Potassium Hydroxide → 2,2-Bis-fluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-one

HRID 1732169Notes

Reaction equation

HRID 1732169 reaction equation
[OH-].[K+].[F:3][CH2:4][C:5]([CH2:15][F:16])([C:7](=[O:14])[CH2:8][N:9]1[CH:13]=[N:12][CH:11]=[N:10]1)[CH3:6].[CH:17]1([CH2:23]Br)[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1>O.CS(C)=O>[F:16][CH2:15][C:5]([CH2:4][F:3])([C:7](=[O:14])[CH:8]([N:9]1[CH:13]=[N:12][CH:11]=[N:10]1)[CH2:23][CH:17]1[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1)[CH3:6]

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 137636Cyclohexane, (bromomethyl)-HCID 135325004-Fluoro-3-(fluoromethyl)-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one

Product 1

HCID 134905552,2-Bis-fluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-oneYield 63%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent2×

Procedure

A solution of 101.4 g (1.81 moles) of potassium hydroxide in 217.2 ml of water was added to a solution of 369.4 g (1.81 moles) of 2,2-bis-fluoromethyl-4-(1,2,4-triazol-1-yl)-butan-3-one in 2 liters of dimethyl sulfoxide at room temperature, with stirring. 320.5 g (1.81 moles) of cyclohexylmethyl bromide were added dropwise to this mixture, with stirring, the temperature of the reaction mixture being kept between 20° and 40° C. by cooling. The reaction mixture was stirred at 60° C. for a further 15 hours and then poured into 2 liters of water. The resulting mixture was extracted twice with 1 liter of methylene chloride each time, the combined organic phases were washed four times with 2 liters of water each time and dried over sodium sulphate and the solvent was stripped off. The oily product which remained was taken up in acetone and 326 g of naphthalene-1,5-disulphonic acid were added to the solution. The precipitate which thereby formed was filtered off with suction and suspended in 2 liters of methylene chloride. This suspension was shaken twice with 2 liters of saturated aqueous sodium bicarbonate solution each time. The organic phase was then washed with 2 liters of water and, after drying over sodium sulphate, was concentrated under reduced pressure. 297.5 g (63% of theory) of 2,2-bis-fluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-one were obtained in this manner in the form of an oil.

Workup

  1. stirringwith stirring
  2. custombeing kept between 20° and 40° C.
  3. temperatureby cooling
  4. stirringThe reaction mixture was stirred at 60° C. for a further 15 hours
  5. extractionThe resulting mixture was extracted twice with 1 liter of methylene chloride each time
  6. washthe combined organic phases were washed four times with 2 liters of water each time
  7. dry with materialdried over sodium sulphate
  8. addition326 g of naphthalene-1,5-disulphonic acid were added to the solution
  9. customThe precipitate which thereby formed
  10. filtrationwas filtered off with suction
  11. stirringThis suspension was shaken twice with 2 liters of saturated aqueous sodium bicarbonate solution each time
  12. washThe organic phase was then washed with 2 liters of water
  13. dry with materialafter drying over sodium sulphate
  14. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-4550ec825c2e44d6906b41328cd59fd4
Source dataset
uspto-grants-1986_11
Patent number
US04625066

Reaction notes

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