5-Bromothiophene-2-carbaldehyde → 5-(3-Methylphenyl)-2-thiophenecarboxaldehyde

HRID 235100Notes

Reaction equation

HRID 235100 reaction equation
Br[C:2]1[S:6][C:5]([CH:7]=[O:8])=[CH:4][CH:3]=1.[CH3:9][C:10]1[CH:11]=[C:12](B(O)O)[CH:13]=[CH:14][CH:15]=1>COCCOC.C(O)C.C([O-])([O-])=O.[Na+].[Na+].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:9][C:10]1[CH:15]=[C:14]([C:2]2[S:6][C:5]([CH:7]=[O:8])=[CH:4][CH:3]=2)[CH:13]=[CH:12][CH:11]=1

Participants

7

Reactant 2

HCID 784285-Bromothiophene-2-carbaldehydeHCID 27339503-Tolylboronic acid

Product 1

HCID 35871725-(3-Methylphenyl)-2-thiophenecarboxaldehydeYield 90%

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 702EthanolSolventHCID 80711,2-DimethoxyethaneSolventHCID 10340Sodium CarbonateSolvent

Procedure

5-Bromo-2-thiophenecarboxaldehyde (5.09 g, 26.2 mmol) was added to a suspension of 907 mg (0.78 mmol) of tetrakis(triphenylphosphine) palladium (0) in 50 mL of DME, and the resulting mixture was stirred at room temperature for 15 min. To this mixture was added a solution of the 3-methylphenyl boronic acid (prepared above) in 10 mL of ethanol and 26 mL of 2M aqueous Na2CO3. The reaction was stirred at reflux for 24 hours, then cooled to room temperature, diluted, and extracted with ether. The organic extract was washed with water and brine, dried over MgSO4, and concentrated. The residue was purified by flash chromatography on silica gel, eluting with 5% ethyl acetate in hexane, to give 4.75 g (90% yield) of 5-(3-methylphenyl)-2-thiophenecarboxaldehyde. MS: 203 (M+H)+ 220 (M+NH4)+. NMR (CDCl3) d: 9.89 (s, 1H), 7.74 (d, 1H, J=5 Hz), 7.55-7.20 (m, 5H), 2.42 (s, 3H).

Workup

  1. stirringThe reaction was stirred
  2. temperatureat reflux for 24 hours
  3. temperaturecooled to room temperature
  4. additiondiluted
  5. extractionextracted with ether
  6. extractionThe organic extract
  7. washwas washed with water and brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. customThe residue was purified by flash chromatography on silica gel
  11. washeluting with 5% ethyl acetate in hexane

Sources & evidence

ORD record
ord-b6a7802920cb410fad2359108b0c9e15
Source dataset
uspto-grants-1997_01
Patent number
US05597832

Reaction notes

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