Acetic Acid → 4-(5-Chloro-6-methylene-2,2-dimethylcyclohexyl)-2-butanone

HRID 36575Notes

Reaction equation

HRID 36575 reaction equation
[CH3:1][C:2]1[CH:7]([CH2:8][CH2:9][C:10]([CH3:12])=[O:11])[C:6]([CH3:14])([CH3:13])[CH2:5][CH2:4][CH:3]=1.P([O-])(O)(O)=O.[K+].[Cl:21][O-].[Na+].C(O)(=O)C>C(Cl)Cl.O>[Cl:21][CH:3]1[CH2:4][CH2:5][C:6]([CH3:14])([CH3:13])[CH:7]([CH2:8][CH2:9][C:10](=[O:11])[CH3:12])[C:2]1=[CH2:1]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 35821Dihydro-alpha-iononeHCID 516951Monobasic potassium phosphateHCID 23665760Sodium Hypochlorite

Product 1

HCID 199372844-(5-Chloro-6-methylene-2,2-dimethylcyclohexyl)-2-butanone

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

388 g (2 mol) of dihydro-α-ionone was placed in 2.2 l of methylene chloride in a 10 l four-necked flask fitted with a stirrer, thermometer, condenser and dropping funnel. Then, 660 g (4.6 mol) of potassium dihydrogen phosphate dissolved in 3 l of water was added and the resulting emulsion was cooled in an ice bath. 1.6 (2.3 mol) of sodium hypochlorite solution (~12%) was added at about 10° within 1.5 hours and, after about 3 hours at 15°, a further 350 ml (0.5 mol) was added. The pH value of the mixture was adjusted to ~5.5 with acetic acid and it was stirred at room temperature. After a total reaction time of 27 hours the phases were separated and the aqueous phase was extracted 4 times with methylene chloride. The combined organic phases were washed neutral once with water, twice with saturated NaHCO3 solution and a further 3 times with water, dried over MgSO4, filtered and evaporated (bath temperature=room temperature). 407.45 g 4-(3-chloro-2-methylidene-6,6-dimethyl-cyclohex-1-yl)-butan-2-one was obtained as a yellow liquid.

Workup

  1. customfitted with a stirrer
  2. customthermometer, condenser and dropping
  3. additionwas added
  4. temperaturethe resulting emulsion was cooled in an ice bath
  5. additiona further 350 ml (0.5 mol) was added
  6. customAfter a total reaction time of 27 hours the phases were separated
  7. extractionthe aqueous phase was extracted 4 times with methylene chloride
  8. washThe combined organic phases were washed neutral once with water, twice with saturated NaHCO3 solution
  9. dry with materiala further 3 times with water, dried over MgSO4
  10. filtrationfiltered
  11. customevaporated (bath temperature=room temperature)

Sources & evidence

ORD record
ord-b93882487f05419a874ba4229e8494b8
Source dataset
uspto-grants-1995_05
Patent number
US05416069

Reaction notes

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