Ethyl Bromide → Methyl 4-(3-(2,6-dichlorophenyl)-4-ethyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)-2-methoxybenzoate

HRID 59304Notes

Reaction equation

HRID 59304 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[C:9]1[NH:13][C:12](=[O:14])[N:11]([C:15]2[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[C:17]([O:25][CH3:26])[CH:16]=2)[N:10]=1.[H-].[Na+].[CH2:29](Br)[CH3:30]>CN(C=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[C:9]1[N:13]([CH2:29][CH3:30])[C:12](=[O:14])[N:11]([C:15]2[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[C:17]([O:25][CH3:26])[CH:16]=2)[N:10]=1

Participants

5

Reactant 3

HCID 6332Ethyl BromideHCID 24758Sodium hydrideHCID 136492365methyl 4-(3-(2,6-dichlorophenyl)-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)-2-methoxybenzoate

Product 1

HCID 90026874Methyl 4-(3-(2,6-dichlorophenyl)-4-ethyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)-2-methoxybenzoateYield 37.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of methyl 4-(3-(2,6-dichlorophenyl)-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)-2-methoxybenzoate (Intermediate-21, 0.100 g, 0.25 mmol) in dry DMF (3 mL) was added NaH (0.012 g, 0.30 mmol) at 0° C. and the reaction mixture was stirred for 20-30 minutes. Ethyl bromide (0.028 g, 0.25 mmol) was added and the reaction mixture was further stirred at 60° C. for 5-6 h. The reaction mass was quenched with water and extracted in ethyl acetate. The organic layer was dried and concentrated to afford 0.040 g of the crude product which was further purified by column chromatography in basic alumina eluting with 0.5-1.0% methanol:DCM to afford 0.040 g of pure product. 1H NMR (300 MHz, DMSO d6): δ 1.13 (t, 3H), 3.54-3.56 (m, 2H), 3.78 (s, 3H), 3.86 (s, 3H), 7.65 (d, J=8.4 Hz, 1H), 7.77 (m, 4H), 7.84 (d, J=8.4 Hz, 1H); MS (m/z): 421.95 (M+H)+.

Workup

  1. stirringthe reaction mixture was further stirred at 60° C. for 5-6 h
  2. customThe reaction mass was quenched with water
  3. extractionextracted in ethyl acetate
  4. customThe organic layer was dried
  5. concentrationconcentrated
  6. customto afford 0.040 g of the crude product which
  7. customwas further purified by column chromatography in basic alumina eluting with 0.5-1.0% methanol

Sources & evidence

ORD record
ord-169c942ba65a42eeadf179f705b78389
Source dataset
uspto-grants-2016_09
Patent number
US09439890B2

Reaction notes

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