1,2-Difluoro-4-nitrobenzene → 1-(2-fluoro-4-nitrophenyl)-5-methyl-1H-1,2,4-triazole

HRID 1855499Notes

Reaction equation

HRID 1855499 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:6][C:7]=1F.[CH3:12][C:13]1[N:17]=[CH:16][NH:15][N:14]=1.O.O.O.P([O-])([O-])(O)=O.[K+].[K+]>CS(C)=O>[F:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:6][C:7]=1[N:14]1[C:13]([CH3:12])=[N:17][CH:16]=[N:15]1

Participants

5

Reactant 3

HCID 1230531,2-Difluoro-4-nitrobenzeneHCID 16217523Potassium phosphate, dibasic, trihydrateHCID 178433329HCID 178433329, compound

Product 1

HCID 584144611-(2-fluoro-4-nitrophenyl)-5-methyl-1H-1,2,4-triazoleYield 22.3%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

3,4-Difluoronitrobenzene (514 mg, 3.23 mmol), 3-methyl-1H-1,2,4-triazole (325 mg, 3.72 mmol) and di-potassium hydrogen phosphate trihydrate (1.49 g, 6.46 mmol) in dimethyl sulfoxide (1.5 mL) were stirred for 6 hours at 70° C. The mixture was concentrated in vacuo; the residue was diluted in water and extracted three times with ethyl acetate. The combined organic layers were washed four times with water, twice with brine, dried with magnesium sulfate and evaporated. Column chromatography (30 g silica, heptane/ethyl acetate 1:1 v/v) afforded the title compound (160 mg, 22%) as white crystals MS ISP (m/e): 223.2[(M+H)+]. 1H NMR (CDCl3, 300 MHz): δ (ppm)=8.22 (m, 2H), 8.04 (s, 1H), 7.74 (dd, 1H), 2.48 (d, 3H). Mp 56-58° C.

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. additionthe residue was diluted in water
  3. extractionextracted three times with ethyl acetate
  4. washThe combined organic layers were washed four times with water
  5. dry with materialtwice with brine, dried with magnesium sulfate
  6. customevaporated

Sources & evidence

ORD record
ord-f0deee69c8ae40d2a8e717f6d33a05d1
Source dataset
uspto-grants-2015_02
Patent number
US08962834B2

Reaction notes

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