Acetic Acid → HCID 59320802, compound

HRID 341184Notes

Reaction equation

HRID 341184 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]([N+:22]([O-])=O)[C:11]([NH:14][C:15]3[CH:20]=[CH:19][CH:18]=[C:17]([NH2:21])[CH:16]=3)=[N:12][CH:13]=2)=[CH:4][CH:3]=1.[CH3:25]C(O)=O>[Zn]>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]3[N:22]=[CH:25][N:14]([C:15]4[CH:16]=[C:17]([NH2:21])[CH:18]=[CH:19][CH:20]=4)[C:11]3=[N:12][CH:13]=2)=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 176Acetic AcidHCID 59320849HCID 59320849, compound

Product 1

HCID 59320802HCID 59320802, compound

Reagents, catalysts & solvents 1

HCID 23994ZincCatalyst

Conditions

Temperature
60 °C

Procedure

Zinc dust (9.3 g, 142 mmol) was added to a stirred solution of N-[5-(4-fluoro-phenyl)-3-nitro-pyridin-2-yl]-benzene-1,3-diamine (2.3 g, 7.1 mmol) in AcOH (35 ml) at RT. After the exotherm had subsided the reaction was stirred and heated at 60° C. for 3 hours. The mixture was allowed to cool to RT then filtered through Celite—washing with AcOH (˜150 ml). The filtrate was evaporated and the residue was azeotroped with toluene (×2). The residue was taken up in trimethylorthoformate (50 ml) and then stirred and heated at reflux under N2 for 1 hour. After cooling to RT, the volatiles were removed in vacuo. The residue was taken up in EtOH (100 ml). c. HCl (4 ml) was added and the mixture was heated at reflux for 2 hours. After cooling, the mixture was concentrated to ˜4 ml and basified with saturated aqueous NaHCO3. The aqueous mixture was extracted with CH2Cl2 (×3). The combined extracts were dried (MgSO4), filtered and evaporated. The residue was purified by chromatography on silica (40→100% EtOAc/petrol) to give the title compound (0.86 g).

Workup

  1. temperatureto cool to RT
  2. filtrationthen filtered
  3. washthrough Celite—washing with AcOH (˜150 ml)
  4. customThe filtrate was evaporated
  5. customthe residue was azeotroped with toluene (×2)
  6. stirringstirred
  7. temperatureheated
  8. temperatureat reflux under N2 for 1 hour
  9. temperatureAfter cooling to RT
  10. customthe volatiles were removed in vacuo
  11. additionHCl (4 ml) was added
  12. temperaturethe mixture was heated
  13. temperatureat reflux for 2 hours
  14. temperatureAfter cooling
  15. concentrationthe mixture was concentrated to ˜4 ml
  16. extractionThe aqueous mixture was extracted with CH2Cl2 (×3)
  17. dry with materialThe combined extracts were dried (MgSO4)
  18. filtrationfiltered
  19. customevaporated
  20. customThe residue was purified by chromatography on silica (40→100% EtOAc/petrol)

Sources & evidence

ORD record
ord-221f72b2a9e14a6f860a244bb946ec16
Source dataset
uspto-grants-2014_11
Patent number
US08895745B2

Reaction notes

Loading…