Dichloromethane → 1-(5-Chloro-2-methoxy-4-methyl-3-vinylphenyl)ethanone

HRID 1499825Notes

Reaction equation

HRID 1499825 reaction equation
[Cl:1][C:2]1[C:3]([CH3:14])=[C:4](I)[C:5]([O:11][CH3:12])=[C:6]([C:8](=[O:10])[CH3:9])[CH:7]=1.[CH3:15][C:16]1(C)C(C)(C)OB(C=C)O1.ClCCl.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:1][C:2]1[C:3]([CH3:14])=[C:4]([CH:15]=[CH2:16])[C:5]([O:11][CH3:12])=[C:6]([C:8](=[O:10])[CH3:9])[CH:7]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 52330122-Ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 866667971-(5-Chloro-3-iodo-2-methoxy-4-methylphenyl)ethanone

Product 1

HCID 866777491-(5-Chloro-2-methoxy-4-methyl-3-vinylphenyl)ethanoneYield 83.5%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1-(5-chloro-3-iodo-2-methoxy-4-methylphenyl)ethanone (1.0 g, 3.2 mmol, from Example 1, Step 2), 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane (0.66 mL, 3.9 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (0.26 g, 0.32 mmol) and potassium carbonate (1.3 g, 9.4 mmol) in 1,4-dioxane (10 mL) and water (5 mL) was degassed with N2 and heated at 80° C. overnight. After cooled to room temperature, the reaction mixture was diluted with water and ethyl acetate. The organic layer was washed with brine, dried over MgSO4, concentrated and purified on a silica gel column (eluting with 0 to 10% EtOAc in hexanes) to give the desired product (0.60 g, 82%). LCMS calculated for C12H14ClO2 (M+H)+: m/z=225.1; Found:225.1

Workup

  1. customwas degassed with N2
  2. temperatureAfter cooled to room temperature
  3. additionthe reaction mixture was diluted with water and ethyl acetate
  4. washThe organic layer was washed with brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. custompurified on a silica gel column (eluting with 0 to 10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-8fe16e7572cc4be6af057d9266233f16
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

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