1-(2-fluoro-6-methoxy-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole → 3-fluoro-5-methoxy-4-(3-methyl-1H-1,2,4-triazol-1-yl)aniline

HRID 1803175Notes

Reaction equation

HRID 1803175 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[CH:5]=[C:4]([O:11][CH3:12])[C:3]=1[N:13]1[CH:17]=[N:16][C:15]([CH3:18])=[N:14]1>[Pd].CO>[F:1][C:2]1[CH:7]=[C:6]([CH:5]=[C:4]([O:11][CH3:12])[C:3]=1[N:13]1[CH:17]=[N:16][C:15]([CH3:18])=[N:14]1)[NH2:8]

Participants

4

Reactant 1

HCID 668608961-(2-fluoro-6-methoxy-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole

Product 1

HCID 668594543-fluoro-5-methoxy-4-(3-methyl-1H-1,2,4-triazol-1-yl)anilineYield 133.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

Step S (2): 10% Palladium on carbon (0.776 g, 0.730 mmol) was added under an atmosphere of nitrogen to a chilled (ice-water bath) solution of 1-(2-fluoro-6-methoxy-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole (1.84 g, 7.30 mmol) dissolved in methanol (150 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 the Celite® were rinsed with fresh methanol. The combined filtrates were concentrated in vacuo. The residue was dried under high vacuum overnight to afford 3-fluoro-5-methoxy-4-(3-methyl-1H-1,2,4-triazol-1-yl)aniline (2.17 g, quantitative % yield) as a blackish/gray solid. LC-MS (M+H)+ 223.2. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 8.02 (s, 1 H), 6.11 (dd, J=11.1, 2.3 Hz, 1 H), 6.06 (d, J=1.5 Hz, 1 H), 4.04 (br. s., 2 H), 3.74 (s, 3 H), 2.48 (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 the Celite® were rinsed with fresh methanol
  8. concentrationThe combined filtrates were concentrated in vacuo
  9. customThe residue was dried under high vacuum overnight

Sources & evidence

ORD record
ord-75329fc98cd045fca92b3106991ebb75
Source dataset
uspto-grants-2013_01
Patent number
US08349880B2

Reaction notes

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