3-Carboxyphenylboronic acid → 5'-Fluoro-2'-methoxy-3'-nitro-[1,1'-biphenyl]-3-carboxylic acid

HRID 384293Notes

Reaction equation

HRID 384293 reaction equation
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[C:4]([N+:9]([O-:11])=[O:10])[C:3]=1[O:12][CH3:13].[C:14]([C:17]1[CH:18]=[C:19](B(O)O)[CH:20]=[CH:21][CH:22]=1)([OH:16])=[O:15]>C(=O)([O-])[O-].[Na+].[Na+].O1CCOCC1.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>[F:8][C:6]1[CH:5]=[C:4]([N+:9]([O-:11])=[O:10])[C:3]([O:12][CH3:13])=[C:2]([C:21]2[CH:20]=[CH:19][CH:18]=[C:17]([C:14]([OH:16])=[O:15])[CH:22]=2)[CH:7]=1

Participants

6

Reactant 2

HCID 27339573-Carboxyphenylboronic acidHCID 234336121-Bromo-5-fluoro-2-methoxy-3-nitrobenzene

Product 1

HCID 574837925'-Fluoro-2'-methoxy-3'-nitro-[1,1'-biphenyl]-3-carboxylic acidYield 41.7%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 10340Sodium CarbonateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

1-Bromo-5-fluoro-2-methoxy-3-nitro-benzene 2c (16.18 g, 64.7 mmol), 3-carboxyphenylboronic acid (13.88 g, 77.7 mmol) and tetrakis(triphenylphosphine)palladium (3.73 g, 3.2 mmol) were dissolved in the solvent mixture of 65 mL of aqueous sodium carbonate (2 N) and 300 mL of 1,4-dioxane. The reaction mixture was heated to reflux at 120° C. for 24 hours. The reaction was monitored by TLC until the disappearance of the starting materials. The mixture was concentrated under reduced pressure and diluted with 150 mL of hydrochloric acid (6 N) and 200 mL of ethyl acetate. The aqueous layer was extracted with ethyl acetate (100 mL×2). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to obtain the title compound 5′-fluoro-2′-methoxy-3′-nitro-biphenyl-3-carboxylic acid 2d (7.86 g, yield 41.7%) as a yellow solid.

Workup

  1. temperatureThe reaction mixture was heated
  2. concentrationThe mixture was concentrated under reduced pressure
  3. additiondiluted with 150 mL of hydrochloric acid (6 N) and 200 mL of ethyl acetate
  4. extractionThe aqueous layer was extracted with ethyl acetate (100 mL×2)
  5. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3f20d75dba8c4af690d97dc19ae6b4ed
Source dataset
uspto-grants-2013_02
Patent number
US08367710B2

Reaction notes

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