2-Chlorophenylboronic acid → 5-(2-Chlorophenyl)-4-cyano-3-nitroanisole

HRID 353042Notes

Reaction equation

HRID 353042 reaction equation
Br[C:2]1[C:3]([C:13]#[N:14])=[C:4]([N+:10]([O-:12])=[O:11])[CH:5]=[C:6]([O:8][CH3:9])[CH:7]=1.[Cl:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1B(O)O>C1(C)C=CC=CC=1.CCO.C(=O)([O-])[O-].[Na+].[Na+].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>[Cl:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[C:2]1[C:3]([C:13]#[N:14])=[C:4]([N+:10]([O-:12])=[O:11])[CH:5]=[C:6]([O:8][CH3:9])[CH:7]=1

Participants

7

Reactant 2

HCID 27343222-Chlorophenylboronic acidHCID 227070275-Bromo-4-cyano-3-nitroanisole

Product 1

HCID 227070565-(2-Chlorophenyl)-4-cyano-3-nitroanisoleYield 100%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolventHCID 10340Sodium CarbonateSolvent

Procedure

5-Bromo-4-cyano-3-nitroanisole [prepared by the method of Harrison et al, J. Chem. Soc. C, 1769 (1966)] (250 mg, 0.86 mmol) and 2-chlorophenylboronic acid (150 mg, 0.96 mmol) were dissolved in a mixture of toluene (10 ml), EtOH (5.6 ml), and 1N aqueous sodium carbonate (1.7 ml). The solution was placed under a nitrogen atmosphere and tetrakis(triphenylphosphine)palladium (30 mg, 0.03 mmol) added. After refluxing for 3 h, the solvent was removed from the reaction mixture under reduced pressure. The residue was partitioned between H2O (50 ml) and EtOAc (50 ml) and the EtOAc layer washed with H2O (2×50 ml), and dried over MgSO4. Following removal of the solvent, the crude material was purified on silica gel, eluting with hexane/ether (1/1, v/v). This gave the subtitle compound as a colourless gum (252 mg, 100%). Rf 0.38 (hexane/ether 1:1, v/v). MS m/z 306 and 308 (MNH4+).

Workup

  1. temperatureAfter refluxing for 3 h
  2. customthe solvent was removed from the reaction mixture under reduced pressure
  3. customThe residue was partitioned between H2O (50 ml) and EtOAc (50 ml)
  4. washthe EtOAc layer washed with H2O (2×50 ml)
  5. dry with materialdried over MgSO4
  6. customremoval of the solvent
  7. customthe crude material was purified on silica gel
  8. washeluting with hexane/ether (1/1

Sources & evidence

ORD record
ord-3f317aa58e3b4b10a40dc6de244f7d94
Source dataset
uspto-grants-2004_06
Patent number
US06750214B2

Reaction notes

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