Acetic Acid → HCID 86600187, compound

HRID 1373452Notes

Reaction equation

HRID 1373452 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:10](=[O:16])/[CH:11]=[CH:12]/[C:13]([OH:15])=[O:14])[CH:5]=[CH:6][C:7]=1[O:8][CH3:9].S(OCC)(O[CH2:21][CH3:22])(=O)=O.C(=O)([O-])[O-].[K+].[K+].C(O)(=O)C>CN(C)C=O>[Cl:1][C:2]1[CH:3]=[C:4]([C:10](=[O:16])/[CH:11]=[CH:12]/[C:13]([O:15][CH2:21][CH3:22])=[O:14])[CH:5]=[CH:6][C:7]=1[O:8][CH3:9]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 6163Diethyl Sulfate2×HCID 11430Potassium CarbonateHCID 18794924HCID 18794924, compound

Product 1

HCID 86600187HCID 86600187, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
32.5 °C

Procedure

Into a 500 ml four-neck flask were charged 26.5 g (0.11 mol) of (E)-4-(3-chloro-4-methoxyphenyl)-4-oxo-2-butenoic acid obtained in Step 1, 260 ml of dimethylformamide (DMF), 24.7 g (0.16 mol) of diethyl sulfate, and 30.4 g (0.22 mol) of potassium carbonate under a nitrogen atmosphere, followed by 2 hours of reaction at 35 to 45° C. After completion of the reaction was confirmed by HPLC analysis, a mixed solution of 3.6 g (0.06 mol) of acetic acid/3.6 g of DMF was added dropwise and the whole was stirred at 30 to 35° C. for 1 hour to decompose excess diethyl sulfate. Thereafter, extraction with a mixed solution of 400 ml of ethyl acetate/400 ml of water/23.4 g of hydrochloric acid was conducted and the organic layer was washed twice with 400 ml of water. After the solvent was removed by evaporation under reduced pressure, the residue was crystallized from 9 ml of ethanol, and 19 ml of water to obtain 25.4 g (yield 86.0%) of the aimed compound as light yellow crystals. The total yield from 1-chloro-2-methoxybenzene was 52.0% and the purity was found to be 99.6%.

Workup

  1. customfollowed by 2 hours of reaction at 35 to 45° C
  2. extractionThereafter, extraction with a mixed solution of 400 ml of ethyl acetate/400 ml of water/23.4 g of hydrochloric acid
  3. washthe organic layer was washed twice with 400 ml of water
  4. customAfter the solvent was removed by evaporation under reduced pressure
  5. customthe residue was crystallized from 9 ml of ethanol, and 19 ml of water

Sources & evidence

ORD record
ord-2b801d6b6252400fafff2ca6f8882b8c
Source dataset
uspto-grants-2007_01
Patent number
US07161022B2

Reaction notes

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