1,2-Difluoro-4-nitrobenzene → 1-(2-fluoro-4-nitrophenyl)-3-methyl-1H-1,2,4-triazole

HRID 1855497Notes

Reaction equation

HRID 1855497 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:15]1[CH:16]=[N:17][C:13]([CH3:12])=[N:14]1

Participants

5

Reactant 3

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

Product 1

HCID 575269631-(2-fluoro-4-nitrophenyl)-3-methyl-1H-1,2,4-triazoleYield 36.4%

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 1 dimethyl sulfoxide (5 mL) were stirred for 6 hours at 70° C. The mixture was concentrated in vacuo; the residue was diluted with water and extracted three times with ethyl acetate. The combined organic layers were washed four times with water, twice with brine, dried over magnesium sulfate and evaporated. Column chromatography (30 g silica, heptane/ethyl acetate 1:1 v/v) afforded the title compound (261 mg, 36%) as white crystals MS ISP (m/e): 223.3[(M+H)+]. 1H NMR (CDCl3, 300 MHz): δ (ppm)=8.72 (d, 1H), 8.20 (m, 3H), 2.52 (s, 3H). Mp 105-107° C.

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. additionthe residue was diluted with 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 over magnesium sulfate
  6. customevaporated

Sources & evidence

ORD record
ord-ba660dcbe2dc402fac6f24739c87af37
Source dataset
uspto-grants-2015_02
Patent number
US08962834B2

Reaction notes

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