Stannane, tributyl(1-ethoxyethenyl)- → 6-(1-Ethoxyvinyl)-2-(dimethylamino)-7-fluoro-5-methyl-1,3-benzoxazole-4-carbonitrile

HRID 17439

Reaction equation

HRID 17439 reaction equation
Br[C:2]1[C:3]([F:17])=[C:4]2[O:8][C:7]([N:9]([CH3:11])[CH3:10])=[N:6][C:5]2=[C:12]([C:15]#[N:16])[C:13]=1[CH3:14].C([Sn](CCCC)(CCCC)[C:23]([O:25][CH2:26][CH3:27])=[CH2:24])CCC>C1(C)C=CC=CC=1.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.C(C1(C)C(O)=C(C(C)(C)C)C=CC1)(C)(C)C>[CH2:26]([O:25][C:23]([C:2]1[C:3]([F:17])=[C:4]2[O:8][C:7]([N:9]([CH3:11])[CH3:10])=[N:6][C:5]2=[C:12]([C:15]#[N:16])[C:13]=1[CH3:14])=[CH2:24])[CH3:27]

Participants

6

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 685849786-Bromo-2-(dimethylamino)-7-fluoro-5-methyl-1,3-benzoxazole-4-carbonitrile

Product 1

HCID 685855916-(1-Ethoxyvinyl)-2-(dimethylamino)-7-fluoro-5-methyl-1,3-benzoxazole-4-carbonitrileYield 66%

Reagents, catalysts & solvents 3

HCID 666371922,6-Di-t-butylcresolCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Procedure

6-Bromo-2-(dimethylamino)-7-fluoro-5-methyl-1,3-benzoxazole-4-carbonitrile (I-168) (0.80 g, 2.68 mmol) was dissolved in toluene (25 ml), then tributyl(1-ethoxyvinyl)tin (1.30 ml, 3.85 mmol), 2,6-di-tert-butylcresol (12 mg, 0.05 mmol) and bis(triphenylphosphine)palladium(II) dichloride (0.10 g, 0.14 mmol) were added followed by heating under reflux for 3 days. The insoluble matter was removed by filtration through Celite, followed by washing with ethyl acetate. The solvent was evaporated away under reduced pressure, and the resulting residue was purified by silica gel column chromatography (dichloromethane:hexane=1:2 to 2:3 to 9:1 to dichloromethane:methanol=200:1) to obtain a brown solid (0.51 g, 66%).

Workup

  1. temperatureby heating
  2. temperatureunder reflux for 3 days
  3. customThe insoluble matter was removed by filtration through Celite
  4. washby washing with ethyl acetate
  5. customThe solvent was evaporated away under reduced pressure
  6. customthe resulting residue was purified by silica gel column chromatography (dichloromethane:hexane=1:2 to 2:3 to 9:1 to dichloromethane:methanol=200:1)

Sources & evidence

ORD record
ord-9295067eed32455cb27d4142ccdc3865
Source dataset
uspto-grants-2010_06
Patent number
US07737166B2

Linked notes

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