Hydrochloric Acid → HCID 18794924, compound

HRID 1373451Notes

Reaction equation

HRID 1373451 reaction equation
[C:1]1(=[O:7])[O:6][C:4](=[O:5])[CH:3]=[CH:2]1.[Cl-].[Al+3].[Cl-].[Cl-].[Cl:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[O:19][CH3:20].Cl>ClC1C=CC=CC=1>[Cl:12][C:13]1[CH:18]=[C:17]([C:4](=[O:5])/[CH:3]=[CH:2]/[C:1]([OH:6])=[O:7])[CH:16]=[CH:15][C:14]=1[O:19][CH3:20]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7923Maleic AnhydrideHCID 130112-ChloroanisoleHCID 6451240Aluminum(III) Chloride2×

Product 1

HCID 18794924HCID 18794924, compoundYield 60.5%

Reagents, catalysts & solvents 1

HCID 7964ChlorobenzeneSolvent

Conditions

Temperature
10 °C

Procedure

Into a 500 ml four-neck flask were charged 66.9 g (0.682 mol) of maleic anhydride and 150 ml of chlorobenzene under a nitrogen atmosphere. Then, the whole was cooled to 10° C. or lower and 67.6 g (0.507 mol) of aluminum chloride was added thereto. While temperature was maintained at 10 to 15° C., 23.2 ml (0.195 mol) of 1-chloro-2-methoxybenzene was added dropwise, followed by 51 hours of reaction at 20 to 30° C. After termination of the reaction was confirmed by HPLC analysis, the reaction solution was added dropwise to 200 ml of a 1N hydrochloric acid aqueous solution cooled to 0° C. to decompose excess aluminum chloride. Extraction with 400 ml of ethyl acetate was conducted and the organic layer was washed twice with 200 ml of a 1N hydrochloric acid aqueous solution. Then, the organic layer was extracted three times with 200 ml of a saturated sodium hydrogen carbonate aqueous solution to extract (E)-4-(3-chloro-4-methoxyphenyl)-4-oxo-2-butenoic acid into the aqueous layer, followed by adjusting the aqueous layer to pH 2.0. After 24 hours of stirring at 5° C., filtration was carried out to obtain 28.4 g (yield 60.5%) of the aimed compound as light yellow crystals. As a result of HPLC analysis, the purity was found to be 96.3%.

Workup

  1. temperatureWhile temperature was maintained at 10 to 15° C.
  2. customfollowed by 51 hours of reaction at 20 to 30° C
  3. temperaturecooled to 0° C.
  4. extractionExtraction with 400 ml of ethyl acetate
  5. washthe organic layer was washed twice with 200 ml of a 1N hydrochloric acid aqueous solution
  6. extractionThen, the organic layer was extracted three times with 200 ml of a saturated sodium hydrogen carbonate aqueous solution
  7. extractionto extract (E)-4-(3-chloro-4-methoxyphenyl)-4-oxo-2-butenoic acid into the aqueous layer
  8. filtrationfiltration

Sources & evidence

ORD record
ord-848d86b4f47c4b768deafb70e112cc75
Source dataset
uspto-grants-2007_01
Patent number
US07161022B2

Reaction notes

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