1-(5-fluoro-2-methoxy-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole → 2-fluoro-5-methoxy-4-(3-methyl-1H-1,2,4-triazol-1-yl)aniline

HRID 475728Notes

Reaction equation

HRID 475728 reaction equation
[F:1][C:2]1[C:3]([N+:16]([O-])=O)=[CH:4][C:5]([O:14][CH3:15])=[C:6]([N:8]2[CH:12]=[N:11][C:10]([CH3:13])=[N:9]2)[CH:7]=1>[Pd].CO>[F:1][C:2]1[CH:7]=[C:6]([N:8]2[CH:12]=[N:11][C:10]([CH3:13])=[N:9]2)[C:5]([O:14][CH3:15])=[CH:4][C:3]=1[NH2:16]

Participants

4

Reactant 1

HCID 580757621-(5-fluoro-2-methoxy-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole

Product 1

HCID 580756292-fluoro-5-methoxy-4-(3-methyl-1H-1,2,4-triazol-1-yl)anilineYield 96%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

10% Palladium on carbon (0.523 g, 4.92 mmol) was added under an atmosphere of nitrogen to a chilled (ice-water bath) solution of 1-(5-fluoro-2-methoxy-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole (1.24 g, 4.92 mmol) dissolved in methanol (100 mL). The flask was repeatedly evacuated and flushed with hydrogen gas (double balloon). The resulting mixture was allowed to warm to rt and left to stir for 18 h under the hydrogen atmosphere. The vessel was subsequently purged with nitrogen gas. The crude reaction mixture was filtered through a short diatomaceous earth (Celite®) plug. The reaction vessel and plug were rinsed with fresh methanol. The combined filtrates were concentrated in vacuo. The residue was dried on high vacuum overnight to afford 2-fluoro-5-methoxy-4-(3-methyl-1H-1,2,4-triazol-1-yl)aniline (1.05 g, 96% yield) as a gray solid. LC-MS (M+H)+ 223.1. 1H NMR (500 MHz, CDCl3) δ ppm 8.46 (s, 1H) 7.39 (d, J=11.29 Hz, 1H) 6.44 (d, J=7.63 Hz, 1H) 3.89 (br. s., 2H) 3.83 (s, 3H) 2.47 (s, 3H).

Workup

  1. customThe flask was repeatedly evacuated
  2. customflushed with hydrogen gas (double balloon)
  3. waitleft
  4. customThe vessel was subsequently purged with nitrogen gas
  5. customThe crude reaction mixture
  6. filtrationwas filtered through a short diatomaceous earth (Celite®) plug
  7. washThe reaction vessel and plug were rinsed with fresh methanol
  8. concentrationThe combined filtrates were concentrated in vacuo
  9. customThe residue was dried on high vacuum overnight

Sources & evidence

ORD record
ord-6e00d014fa414e7db132205aff0c0098
Source dataset
uspto-grants-2014_01
Patent number
US08637525B2

Reaction notes

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