1H-1,2,4-Triazole → HCID 13176306, compound

HRID 1981306Notes

Reaction equation

HRID 1981306 reaction equation
Br[CH:2]([O:10][C:11]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=1)[C:3](=[O:9])[C:4]([CH3:8])([CH3:7])[CH:5]=[CH2:6].[NH:18]1[CH:22]=[N:21][CH:20]=[N:19]1>C(#N)C>[Cl:17][C:14]1[CH:15]=[CH:16][C:11]([O:10][CH:2]([N:21]2[CH:20]=[N:19][N:18]=[CH:22]2)[C:3](=[O:9])[C:4]([CH3:8])([CH3:7])[CH:5]=[CH2:6])=[CH:12][CH:13]=1

Participants

4

Reactant 2

HCID 92571H-1,2,4-TriazoleHCID 13176302HCID 13176302, compound

Product 1

HCID 13176306HCID 13176306, compoundYield 20%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

89 g (0.28 mol) of 5-bromo-5-(4-chlorophenoxy)-3,3-dimethylpent-1-en-4-one, dissolved in 120 ml of acetonitrile, were added dropwise, in the course of 30 minutes, to a solution of 115.9 g (1.68 mols) of 1,2,4-triazole in 1,000 ml of acetonitrile at 50° C. After the solution had been heated at the boil for three hours, the solvent was distilled off and the residue was taken up in 300 ml of ethyl acetate. The solution was washed three times with 50 ml of water, and the organic phase, after having been dried over anhydrous sodium sulphate, was concentrated by evaporation under reduced pressure. The residual oil was dissolved in 400 ml of acetone, and a solution of 80.6 g of naphthalene-1,5-disulphonic acid in 400 ml of acetone was added. The salt which had crystallized out was filtered off under suction and washed with acetone, 250 ml each of water and dichloromethane were stirred with the salt, and the mixture was then rendered alkaline with a 10% strength sodium carbonate solution. The oil which remained after the organic phase had been evaporated off was dissolved in a small amount of ether, and petroleum ether was then slowly added to the solution. The product which crystallized out in the process was filtered off and washed with a small amount of ether/petroleum ether. 17.1 g (20% of theory) of 5-(4-chlorophenoxy)-3,3-dimethyl-5-(1,2,4-triazol-4-yl)-pent-1-en-4-one (Compound 3) of melting point 124° to 126° C. were obtained.

Workup

  1. temperatureAfter the solution had been heated at the boil for three hours
  2. distillationthe solvent was distilled off
  3. washThe solution was washed three times with 50 ml of water
  4. dry with materialthe organic phase, after having been dried over anhydrous sodium sulphate
  5. concentrationwas concentrated by evaporation under reduced pressure
  6. dissolutionThe residual oil was dissolved in 400 ml of acetone
  7. additiona solution of 80.6 g of naphthalene-1,5-disulphonic acid in 400 ml of acetone was added
  8. customThe salt which had crystallized out
  9. filtrationwas filtered off under suction
  10. washwashed with acetone, 250 ml each of water and dichloromethane
  11. customhad been evaporated off
  12. dissolutionwas dissolved in a small amount of ether, and petroleum ether
  13. additionwas then slowly added to the solution
  14. customThe product which crystallized out in the process
  15. filtrationwas filtered off
  16. washwashed with a small amount of ether/petroleum ether

Sources & evidence

ORD record
ord-bbd3a3c467a547f38b01c806eb8bbd18
Source dataset
uspto-grants-1985_04
Patent number
US04514409

Reaction notes

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