Ethylene Glycol → HCID 178466006, compound

HRID 1276125Notes

Reaction equation

HRID 1276125 reaction equation
[H-].[Na+].[Cl:3][C:4]1[C:13]([CH:14]=[N:15][NH:16]S(C2C=CC(C)=CC=2)(=O)=O)=[C:12]([Cl:27])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7].[CH3:28][C:29](=[O:32])[C:30]#[CH:31].C(O)[CH2:34][OH:35]>>[Cl:3][C:4]1[C:13]([C:14]2[NH:15][N:16]=[C:30]([C:29]([CH3:28])=[O:32])[CH:31]=2)=[C:12]([Cl:27])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH2:9][CH2:34][OH:35])=[O:7]

Participants

5

Reactant 4

HCID 174Ethylene GlycolHCID 15018Butyn-2-oneHCID 24758Sodium hydrideHCID 57220738HCID 57220738, compound

Product 1

HCID 178466006HCID 178466006, compoundYield 54%

Procedure

At -10° C. and under an atmosphere of protective gas, 250 ml of ethylene glycol were added to 1.5 g (62.3 mmol) of sodium hydride. The mixture was warmed to room temperature, 12.5 g (31.2 mmol) of methyl 2,4-dichloro-3-[N-(4-methylphenylsulfonylamino)iminomethyl]benzoate were added and the mixture was heated at 85° C. for 15 minutes. After cooling, the diazo compound was extracted with diethyl ether or ethyl acetate, the combined organic phases were washed with 10% strength aqueous sodium hydroxide solution and water and dried and a large part of the solvent was removed. 4.7 g (68.6 mmol) of 3-butyn-2-one were subsequently added and the mixture was heated at 80° C. for 2.5 hours. The mixture was stirred at room temperature for 48 hours and then washed with water, dried and concentrated. The residue was chromatographed over silica gel (eluent: cyclohexane/ethyl acetate=1/1). 5.75 g (54% of theory) of 2-hydroxyethyl 2,4-dichloro-3-(3-methylcarbonyl-1H-pyrazol-5-yl)benzoate were obtained.

Workup

  1. temperaturethe mixture was heated at 85° C. for 15 minutes
  2. temperatureAfter cooling
  3. extractionthe diazo compound was extracted with diethyl ether or ethyl acetate
  4. washthe combined organic phases were washed with 10% strength aqueous sodium hydroxide solution and water
  5. customdried
  6. customa large part of the solvent was removed
  7. temperaturethe mixture was heated at 80° C. for 2.5 hours
  8. washwashed with water
  9. customdried
  10. concentrationconcentrated
  11. customThe residue was chromatographed over silica gel (eluent: cyclohexane/ethyl acetate=1/1)

Sources & evidence

ORD record
ord-5e5d495d633b4c04bba7933a2d34f5fc
Source dataset
uspto-grants-2000_12
Patent number
US06165944

Reaction notes

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