Sodium Carbonate → Methyl 2-chloro-6-vinylbenzoate

HRID 1476821Notes

Reaction equation

HRID 1476821 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([Cl:12])[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:8]1[CH:9]=[CH:10][CH:11]=[C:2]([CH:14]=[CH2:15])[C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 2759827Methyl 2-bromo-6-chlorobenzoateHCID 23679353Potassium vinyltrifluoroborate

Product 1

HCID 90041379Methyl 2-chloro-6-vinylbenzoateYield 113.6%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
100 °C

Procedure

To a solution of methyl 2-bromo-6-chlorobenzoate (7.5 g, 0.03 mol) and potassium trifluoro(vinyl)borate (6.07 g, 0.045 mol) in dioxane and H2O (10:1, 100 mL) was added Pd(dppf)Cl2 (739 mg, 0.906 mmol), and sodium carbonate (6.4 g, 0.06 mol) at RT. The reaction mixture was heated at 100° C. for 12 hours under a nitrogen atmosphere. The mixture was subsequently concentrated in vacuo and diluted with water. The aqueous phase was extracted with EtOAc (3×100 mL). The organic layers were combined, washed with brine, dried over anhydrous Na2CO3, filtered, and concentrated. The crude product was purified by column chromatography eluting with a gradient of EtOAc (0-90%) and PE to give the title compound (6.7 g, 85%). 1H NMR (400 MHz, CDCl3) δ ppm 7.39-7.41 (m, 1H), 7.22-7.26 (m, 2H), 6.55-6.62 (m, 1H), 5.68 (d, J=17.2 Hz, 1H), 5.31 (d, J=11.2 Hz, 1H).

Workup

  1. concentrationThe mixture was subsequently concentrated in vacuo
  2. additiondiluted with water
  3. extractionThe aqueous phase was extracted with EtOAc (3×100 mL)
  4. washwashed with brine
  5. dry with materialdried over anhydrous Na2CO3
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was purified by column chromatography
  9. washeluting with a gradient of EtOAc (0-90%) and PE

Sources & evidence

ORD record
ord-e311476a99264ac8b199f1e3082f1635
Source dataset
uspto-grants-2016_08
Patent number
US09402841B2

Reaction notes

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