Dimethylformamide → HCID 90011519, compound

HRID 1481483Notes

Reaction equation

HRID 1481483 reaction equation
BrC1C=CC(N2C(C(F)(F)F)=CC(C(N)=O)=N2)=NC=1.[Br:20][C:21]1[CH:22]=[CH:23][C:24]([N:27]2[C:31]([C:32]([F:35])([F:34])[F:33])=[CH:30][C:29]([C:36](O)=O)=[N:28]2)=[N:25][CH:26]=1.C(Cl)(=O)C(Cl)=O.C[N:46]([CH:48]=[O:49])[CH3:47].[OH-:50].[NH4+:51]>C(Cl)Cl>[Br:20][C:21]1[CH:22]=[CH:23][C:24]([N:27]2[C:31]([C:32]([F:33])([F:34])[F:35])=[CH:30][C:29]([C:36]3[N:46]([CH3:47])[C:48](=[O:49])[O:50][N:51]=3)=[N:28]2)=[N:25][CH:26]=1

Participants

7

Reactant 5

HCID 6228DimethylformamideHCID 14923Ammonium HydroxideHCID 65578Oxalyl chlorideHCID 90010972HCID 90010972, compoundHCID 90011004HCID 90011004, compound

Product 1

HCID 90011519HCID 90011519, compoundYield 576%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Step-1: 1-(5-Bromopyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazole-3-carboxamide: To a (0° C.) cooled solution of 1-(5-bromopyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazole-3-carboxylic acid (5.0 g, 14.88 mmol) in DCM (50 mL) was added oxalyl chloride (3.91 mL, 44.6 mmol) followed by catalytic amount of DMF (0.14 mL, 1.78 mmol). The resulting mixture was stirred at room temperature for 1 h. The excess of oxalyl chloride was removed under vacuum and the residue was again diluted with DCM (100 mL). Aqueous ammonium hydroxide solution (29.0 mL, 744 mmol) was added drop-wise to the above mixture at 0° C. and the reaction mixture was stirred at room temperature overnight. The solvent was evaporated under vacuum and concentrate was diluted with ethyl acetate (100 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (2×100 mL). The combined organic layers were washed with brine (100 mL), dried (Na2SO4) and filtered. The filtrate was rotary evaporated to afford 4.0 g (80%) of the title compound as white solid. 1HNMR (400 MHz, DMSO-d6) δ 8.73 (d, J=2.0 Hz, 1H), 8.41 (dd, J=2.0 & 8.0 Hz, 1H), 8.09 (s, 1H, D2O exchangeable), 7.97 (d, J=8.0 Hz, 1H), 7.70 (s, 1H, D2O exchangeable), 7.52 (s, 1H); ESI-MS (m/z) 335, 337 [(MH)+, Br79,81].

Workup

  1. customThe excess of oxalyl chloride was removed under vacuum
  2. additionthe residue was again diluted with DCM (100 mL)
  3. stirringthe reaction mixture was stirred at room temperature overnight
  4. customThe solvent was evaporated under vacuum
  5. concentrationconcentrate
  6. additionwas diluted with ethyl acetate (100 mL)
  7. customThe layers were separated
  8. extractionthe aqueous layer was extracted with ethyl acetate (2×100 mL)
  9. washThe combined organic layers were washed with brine (100 mL)
  10. dry with materialdried (Na2SO4)
  11. filtrationfiltered
  12. customThe filtrate was rotary evaporated

Sources & evidence

ORD record
ord-caab212d6d0e43ec956506a9d0be6990
Source dataset
uspto-grants-2016_08
Patent number
US09409898B2

Reaction notes

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