Sodium Carbonate → Methyl 3-bromobiphenyl-2-carboxylate

HRID 84949Notes

Reaction equation

HRID 84949 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([Br:12])[C:3]=1[C:4]([O:6][CH3:7])=[O:5].[C:13]1(B(O)O)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Na+].[Na+]>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.C1(C)C=CC=CC=1>[Br:12][C:8]1[CH:9]=[CH:10][CH:11]=[C:2]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 817273Methyl 2,6-dibromobenzoate

Product 1

HCID 13352656Methyl 3-bromobiphenyl-2-carboxylate

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

A mixture of the product from Example 114A (2.2 g, 7.5 mmol), phenylboronic acid (919 mg, 7.5 mmol), sodium carbonate (7.55 mL, 2 M aqueous solution, 15.1 mmol) tetrakis(triphenylphosphine)palladium(0) (261 mg, 0.23 mmol) and 50 mL of toluene were refluxed for 16 hours under nitrogen. The reaction was cooled and partitioned between 50 mL of water and 50 mL of ethyl acetate. The aqueous portion was separated and extracted with 2×25 mL of ethyl acetate and the combined organic extracts were washed with 2×25 mL of water and 1×25 mL of brine and dried over sodium sulfate. The organic solution was concentrated and the residue was purified via flash chromatography on a silica gel column (95:5 hexane:ethyl acetate) to afford the title compound. 1H NMR (300 MHz, DMSO-d6) δ ppm 3.63 (s, 3H) 7.35-7.60 (m, 6H) 7.71-7.79 (m, 2H); MS (DCI+) m/z 308.0 [M+NH4]+.

Workup

  1. temperaturewere refluxed for 16 hours under nitrogen
  2. temperatureThe reaction was cooled
  3. custompartitioned between 50 mL of water and 50 mL of ethyl acetate
  4. customThe aqueous portion was separated
  5. extractionextracted with 2×25 mL of ethyl acetate
  6. washthe combined organic extracts were washed with 2×25 mL of water and 1×25 mL of brine
  7. dry with materialdried over sodium sulfate
  8. concentrationThe organic solution was concentrated
  9. customthe residue was purified via flash chromatography on a silica gel column (95:5 hexane:ethyl acetate)

Sources & evidence

ORD record
ord-c1cb02d738834c31ad8427d728482b7e
Source dataset
uspto-grants-2014_09
Patent number
US08846951B2

Reaction notes

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