Allyl Alcohol → 1-(2-(allyloxy)-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole

HRID 474229Notes

Reaction equation

HRID 474229 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[CH:17]=[N:16][C:15]([CH3:18])=[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[CH:17]=[N:16][C:15]([CH3:18])=[N:14]1)[CH:20]=[CH2:21]

Participants

5

Reactant 3

HCID 7858Allyl AlcoholHCID 24758Sodium hydrideHCID 575269631-(2-fluoro-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole

Product 1

HCID 666658661-(2-(allyloxy)-4-nitrophenyl)-3-methyl-1H-1,2,4-triazoleYield 50.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of NaH (2.295 g 57.4 mmol, 60% dispersion in mineral oil) in DMF (85 mL) was cooled at 0° C. and a solution 1-(2-fluoro-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole (8.50 g 38.3 mmol) was added dropwise. Allyl alcohol (2.67 g, 49.9 mmol) was added via syringe over 10 min. The reaction mixture was allowed to warm to room temperature. After 30 min, TLC showed completion of reaction. The reaction mixture was slowly quenched with water (20 mL), treated with 200 mL of brine and extracted with EtOAc (3×200 mL). The combined organic extracts were washed with water (3×200 mL) and brine solution (100 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)-3-methyl-1H-1,2,4-triazole (5 g, 19.21 mmol 50% yield) as a yellow colored solid. LC-MS (M+H)+=261.0. 1H NMR (400 MHz, CDCl3) δ ppm 8.906 (s, 1H), 8.09 (d, 1H, J=8.8 Hz), 7.99-7.94 (m, 2H), 6.13-6.03 (m, 1H), 5.50-5.54 (m, 2H), 4.80-4.79 (m, 2H), 2.497 (s, 3H).

Workup

  1. temperatureto warm to room temperature
  2. customcompletion of reaction
  3. customThe reaction mixture was slowly quenched with water (20 mL)
  4. additiontreated with 200 mL of brine
  5. extractionextracted with EtOAc (3×200 mL)
  6. washThe combined organic extracts were washed with water (3×200 mL) and brine solution (100 mL)
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude reaction mixture
  11. customwas purified
  12. concentrationPure fractions were concentrated under reduced pressure

Sources & evidence

ORD record
ord-4f088a8032eb4a6d9a703941782b3068
Source dataset
uspto-grants-2014_01
Patent number
US08637523B2

Reaction notes

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