Acetic Anhydride → 1,2-Dimethyl 4,5-dimethyl-1,2-benzenedicarboxylate

HRID 596547Notes

Reaction equation

HRID 596547 reaction equation
[CH3:1][O:2][C:3](=[O:16])[CH:4]1[C:13](C)=[C:12]([CH3:15])[CH2:11][CH:10]=[C:5]1[C:6]([O:8][CH3:9])=[O:7].[Se](=O)=O.[C:20](OC(=O)C)(=O)C>C(Cl)Cl>[CH3:9][O:8][C:6](=[O:7])[C:5]1[C:4](=[CH:13][C:12]([CH3:15])=[C:11]([CH3:20])[CH:10]=1)[C:3]([O:2][CH3:1])=[O:16]

Participants

5

Reactant 3

HCID 7918Acetic Anhydride2×HCID 24007Selenium DioxideHCID 536587435,6 Dimethyl-1,4-dihydro-phthalic acid dimethyl ester

Product 1

HCID 6058061,2-Dimethyl 4,5-dimethyl-1,2-benzenedicarboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
100 °C

Procedure

232 parts of the 5,6-dimethyl-1,4-dihydro-phthalic acid dimethyl ester (I) obtained in A) are first freed from readily volatile constituents in vacuo and then diluted with 400 parts by volume of acetic anhydride. Then 133 parts of selenium dioxide are slowly added by small amounts to the reaction mixture, which is heated to 100° C, and the temperature rises to 130° C without external application of heat. The reaction mixture is subsequently refluxed for 3 hours and freed from acetic anhydride in vacuo. The residue is taken up in methylene chloride, the solution is freed from precipitated selenium by filtration, then freed from acid constituents with a saturated aqueous sodium bicarbonate solution, washed neutral with water, dried over sodium sulphate and concentrated to dryness in vacuo. Yield: 230 parts of a yellowish brown oil which a gas chromatogram shows to have a 94% content of 4,5-dimethyl-phthalic acid dimethyl ester (II). The product is distilled under a high vacuum. The fraction with a boiling range of 116°-120° C (0.04 Torr) contains 174 parts (78% of theory) of 4,5-dimethyl-phthalic acid dimethyl ester (II) with a melting point of 54°-55° C.

Workup

  1. customrises to 130° C without external application
  2. temperatureof heat
  3. temperatureThe reaction mixture is subsequently refluxed for 3 hours
  4. customfrom precipitated selenium
  5. filtrationby filtration
  6. washwashed neutral with water
  7. dry with materialdried over sodium sulphate
  8. concentrationconcentrated to dryness in vacuo
  9. distillationThe product is distilled under a high vacuum

Sources & evidence

ORD record
ord-903e21612c1f425d9969597fde69ae33
Source dataset
uspto-grants-1977_03
Patent number
US04011261

Reaction notes

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