Sodium Carbonate → Methyl 2-ethenyl-6-methoxybenzoate

HRID 1476827Notes

Reaction equation

HRID 1476827 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([O:12][CH3:13])[C:3]=1[C:4]([O:6][CH3:7])=[O:5].[B-](F)(F)(F)[CH:15]=[CH2:16].[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]>[CH3:13][O:12][C:8]1[CH:9]=[CH:10][CH:11]=[C:2]([CH:15]=[CH2:16])[C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 13940770Methyl 2-bromo-6-methoxybenzoateHCID 23679353Potassium vinyltrifluoroborate

Product 1

HCID 15953550Methyl 2-ethenyl-6-methoxybenzoateYield 95.4%

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 mixture of methyl 2-bromo-6-methoxybenzoate (30 g, 0.12 mol) and potassium trifluoro(vinyl)borate (18 g, 0.13 mol) in dioxane and H2O (5:1, 360 mL) was added Pd(dppf)Cl2 (2.63 g, 0.0036 mol) and Na2CO3 (25.4 g, 0.24 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, diluted with water, and 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 petroleum ether (1-2%) and EtOAc to give the title compound (22 g, 95%). 1H NMR (400 MHz, CDCl3) δ ppm 7.33 (t, J=8.0 Hz, 1H), 7.18 (d, J=8.0 Hz, 1H), 6.85 (d, J=8.0 Hz, 1H), 6.67 (dd, J=11.0, 17.4 Hz, 1H), 5.75 (d, J=17.4 Hz, 1H), 5.35 (d, J=11.0 Hz, 1H), 3.93 (s, 3H), 3.84 (s, 3H); ESI-MS m/z [M+H]+ 193.

Workup

  1. concentrationThe mixture was subsequently concentrated in vacuo
  2. additiondiluted with water
  3. extractionextracted 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 petroleum ether (1-2%) and EtOAc

Sources & evidence

ORD record
ord-e10654343dbd4db4b39dc365d21d03df
Source dataset
uspto-grants-2016_08
Patent number
US09402841B2

Reaction notes

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