Toluene → HCID 86666835, compound

HRID 510922Notes

Reaction equation

HRID 510922 reaction equation
FC(F)(F)S(O[C:7]1[C:12]([C:13](=[O:15])[CH3:14])=[CH:11][C:10]([Cl:16])=[C:9]([CH3:17])[C:8]=1[C:18]1[CH:23]=[CH:22][N:21]=[CH:20][CH:19]=1)(=O)=O.O1CCOC[CH2:27]1.ClCCl.C[Zn]C.C1(C)C=CC=CC=1>C(OCC)(=O)C.O>[Cl:16][C:10]1[C:9]([CH3:17])=[C:8]([C:18]2[CH:23]=[CH:22][N:21]=[CH:20][CH:19]=2)[C:7]([CH3:27])=[C:12]([C:13](=[O:15])[CH3:14])[CH:11]=1

Participants

8

Reactant 5

HCID 1140TolueneHCID 6344DichloromethaneHCID 312751,4-DioxaneHCID 86666836HCID 86666836, compoundHCID 178477796HCID 178477796, compound

Product 1

HCID 86666835HCID 86666835, compoundYield 69.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

A solution of 6-acetyl-4-chloro-3-methyl-2-pyridin-4-ylphenyl trifluoromethanesulfonate (0.40 g, 1.0 mmol) in 1,4-dioxane (10 mL, 130 mmol) was degassed with nitrogen and treated with [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (1:1) (41 mg, 0.051 mmol). The reaction mixture was degassed with nitrogen for 5 minutes, treated with 2.0 M dimethylzinc in toluene (0.76 mL, 1.5 mmol), and heated at 70° C. for 1.5 hours. The reaction mixture was cooled to room temperature diluted with ethyl acetate and water and filtered over celite to remove solids. The ethyl acetate layer was separated, washed with brine, dried over sodium sulfate, filtered, and concentrated to a crude brown gum. Purification by flash column chromatography using ethyl acetate in hexanes (0%-20%) gave the desired product (0.18 g, 69%). LCMS for C15H15ClNO (M+H)+: m/z=260.1. Found: 260.1.

Workup

  1. customThe reaction mixture was degassed with nitrogen for 5 minutes
  2. temperatureThe reaction mixture was cooled to room temperature
  3. filtrationfiltered over celite
  4. customto remove solids
  5. customThe ethyl acetate layer was separated
  6. washwashed with brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated to a crude brown gum
  10. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-b75b98a4bb044b95b0e15ae3eb8f1e82
Source dataset
uspto-grants-2015_08
Patent number
US09096600B2

Reaction notes

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