Ethanol → 4'-Methylsulfanyl-biphenyl-2-carbaldehyde

HRID 2416593Notes

Reaction equation

HRID 2416593 reaction equation
Br[C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].[CH3:10][S:11][C:12]1[CH:17]=[CH:16][C:15](B(O)O)=[CH:14][CH:13]=1.C(=O)([O-])[O-].[Na+].[Na+].C(O)C>C1(C)C=CC=CC=1.O>[CH3:10][S:11][C:12]1[CH:17]=[CH:16][C:15]([C:2]2[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=2[CH:4]=[O:5])=[CH:14][CH:13]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 811292-BromobenzaldehydeHCID 27339594-(Methylthio)phenylboronic acid

Product 1

HCID 13922174'-Methylsulfanyl-biphenyl-2-carbaldehydeYield 96.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

2-Bromobenzaldehyde (3.7 g, 20 mmol) and 4-(methylthio) benzeneboronic acid (3.36 g, 20 mmol) were dissolved in toluene (80 mL) and sodium carbonate (2M, 10 mL, 20 mmol) was added. To this reaction mixture was added ethanol (5 mL) followed by tetrakis (triphenylphosphine)palladium (240 mg, 0.2 mmol) and the reaction mixture was refluxed overnight under nitrogen atmosphere. The reaction mixture was cooled to room temperature and diluted with water (50 mL), stirred well, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water (2×50 mL), brine (1×50 mL), dried over sodium sulfate, filtered and the filtrate concentrated under reduced pressure to give the crude product. Purification by flash column chromatography using 5% ethyl acetate in hexane gave the title compound as a colorless thick oil (4.4 g, 96% yield). 1H NMR (CDCl3) δ9.98 (s, 1H), 8.01 (dd, J=7.8 Hz and 1.2 Hz, 1H), 7.6 (dt, J=7.5 and 1.4 Hz, 2H), 7.62-7.40 (m, 2H), 7.3-7.25 (m, 3H), 2.53 (s, 3H); LRMS (APIMS) m/z 329 (M+H)+.

Workup

  1. temperaturethe reaction mixture was refluxed overnight under nitrogen atmosphere
  2. customthe organic layer was separated
  3. extractionThe aqueous layer was extracted with ethyl acetate
  4. washThe combined organic layers were washed with water (2×50 mL), brine (1×50 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate concentrated under reduced pressure
  8. customto give the crude product
  9. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-fc572af570f54c319972e994ae65d9be
Source dataset
uspto-grants-2004_11
Patent number
US06825185B2

Reaction notes

Loading…