Propyl mercaptan → Tert-butyl 1-(4-methoxycarbonylphenyl)-5-propylsulfanyl-pyrazole-4-carboxylate

HRID 1799387Notes

Reaction equation

HRID 1799387 reaction equation
Cl[C:2]1[N:6]([C:7]2[CH:12]=[CH:11][C:10]([C:13]([O:15][CH3:16])=[O:14])=[CH:9][CH:8]=2)[N:5]=[CH:4][C:3]=1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18].C(=O)([O-])[O-].[K+].[K+].[CH2:30]([SH:33])[CH2:31][CH3:32].C(OCC)(=O)C>C(#N)CCC>[CH3:16][O:15][C:13]([C:10]1[CH:11]=[CH:12][C:7]([N:6]2[C:2]([S:33][CH2:30][CH2:31][CH3:32])=[C:3]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH:4]=[N:5]2)=[CH:8][CH:9]=1)=[O:14]

Participants

6

Reactant 4

HCID 7848Propyl mercaptanHCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 57437894Tert-butyl 5-chloro-1-(4-methoxycarbonylphenyl)pyrazole-4-carboxylate2×

Product 1

HCID 59516064Tert-butyl 1-(4-methoxycarbonylphenyl)-5-propylsulfanyl-pyrazole-4-carboxylate

Reagents, catalysts & solvents 1

HCID 8008ButyronitrileSolvent

Procedure

tert-butyl 5-chloro-1-(4-methoxycarbonylphenyl)pyrazole-4-carboxylate (Intermediate #9) (2.016 g, 6.0 mmol) was dissolved in butyronitrile (30 mL), potassium carbonate (2.48 g, 18 mmol) and propanethiol (678 μL, 7.5 mmol) were added and the mixture heated to reflux for 5 h. Ethyl acetate (150 mL) was added and the mixture washed with water (4×25 mL), dried (MgSO4) and evaporated under reduced pressure. The residue was purified by chromatography on silica gel (120 g silica 0-25% EtOAc/isohexane) to give the title compound as a clear pale yellow oil that slowly crystallised on standing to a white solid. (2.01 g, 89%)

Workup

  1. temperaturethe mixture heated
  2. temperatureto reflux for 5 h
  3. washthe mixture washed with water (4×25 mL)
  4. dry with materialdried (MgSO4)
  5. customevaporated under reduced pressure
  6. customThe residue was purified by chromatography on silica gel (120 g silica 0-25% EtOAc/isohexane)

Sources & evidence

ORD record
ord-a94ee087a8e84296afdc5a213c1b95fc
Source dataset
uspto-grants-2013_01
Patent number
US08344016B2

Reaction notes

Loading…