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

HRID 1348886Notes

Reaction equation

HRID 1348886 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-80d2609bdae54374be92094a064a5733
Source dataset
uspto-grants-2007_05
Patent number
US07211595B2

Reaction notes

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