Hydrochloric Acid → HCID 18962629, compound

HRID 257121Notes

Reaction equation

HRID 257121 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:27]=[CH:28][C:29]=1[F:30])[C:7]([C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([C:15](=[O:26])[C:16]2[CH:21]=[CH:20][C:19]([F:22])=[C:18]([N+:23]([O-])=O)[CH:17]=2)[CH:10]=1)=[O:8])([O-])=O.Cl.O.[Cl-].[Na+]>C(O)C.COCCO.[Fe]>[NH2:23][C:18]1[CH:17]=[C:16]([CH:21]=[CH:20][C:19]=1[F:22])[C:15]([C:11]1[CH:12]=[CH:13][CH:14]=[C:9]([C:7](=[O:8])[C:6]2[CH:27]=[CH:28][C:29]([F:30])=[C:4]([NH2:1])[CH:5]=2)[CH:10]=1)=[O:26]

Participants

8

Reactant 4

HCID 313Hydrochloric Acid2×HCID 962WaterHCID 5234Sodium ChlorideHCID 19708178HCID 19708178, compound

Product 1

HCID 18962629HCID 18962629, compoundYield 83%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolvent2×HCID 80192-MethoxyethanolSolvent

Conditions

Temperature
65 °C

Procedure

Next, a glass reaction vessel equipped with a stirrer, reflux condenser and a thermometer was charged with 82.4 g (0.2 mole) of the above 1,3-bis(3-nitro-4-fluorobenzoyl) benzene, 820 ml of a 80% aqueous ethanol solution and 82.0 g (1.46 mole) of iron powder were charged and the internal temperature was raised to 65° C. Successively, a solution containing 6.08 g of 36% hydrochloric acid in 80 ml of 80% ethanol was added dropwise over 2 hours and the reaction was continued further for an hour with stirring. The reaction mixture was cooled to room temperature and filtered. The residue obtained was dissolved in 280 g of hot 2-methoxyethanol and hot filtered to remove iron powder. The filtrate was poured into 2 l of water. The precipitated crystals were filtered, washed with water and dried to obtain 63.5 g of crude crystals of 1,3-bis(3-amino-4-fluorobenzoyl) benzene. The crude crystals were mixed with 120 ml of water, 36% hydrochloric acid and activated carbon, and dissolved by heating. The solution was hot filtered. To the filtrate, 12 g of sodium chloride was added and dissolved. The solution thus obtained was gradually cooled to precipitate 1,3-bis(3-amino-4-fluorobenzoyl)benzene hydrochloride. The hydrochloride was filtered and neutralized in water with a 28% aqueous ammonia solution to obtain 58.4 g (83.0% yield) of 1,3-bis(3-amino-4-fluorobenzoyl)benzene. The purified product had purity of 99.1% by high performance liquid chromatography and a melting point of 169.7°-170.7° C.

Workup

  1. customNext, a glass reaction vessel
  2. customequipped with a stirrer
  3. temperaturereflux condenser
  4. additionwere charged
  5. additionwas added dropwise over 2 hours
  6. waitthe reaction was continued further for an hour
  7. temperatureThe reaction mixture was cooled to room temperature
  8. filtrationfiltered
  9. customThe residue obtained
  10. filtrationhot filtered
  11. customto remove iron powder
  12. additionThe filtrate was poured into 2 l of water
  13. filtrationThe precipitated crystals were filtered
  14. washwashed with water
  15. customdried
  16. customto obtain 63.5 g of crude crystals of 1,3-bis(3-amino-4-fluorobenzoyl) benzene
  17. dissolutiondissolved
  18. temperatureby heating
  19. dissolutiondissolved
  20. customThe solution thus obtained
  21. temperaturewas gradually cooled
  22. customto precipitate 1,3-bis(3-amino-4-fluorobenzoyl)benzene hydrochloride
  23. filtrationThe hydrochloride was filtered

Sources & evidence

ORD record
ord-b0b3b700168842fe8dfed6b2c573378a
Source dataset
uspto-grants-1993_11
Patent number
US05260388

Reaction notes

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