Potassium Carbonate → Ethyl 6-(prop-1-en-2-yl)picolinate

HRID 706722Notes

Reaction equation

HRID 706722 reaction equation
Cl[C:2]1[N:7]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=1.[C:13]([B-](F)(F)F)([CH3:15])=[CH2:14].[K+].C([O-])([O-])=O.[K+].[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=C(S([O-])(=O)=O)C=2OC)CCCCC1.[Na+]>C(O[Pd]OC(=O)C)(=O)C.O1CCOCC1.O>[CH2:14]=[C:13]([C:2]1[N:7]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=1)[CH3:15]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 11063114Ethyl 6-chloropicolinateHCID 23670158Potassium (prop-1-en-2-yl)trifluoroborateHCID 23677046Sodium 2'-(dicyclohexylphosphino)-2,6-dimethoxybiphenyl-3-sulfonate

Product 1

HCID 67974687Ethyl 6-(prop-1-en-2-yl)picolinate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
0 °C

Procedure

A first flask was charged with 1,4-dioxane/H2O (50 mL/10 mL). The flask was cooled to 0° C. and vacuum was applied for 20 minutes. A second flask was charged with ethyl 6-chloropicolinate (4.200 g, 22.63 mmol), potassium isopropenyltrifluoroborate (4.353 g, 29.42 mmol), K2CO3 (4.378 g, 31.68 mmol), diacetoxypalladium (0.1524 g, 0.6789 mmol) and sodium 2′-(dicyclohexylphosphino)-2,6-dimethoxybiphenyl-3-sulfonate (0.6959 g, 1.358 mmol). The flask was also evacuated with vacuum and back filled with N2 three times. The cold degassed dioxane/H2O solution was added to the second flask, which was evacuated with vacuum and back filled with argon five times. The reaction mixture was then heated to 80° C. for 3 hours. The reaction was cooled to ambient temperature, filtered and concentrated under reduced pressure. The residue was diluted with EtOAc (200 mL), washed with saturated NaHCO3, dried (Na2SO4) and concentrated to give the desired product, which was used without further purification.

Workup

  1. customThe flask was also evacuated with vacuum
  2. additionback filled with N2 three times
  3. customThe cold degassed dioxane/H2O solution
  4. additionwas added to the second flask, which
  5. customwas evacuated with vacuum
  6. additionback filled with argon five times
  7. temperatureThe reaction mixture was then heated to 80° C. for 3 hours
  8. temperatureThe reaction was cooled to ambient temperature
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. additionThe residue was diluted with EtOAc (200 mL)
  12. washwashed with saturated NaHCO3
  13. dry with materialdried (Na2SO4)
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-b1ef068db361409dad5c94bbd075c340
Source dataset
uspto-grants-2015_11
Patent number
US09174981B2

Reaction notes

Loading…