3-Chloro-p-toluonitrile → HCID 17965937, compound

HRID 2253320Notes

Reaction equation

HRID 2253320 reaction equation
Cl[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[CH3:10])[C:5]#[N:6].[CH2:11]([O:13][C:14]1[CH:15]=[C:16](B(O)O)[CH:17]=[CH:18][CH:19]=1)[CH3:12].[F-].[K+]>C1COCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1>[CH2:11]([O:13][C:14]1[CH:19]=[C:18]([C:2]2[C:9]([CH3:10])=[CH:8][CH:7]=[C:4]([C:5]#[N:6])[CH:3]=2)[CH:17]=[CH:16][CH:15]=1)[CH3:12]

Participants

7

Reactant 3

HCID 888943-Chloro-p-toluonitrileHCID 522689Potassium FluorideHCID 27739203-Ethoxybenzeneboronic acid

Product 1

HCID 17965937HCID 17965937, compoundYield 99%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 27342162-(Dicyclohexylphosphino)biphenylCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 3-chloro-4-methylbenzonitrile (3.03 g, 20 mmol), 3-ethoxyphenylboronic acid (4.98 g, 30 mmol), palladium acetate (74 mg, 0.4 mmol), 2-dicyclohexylphosphanyl-biphenyl (0.210 g, 0.6 mmol), and KF (3.48 g, 60 mmol) in THF (25 mL) at room temperature was stirred for 12 hours and concentrated. The concentrate was dissolved in ethyl acetate (10 mL), washed with brine, dried (MgSO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 4:100 ethyl acetate/hexanes to provide 4.68 g (99%) of the desired product. MS (DCI/NH3) m/z 255 (M+NH4)+; 1H NMR (CDCl3) δ 7.54-7.51 (m, 2H), 7.36-7.31 (m, 2H), 6.93 (m, 1H), 6.85-6.78 (m, 2H), 4.07 (q, 2H), 2.32 (s, 3H), 1.34 (t, 3H).

Workup

  1. concentrationconcentrated
  2. dissolutionThe concentrate was dissolved in ethyl acetate (10 mL)
  3. washwashed with brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe concentrate was purified by flash column chromatography on silica gel with 4:100 ethyl acetate/hexanes

Sources & evidence

ORD record
ord-b8b9142d52844dc39579e46f2adf81b4
Source dataset
uspto-grants-2008_01
Patent number
US07323570B2

Reaction notes

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