Ethanol → 2'-Methoxy-5-nitro[1,1'-biphenyl]-3-carboxylic acid

HRID 1013263Notes

Reaction equation

HRID 1013263 reaction equation
I[C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)[C:5]([OH:7])=[O:6].CCO.[CH3:17][O:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1B(O)O.C([O-])([O-])=O.[Cs+].[Cs+]>C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].C1(C)C=CC=CC=1>[CH3:17][O:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[C:2]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[C:4]([C:5]([OH:7])=[O:6])[CH:3]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 10796Cesium carbonateHCID 805803-Iodo-5-nitrobenzoic acidHCID 27339582-Methoxyphenylboronic acid

Product 1

HCID 532254102'-Methoxy-5-nitro[1,1'-biphenyl]-3-carboxylic acidYield 92.8%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
130 °C

Procedure

3-Iodo-5-nitro-benzoic acid (10.0 g, 34 mmol) was dissolved in 17.5 mL warm EtOH. Toluene (17.5 mL) was added, followed by 2-methoxy-phenyl-boronic acid (5.7 g), Palladium tetra(triphenylphosphine) (1.26 g) and aqueous Cs2CO3 solution (12.23 g in 12.5 mL H2O). The reaction mixture was stirred under Argon atmosphere at 130° C. for 18 hours, then cooled to room temperature. Solvent was removed under reduced pressure, and the residue was partitioned between aqueous 1N HCl and EtOAc. The combined organic layers were washed with water, dried over Na2SO4, filtered and concentrated under reduced pressure. The resulting solid residue was added to a mixture of methylene chloride (50 mL)and hexanes (10 mL) and stirred for two hours. The mixture was filtered, and the resulting white solid was washed with cold methylene chloride/hexanes (5:1) and dried to give 8.62 g of 2′-methoxy-5-nitro-biphenyl-3-carboxylic acid, MS (M+H)=274.

Workup

  1. temperaturecooled to room temperature
  2. customSolvent was removed under reduced pressure
  3. customthe residue was partitioned between aqueous 1N HCl and EtOAc
  4. washThe combined organic layers were washed with water
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. additionThe resulting solid residue was added to a mixture of methylene chloride (50 mL)and hexanes (10 mL)
  9. stirringstirred for two hours
  10. filtrationThe mixture was filtered
  11. washthe resulting white solid was washed with cold methylene chloride/hexanes (5:1)
  12. customdried

Sources & evidence

ORD record
ord-6635258d2c594875bf7d82a0d53d8b46
Source dataset
uspto-grants-2011_07
Patent number
US07981914B2

Reaction notes

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