Stannane, tributyl(1-ethoxyethenyl)- → (+/-)-3-[(4-Acetyl-2,6-dimethylphenyl)amino]-5-chloro-1-[1-(methoxymethyl)propyl]-2(1H)-pyrazinone

HRID 324291Notes

Reaction equation

HRID 324291 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([NH:9][C:10]2[C:11](=[O:23])[N:12]([CH:17]([CH2:20][O:21][CH3:22])[CH2:18][CH3:19])[CH:13]=[C:14]([Cl:16])[N:15]=2)=[C:4]([CH3:24])[CH:3]=1.[CH2:25]([O:27]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:26]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=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.C1(C)C=CC=CC=1>[C:25]([C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([NH:9][C:10]2[C:11](=[O:23])[N:12]([CH:17]([CH2:20][O:21][CH3:22])[CH2:18][CH3:19])[CH:13]=[C:14]([Cl:16])[N:15]=2)=[C:4]([CH3:24])[CH:3]=1)(=[O:27])[CH3:26]

Participants

6

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 15485773(+/-)-3-[(4-Bromo-2,6-dimethylphenyl)amino]-5-chloro-1-[1-(methoxymethyl)propyl]-2(1H)-pyrazinone

Product 1

HCID 17870523(+/-)-3-[(4-Acetyl-2,6-dimethylphenyl)amino]-5-chloro-1-[1-(methoxymethyl)propyl]-2(1H)-pyrazinoneYield 39.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Procedure

To the product of Example 15 (250 mg), bis(triphenylphosphine)palladium(II) chloride (11 mg), and tetrakis(triphenylphosphine)palladium(0) (17 mg) in a dry flask under nitrogen was added toluene (1.5 mL) and 1-ethoxyvinyl tributyl tin (260 mg). The reaction was heated at reflux 18 hours, and then concentrated in vacuo. The residue was taken up in ether (15 mL) and saturated aqueous potassium fluoride (15 mL), and filtered. The layers were separated, and the ether layer was stirred with 1N HCl (aq., 15 mL). The layers were separated and the ether layer was dried over MgSO4 and concentrated. The crude product was chromatographed on silica gel using ethyl acetate/hexane (3:7) as eluent to afford the title compound (90 mg). Elemental analysis calcd. for C19H24N3O3Cl: C, 60.39; H, 6.40; N, 11.12. Found: C, 60.51; H, 6.31; N, 11.00.

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux 18 hours
  3. concentrationconcentrated in vacuo
  4. filtrationsaturated aqueous potassium fluoride (15 mL), and filtered
  5. customThe layers were separated
  6. customThe layers were separated
  7. dry with materialthe ether layer was dried over MgSO4
  8. concentrationconcentrated
  9. customThe crude product was chromatographed on silica gel

Sources & evidence

ORD record
ord-da2ae81c3e2242b48e944b07f11479ca
Source dataset
uspto-grants-2001_04
Patent number
US06218391B1

Reaction notes

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