1H-1,2,4-Triazole → Acetylene

HRID 373165Notes

Reaction equation

HRID 373165 reaction equation
Cl[CH2:2][C:3]([C:7]1([Cl:10])[CH2:9][CH2:8]1)([OH:6])[C:4]#[CH:5].[NH:11]1[CH:15]=[N:14][CH:13]=[N:12]1.C(=O)([O-])[O-].[K+].[K+]>CC(C)=O.O1CCCC1>[Cl:10][C:7]1([C:3]([OH:6])([CH2:2][N:11]2[CH:15]=[N:14][CH:13]=[N:12]2)[C:4]#[CH:5])[CH2:9][CH2:8]1.[CH:2]#[CH:3]

Participants

7

Reactant 3

HCID 92571H-1,2,4-TriazoleHCID 11430Potassium CarbonateHCID 15022045HCID 15022045, compound

Product 2

HCID 6326AcetyleneYield 400%HCID 15022046HCID 15022046, compoundYield 46%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 18.0 g (0.1 mol) of 4-chloro-3-(1-chlorocyclopropyl)-3-hydroxy-1-butine, 13.9 g (0.201 mol) of 1,2,4-triazole and 55.5 g (0.402 mol) of potassium carbonate in 250 ml of absolute acetone is refluxed for 2 hours. The mixture is subsequently concentrated by stripping off the diluent under reduced pressure, and the concentrate is then treated with water. The resulting mixture is extracted using methylene chloride. The combined organic phases are dried and concentrated under reduced pressure. The residue which remains is chromatographed on silica gel using a mixture of cyclohexane/ethyl acetate = 1:1 as the eluent. After the eluate has been evaporated, 9.7 g (46% of theory)of 3-(1-chloro-1cyclopropyl)-3-hydroxy-4-(1,2,4-triazol-1-yl)-but-1-ine are obtained in the form of a solid substance of melting point 70°-72° C. ##STR33## To a solution of 5.2 g (0.2 mol) of acetylene in 200 ml of absolute tetrahydrofuran there are added dropwise at 70° C. 80 ml (0.2 mol) of a 23% strength butyllithium solution in hexane. After 10 minutes, a solution of 20 g (0.13 mol) of 2-chloro-1-(1-chlorocyclopropyl-1-)ethanone in 100 ml of absolute tetrahydrofuran is added. Stirring is continued for 2 hours at -70° C. The reaction is then stopped by dropwise addition of the mixture of 20 ml of methanol and 20 ml of acetic acid. The solvent is stripped off in vacuo and the remaining mixture is dissolved in dichloromethane and then extracted several times by shaking with saturated aqueous ammonium chloride solution. After the organic phase has been dried and distilled off, 24.4 g of crude product with a content of 83.1% of 4-chloro-3-(1-chloro-cyclopropyl)-3-hydroxy1-butine are obtained.

Workup

  1. temperatureis refluxed for 2 hours
  2. concentrationThe mixture is subsequently concentrated
  3. additionthe concentrate is then treated with water
  4. extractionThe resulting mixture is extracted
  5. customThe combined organic phases are dried
  6. concentrationconcentrated under reduced pressure
  7. customThe residue which remains is chromatographed on silica gel using
  8. additiona mixture of cyclohexane/ethyl acetate = 1:1 as the eluent
  9. customAfter the eluate has been evaporated

Sources & evidence

ORD record
ord-c6a68a9d10bf4c569fb000d7d2729d5e
Source dataset
uspto-grants-1992_11
Patent number
US05162358

Reaction notes

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