Water → Ethyl 6-bromo-1-benzothiophene-2-carboxylate

HRID 1802561Notes

Reaction equation

HRID 1802561 reaction equation
[H-].[Na+].[SH:3][CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[Br:10][C:11]1[CH:18]=[CH:17][C:14]([CH:15]=O)=[C:13](F)[CH:12]=1.O>CS(C)=O>[Br:10][C:11]1[CH:18]=[CH:17][C:14]2[CH:15]=[C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[S:3][C:13]=2[CH:12]=1

Participants

6

Reactant 4

HCID 962WaterHCID 12185Ethyl ThioglycolateHCID 24758Sodium hydrideHCID 1435174-Bromo-2-fluorobenzaldehyde

Product 1

HCID 13567982Ethyl 6-bromo-1-benzothiophene-2-carboxylate

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

Ethyl 6-bromo-1-benzothiophene-2-carboxylate was prepared by the following procedure: Sodium hydride (60% dispersion in mineral oil, 0.73 g, 18.3 mmol) was suspended in DMSO (10 mL) and ethyl mercaptoacetate (1.11 mL, 10.1 mmol) was added potionwise using a water bath to moderate the exotherm. On complete addition, the water bath was removed and stirring continued for 15 minutes. A solution of 4-bromo-2-fluorobenzaldehyde (1.86 g, 9.16 mmol) in DMSO (2 mL) was added in one portion. The dark solution was stirred for 15 minutes before pouring into cold water (300 mL). The products were extracted into Et2O (2×200 mL). The combined organic extracts were washed with brine, dried over MgSO4 and concentrated in vacuo. Purification of the residue by MPLC gave the desired product (pale yellow solid). 1H NMR (DMSO-d6) δ 8.37 (d, J=1.8 Hz, 1H), 8.17 (s, 1H), 7.94 (d, J=8.4 Hz, 1H), 7.60 (dd, J=8.4, 1.8 Hz, 1H), 4.32 (q, J=7.2 Hz, 2H), 1.30 (t, J=7.2 Hz, 3H).

Workup

  1. additionOn complete addition
  2. customthe water bath was removed
  3. stirringThe dark solution was stirred for 15 minutes
  4. extractionThe products were extracted into Et2O (2×200 mL)
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customPurification of the residue by MPLC

Sources & evidence

ORD record
ord-532ca82bf72442a29d944f8e1914d918
Source dataset
uspto-grants-2013_01
Patent number
US08349825B2

Reaction notes

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