4-Nitroaniline → HCID 19817751, compound

HRID 1087201Notes

Reaction equation

HRID 1087201 reaction equation
[F:1][C:2]1[CH:10]=[C:9]([F:11])[CH:8]=[CH:7][C:3]=1[C:4](Cl)=[O:5].[N+:12]([C:15]1[CH:21]=[CH:20][C:18]([NH2:19])=[CH:17][CH:16]=1)([O-:14])=[O:13]>[Cl-].[Zn+2].[Cl-].Cl>[NH2:19][C:18]1[CH:20]=[CH:21][C:15]([N+:12]([O-:14])=[O:13])=[CH:16][C:17]=1[C:4]([C:3]1[CH:7]=[CH:8][C:9]([F:11])=[CH:10][C:2]=1[F:1])=[O:5]

Participants

5

Reactant 2

HCID 74754-NitroanilineHCID 5880812,4-Difluorobenzoyl chloride

Product 1

HCID 19817751HCID 19817751, compoundYield 9.5%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 313Hydrochloric AcidSolvent

Conditions

Temperature
180 °C

Procedure

A mixture of 2,4-difluorobenzoyl chloride (88.3 g) and 4-nitroaniline (32.9 g) was heated at 180° C. for 25 minutes. Zinc chloride (39 g) was added portionwise to the resulting mixture. The mixture was stirred for 2.5 hours at 195° C. and cooled to 130° C. To the mixture was added 3N hydrochloric acid (100 ml) and the resulting mixture was refluxed for 2 hours, then the supernatant was decanted out. 75% Sulfuric acid was added to the residue and the mixture was stirred at 130° C. for 2 hours. The reaction mixture was poured into ice and extracted with dichloromethane. The organic layer was washed with 3N hydrochloric acid (600 ml), 3N sodium hydroxide (1 l), and water successively, dried, and evaporated. The solid residue (15 g) was recrystallized from ethanol to give crystals of 2-amino-5-nitro-2',4'-difluorobenzophenone (6.3 g).

Workup

  1. temperaturecooled to 130° C
  2. temperaturethe resulting mixture was refluxed for 2 hours
  3. customthe supernatant was decanted out
  4. addition75% Sulfuric acid was added to the residue
  5. stirringthe mixture was stirred at 130° C. for 2 hours
  6. additionThe reaction mixture was poured into ice
  7. extractionextracted with dichloromethane
  8. washThe organic layer was washed with 3N hydrochloric acid (600 ml), 3N sodium hydroxide (1 l), and water successively
  9. customdried
  10. customevaporated
  11. customThe solid residue (15 g) was recrystallized from ethanol

Sources & evidence

ORD record
ord-04a4aaf9f6994685a66b93a46b1e5f66
Source dataset
uspto-grants-1991_07
Patent number
US05034417

Reaction notes

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