Sodium Carbonate → Methyl 5-chloro-2-ethenylbenzoate

HRID 1476815Notes

Reaction equation

HRID 1476815 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:9]([Cl:12])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[B-](F)(F)(F)[CH:14]=[CH2:15].[K+].C(=O)([O-])[O-].[Na+].[Na+]>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:12][C:9]1[CH:10]=[CH:11][C:2]([CH:14]=[CH2:15])=[C:3]([CH:8]=1)[C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 280500Methyl 2-Bromo-5-chlorobenzoateHCID 23679353Potassium vinyltrifluoroborate

Product 1

HCID 15110998Methyl 5-chloro-2-ethenylbenzoateYield 398.4%

Reagents, catalysts & solvents 3

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

Procedure

A stirred suspension of methyl 2-bromo-5-chlorobenzoate (10 g, 40.08 mmol), potassium trifluoro(vinyl)borate (8.05 g, 60.12 mmol), Pd(dppf)Cl2 (1.64 g, 2.0 mmol) and sodium carbonate (8.5 g, 80.16 mmol) in dioxane (150 mL) and water (15 mL) was refluxed for 8 hours under a nitrogen atmosphere. After cooling to RT, the mixture was filtered, concentrated, and the crude product was purified by column chromatography eluting with petroleum ether and ethyl acetate (PE/EtOAc=100:1-50:1 gradient) to give the title compound (31.4 g, 76.4%). 1H NMR (400 MHz, CDCl3) δ ppm 7.80 (d, J=2.0 Hz, 1H), 7.45 (d, J=8.0 Hz, 1H), 7.31-7.39 (m, 2H), 5.57 (d, J=17.6 Hz, 1H), 5.31 (d, J=10.8 Hz, 1H), 3.83 (s, 3H).

Workup

  1. temperaturewas refluxed for 8 hours under a nitrogen atmosphere
  2. filtrationthe mixture was filtered
  3. concentrationconcentrated
  4. customthe crude product was purified by column chromatography
  5. washeluting with petroleum ether and ethyl acetate (PE/EtOAc=100:1-50:1 gradient)

Sources & evidence

ORD record
ord-386f2988871846848f84978549f642f5
Source dataset
uspto-grants-2016_08
Patent number
US09402841B2

Reaction notes

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