Ethanol → HCID 18448504, compound

HRID 1269519Notes

Reaction equation

HRID 1269519 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]([CH3:13])=[C:6]([CH:12]=1)[C:7]([O:9][CH2:10][CH3:11])=[O:8].C(B(CC)[C:17]1[CH:18]=[N:19][CH:20]=[CH:21][CH:22]=1)C.C(=O)([O-])[O-].[Na+].[Na+].C(O)C>O1CCCC1.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2N(C)C)CCCCC1>[N:19]1[CH:20]=[CH:21][CH:22]=[C:17]([C:2]2[CH:3]=[CH:4][C:5]([CH3:13])=[C:6]([CH:12]=2)[C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH:18]=1

Participants

9

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 6428513-(Diethylboryl)pyridineHCID 21269135Ethyl 5-chloro-2-methylbenzoate

Product 1

HCID 18448504HCID 18448504, compoundYield 97.1%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

Ethyl 5-chloro-2-methylbenzoate (16.60 g, 83.56 mmol) and diethyl-(3-pyridyl)borane (13.52 g, 91.92 mmol) were dissolved in 100 mL tetrahydrofuran in a 500 mL round bottom flask equipped with a magnetic stirrer. Sodium carbonate (26.57 g, 250.69 mmol) and 50 mL water were added followed by palladium acetate (0.38 g, 1.67 mmol) and (2′-dicyclohexylphosphanyl-biphenyl-2-yl)-dimethyl-amine (AmPhos, 0.92 g, 2.51 mmol) and 25 mL ethanol. The mixture was heated at reflux for 6 h then cooled to ambient temperature. The mixture was diluted with 600 mL water and extracted with diethyl ether (2×300 mL). The organic phases were combined and extracted with 1N HCl (3×200 mL). The acidic extractions were combined and made basic with 5N aqueous sodium hydroxide. This basic layer was extracted with diethyl ether (3×500 mL) and the extracts were combined and dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield 19.57 g (97%) of ethyl 5-(3-pyridyl)-2-methylbenzoate as a brown oil.

Workup

  1. customequipped with a magnetic stirrer
  2. temperatureThe mixture was heated
  3. temperatureat reflux for 6 h
  4. extractionextracted with diethyl ether (2×300 mL)
  5. extractionextracted with 1N HCl (3×200 mL)
  6. extractionThe acidic extractions
  7. extractionThis basic layer was extracted with diethyl ether (3×500 mL)
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-6950fb9129b7406992e9ec8a239e1d5e
Source dataset
uspto-grants-2007_04
Patent number
US07199243B2

Reaction notes

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