Toluene → Ethyl 4'-chloro-2'-methyl-biphenyl-2-carboxylate

HRID 1799012Notes

Reaction equation

HRID 1799012 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1[CH3:9].CC1(C)C(C)(C)OB([C:18]2[CH:28]=[CH:27][CH:26]=[CH:25][C:19]=2[C:20]([O:22][CH2:23][CH3:24])=[O:21])O1.C1(C)C=CC=CC=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([C:18]2[C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:25][CH:26]=[CH:27][CH:28]=2)=[C:3]([CH3:9])[CH:4]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 62657Potassium Phosphate, TribasicHCID 844762-Bromo-5-chlorotolueneHCID 2773962Ethyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate

Product 1

HCID 59492872Ethyl 4'-chloro-2'-methyl-biphenyl-2-carboxylateYield 99%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Under an argon atmosphere, a mixture of 2-bromo-5-chloro-toluene (20.55 g), ethyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (55.23 g), toluene (200 ml), water (125 ml), tripotassium phosphate (53.07 g) and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride-dichloromethane complex (1.633 g) was stirred with heating under reflux for 1 hr. The reaction mixture was cooled to room temperature, activated carbon (1 g) was added and the mixture was stirred for 10 min at room temperature. The insoluble material was filtered off, and the filtrate was partitioned in a separatory funnel. The organic layer was washed twice with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure and the obtained residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=98/2) to give the title compound (27.20 g, 99%).

Workup

  1. temperaturewith heating
  2. temperatureunder reflux for 1 hr
  3. additionactivated carbon (1 g) was added
  4. stirringthe mixture was stirred for 10 min at room temperature
  5. filtrationThe insoluble material was filtered off
  6. customthe filtrate was partitioned in a separatory funnel
  7. washThe organic layer was washed twice with water
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated under reduced pressure
  11. customthe obtained residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=98/2)

Sources & evidence

ORD record
ord-7dea1526d28a46be8d2f20d49bab3a8e
Source dataset
uspto-grants-2013_01
Patent number
US08343994B2

Reaction notes

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