Ethyl Acetate → 5-methoxy-2-methyl-4-{2-methyl-5-(2-pyridyl)benzyl}-2,4-dihydro-3H-1,2,4-triazol-3-one

HRID 2296991Notes

Reaction equation

HRID 2296991 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([CH3:18])=[C:6]([CH:17]=1)[CH2:7][N:8]1[C:12]([O:13][CH3:14])=[N:11][N:10]([CH3:15])[C:9]1=[O:16].C[Sn](C)(C)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][N:22]=1.C(OCC)(=O)C>CN(C)C=O.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.[Cu]=O>[CH3:14][O:13][C:12]1[N:8]([CH2:7][C:6]2[CH:17]=[C:2]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][N:22]=3)[CH:3]=[CH:4][C:5]=2[CH3:18])[C:9](=[O:16])[N:10]([CH3:15])[N:11]=1

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 11021057Pyridine, 2-(trimethylstannyl)-HCID 120565184-(5-bromo-2-methylbenzyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

Product 1

HCID 183888005-methoxy-2-methyl-4-{2-methyl-5-(2-pyridyl)benzyl}-2,4-dihydro-3H-1,2,4-triazol-3-oneYield 41.4%

Reagents, catalysts & solvents 3

HCID 14829Copper oxideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
80 °C

Procedure

To a solution of 0.44 g (1.4 mmol) of 4-(5-bromo-2-methylbenzyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (the compound 299 of the present invention) in 8 ml of N,N-dimethylformamide were added 30 mg (0.042 mmol) of PdCl2(PPh3)2 and 0.12 g (1.4 mmol) of copper (II) oxide powder and the mixture was stirred at 80° C. under an atmosphere of nitrogen for 30 minutes. To the reaction mixture was added a solution of 0.48 g (2.0 mmol) of trimethyl(2-pyridyl)tin in 4 ml of N,N-dimethylformamide and the mixture was stirred at 80° C. under an atmosphere of nitrogen for 3 hours. After cooling to room temperature, the reaction mixture was poured into ice water, and ethyl acetate was added thereto. The mixture was filtered with cotton and separated, and the organic layer was washed twice with water, dried and concentrated. The residue (0.43 g) was subjected to silica gel preparative thin layer chromatography (developed with ethyl acetate) to obtain 0.18 g of 5-methoxy-2-methyl-4-{2-methyl-5-(2-pyridyl)benzyl}-2,4-dihydro-3H-1,2,4-triazol-3-one (the compound 152 of the present invention) as a viscous oil.

Workup

  1. stirringthe mixture was stirred at 80° C. under an atmosphere of nitrogen for 3 hours
  2. temperatureAfter cooling to room temperature
  3. additionwas added
  4. filtrationThe mixture was filtered with cotton
  5. customseparated
  6. washthe organic layer was washed twice with water
  7. customdried
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-ab854a2303bb43faaa59c3b9adbba2e8
Source dataset
uspto-grants-2002_12
Patent number
US06489487B1

Reaction notes

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