Tributylvinyltin → 4-Ethenyl-5-methoxy-3-[3-(trifluoromethyl)phenyl]pyridazine

HRID 54653Notes

Reaction equation

HRID 54653 reaction equation
Br[C:2]1[C:7]([O:8][CH3:9])=[CH:6][N:5]=[N:4][C:3]=1[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([F:19])([F:18])[F:17])[CH:11]=1.[CH:20]([Sn](CCCC)(CCCC)CCCC)=[CH2:21]>CN(C=O)C.[CH2-]C1C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd+]>[CH:20]([C:2]1[C:7]([O:8][CH3:9])=[CH:6][N:5]=[N:4][C:3]=1[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([F:19])([F:18])[F:17])[CH:11]=1)=[CH2:21]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 199596684-Bromo-5-methoxy-3-[3-(trifluoromethyl)phenyl]pyridazine

Product 1

HCID 199596644-Ethenyl-5-methoxy-3-[3-(trifluoromethyl)phenyl]pyridazineYield 42%

Reagents, catalysts & solvents 2

HCID 11007180Palladium(2+) chloride phenylmethanide--triphenylphosphane (1/1/1/2)CatalystHCID 6228DimethylformamideSolvent

Procedure

4-Bromo-5-methoxy-3-[3-(trifluoromethyl)phenyl]pyridazine (1.0 g, 0.003 mole, Compound No. 57), vinyltributyltin (1.1 g, 0.0034 mole) and trans-benzyl(chloro)bis-(triphenylphosphine)-palladium(II) (20 mg) were heated to 110° C. in DMF (50 mL) under N2 for 4 h. The reaction was then cooled and partitioned between aqueous KF and ethyl acetate. The KF solution was extracted with additional ethyl acetate. The organic layers were washed with brine, dried (MgSO4), filtered through silica gel and then evaporated in vacuo. The crude oil was then chromatographed on a Prep-500 to give 4-ethenyl-5-methoxy-3-[3-(trifluoromethyl) phenyl]pyridazine (0.35 g, 42% yield, Compound No. 55) as a light brown solid.

Workup

  1. temperatureThe reaction was then cooled
  2. custompartitioned between aqueous KF and ethyl acetate
  3. extractionThe KF solution was extracted with additional ethyl acetate
  4. washThe organic layers were washed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered through silica gel
  7. customevaporated in vacuo
  8. customThe crude oil was then chromatographed on a Prep-500

Sources & evidence

ORD record
ord-9e11f7ea32a44890a8ea5e1631cd94c1
Source dataset
uspto-grants-1997_04
Patent number
US05623072

Reaction notes

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