Sodium Carbonate → Ethyl 3-bromo-1-(4-methoxybenzyl)-1H-thieno[2,3-c]pyrazole-5-carboxylate

HRID 1047614Notes

Reaction equation

HRID 1047614 reaction equation
[Br:1][C:2]1[C:6]([CH:7]=O)=[C:5](Br)[N:4]([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=2)[N:3]=1.[C:19]([O:23][CH2:24][CH3:25])(=[O:22])[CH2:20][SH:21].C(=O)([O-])[O-].[Na+].[Na+]>C(O)C>[Br:1][C:2]1[C:6]2[CH:7]=[C:20]([C:19]([O:23][CH2:24][CH3:25])=[O:22])[S:21][C:5]=2[N:4]([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=2)[N:3]=1

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 12185Ethyl ThioglycolateHCID 58051757HCID 58051757, compound

Product 1

HCID 66661729Ethyl 3-bromo-1-(4-methoxybenzyl)-1H-thieno[2,3-c]pyrazole-5-carboxylateYield 86%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

3,5-Dibromo-1-(4-methoxybenzyl)-1H-pyrazole-4-carbaldehyde (1.3301 g, 3.56 mmol), ethyl thioglycolate (0.419 ml, 3.73 mmol), and sodium carbonate (0.761 g, 7.18 mmol) were dissolved in ethanol (35 ml) at 25° C. under Ar in a sealed heavy-walled reaction vessel. The reaction mixture was warmed to 80° C. and allowed to stir for 4 h. The reaction was stopped, cooled to room temperature, quenched by addition of saturated aqueous ammonium chloride (40 mL), and the mixture extracted with ethyl acetate (3×30 mL). The combined organic phases were washed with saturated aqueous sodium chloride (1×20 mL), dried (sodium sulfate), filtered, and the solvent evaporated under reduced pressure. The crude product was purified by flash chromatography (RediSep SiO2, 120 g column) on a CombiFlash Rf purification system eluting with ethyl acetate-hexanes (0-25%). The title compound (1.2063 g, 3.05 mmol, 86% yield) was recovered as a white solid. LC-MS [M+1]=395.2.

Workup

  1. temperaturecooled to room temperature
  2. customquenched by addition of saturated aqueous ammonium chloride (40 mL)
  3. extractionthe mixture extracted with ethyl acetate (3×30 mL)
  4. washThe combined organic phases were washed with saturated aqueous sodium chloride (1×20 mL)
  5. dry with materialdried (sodium sulfate)
  6. filtrationfiltered
  7. customthe solvent evaporated under reduced pressure
  8. customThe crude product was purified by flash chromatography (RediSep SiO2, 120 g column) on a CombiFlash Rf purification system
  9. washeluting with ethyl acetate-hexanes (0-25%)

Sources & evidence

ORD record
ord-0f2d46e88b4a4c5d907b28ee5a41374e
Source dataset
uspto-grants-2013_10
Patent number
US08569512B2

Reaction notes

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