Hypodiphosphorous tetraiodide → 5-(3,5-Dichloro-phenylsulfanyl)-1-isopropyl-4-pyridin-4-ylmethyl-1H-pyrazole-3-carboxylic acid ethyl ester

HRID 1862465Notes

Reaction equation

HRID 1862465 reaction equation
P(I)(I)P(I)I.[CH2:7]([O:9][C:10]([C:12]1[C:16]([CH:17]([C:19]2[CH:24]=[CH:23][N:22]=[CH:21][CH:20]=2)O)=[C:15]([S:25][C:26]2[CH:31]=[C:30]([Cl:32])[CH:29]=[C:28]([Cl:33])[CH:27]=2)[N:14]([CH:34]([CH3:36])[CH3:35])[N:13]=1)=[O:11])[CH3:8].S(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1>[CH2:7]([O:9][C:10]([C:12]1[C:16]([CH2:17][C:19]2[CH:20]=[CH:21][N:22]=[CH:23][CH:24]=2)=[C:15]([S:25][C:26]2[CH:27]=[C:28]([Cl:33])[CH:29]=[C:30]([Cl:32])[CH:31]=2)[N:14]([CH:34]([CH3:35])[CH3:36])[N:13]=1)=[O:11])[CH3:8]

Participants

5

Reactant 3

HCID 83484Hypodiphosphorous tetraiodideHCID 23665763Sodium BisulfiteHCID 693543725-(3,5-dichlorophenylsulfanyl)-4-[(4-pyridyl)hydroxymethyl]-1-isopropyl-1H-pyrazole-3-carboxylic acid ethyl ester

Product 1

HCID 693539885-(3,5-Dichloro-phenylsulfanyl)-1-isopropyl-4-pyridin-4-ylmethyl-1H-pyrazole-3-carboxylic acid ethyl esterYield 74.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
80 °C

Procedure

A solution containing 660 mg of diphosphorus tetraiodide in 5 ml of anhydrous toluene was heated at 80° C. for 20 min under nitrogen in the dark. The mixture was then treated dropwise with a solution of 674 mg of 5-(3,5-dichlorophenylthio)-4-[(4-pyridyl)hydroxymethyl]-1-isopropyl-1H-pyrazole-3-carboxylic acid ethyl ester in 5 ml of anhydrous toluene. The mixture was stirred at 80° C. for 1 h and then left to cool to room temperature. The mixture was treated with 10 ml of a 10% solution of sodium bisulphite and then stirred at room temperature for 1 h. The mixture was partitioned between ethyl acetate and water then extracted 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 483 mg of 5-(3,5-dichlorophenylthio)-1-isopropyl-4-[(4-pyridyl)methyl]-1H-pyrazole-3-carboxylic acid ethyl ester as a pale yellow gum. Mass spectrum (ESI) m/z 450 [M+H]+.

Workup

  1. waitleft
  2. temperatureto cool to room temperature
  3. stirringstirred at room temperature for 1 h
  4. customThe mixture was partitioned between ethyl acetate and water
  5. extractionthen extracted three times
  6. washThe combined extracts were washed with brine
  7. dry with materialthen dried over anhydrous magnesium sulphate
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by flash chromatography on silica gel
  11. washfor the elution

Sources & evidence

ORD record
ord-bb5698c1e27a45228f3bcbfcbb7185ca
Source dataset
uspto-grants-2003_03
Patent number
US06538015B1

Reaction notes

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