Water → 3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-(2-methyl-2-nitropropoxy)aniline

HRID 521639Notes

Reaction equation

HRID 521639 reaction equation
[Br:1]N1C(=O)CCC1=O.[CH3:9][N:10]1[C:14]([C:15]2[CH:16]=[C:17]([NH:29]C(=O)C)[CH:18]=[CH:19][C:20]=2[O:21][CH2:22][C:23]([CH3:28])([N+:25]([O-:27])=[O:26])[CH3:24])=[CH:13][CH:12]=[N:11]1.[OH-].[Na+].O>CO>[Br:1][C:13]1[CH:12]=[N:11][N:10]([CH3:9])[C:14]=1[C:15]1[CH:16]=[C:17]([CH:18]=[CH:19][C:20]=1[O:21][CH2:22][C:23]([CH3:28])([N+:25]([O-:27])=[O:26])[CH3:24])[NH2:29]

Participants

6

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 67265394HCID 67265394, compound

Product 1

HCID 672655183-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-(2-methyl-2-nitropropoxy)anilineYield 61%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

N-Bromosuccinimide (0.931 g, 5.23 mmol) was added to a suspension of N-(3-(2-Methyl-2H-pyrazol-3-yl)-4-(2-methyl-2-nitropropoxy)phenyl)acetamide (1.58 g, 4.75 mmol) in 10 mL of methanol, and the mixture was stirred at room temperature. A clear solution was obtained within minutes. After 20 min, a solution of sodium hydroxide (1.14 g, 28.5 mmol) in water (1.00 mL, 55.5 mmol) was added, and the solution was heated to 160° C. for 0.5 hr under microwave irradiation in a heavy walled sealed tube. The solvent was evaporated under reduced pressure, and the residue was taken up in saturated sodium bicarbonate and extracted twice with dichloromethane. The extracts were combined, dried with sodium sulfate, filtered, and evaporated to dryness. The crude product was purified by flash chromatography (ethyl acetate-hexanes 1:2, then 1:1) to afford the title compound as an off-white solid (1.07 g, 61%). LCMS m/z (%)=371.0 (M+H 81Br 36%), 369.1 (M+H 79Br 30%). 1H NMR (400 MHz, CDCl3) δ ppm 1.44 (s, 3H), 1.50 (s, 3H), 3.63 (s, 3H), 3.81 (d, J=9.85 Hz, 1H), 4.34 (d, J=9.85 Hz, 1H), 6.72 (d, J=1.52 Hz, 1H), 6.87-6.93 (m, 2H), 7.51 (s, 1H).

Workup

  1. customA clear solution was obtained within minutes
  2. temperaturethe solution was heated to 160° C. for 0.5 hr under microwave irradiation in a heavy walled sealed tube
  3. customThe solvent was evaporated under reduced pressure
  4. extractionextracted twice with dichloromethane
  5. dry with materialdried with sodium sulfate
  6. filtrationfiltered
  7. customevaporated to dryness
  8. customThe crude product was purified by flash chromatography (ethyl acetate-hexanes 1:2

Sources & evidence

ORD record
ord-761d52abfce64719942f55bf0ff28af9
Source dataset
uspto-grants-2016_05
Patent number
US09328107B2

Reaction notes

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