4-Bromo-6-methoxyquinoline → 6-Methoxy-4-vinyl-quinoline

HRID 1364305Notes

Reaction equation

HRID 1364305 reaction equation
[CH:1]([Mg]Cl)=[CH2:2].Br[C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([O:16][CH3:17])[CH:14]=2)[N:9]=[CH:8][CH:7]=1>C1COCC1.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]>[CH3:17][O:16][C:13]1[CH:14]=[C:15]2[C:10](=[CH:11][CH:12]=1)[N:9]=[CH:8][CH:7]=[C:6]2[CH:1]=[CH2:2]

Participants

5

Reactant 2

HCID 111607474-Bromo-6-methoxyquinolineHCID 178461836HCID 178461836, compound

Product 1

HCID 590262186-Methoxy-4-vinyl-quinolineYield 21.6%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

InCl3 (1.1 g, 5 mmol) was dried under HV by heating with a heat gun. After cooling under N2 atmosphere, THF (25 mL) was added and the mixture sonicated until a solution had formed. This solution was cooled to −78° C., and a 1.7M solution of vinyl magnesium chloride (15 mmol) was added dropwise. The mixture was stirred at −78° C. for 15 min, warmed to rt and the resulting solution was added to a refluxing mixture of 4-bromo-6-methoxy-quinoline (1.85 g, 10 mmol) and Pd(dppf)Cl2.CH2Cl2 complex (0.408 g) in THF (25 mL). The mixture was refluxed for 2 h until tlc indicated complete conversion. The mixture was cooled to rt, quenched by addition of a few drops of MeOH and SiO2 (20 g) was added. The volatiles were removed under reduced pressure and the residue was chromatographed over SiO2 (Hex/EA 1:1) to give the desired compound (0.4 g, 21% yield) as a yellowish oil.

Workup

  1. temperatureby heating with a heat gun
  2. temperatureAfter cooling under N2 atmosphere
  3. customthe mixture sonicated until a solution
  4. customhad formed
  5. temperaturewarmed to rt
  6. temperatureThe mixture was refluxed for 2 h until tlc indicated complete conversion
  7. temperatureThe mixture was cooled to rt
  8. customquenched by addition of a few drops of MeOH and SiO2 (20 g)
  9. additionwas added
  10. customThe volatiles were removed under reduced pressure
  11. customthe residue was chromatographed over SiO2 (Hex/EA 1:1)

Sources & evidence

ORD record
ord-53f22173915945b7b4f8d9ca7e7cead6
Source dataset
uspto-grants-2011_02
Patent number
US07888359B2

Reaction notes

Loading…