Dimethylformamide → 4-Phenoxy-5-(trimethylsilyl)-2-thiophenecarboxaldehyde

HRID 2081758Notes

Reaction equation

HRID 2081758 reaction equation
[O:1]([C:8]1[CH:12]=[CH:11][S:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.[CH3:18][Si:19](Cl)([CH3:21])[CH3:20].CN([CH:26]=[O:27])C>CCOCC.O>[O:1]([C:8]1[CH:12]=[C:11]([CH:26]=[O:27])[S:10][C:9]=1[Si:19]([CH3:21])([CH3:20])[CH3:18])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 6397ChlorotrimethylsilaneHCID 70189473-phenoxythiopheneHCID 178418339Butyllithium2×

Product 1

HCID 197804334-Phenoxy-5-(trimethylsilyl)-2-thiophenecarboxaldehydeYield 83%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

To a 0° C. solution of 3-phenoxythiophene (9.5 g, 53.9 mMol) in ether (200 mL) was added n-butyllithium (24 mL, 60 mMol, 2.5M in hexanes). The reaction was stirred for 15 min and trimethylsilyl chloride (6.45 g, 59.4 mMol) was added via syringe. The reaction was stirred 15 min and additional n-butyllithium (24 mL, 60 mMol, 2.5M in hexanes) was added and the reaction stirred 15 min. To the cold reaction mixture is added DMF (14 mL) and the reaction allowed to warm to room temperature over night. Water (5 mL) was added cautiously while stirring. The reaction mixture was diluted with ether and washed with water. The aqueous layer was washed with ether and the organic layer combined, washed with brine, dried (MgSO4), and concentrated. Purification by flash chromatography (SiO2, eluted with 5% ether/hexanes) afforded 4-phenoxy-5-trimethylsilylthiophene-2-carboxaldehyde (12.1 g, 83%) as a slightly yellow oil.

Workup

  1. stirringThe reaction was stirred 15 min
  2. stirringthe reaction stirred 15 min
  3. customTo the cold reaction mixture
  4. stirringwhile stirring
  5. washwashed with water
  6. washThe aqueous layer was washed with ether
  7. washwashed with brine
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated
  10. customPurification
  11. washby flash chromatography (SiO2, eluted with 5% ether/hexanes)

Sources & evidence

ORD record
ord-94af87b9e1624613806a3ec4b7106325
Source dataset
uspto-grants-1993_02
Patent number
US05185363

Reaction notes

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