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

HRID 1499763Notes

Reaction equation

HRID 1499763 reaction equation
[Cl:1][C:2]1[C:3]([CH3:15])=[C:4](I)[C:5]([O:11][CH2:12][CH3:13])=[C:6]([C:8](=[O:10])[CH3:9])[CH:7]=1.[CH3:16][C:17]1(C)C(C)(C)OB(C=C)O1.ClCCl.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.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].O>[Cl:1][C:2]1[C:3]([CH3:15])=[C:4]([CH:16]=[CH2:17])[C:5]([O:11][CH2:12][CH3:13])=[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 866668651-(5-Chloro-2-ethoxy-3-iodo-4-methylphenyl)ethanone

Product 1

HCID 866776941-(5-Chloro-2-ethoxy-4-methyl-3-vinylphenyl)ethanoneYield 83.8%

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-2-ethoxy-3-iodo-4-methylphenyl)ethanone (1.1 g, 3.2 mmol, from Example 14, Step 1), 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)/water (5 mL) was degassed with N2 and heated at 80° C. overnight. After cooling to room temperature, the reaction mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, filtered, concentrated and purified on silica gel (eluting with 0 to 10% EtOAc in hexanes) to give the desired product (0.64 g, 82%). LCMS calculated for C13H16ClO2 (M+H)+: m/z=239.1; Found: 239.1.

Workup

  1. customwas degassed with N2
  2. temperatureAfter cooling to room temperature
  3. extractionthe reaction mixture was extracted with EtOAc
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified on silica gel (eluting with 0 to 10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-fc8a0633b1f64d0e9627f329208eb79b
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

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