Toluene → 4-(1,3-Thiazol-2-yl)benzaldehyde

HRID 341325Notes

Reaction equation

HRID 341325 reaction equation
Br[C:2]1[S:3][CH:4]=[CH:5][N:6]=1.[CH:7]([C:9]1[CH:14]=[CH:13][C:12](B(O)O)=[CH:11][CH:10]=1)=[O:8].C([O-])([O-])=O.[Na+].[Na+].C1(C)C=CC=CC=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(C)=O.O.CCCCCC.C(O)C>[S:3]1[CH:4]=[CH:5][N:6]=[C:2]1[C:12]1[CH:13]=[CH:14][C:9]([CH:7]=[O:8])=[CH:10][CH:11]=1

Participants

10

Reactant 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 764302-BromothiazoleHCID 5910734-Formylphenylboronic Acid

Product 1

HCID 105356554-(1,3-Thiazol-2-yl)benzaldehydeYield 85.9%

Reagents, catalysts & solvents 5

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

2-Bromothiazole (0.538 ml, 6.06 mmol), 4-formylphenylboronic acid (1.0 g, 6.67 mmol), and Na2CO3 (1.61 g) were suspended in the mixed solution of toluene (25 ml), ethanol (5 ml), and H2O (5 ml). The mixture was stirred at room temperature for 15 minutes under an argon gas atmosphere. After reducing the pressure inside of the reaction container by using a vacuum line, the mixture was degassed by introducing Ar gas and this procedure was repeated twice. After that, tetrakis(triphenylphosphine)palladium (0.701 g, 0.606 mmol) was added, and the mixture was stirred for 15 hours by heating under reflux. The end point of the reaction was confirmed on TLC (EtOAc:n-hexane=1:4), and the mixture was cooled to room temperature. H2O (50 ml) and EtOAc (50 ml) were added and the mixture was stirred for 15 minutes. Black insoluble matter was removed by filtration with Celite and the filtrate was separated by the step of extraction/separation. The organic layer was washed with saturated brine (50 ml) and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The resulting residue was purified on silica gel column chromatography (EtOAc:hexane=1:3) to obtain the title compound (985 mg) as an opaque white solid.

Workup

  1. customthe mixture was degassed
  2. additionby introducing Ar gas
  3. stirringthe mixture was stirred for 15 hours
  4. temperatureby heating
  5. temperatureunder reflux
  6. temperaturethe mixture was cooled to room temperature
  7. stirringthe mixture was stirred for 15 minutes
  8. customBlack insoluble matter was removed by filtration with Celite
  9. customthe filtrate was separated by the step of extraction/separation
  10. washThe organic layer was washed with saturated brine (50 ml)
  11. dry with materialdried over anhydrous magnesium sulfate
  12. customThe solvent was evaporated under reduced pressure
  13. customThe resulting residue was purified on silica gel column chromatography (EtOAc:hexane=1:3)

Sources & evidence

ORD record
ord-47e826acf11e4a37b03182eefe2b78e0
Source dataset
uspto-grants-2014_11
Patent number
US08895753B2

Reaction notes

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