Sodium Phosphate, Dibasic → HCID 22120898, compound

HRID 1274355Notes

Reaction equation

HRID 1274355 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[C:21]1[O:22][CH:23]=[CH:24][CH:25]=1.S(S([O-])=O)([O-])=O.[Na+].[Na+].P([O-])([O-])(O)=O.[Na+].[Na+]>CN(C)C=O.O>[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:15])[F:16])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[C:21]1[O:22][C:23]([C:14]([F:17])([F:16])[F:15])=[CH:24][CH:25]=1

Participants

6

Reactant 3

HCID 24203Sodium Phosphate, DibasicHCID 24489Sodium DithioniteHCID 9821578HCID 9821578, compound

Product 1

HCID 22120898HCID 22120898, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
45 °C

Procedure

To a solution of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-(furan-2-yl)pyrazole (0.46 g) in dimethylformamide (15 ml) and water (5 ml) was added sodium dithionite (0.286 g) and disodium hydrogen phosphate (0.17 g). The mixture placed in a 400 ml Parr vessel, which was evacuated, then charged with trifluoromethylbromide gas to 40 psi. The mixture was shaken and heated at 45° C., for 3 hours, then left at room temperature for 16 hours. The vessel was then evacuated, then recharged with trifluoromethylbromide to 40 psi, then shaken and heated to 45° C. for a further 9 hours, then left at room temperature for 48 hours. The vessel was then evacuated, then recharged with trifluoromethylbromide to 40 psi, then shaken and heated to 45° C. for a further 7 hours, then left at room temperature for 16 hours. The mixture was filtered and then poured into brine (25 ml) and extracted with ether (25 ml, ×3). The combined organic layers were washed with water (20 ml), dried (Na2SO4), and evaporated. The residue was purified by column chromatography on silica gel (25 g) eluted with hexane:ether (50:50 changing gradually to 20:80). Combination and evaporation of suitable fractions gave the title compound as a pale yellow solid, m.p. 148-151° C.

Workup

  1. customwas evacuated
  2. additioncharged with trifluoromethylbromide gas to 40 psi
  3. customThe vessel was then evacuated
  4. stirringshaken
  5. temperatureheated to 45° C. for a further 9 hours
  6. waitleft at room temperature for 48 hours
  7. customThe vessel was then evacuated
  8. stirringshaken
  9. temperatureheated to 45° C. for a further 7 hours
  10. waitleft at room temperature for 16 hours
  11. filtrationThe mixture was filtered
  12. additionpoured into brine (25 ml)
  13. extractionextracted with ether (25 ml, ×3)
  14. washThe combined organic layers were washed with water (20 ml)
  15. dry with materialdried (Na2SO4)
  16. customevaporated
  17. customThe residue was purified by column chromatography on silica gel (25 g)
  18. washeluted with hexane:ether (50:50 changing gradually to 20:80)
  19. customCombination and evaporation of suitable fractions

Sources & evidence

ORD record
ord-5280825ea9e344e893e1e7d260b8e941
Source dataset
uspto-grants-2000_12
Patent number
US06156782

Reaction notes

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