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • 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
AppearanceWhite 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 an organic compound with the formula (CO2CH3)2 or (CH3)2C2O4. It is the dimethyl ester of oxalic acid. Dimethyl oxalate is a colorless or white solid that is soluble in water.

Contents

Production

Dimethyl oxalate can be obtained by esterification of oxalic acid with methanol using sulfuric acid as a catalyst: [2]

Oxidative carbonylation route

The preparation by oxidative carbonylation has attracted interest because it requires only C1 precursors: [3]

The reaction is catalyzed by Pd2+. [4] [5] 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: [6]

Methylnitrite Synthesis.svg

In the next 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 Synthesis Summary.svg

The sum equation:

DMO from MeOH via oxidative carbonylation.svg

This method is lossless with respect to methyl nitrite, which acts practically as a carrier of oxidation equivalents. However, the water formed must be removed to prevent hydrolysis of the dimethyl oxalate product. 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.svg

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: [5]

Oxidative carbonylation with BQ corr.svg

Reactions

Dimethyl oxalate (and the related diethyl ester) is used in diverse condensation reactions. [7] For example, diethyl oxalate condenses with cyclohexanone to give the diketo-ester, a precursor to pimelic acid. [8] With diamines, the diesters of oxalic acid condense to give cyclic diamides. Quinoxalinedione is produced by condensation of dimethyloxalate and o-phenylenediamine:

C2O2(OMe)2 + C6H4(NH2)2 → C6H4(NHCO)2 + 2 MeOH

Hydrogenation gives ethylene glycol. [9] Dimethyl oxalate can be converted into ethylene glycol in high yields (94.7%) [10] [11]

MEG from DMO.svg

The methanol formed is recycled in the process of oxidative carbonylation. [12] Other plants with a total annual capacity of more than 1 million tons of ethylene glycol per year are planned.

Decarbonylation gives dimethyl carbonate. [13]

DMC from DMO.svg

Diphenyl oxalate is obtained by transesterification with phenol in the presence of titanium catalysts, [14] which is again decarbonylated to diphenyl carbonate in the liquid or gas phase.

Dimethyl oxalate can also be used as a methylating agent. It is notably less toxic than other methylating agents such as methyl iodide or dimethyl sulfate. [15]

Methylation Rxn Example dimethyloxalate.png

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

<span class="mw-page-title-main">Ethylene glycol</span> Organic compound ethane-1,2-diol

Ethylene glycol is an organic compound with the formula (CH2OH)2. It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odorless, colorless, flammable, viscous liquid. It has a sweet taste, but is toxic in high concentrations. This molecule has been observed in outer space.

Transesterification is the process of exchanging the organic functional group R″ of an ester with the organic group R' of an alcohol. These reactions are often catalyzed by the addition of an acid or base catalyst. Strong acids catalyze the reaction by donating a proton to the carbonyl group, thus making it a more potent electrophile. Bases catalyze the reaction by removing a proton from the alcohol, thus making it more nucleophilic. The reaction can also be accomplished with the help of other enzymes, particularly lipases.

<span class="mw-page-title-main">Ethylene oxide</span> Cyclic compound (C2H4O)

Ethylene oxide is an organic compound with the formula C2H4O. It is a cyclic ether and the simplest epoxide: a three-membered ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a colorless and flammable gas with a faintly sweet odor. Because it is a strained ring, ethylene oxide easily participates in a number of addition reactions that result in ring-opening. Ethylene oxide is isomeric with acetaldehyde and with vinyl alcohol. Ethylene oxide is industrially produced by oxidation of ethylene in the presence of a silver catalyst.

<span class="mw-page-title-main">Oxalic acid</span> Simplest dicarboxylic acid

Oxalic acid is an organic acid with the systematic name ethanedioic acid and chemical formula HO−C(=O)−C(=O)−OH, also written as (COOH)2 or (CO2H)2 or H2C2O4. It is the simplest dicarboxylic acid. It is a white crystalline solid that forms a colorless solution in water. Its name comes from the fact that early investigators isolated oxalic acid from flowering plants of the genus Oxalis, commonly known as wood-sorrels. It occurs naturally in many foods. Excessive ingestion of oxalic acid or prolonged skin contact can be dangerous.

<span class="mw-page-title-main">Oxalyl chloride</span> Chemical compound

Oxalyl chloride is an organic chemical compound with the formula Cl−C(=O)−C(=O)−Cl. This colorless, sharp-smelling liquid, the diacyl chloride of oxalic acid, is a useful reagent in organic synthesis.

<span class="mw-page-title-main">Dimethyl terephthalate</span> Chemical compound

Dimethyl terephthalate (DMT) is an organic compound with the formula C6H4(COOCH3)2. It is the diester formed from terephthalic acid and methanol. It is a white solid that melts to give a distillable colourless liquid.

<span class="mw-page-title-main">Dimethyl sulfate</span> Chemical compound

Dimethyl sulfate (DMS) is a chemical compound with formula (CH3O)2SO2. As the diester of methanol and sulfuric acid, its formula is often written as (CH3)2SO4 or Me2SO4, where CH3 or Me is methyl. Me2SO4 is mainly used as a methylating agent in organic synthesis.

<span class="mw-page-title-main">Carbonate ester</span> Chemical group (R–O–C(=O)–O–R)

In organic chemistry, a carbonate ester 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 R−O−C(=O)−O−R' and they are related to esters, ethers and also to the inorganic carbonates.

This is the list of extremely hazardous substances defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act. The list can be found as an appendix to 40 CFR 355. Updates as of 2006 can be seen on the Federal Register, 71 FR 47121.

<span class="mw-page-title-main">Dimethyl carbonate</span> Chemical compound

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. Notably, dimethyl carbonate is a weak methylating agent, and thus is not considered as a carcinogen. Instead, dimethyl carbonate is often considered to be a green reagent, and it is exempt from the restrictions placed on most volatile organic compounds (VOCs) in the United States.

<span class="mw-page-title-main">Ethylene carbonate</span> Chemical compound

Ethylene carbonate (sometimes abbreviated EC) is the organic compound with the formula (CH2O)2CO. It is classified as the cyclic carbonate ester of ethylene glycol and carbonic acid. At room temperature (25 °C) ethylene carbonate is a transparent crystalline solid, practically odorless and colorless, and somewhat soluble in water. In the liquid state (m.p. 34-37 °C) it is a colorless odorless liquid.

In chemistry, carbonylation refers to reactions that introduce carbon monoxide (CO) into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

<span class="mw-page-title-main">Acetic acid</span> Colorless and faint organic acid found in vinegar

Acetic acid, systematically named ethanoic acid, is an acidic, colourless liquid and organic compound with the chemical formula CH3COOH. Vinegar is at least 4% acetic acid by volume, making acetic acid the main component of vinegar apart from water. It has been used, as a component of vinegar, throughout history from at least the third century BC.

<span class="mw-page-title-main">Diethyl carbonate</span> Chemical compound

Diethyl carbonate (sometimes abbreviated DEC) is an ester of carbonic acid and ethanol with the formula OC(OCH2CH3)2. At room temperature (25 °C) diethyl carbonate is a colorless liquid with a low flash point.

<span class="mw-page-title-main">2-Methylglutaronitrile</span> Chemical compound

2-Methylglutaronitrile is the organic compound with the formula NCCH2CH2CH(CH3)CN. This dinitrile is obtained in the large-scale synthesis of adiponitrile. It is a colorless liquid with an unpleasant odor. It is the starting compound for the vitamin nicotinamide and for the diester dimethyl-2-methylglutarate and the ester amide methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, which are promoted as green solvents. 2-Methylglutaronitrile is chiral but is mainly encountered as the racemate. It is also used to make Dytek A.

Oxidative carbonylation is a class of reactions that use carbon monoxide in combination with an oxidant to generate esters and carbonate esters. These transformations utilize transition metal complexes as homogeneous catalysts. Many of these reactions employ palladium catalysts. Mechanistically, these reactions resemble the Wacker process.

<span class="mw-page-title-main">Tin(II) oxalate</span> Chemical compound

Tin(II) oxalate is an inorganic compound, a salt of tin and oxalic acid with the chemical formula SnC
2O
4. The compound looks like colorless crystals, does not dissolve in water, and forms crystalline hydrates.

<span class="mw-page-title-main">Glycerol-1,2-carbonate</span> Organic chemical compound

Glycerol-1,2-carbonate is formally the cyclic ester of carbonic acid with glycerol and has aroused great interest as a possible product from the "waste materials" carbon dioxide CO2 and glycerol (especially from biodiesel production) with a wide range of applications.

References

  1. 1 2 P. P. T. Sah and S-L. Chien, Journal of the American Chemical Society, 1931, 53, 3901-3903.
  2. ↑ Everett Bowden (1930). "Methyl Oxalate". Organic Syntheses. 10: 78. doi:10.15227/orgsyn.010.0078.
  3. ↑ Hans-Jürgen Arpe: Industrielle Organische Chemie: Bedeutende Vor- und Zwischenprodukte, S. 168; ISBN   978-3-527-31540-6.
  4. ↑ 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 EP 425197,K. Nishihira&K. Mizutare,"Process for preparing diester of carbonic acid",published 1991-05-2, assigned to Ube Industries 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.
  5. 1 2 E. Amadio: Oxidative Carbonylation of Alkanols Catalyzed by Pd(II)-Phosphine Complexes, PhD Thesis, Ca'Foscari University Venice, 2009
  6. ↑ X.-Z. Jiang, Palladium Supported Catalysts in CO + RONO Reactions, Platinum Metals Rev., 1990, 34, (4), 178–180
  7. ↑ Bergman, Jan; Norrby, Per-Ola; Sand, Peter (1990). "Alkylation with Oxalic Esters. Scope and mechanism". Tetrahedron. 46 (17): 6113–6124. doi:10.1016/S0040-4020(01)87933-3. S2CID   94945519.
  8. ↑ H. R. Snyder; L. A. Brooks; S. H. Shapiro; A. Müller (1931). "Pimelic Acid". Organic Syntheses. 11: 42. doi:10.15227/orgsyn.011.0042.
  9. ↑ Nexant/Chemsystems, "Coal to MEG, Changing the Rules of the Game" (PDF). Archived from the original on July 14, 2011. Retrieved 2016-08-08.{{cite web}}: CS1 maint: bot: original URL status unknown (link) (PDF; 5,4 MB), 2011 Prospectus
  10. ↑ 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.
  11. ↑ 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
  12. ↑ "Individual news".
  13. ↑ US 4544507,P. Foley,"Production of carbonate diesters from oxalate diesters", assigned to Celanese Corp
  14. ↑ 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.
  15. ↑ Bergman, Jan; Norrby, Per-Ola; Sand, Peter (1990-01-01). "Alkylation with Oxalic Esters. Scope and mechanism". Tetrahedron. 46 (17): 6113–6124. doi:10.1016/S0040-4020(01)87933-3. ISSN   0040-4020. S2CID   94945519.
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