Cesium carbonate → 3-bromo-1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazole

HRID 62033

Reaction equation

HRID 62033 reaction equation
[Br:1][C:2]1[N:6]=[CH:5][N:4]([C:7]2[CH:12]=[CH:11][C:10](OC(C)C)=[CH:9][CH:8]=2)[N:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].IC1C=CC([C:30]([F:33])([F:32])[F:31])=CC=1>[Cu]I.CS(C)=O>[Br:1][C:2]1[N:6]=[CH:5][N:4]([C:7]2[CH:8]=[CH:9][C:10]([C:30]([F:33])([F:32])[F:31])=[CH:11][CH:12]=2)[N:3]=1

Participants

6

Conditions

Temperature
100 °C

Procedure

3-Bromo-1-(4-isopropoxyphenyl)-1H-1,2,4-triazole (7.15 g, 48.3 mmol), copper(I) iodide (1.25 g, 6.56 mmol), cesium carbonate (18.9 g, 58.0 mmol), and 1-iodo-4-(trifluoromethyl)benzene (8.29 g, 30.5 mmol) were added to dimethylsulfoxide (50 mL) and the solution was degassed with nitrogen for 10 minutes. The solution was heated at 100° C. for 20 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate and filtered through Celite®. The resulting filter cake was rinsed with additional ethyl acetate (100 mL). Saturated aqueous ammonium chloride was added to the filtrate which was then stirred for 30 minutes. The layers were separated and the aqueous layer was extracted with ethyl acetate (2×50 mL). The combined organic extracts were dried over anhydrous magnesium sulfate and concentrated onto Celite®. Purification by silica gel chromatography using 0-100% ethyl acetate/hexanes as eluent provided the title compound as a white solid (5.64 g, 64%): mp 87-89° C.; 1H NMR (400 MHz, CDCl3) δ 8.53 (s, 1H), 7.85-7.77 (m, 4H); ESIMS m/z 292.0 ([M+H]+).

Workup

  1. customthe solution was degassed with nitrogen for 10 minutes
  2. temperatureAfter cooling to room temperature
  3. additionthe reaction mixture was diluted with ethyl acetate
  4. filtrationfiltered through Celite®
  5. filtrationThe resulting filter cake
  6. washwas rinsed with additional ethyl acetate (100 mL)
  7. additionSaturated aqueous ammonium chloride was added to the filtrate which
  8. customThe layers were separated
  9. extractionthe aqueous layer was extracted with ethyl acetate (2×50 mL)
  10. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulfate
  11. concentrationconcentrated onto Celite®
  12. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-665c7987de404b1abc01902c47a9b5a4
Source dataset
uspto-grants-2016_09
Patent number
US09445594B2

Linked notes

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