Sodium Carbonate → 5-(4-Chlorophenyl)-2-methylaniline

HRID 1191529Notes

Reaction equation

HRID 1191529 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](B(O)O)=[CH:4][CH:3]=1.Br[C:12]1[CH:13]=[CH:14][C:15]([CH3:19])=[C:16]([CH:18]=1)[NH2:17].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>[NH2:17][C:16]1[CH:18]=[C:12]([C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=2)[CH:13]=[CH:14][C:15]=1[CH3:19]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 742994-Chlorophenylboronic acidHCID 27348055-Bromo-o-toluidine

Product 1

HCID 233905465-(4-Chlorophenyl)-2-methylanilineYield 96.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
20 °C

Procedure

Tetrakis(triphenylphosphine)palladium (0) (3.7 g, 0.003 mol) and 4-chlorophenylboronic acid (20.2 g, 0.13 mol) are added to a solution of 5-bromo-2-methylaniline (20 g, 0.1 mol) in 1,2-dimethoxyethane (200 ml). After stirring the reaction mixture for 15 minutes at 20° C., a solution of 20% aqueous sodium carbonate (300 ml) is added to the mixture, and the resulting mixture is heated at reflux for 24 hours. The reaction mixture is cooled to room temperature, diluted with water (600 ml) and extracted using ethyl acetate. The combined organic extracts are dried over anhydrous sodium sulfate, filtered and the filtrate evaporated in vacuo. The residue is further purified by column chromatography on silica gel, eluting with 7% ethyl acetate in hexane to give 3-amino-4′-chloro-4-methylbiphenyl (21.0 g).

Workup

  1. temperaturethe resulting mixture is heated
  2. temperatureat reflux for 24 hours
  3. temperatureThe reaction mixture is cooled to room temperature
  4. extractionextracted
  5. dry with materialThe combined organic extracts are dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customthe filtrate evaporated in vacuo
  8. customThe residue is further purified by column chromatography on silica gel
  9. washeluting with 7% ethyl acetate in hexane

Sources & evidence

ORD record
ord-fd2195e1600e4dfcab80cc22ff208c19
Source dataset
uspto-grants-2014_03
Patent number
US08680012B2

Reaction notes

Loading…