Tributylvinyltin → 6-methoxy-1-methyl-7-vinyl-3,4-dihydro-1H-[1,5]naphthyridin-2-one

HRID 1244057Notes

Reaction equation

HRID 1244057 reaction equation
Br[C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][C:8](=[O:13])[N:9]2[CH3:12])=[N:4][C:3]=1[O:14][CH3:15].[CH2:16]([Sn](CCCC)(CCCC)C=C)[CH2:17]CC>O1CCOCC1.O.C(OCC)(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd](Cl)Cl>[CH3:15][O:14][C:3]1[N:4]=[C:5]2[C:10](=[CH:11][C:2]=1[CH:16]=[CH2:17])[N:9]([CH3:12])[C:8](=[O:13])[CH2:7][CH2:6]2

Participants

7

Reactant 2

HCID 81998TributylvinyltinHCID 219318227-bromo-6-methoxy-1-methyl-3,4-dihydro-1H-[1,5]naphthyridin-2-one

Product 1

HCID 219317566-methoxy-1-methyl-7-vinyl-3,4-dihydro-1H-[1,5]naphthyridin-2-oneYield 36.7%

Reagents, catalysts & solvents 4

HCID 13169693Triphenylphosphine palladium dichlorideCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 690 mg (2.5 mmol) of 7-bromo-6-methoxy-1-methyl-3,4-dihydro-1H-[1,5]naphthyridin-2-one, 0.8 ml (2.7 mmol) of tri-n-butyl-vinyltin and 100 mg of bis(triphenylphosphine-palladium(II) chloride in 20 ml of dioxane was heated under nitrogen to 100° C. for 6 hours. The reaction mixture was cooled to room temperature and diluted with water and ethyl acetate. The ethyl acetate solution was washed with water several times. To this ethyl acetate solution was added 1 ml of saturated KF, and the mixture filtered. The filtrate was dried, evaporated, and the residue chromatographed on silica using 1 5 ethyl acetate/hexanes as the elutant. Appropriate fractions were combined and evaporated to afford 200 mg of 6-methoxy-1-methyl-7-vinyl-3,4-dihydro-1H-[1,5]naphthyridin-2-one. 1H NMR (CDCl3) δ 7.28 (s, 1H), 6.90 (d,d 1H), 5.75 (d, 1H), 5.35 (d, 1H), 3.95 (s, 3H), 3.26 (s, 3H), 3.0 (m, 2H), 2.7 (m, 2H) Mass spectrum: m/e=219.3 (p+1).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. washThe ethyl acetate solution was washed with water several times
  3. additionTo this ethyl acetate solution was added 1 ml of saturated KF
  4. filtrationthe mixture filtered
  5. customThe filtrate was dried
  6. customevaporated
  7. customthe residue chromatographed on silica using 1 5 ethyl acetate/hexanes as the elutant
  8. customevaporated

Sources & evidence

ORD record
ord-f0dc5f7502754a6cb5e5a63540cd4006
Source dataset
uspto-grants-2006_10
Patent number
US07119207B2

Reaction notes

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