Dimethyl acetylenedicarboxylate

Last updated
Dimethyl acetylenedicarboxylate
DMAD.png
Dimethyl-acetylenedicarboxylate-3D-balls.png
Names
Preferred IUPAC name
Dimethyl but-2-ynedioate
Other names
DMAD
Acetylenedicarboxylic
acid dimethyl ester
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.010.999 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 212-098-4
PubChem CID
RTECS number
  • ES0175000
UNII
  • InChI=1S/C6H6O4/c1-9-5(7)3-4-6(8)10-2/h1-2H3 Yes check.svgY
    Key: VHILMKFSCRWWIJ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C6H6O4/c1-9-5(7)3-4-6(8)10-2/h1-2H3
    Key: VHILMKFSCRWWIJ-UHFFFAOYAX
  • COC(=O)C#CC(=O)OC
Properties
C6H6O4
Molar mass 142.11 g/mol
AppearanceColorless liquid
Density 1.1564 g/cm3
Melting point −18 °C (0 °F; 255 K)
Boiling point 195 to 198 °C (383 to 388 °F; 468 to 471 K) (96–98° at 8 mm Hg)
Insoluble
Solubility in other solventsSoluble in most
organic solvents
1.447
Structure
0 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Toxic
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H302, H314
P260, P264, P270, P280, P301+P312, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P330, P363, P405, P501
Flash point 187 °C (369 °F; 460 K)
Related compounds
Related compounds
Methyl propiolate,
Hexafluoro-2-butyne,
Acetylene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Dimethyl acetylenedicarboxylate (DMAD) is an organic compound with the formula CH3O2CC2CO2CH3. It is a di-ester in which the ester groups are conjugated with a C-C triple bond. As such, the molecule is highly electrophilic, and is widely employed as a dienophile in cycloaddition reactions, such as the Diels-Alder reaction. It is also a potent Michael acceptor. [1] [2] This compound exists as a colorless liquid at room temperature. This compound was used in the preparation of nedocromil.

Contents

Preparation

Although inexpensively available, DMAD is prepared today as it was originally. Maleic acid is brominated and the resulting dibromosuccinic acid is dehydrohalogenated with potassium hydroxide yielding acetylenedicarboxylic acid. [3] [4] The acid is then esterified with methanol and sulfuric acid as a catalyst: [5]

Preparation of dimethyl acetylenedicarboxylate.png

Safety

DMAD is a lachrymator and a vesicant.

Related Research Articles

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References

  1. Stelmach, J. E.; Winkler, J. D. "Dimethyl Acetylenedicarboxylate"in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi : 10.1002/047084289X.
  2. Sahoo, Manoj (2007). "Dimethyl Acetylene Dicarboxylate". Synlett. 2007 (13): 2142–2143. doi: 10.1055/s-2007-984894 .
  3. Bandrowski, E. (1877). "Ueber Acetylendicarbonsäure". Berichte der Deutschen Chemischen Gesellschaft. 10: 838–842. doi:10.1002/cber.187701001231.
  4. Abbott, T. W.; Arnold, R. T.; Thompson, R. B. (1938). "Acetylenedicarboxylic acid". Organic Syntheses . 18: 3. doi:10.15227/orgsyn.018.0003.; Collective Volume, vol. 2, p. 10
  5. Huntress, E. H.; Lesslie, T. E.; Bornstein, J. (1952). "Dimethyl Acetylenedicarboxylate". Organic Syntheses . 32: 55. doi:10.15227/orgsyn.032.0055.; Collective Volume, vol. 4, p. 329