Sodium Carbonate → 5-(3,5-dichlorophenylsulfanyl)-4-[(4-pyridyl)hydroxymethyl]-1-isopropyl-1H-pyrazole-3-carboxylic acid ethyl ester

HRID 1862464Notes

Reaction equation

HRID 1862464 reaction equation
Cl.Br[C:3]1[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=1.C(=O)([O-])[O-].[Na+].[Na+].C([Mg]Cl)(C)C.[CH2:20]([O:22][C:23]([C:25]1[C:29]([CH:30]=[O:31])=[C:28]([S:32][C:33]2[CH:38]=[C:37]([Cl:39])[CH:36]=[C:35]([Cl:40])[CH:34]=2)[N:27]([CH:41]([CH3:43])[CH3:42])[N:26]=1)=[O:24])[CH3:21]>O1CCCC1.O>[CH2:20]([O:22][C:23]([C:25]1[C:29]([CH:30]([C:3]2[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=2)[OH:31])=[C:28]([S:32][C:33]2[CH:38]=[C:37]([Cl:39])[CH:36]=[C:35]([Cl:40])[CH:34]=2)[N:27]([CH:41]([CH3:42])[CH3:43])[N:26]=1)=[O:24])[CH3:21]

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 881004-Bromopyridinium chlorideHCID 867588885-(3,5-dichlorophenylsulfanyl)-4-formyl-1-isopropyl-1H-pyrazole-3-carboxylic acid ethyl esterHCID 178418918HCID 178418918, compound

Product 1

HCID 693543725-(3,5-dichlorophenylsulfanyl)-4-[(4-pyridyl)hydroxymethyl]-1-isopropyl-1H-pyrazole-3-carboxylic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

582 mg of 4-Bromopyridine hydrochloride was treated with a 5% sodium carbonate solution then extracted three times with anhydrous diethyl ether. The combined extracts were then dried over anhydrous magnesium sulphate, filtered and evaporated to give a colourless oil. The colourless oil was dissolved in 3 ml of anhydrous terahydrofuran under nitrogen at room temperature and then treated with 1.5 ml of isopropylmagnesium chloride (2M solution in tetrahydrofuran). The mixture was stirred at room temperature for 1.5 h and then treated with a solution of 5-(3,5-dichlorophenylsulfanyl)-4-formyl-1-isopropyl-1H-pyrazole-3-carboxylic acid ethyl ester in 3 ml of anhydrous tetrahydrofuran. The mixture was then stirred for 1 h. The mixture was then treated with water and extracted with dichloromethane three times. The combined extracts were washed with brine then dried over anhydrous magnesium sulphate, filtered and evaporated. The residue was purified by flash chromatography on silica gel using ethyl acetate/petroleum ether (1:1 to 2:1) for the elution to give 690 mg of 5-(3,5-dichlorophenylsulfanyl)-4-[(4-pyridyl)hydroxymethyl]-1-isopropyl-1H-pyrazole-3-carboxylic acid ethyl ester as a pale yellow oil. Mass spectrum (EST) m/z 466 [M+H]+.

Workup

  1. extractionthen extracted three times with anhydrous diethyl ether
  2. dry with materialThe combined extracts were then dried over anhydrous magnesium sulphate
  3. filtrationfiltered
  4. customevaporated
  5. customto give a colourless oil
  6. stirringThe mixture was then stirred for 1 h
  7. extractionextracted with dichloromethane three times
  8. washThe combined extracts were washed with brine
  9. dry with materialthen dried over anhydrous magnesium sulphate
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue was purified by flash chromatography on silica gel
  13. washfor the elution

Sources & evidence

ORD record
ord-7bb9a146bac746f6a25a66e522fd74c6
Source dataset
uspto-grants-2003_03
Patent number
US06538015B1

Reaction notes

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