Sodium Fluoride → 4-Methoxy-3-(2-methylphenoxy)-6-vinylpyridazine

HRID 2424299Notes

Reaction equation

HRID 2424299 reaction equation
Cl[C:2]1[N:7]=[N:6][C:5]([O:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[CH3:15])=[C:4]([O:16][CH3:17])[CH:3]=1.[CH2:18]([Sn](CCCC)(CCCC)C=C)[CH2:19]CC.C(OCC)(=O)C.[F-].[Na+]>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH3:17][O:16][C:4]1[CH:3]=[C:2]([CH:18]=[CH2:19])[N:7]=[N:6][C:5]=1[O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[CH3:15]

Participants

8

Reactant 4

HCID 5235Sodium FluorideHCID 8857Ethyl AcetateHCID 81998TributylvinyltinHCID 229401366-Chloro-4-methoxy-3-(2-methylphenoxy)pyridazine

Product 1

HCID 230140894-Methoxy-3-(2-methylphenoxy)-6-vinylpyridazineYield 88.6%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

In toluene (2 mL) was dissolved 123 mg (0.490 mmol) of 6-chloro-4-methoxy-3-(2-methylphenoxy)pyridazine obtained in Example 2 (1), 246 mg (0.776 mmol) of tributyl(vinyl) tin, and then, 119 mg (0.103 mmol) of tetrakis(triphenylphosphine)palladium were successively added to the solution at room temperature, and the resulting mixture was refluxed for 3 hours. The reaction mixture was allowed to stand for cooling, ethyl acetate (5 mL), water (3 mL) and sodium fluoride were added to the mixture, and the resulting mixture was stirred for 30 minutes and allowed to stand at room temperature overnight. The mixture was filtered through Celite, ethyl acetate was added to the filtrate, then the organic layer was separated and washed with brine. After drying over anhydrous sodium sulfate, the solvent was removed. The obtained residue was purified by silica gel column chromatography (eluted with hexane:ethyl acetate=1:2) to obtain 105 mg (0.434 mmol, Yield: 88.6%) of 4-methoxy-3-(2-methylphenoxy)-6-vinylpyridazine.

Workup

  1. temperaturethe resulting mixture was refluxed for 3 hours
  2. temperaturefor cooling
  3. waitto stand at room temperature overnight
  4. filtrationThe mixture was filtered through Celite, ethyl acetate
  5. additionwas added to the filtrate
  6. customthe organic layer was separated
  7. washwashed with brine
  8. dry with materialAfter drying over anhydrous sodium sulfate
  9. customthe solvent was removed
  10. customThe obtained residue was purified by silica gel column chromatography (eluted with hexane:ethyl acetate=1:2)

Sources & evidence

ORD record
ord-240f5794aef6411b96a115fc5b6726ba
Source dataset
uspto-grants-2011_06
Patent number
US07964531B2

Reaction notes

Loading…