Hydrochloric Acid → Bis(3-amino-4-fluorophenyl)methanone

HRID 1707799Notes

Reaction equation

HRID 1707799 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:19]=[CH:20][C:21]=1[F:22])[C:7]([C:9]1[CH:14]=[CH:13][C:12]([F:15])=[C:11]([N+:16]([O-])=O)[CH:10]=1)=[O:8])([O-])=O.Cl.O.[Cl-].[Na+]>C(O)C.[Fe]>[NH2:16][C:11]1[CH:10]=[C:9]([CH:14]=[CH:13][C:12]=1[F:15])[C:7]([C:6]1[CH:19]=[CH:20][C:21]([F:22])=[C:4]([NH2:1])[CH:5]=1)=[O:8]

Participants

7

Reactant 4

HCID 313Hydrochloric Acid2×HCID 962WaterHCID 5234Sodium ChlorideHCID 18951956Bis(4-fluoro-3-nitrophenyl)methanone

Product 1

HCID 18691961Bis(3-amino-4-fluorophenyl)methanoneYield 83%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent2×

Conditions

Temperature
75 °C

Procedure

To a glass reaction vessel equipped with a stirrer, reflux condenser and a thermometer, 124 g (0.4 mole) of 3,3'-dinitro-4,4'-difluorobenzophenone, 1100 ml of a 80% aqueous ethanol solution and 280 g (5.0 mole) of iron powder were charged and the internal temperature was raised to 75 ° C. Successively, a solution containing 10.5 g of 36% hydrochloric acid in 124 ml of 80 % ethanol was added dropwise and the reaction was further continued for 3 hours with stirring. After finishing the reaction, the reaction mixture was filtered at the same temperature and the filtrate was poured into 2 l of water. The precipitated crystal was filtered, washed with water and dried to obtain 90.5 g of crude crystal of 3,3'-diamino-4,4'-difluorobenzophenone. The crude crystals were mixed with 180 ml of water, 36% hydrochloric acid and activated carbon, and dissolved by heating. The solution was hot filtered. To the filtrate, 18 g of sodium chloride was added and dissolved. The solution thus obtained was gradually cooled to precipitate 3,3'-diamino-4,4'-difluorobenzophenone hydrochloride. The hydrochloride was filtered and neutralized in water with a 28% aqueous ammonia solution to obtain 82.3 g (83.0% yield) of 3,3'-diamino-4,4'-difluorobenzophenone. The purified product had purity of 99.1% by high performance liquid chromatography and a melting point of 130.8+-131.6° C.

Workup

  1. customTo a glass reaction vessel
  2. customequipped with a stirrer
  3. temperaturereflux condenser
  4. additionwas added dropwise
  5. customthe reaction
  6. filtrationthe reaction mixture was filtered at the same temperature
  7. additionthe filtrate was poured into 2 l of water
  8. filtrationThe precipitated crystal was filtered
  9. washwashed with water
  10. customdried
  11. customto obtain 90.5 g of crude crystal of 3,3'-diamino-4,4'-difluorobenzophenone
  12. dissolutiondissolved
  13. temperatureby heating
  14. dissolutiondissolved
  15. customThe solution thus obtained
  16. temperaturewas gradually cooled
  17. customto precipitate 3,3'-diamino-4,4'-difluorobenzophenone hydrochloride
  18. filtrationThe hydrochloride was filtered

Sources & evidence

ORD record
ord-75e63855a73741efbb956b4e4648d289
Source dataset
uspto-grants-1994_10
Patent number
US05354890

Reaction notes

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