Potassium Hydroxide → 1-(4-Chlorophenyl)-4,4,5-trimethyl-2-(1H-1,2,4-triazol-1-yl)hexan-3-one

HRID 1253126Notes

Reaction equation

HRID 1253126 reaction equation
[N:1]1([CH2:6][C:7](=[O:14])[C:8]([CH3:13])([CH3:12])[CH:9]([CH3:11])[CH3:10])[CH:5]=[N:4][CH:3]=[N:2]1.[OH-].[K+].[Cl:17][C:18]1[CH:25]=[CH:24][C:21]([CH2:22]Br)=[CH:20][CH:19]=1>CS(C)=O.O>[CH3:11][CH:9]([C:8]([CH3:12])([CH3:13])[C:7](=[O:14])[CH:6]([N:1]1[CH:5]=[N:4][CH:3]=[N:2]1)[CH2:22][C:21]1[CH:24]=[CH:25][C:18]([Cl:17])=[CH:19][CH:20]=1)[CH3:10]

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 693291-(Bromomethyl)-4-chlorobenzeneHCID 132952273,3,4-Trimethyl-1-(1H-1,2,4-triazol-1-yl)pentan-2-one

Product 1

HCID 132952281-(4-Chlorophenyl)-4,4,5-trimethyl-2-(1H-1,2,4-triazol-1-yl)hexan-3-oneYield 67.6%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

15.6 g (0.08 mol) of 1-(1,2,4-triazol-1-yl)-3,3,4-trimethylpentan-2-one are dissolved in 100 ml of dimethylsulphoxide, and 4.5 g (0.08 mol) of potassium hydroxide, dissolved in 10 ml of water, are added, while cooling. 16.4 g (0.08 mol) of 4-chlorobenzyl bromide, dissolved in 50 ml of dimethylsulphoxide, are added dropwise to the mixture at a rate such that the temperature does not exceed 40° C. Thereafter, the mixture is slowly warmed to 100° C. and stirred for a further 15 hours at this temperature, and the cooled solution is poured onto 500 ml of water. The mixture is extracted with twice 250 ml of methylene chloride, the methylene chloride phase is then extracted with four times 100 ml of water, and the organic phase is evaporated down. The residue is taken up in 100 ml of acetone, and 14.4 g of naphthalene-1,5-disulphonic acid, dissolved in 50 ml of acetone, are added. The 2,3,3-trimethyl-5-(1,2,4-triazol-1-yl)-6-(4-chlorophenyl)-hexan-3-one salt of naphthalene-1,5-disulphonic acid crystallizes out. The precipitate is filtered off under suction and taken up in 250 ml of saturated sodium bicarbonate solution, the aqueous phase is extracted with four times 100 ml of methylene chloride, the methylene chloride phase is extracted with 100 ml of water, and the solvent is distilled off from the organic phase. 17.3 g (67.6% of theory) of 2,3,3-trimethyl-5-(1,2,4-triazol-1-yl)-6-(4-chlorophenyl)-hexan-4-one are obtained as colorless crystals of melting point 91°-94° C.

Workup

  1. additionare added
  2. temperaturewhile cooling
  3. additionare added dropwise to the mixture at a rate such that the temperature
  4. customdoes not exceed 40° C
  5. extractionThe mixture is extracted with twice 250 ml of methylene chloride
  6. extractionthe methylene chloride phase is then extracted with four times 100 ml of water
  7. customthe organic phase is evaporated down
  8. dissolution14.4 g of naphthalene-1,5-disulphonic acid, dissolved in 50 ml of acetone
  9. additionare added
  10. customThe 2,3,3-trimethyl-5-(1,2,4-triazol-1-yl)-6-(4-chlorophenyl)-hexan-3-one salt of naphthalene-1,5-disulphonic acid crystallizes out
  11. filtrationThe precipitate is filtered off under suction
  12. extractionthe aqueous phase is extracted with four times 100 ml of methylene chloride
  13. extractionthe methylene chloride phase is extracted with 100 ml of water
  14. distillationthe solvent is distilled off from the organic phase

Sources & evidence

ORD record
ord-2c04c029e9aa4f0da359cf47eea86eaf
Source dataset
uspto-grants-1988_05
Patent number
US04747869

Reaction notes

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