Methyl 3-Cyano-4-(trifluoromethylsulfonyloxy)benzoate → 3-Cyano-4-cyclohexylbenzoic acid methyl ester

HRID 2040545Notes

Reaction equation

HRID 2040545 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1OS(C(F)(F)F)(=O)=O)[C:6]([O:8][CH3:9])=[O:7])#[N:2].[Br-].[CH:22]1([Zn+])[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1>O1CCCC1.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[C:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1[CH:22]1[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1)[C:6]([O:8][CH3:9])=[O:7])#[N:2]

Participants

5

Reactant 2

HCID 53821226Methyl 3-Cyano-4-(trifluoromethylsulfonyloxy)benzoateHCID 178418970HCID 178418970, compound

Product 1

HCID 580208003-Cyano-4-cyclohexylbenzoic acid methyl ester

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of methyl 3-cyano-4-(trifluoromethylsulfonyloxy)benzoate (0.7 g, 2.26 mmol) in tetrahydrofuran (30 mL) was added 0.5 M cyclohexylzinc(II) bromide solution in tetrahydrofuran (13.6 mL, 6.8 mmol) and bis(tri-tert-butylphosphine)palladium (0.058 g, 0.113 mmol) at room temperature. The mixture was heated under reflux for 2 h. The mixture was allowed to cool to room temperature, quenched with saturated aqueous sodium bicarbonate solution and filtered through Celite®. The filtrate was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure and purified by silica gel column chromatography to provide the title compound as an oil (0.24 g). 1H NMR (400 MHz, CDCl3) δ ppm 1.24-1.33 (m, 1H), 1.42-1.53 (m, 4H), 1.77-1.84 (m, 1H), 1.86-1.95 (m, 4H), 2.99-3.08 (m, 1H), 3.93 (s, 3H), 7.45 (d, J=8.34 Hz, 1H), 8.17 (dd, J=8.15, 1.71 Hz, 1H), 8.27 (d, J=1.52 Hz, 1H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 2 h
  3. customquenched with saturated aqueous sodium bicarbonate solution
  4. filtrationfiltered through Celite®
  5. extractionThe filtrate was extracted with ethyl acetate
  6. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. custompurified by silica gel column chromatography

Sources & evidence

ORD record
ord-826fb11c4a1b4083a118fd38692761d4
Source dataset
uspto-grants-2013_11
Patent number
US08580841B2

Reaction notes

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