Dimethylformamide → Ethyl 2-bromo-6-formyl-4H-thieno[3,2-b]pyrrole-5-carboxylate

HRID 1428195Notes

Reaction equation

HRID 1428195 reaction equation
O=P(Cl)(Cl)Cl.[Br:6][C:7]1[S:14][C:13]2[CH:12]=[C:11]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[NH:10][C:9]=2[CH:8]=1.CN([CH:23]=[O:24])C>>[Br:6][C:7]1[S:14][C:13]2[C:12]([CH:23]=[O:24])=[C:11]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[NH:10][C:9]=2[CH:8]=1

Participants

4

Reactant 3

HCID 6228Dimethylformamide2×HCID 24813Phosphorus oxychlorideHCID 13164349ethyl 2-bromo-4H-thieno[3,2-b]pyrrole-5-carboxylate

Product 1

HCID 58386865Ethyl 2-bromo-6-formyl-4H-thieno[3,2-b]pyrrole-5-carboxylateYield 75%

Procedure

To DMF (2.05 mL) cooled by ice/water was added POCl3 dropwise and the mixture was stirred for 30 min. A solution of carboxylate 61 (1.96 g, 7.15 mmol) in DMF (2.5 mL) was added at this temperature and the mixture was allowed to warm to room temperature then heated to 60° C. After 16 h, the reaction mixture was cooled to room temperature, and poured into ice/water. The mixture was extracted with EtOAc (3×20 mL) and the combined organic layers were washed with aqueous saturated NaHCO3 and brine, dried over Na2SO4. After removed the organic solvent, the residue was purified by column chromatography (EtOAc/Hexane: 1/4) to give the desired aldehyde 62 (1.62 g, 75%) as a white solid.

Workup

  1. temperaturethen heated to 60° C
  2. waitAfter 16 h
  3. temperaturethe reaction mixture was cooled to room temperature
  4. extractionThe mixture was extracted with EtOAc (3×20 mL)
  5. washthe combined organic layers were washed with aqueous saturated NaHCO3 and brine
  6. dry with materialdried over Na2SO4
  7. customAfter removed the organic solvent
  8. customthe residue was purified by column chromatography (EtOAc/Hexane: 1/4)

Sources & evidence

ORD record
ord-cf65ad3636aa4edd805e7cc351239ed8
Source dataset
uspto-grants-2015_01
Patent number
US08937067B2

Reaction notes

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