1H-1,2,4-Triazole → 3,3-Dimethyl-2-{2-[4-(1,3-dioxolan-2-yl)-phenyl]-ethenyl}-1-(1,2,4-triazol-1-yl)-2-butanol

HRID 464692Notes

Reaction equation

HRID 464692 reaction equation
[O:1]1[CH2:5][CH2:4][O:3][CH:2]1[C:6]1[CH:11]=[CH:10][C:9]([CH:12]=[CH:13][C:14]2([C:17]([CH3:20])([CH3:19])[CH3:18])[CH2:16][O:15]2)=[CH:8][CH:7]=1.N1C=[C-]N=N1.[Na+].[NH:27]1[CH:31]=[N:30][CH:29]=[N:28]1.[H-].[Na+]>CN(C)C=O>[CH3:18][C:17]([CH3:20])([CH3:19])[C:14]([CH:13]=[CH:12][C:9]1[CH:10]=[CH:11][C:6]([CH:2]2[O:3][CH2:4][CH2:5][O:1]2)=[CH:7][CH:8]=1)([OH:15])[CH2:16][N:27]1[CH:31]=[N:30][CH:29]=[N:28]1

Participants

6

Reactant 4

HCID 92571H-1,2,4-TriazoleHCID 24758Sodium hydrideHCID 201978292-{2-[4-(1,3-Dioxolan-2-yl)-phenyl]-ethenyl}-2-tert.-butyl-oxiraneHCID 129663835Sodium triazolide

Product 1

HCID 544901003,3-Dimethyl-2-{2-[4-(1,3-dioxolan-2-yl)-phenyl]-ethenyl}-1-(1,2,4-triazol-1-yl)-2-butanolYield 24.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
80 °C

Procedure

25.6 g (0.093 mol) of 2-{2-[4-(1,3-dioxolan-2-yl)-phenyl]-ethenyl}-2-tert.-butyl-oxirane in 47 ml of absolute dimethylformamide are added dropwise, at room temperature, to a solution of sodium triazolide, prepared by slowly introducing 12.9 g (0.187 mol) of 1,2,4-triazole into a suspension of 5.6 g (0.187 mol) of sodium hydride (80% strength in paraffin oil) in 187 ml of absolute dimethylformamide. The reaction mixture is stirred at 80° C. for 4 hours and left to stand overnight at room temperature. Thereafter, the reaction mixture is poured onto ice water and extracted several times with ethyl acetate. The combined ethyl acetate phases are washed twice with water and once with saturated sodium chloride solution, dried over sodium sulphate and concentrated. The residue is chromatographed over a silica gel column (methylene chloride/ethyl acetate=2:1) and the product is recrystallized from n-hexane/ethyl acetate. 7.75 g (24% of theory) of 3,3-dimethyl-2-{2-[4-(1,3-dioxolan-2-yl)-phenyl]-ethenyl}-1-(1,2,4-triazol-1-yl)-2-butanol of melting point 109.5°-110° C. are obtained.

Workup

  1. customprepared
  2. waitleft
  3. waitto stand overnight at room temperature
  4. additionThereafter, the reaction mixture is poured onto ice water
  5. extractionextracted several times with ethyl acetate
  6. washThe combined ethyl acetate phases are washed twice with water and once with saturated sodium chloride solution
  7. dry with materialdried over sodium sulphate
  8. concentrationconcentrated
  9. customThe residue is chromatographed over a silica gel column (methylene chloride/ethyl acetate=2:1)
  10. customthe product is recrystallized from n-hexane/ethyl acetate

Sources & evidence

ORD record
ord-59fd0999f85a426593fc160475a84e86
Source dataset
uspto-grants-1985_10
Patent number
US04548945

Reaction notes

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