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

HRID 1803110Notes

Reaction equation

HRID 1803110 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[CH:5]=[CH:4][C:3]=1[N:11]1[C:15]([CH3:16])=[N:14][CH:13]=[N:12]1>[Pd].CO>[F:1][C:2]1[CH:7]=[C:6]([CH:5]=[CH:4][C:3]=1[N:11]1[C:15]([CH3:16])=[N:14][CH:13]=[N:12]1)[NH2:8]

Participants

4

Reactant 1

HCID 584144611-(2-fluoro-4-nitrophenyl)-5-methyl-1H-1,2,4-triazole

Product 1

HCID 584144593-fluoro-4-(5-methyl-1H-1,2,4-triazol-1-yl)anilineYield 96.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

Step C (2): 10% Palladium on carbon (1.5 g, 14.1 mmol) was added under an atmosphere of nitrogen to a chilled (ice-water bath) solution of 1-(2-fluoro-4-nitrophenyl)-5-methyl-1H-1,2,4-triazole (3.7 g, 17 mmol) dissolved in methanol (200 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 plug of diatomaceous earth (Celite®). The reaction vessel and Celite® were rinsed with fresh methanol. The combined filtrates were concentrated in vacuo. The residue was dried under high vacuum to afford 3-fluoro-4-(5-methyl-1H-1,2,4-triazol-1-yl)aniline (3.14 g, 91% yield) as a blackish/grey solid. LC-MS (M+H)+ 193.1. 1H NMR (500 MHz, chloroform-d) δ ppm 7.91 (s, 1 H) 7.14 (t, J=8.55 Hz, 1 H) 6.43-6.53 (m, 2 H) 4.04 (br. s., 2 H) 2.36 (s, 3 H).

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 plug of diatomaceous earth (Celite®)
  7. washThe reaction vessel and Celite® were rinsed with fresh methanol
  8. concentrationThe combined filtrates were concentrated in vacuo
  9. customThe residue was dried under high vacuum

Sources & evidence

ORD record
ord-a53c88a6184e4ac194aeca45cd09b7eb
Source dataset
uspto-grants-2013_01
Patent number
US08349880B2

Reaction notes

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