Allyl Alcohol → 1-(2-(allyloxy)-4-nitrophenyl)-5-methyl-1H-1,2,4-triazole

HRID 474230Notes

Reaction equation

HRID 474230 reaction equation
[H-].[Na+].F[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[N:13]1[C:17]([CH3:18])=[N:16][CH:15]=[N:14]1.[CH2:19]([OH:22])[CH:20]=[CH2:21]>CN(C=O)C>[CH2:19]([O:22][C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[N:13]1[C:17]([CH3:18])=[N:16][CH:15]=[N:14]1)[CH:20]=[CH2:21]

Participants

5

Reactant 3

HCID 7858Allyl AlcoholHCID 24758Sodium hydrideHCID 584144611-(2-fluoro-4-nitrophenyl)-5-methyl-1H-1,2,4-triazole

Product 1

HCID 666662931-(2-(allyloxy)-4-nitrophenyl)-5-methyl-1H-1,2,4-triazoleYield 51.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of NaH (0.675 g, 16.88 mmol, 60% dispersion in mineral oil) in DMF (25 mL) was cooled to 0° C. A solution 1-(2-fluoro-4-nitrophenyl)-5-methyl-1H-1,2,4-triazole (2.50 g, 11.25 mmol) was added dropwise. Allyl alcohol (0.784 g, 13.5 mmol) was added via syringe over 5 min. The reaction mixture was allowed to warm up to room temperature. After 30 min, TLC showed completion of reaction. It was slowly quenched with water (10 mL), diluted with brine (100 mL), and extracted with EtOAc (3×50 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo. The crude reaction mixture was purified using silica gel chromatography (20-80% EtOAc/hexane, linear gradient). Pure fractions were concentrated under reduced pressure to afford 1-(2-(allyloxy)-4-nitrophenyl)-5-methyl-1H-1,2,4-triazole (1.5 g 51% yield) as a yellow-brown colored solid. LC-MS (M+H)+=261.0. 1H NMR (400 MHz, CDCl3) δ ppm 8.02-7.94 (m, 3H), 7.58 (d, 1H, J=8.4 Hz), 5.98-5.89 (m, 1H), 5.37-5.32 (m, 2 H), 4.69-4.70 (m, 2H), 2.403 (s, 3H).

Workup

  1. temperatureto warm up to room temperature
  2. customcompletion of reaction
  3. customIt was slowly quenched with water (10 mL)
  4. additiondiluted with brine (100 mL)
  5. extractionextracted with EtOAc (3×50 mL)
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe crude reaction mixture
  10. customwas purified
  11. concentrationPure fractions were concentrated under reduced pressure

Sources & evidence

ORD record
ord-79dd91a546734e5184799170853619b9
Source dataset
uspto-grants-2014_01
Patent number
US08637523B2

Reaction notes

Loading…