Cesium carbonate → Methyl 5'-amino-2'-methyl-1,1'-biphenyl-4-carboxylate

HRID 970220Notes

Reaction equation

HRID 970220 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[CH3:9])[NH2:5].[CH3:10][O:11][C:12]([C:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1)=[O:13].C(=O)([O-])[O-].[Cs+].[Cs+]>COCCOC.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>[NH2:5][C:4]1[CH:6]=[CH:7][C:8]([CH3:9])=[C:2]([C:17]2[CH:18]=[CH:19][C:14]([C:12]([O:11][CH3:10])=[O:13])=[CH:15][CH:16]=2)[CH:3]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 82187Benzenamine, 3-bromo-4-methyl-HCID 27343694-Methoxycarbonylphenylboronic acid

Product 1

HCID 21090583Methyl 5'-amino-2'-methyl-1,1'-biphenyl-4-carboxylateYield 51.8%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

3-Bromo-4-methylaniline (744 mg, 4.0 mmol), (4-methoxycarbonylphenyl)boronic acid (864 mg, 4.8 mmol), tetrakis(triphenylphosphine)palladium (100 mg, 0.087 mmol) and caesium carbonate (2.4 g, 7.37 mmol) were mixed in DME (30 ml) and heated at 90° C. for 20 h. The reaction was absorbed onto silica applied to a silica SPE (10 g) and eluted with ethyl acetate/cyclohexane (0-100% ethyl acetate). The solvent was evaporated from the product fractions under vacuum to give methyl 5′-amino-2′-methyl-1,1′-biphenyl-4-carboxylate (500 mg, 43%). NMR; δH CDCl3 8.07,(2H, d), 7.38,(2H, d), 7.07,(1H, d), 6.67,(1H, dd), 6.60,(1H, d), 3.94,(3H, s), 2.14,(3H, s).

Workup

  1. customThe reaction was absorbed onto silica
  2. washeluted with ethyl acetate/cyclohexane (0-100% ethyl acetate)
  3. customThe solvent was evaporated from the product fractions under vacuum

Sources & evidence

ORD record
ord-a6db0e2759744dc19e4e27cf25ab6f56
Source dataset
uspto-grants-2007_12
Patent number
US07309800B2

Reaction notes

Loading…