Trifluoroacetic acid → HCID 86725521, compound

HRID 514395Notes

Reaction equation

HRID 514395 reaction equation
C(C1[CH:8]=[CH:7][N:6]=[C:5]([N:9]2[C:13]([C:14]3[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=3)=[CH:12][C:11]([NH:21]C(=O)OC(C)(C)C)=[N:10]2)[CH:4]=1)#N.[C:29]([OH:35])([C:31](F)(F)F)=[O:30]>>[NH2:21][C:11]1[CH:12]=[C:13]([C:14]2[CH:15]=[CH:16][C:17]([CH3:20])=[CH:18][CH:19]=2)[N:9]([C:5]2[CH:4]=[C:31]([C:29]([OH:35])=[O:30])[CH:8]=[CH:7][N:6]=2)[N:10]=1

Participants

3

Reactant 2

HCID 6422Trifluoroacetic acidHCID 90211012HCID 90211012, compound

Product 1

HCID 86725521HCID 86725521, compoundYield 48%

Conditions

Temperature
70 °C

Procedure

A solution of tert-butyl [1-(4-cyanopyridin-2-yl)-5-(4-methylphenyl)-1H-pyrazol-3-yl]carbamate (150 mg, 0.4 mmol) in TFA (2 mL) was heated to 50° C. for 30 min and evaporated to an oily residue. To the residue was added 10 N NaOH (2 mL) followed by MeOH (2 mL). The solution was stirred at 70° C. for 4 h and then cooled to rt. Solvent was evaporated, and the pH of the resulting aqueous phase was carefully adjusted to pH=5.5 using conc. HCl and then 1 N HCl. The resulting mixture was extracted with EtOAc (2×20 mL). The organic layers were dried (MgSO4), filtered, concentrated to an oil, and purified by flash column chromatography (MeOH/EtOAc=5:95) to give the title compound (56 mg, 48%) as a beige solid. 1H NMR (400 MHz, DMSO-d6): δ 2.28 (3H, s), 5.73 (1H, s), 5.82 (1H, s), 7.05-7.18 (4H, m), 7.51 (1H, d, J=5.2 Hz), 8.02 (1H, s), 8.22 (1H, d, J=5.2 Hz). [M+H] Calc'd for C16H14N4O2, 295. Found, 295.

Workup

  1. customevaporated to an oily residue
  2. additionTo the residue was added 10 N NaOH (2 mL)
  3. temperaturecooled to rt
  4. customSolvent was evaporated
  5. extractionThe resulting mixture was extracted with EtOAc (2×20 mL)
  6. dry with materialThe organic layers were dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated to an oil
  9. custompurified by flash column chromatography (MeOH/EtOAc=5:95)

Sources & evidence

ORD record
ord-8b1496af369d428980acd3ef4ac5d830
Source dataset
uspto-grants-2015_08
Patent number
US09107916B2

Reaction notes

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