Sodium Carbonate → 4-Methyl[1,1'-biphenyl]-2,3'-dicarboxylic acid

HRID 722789Notes

Reaction equation

HRID 722789 reaction equation
Br[C:2]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[C:12]([C:15]1[CH:16]=[C:17](B(O)O)[CH:18]=[CH:19][CH:20]=1)([OH:14])=[O:13].C([O-])([O-])=O.[Na+].[Na+]>COCCOC.O.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.CCOC(C)=O>[CH3:11][C:8]1[CH:7]=[C:3]([C:4]([OH:6])=[O:5])[C:2]([C:19]2[CH:18]=[CH:17][CH:16]=[C:15]([C:12]([OH:14])=[O:13])[CH:20]=2)=[CH:10][CH:9]=1

Participants

8

Reactant 3

HCID 10340Sodium CarbonateHCID 2280802-Bromo-5-methylbenzoic acidHCID 27339573-Carboxyphenylboronic acid

Product 1

HCID 218884604-Methyl[1,1'-biphenyl]-2,3'-dicarboxylic acidYield 37%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolventHCID 178418397HCID 178418397, compoundSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 2-bromo-5-methylbenzoic acid (5.00 g, 23.3 mmol) in DME (100 mL) were added 3-Carboxyphenylboronic acid (3.86 g; 23.3 mmol), a solution of Na2CO3 (9.90 g, 93 mmol) in H2O and tetrakis(triphenylphosphine)palladium. The mixture was stirred at 90° C. for 4 days. The mixture was allowed to cool to rt, diluted with EtOAc (50 mL), and washed with a saturated NaHCO3 solution. The aqueous layer was separated, acidified with 10% HCl, and extracted with EtOAc (3×20 mL). The combined extracts were dried over MgSO4 and concentrated. The crude material was purified by column chromatography (9:1 hexanes/EtOAc 1% acetic acid) to afford 4-methyl-[1,1′-biphenyl]-2,3′-dicarboxylic acid (2.20 g, 37%) as a solid: 1H NMR (DMSO-d6) δ 2.40 (s, 3H), 7.30 (m, 1H), 7.42 (m, 1H), 7.52–7.57 (m, 2H), 7.60 (s, 1H), 7.85 (s, 1H), 7.91–7.92 (m, 1H).

Workup

  1. temperatureto cool to rt
  2. washwashed with a saturated NaHCO3 solution
  3. customThe aqueous layer was separated
  4. extractionextracted with EtOAc (3×20 mL)
  5. dry with materialThe combined extracts were dried over MgSO4
  6. concentrationconcentrated
  7. customThe crude material was purified by column chromatography (9:1 hexanes/EtOAc 1% acetic acid)

Sources & evidence

ORD record
ord-4b15e76f6a38400f8c126186764da216
Source dataset
uspto-grants-2006_11
Patent number
US07138543B2

Reaction notes

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