Dichloromethane → 4-Acetyl-6-chloro-3-ethoxy-2-vinylbenzonitrile

HRID 1499935Notes

Reaction equation

HRID 1499935 reaction equation
[C:1]([C:4]1[CH:11]=[C:10]([Cl:12])[C:7]([C:8]#[N:9])=[C:6](I)[C:5]=1[O:14][CH2:15][CH3:16])(=[O:3])[CH3:2].[CH3:17][C:18]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]>[C:1]([C:4]1[CH:11]=[C:10]([Cl:12])[C:7]([C:8]#[N:9])=[C:6]([CH:17]=[CH2:18])[C:5]=1[O:14][CH2:15][CH3:16])(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 52330122-Ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 866669594-Acetyl-6-chloro-3-ethoxy-2-iodobenzonitrile

Product 1

HCID 866778524-Acetyl-6-chloro-3-ethoxy-2-vinylbenzonitrile

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 4-acetyl-6-chloro-3-ethoxy-2-iodobenzonitrile (1.3 g, 3.6 mmol), 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane (740 μL, 4.3 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (100 mg, 0.20 mmol) and potassium carbonate (1.5 g, 11 mmol) in 1,4-dioxane (20 mL) and water (10 mL) was heated at 80° C. overnight. The mixture was cooled to room temperature and extracted with ethyl acetate. The extracts were washed with brine, dried over sodium sulfate, filtered and concentrated. Purification on silica gel using ethyl acetate in hexanes (0-20%) gave the desired compound, 780 mg, 87%. LCMS calculated for C13H13ClNO2 (M+H)+: m/z=250.1; found: 250.1. 1H NMR (400 MHz, DMSO-d6): δ 7.78 (s, 1 H), 6.83 (m, 1 H), 6.10 (m, 1 H), 5.83 (m, 1 H), 3.84 (m, 2 H), 2.58 (s, 3 H), 1.22 (m, 3 H).

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. extractionextracted with ethyl acetate
  3. washThe extracts were washed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification on silica gel

Sources & evidence

ORD record
ord-9bcfc61b180646439c1aa5951fa4e3ad
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

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