Hydrochloric Acid → HCID 23069071, compound

HRID 1373453Notes

Reaction equation

HRID 1373453 reaction equation
[C:1]1(=[O:7])[O:6][C:4](=O)[CH:3]=[CH:2]1.S(OCC)(OCC)(=O)=O.[Cl-].[Al+3].[Cl-].[Cl-].[Cl:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[O:28][CH3:29].Cl.[NH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>[Cu](I)I.C(O)C.ClC1C=CC=CC=1>[C:32]1([NH:31][C:4](=[O:6])/[CH:3]=[CH:2]/[C:1]([C:26]2[CH:25]=[CH:24][C:23]([O:28][CH3:29])=[C:22]([Cl:21])[CH:27]=2)=[O:7])[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 6115AnilineHCID 6163Diethyl SulfateHCID 7923Maleic AnhydrideHCID 130112-ChloroanisoleHCID 6451240Aluminum(III) Chloride2×

Product 1

HCID 23069071HCID 23069071, compoundYield 71.5%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 702EthanolSolventHCID 7964ChlorobenzeneSolvent

Conditions

Temperature
10 °C

Procedure

Into a 500 ml four-neck flask were charged 66.9 g (0.682 mol) of maleic anhydride, 150 ml of chlorobenzene, 71.6 ml (0.546 mol) of diethyl sulfate, and 0.186 g (0.975 mmol) of copper iodide 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 2 hours of reaction. 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. After liquid separation, the organic layer was washed with 200 ml of a 10% sodium bicarbonate aqueous solution to remove excess maleic anhydride. Then, 13.3 g (0.143 mol) of aniline was added to the organic layer, followed by 4 hours of reflux while ethanol formed during the reaction was removed. After completion of the reaction, the solvent was removed by evaporation under reduced pressure and the residue was crystallized from 10 ml of ethanol to obtain 32.3 g (yield 52.5%) of the aimed compound. As a result of HPLC analysis, the purity was found to be 99.1%.

Workup

  1. temperatureWhile temperature was maintained at 10 to 15° C.
  2. customfollowed by 2 hours of reaction
  3. temperaturecooled to 0° C.
  4. customAfter liquid separation
  5. washthe organic layer was washed with 200 ml of a 10% sodium bicarbonate aqueous solution
  6. customto remove excess maleic anhydride
  7. customformed during the reaction
  8. customwas removed
  9. customAfter completion of the reaction
  10. customthe solvent was removed by evaporation under reduced pressure
  11. customthe residue was crystallized from 10 ml of ethanol

Sources & evidence

ORD record
ord-78c7ba38163249fd8df294d66e6dad65
Source dataset
uspto-grants-2007_01
Patent number
US07161022B2

Reaction notes

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