Water → Methyl 4-(4-aminophenylthio)-3-nitrobenzoate

HRID 1771864Notes

Reaction equation

HRID 1771864 reaction equation
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7](Cl)=[C:6]([N+:11]([O-:13])=[O:12])[CH:5]=1.[NH2:15][C:16]1[CH:21]=[CH:20][C:19]([SH:22])=[CH:18][CH:17]=1.C([O-])([O-])=O.[K+].[K+].O>CN(C=O)C.O(C(C)C)C(C)C>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7]([S:22][C:19]2[CH:20]=[CH:21][C:16]([NH2:15])=[CH:17][CH:18]=2)=[C:6]([N+:11]([O-:13])=[O:12])[CH:5]=1

Participants

7

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 145104-AminothiophenolHCID 735797Methyl 4-chloro-3-nitrobenzoate

Product 1

HCID 59376804Methyl 4-(4-aminophenylthio)-3-nitrobenzoateYield 90%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 7914Diisopropyl EtherSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 4-chloro-3-nitrobenzoic acid methyl ester (15.0 g, 68 mmol), 4-aminothiophenol (8.8 g, 68 mmol) and K2CO3 (11.8 g, 85 mmol) in DMF (150 mL) was heated at 90° C. for 1.5 hours, cooled to room temperature, and then poured into H2O (450 mL) under stirring. The aqueous mixture was extracted with ethyl acetate (400 mL). The extract was washed with H2O (3 times) and brine, dried over MgSO4, and evaporated to give the crude produce as orange crystal. The crude product was suspended in 150 mL of i-Pr2O and stirred at room temperature for 1 hour. The crystal was collected by filtration, washed with i-Pr2O and dried at 60° C. for 3 days under reduced pressure gave purified title compound as orange crystal (18.6 g, 90% yield).

Workup

  1. temperaturecooled to room temperature
  2. extractionThe aqueous mixture was extracted with ethyl acetate (400 mL)
  3. washThe extract was washed with H2O (3 times) and brine
  4. dry with materialdried over MgSO4
  5. customevaporated
  6. customto give the crude
  7. customproduce as orange crystal
  8. stirringstirred at room temperature for 1 hour
  9. filtrationThe crystal was collected by filtration
  10. washwashed with i-Pr2O
  11. customdried at 60° C. for 3 days under reduced pressure
  12. customgave

Sources & evidence

ORD record
ord-0d736717c6b949b4abecc32bd1afd42c
Source dataset
uspto-grants-2016_02
Patent number
US09249138B2

Reaction notes

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