Potassium Hydroxide → 4-ethoxy-1-(4-fluorophenyl)-1H-pyrazole-3-carboxylic acid

HRID 1465185Notes

Reaction equation

HRID 1465185 reaction equation
[CH2:1]([O:3][C:4]1[C:5]([C:16]([O:18]CC)=[O:17])=[N:6][N:7]([C:9]2[CH:14]=[CH:13][C:12]([F:15])=[CH:11][CH:10]=2)[CH:8]=1)[CH3:2].[OH-].[K+]>CCO.C(Cl)Cl.O>[CH2:1]([O:3][C:4]1[C:5]([C:16]([OH:18])=[O:17])=[N:6][N:7]([C:9]2[CH:10]=[CH:11][C:12]([F:15])=[CH:13][CH:14]=2)[CH:8]=1)[CH3:2]

Participants

6

Reactant 2

HCID 14797Potassium HydroxideHCID 66611816Ethyl 4-ethoxy-1-(4-fluorophenyl)pyrazole-3-carboxylate

Product 1

HCID 336766774-ethoxy-1-(4-fluorophenyl)-1H-pyrazole-3-carboxylic acidYield 93.4%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

D2 (38 mmol, 1.0 eq.) and aq. KOH-solution (3M, 190 mmol, 5.0 eq.) in EtOH (152 mL) were heated for 45 min at 50° C. The mixture was cooled to RT and diluted with DCM and water. The aq. phase was washed a second time with DCM. The aq. phase was acidified with aq. HCl-solution (1N) to pH=1 and extracted with EtOAc. The combined organic phase was washed with brine and dried over Na2SO4. Removal of the solvent yielded the product D3 as a brown solid (8.88 g, 93% over 2 steps). 1H NMR (400 MHz, d6-DMSO, 300K) δ 1.34 (t, J=7.0 Hz, 3H), 4.02 (q, J=7.0 Hz, 2H), 7.37 (dd, J=J=9.0 Hz, 2H), 7.87 (dd, J=9.0 Hz, J=4.6 Hz, 2H), 8.38 (s, 1H), 12.68 (br s, 1H). MS (ES) C12H11FN2O3 requires: 250. Found: 251 (M+H)+ and 273 (M+Na)+.

Workup

  1. washThe aq. phase was washed a second time with DCM
  2. extractionextracted with EtOAc
  3. washThe combined organic phase was washed with brine
  4. dry with materialdried over Na2SO4
  5. customRemoval of the solvent

Sources & evidence

ORD record
ord-2e8ef89d5a6748dfaad9542f25ba378c
Source dataset
uspto-grants-2015_04
Patent number
US08999982B2

Reaction notes

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