Acetic Acid → HCID 11378684, compound

HRID 483899Notes

Reaction equation

HRID 483899 reaction equation
C([O:4][C@H:5]1[CH2:10][C:9]([CH3:12])([CH3:11])[C:8]([C:13]#[CH:14])=[C:7]([CH3:15])[CH2:6]1)(=O)C.[OH-].[K+].O.C(O)(=O)C>CO>[C:13]([C:8]1[C:9]([CH3:11])([CH3:12])[CH2:10][C@H:5]([OH:4])[CH2:6][C:7]=1[CH3:15])#[CH:14]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 14797Potassium HydroxideHCID 11264226HCID 11264226, compound

Product 1

HCID 11378684HCID 11378684, compoundYield 99.8%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

183.8 g of (R)-4-ethynyl-3,5,5-trimethyl-3-cyclohexen-1-yl acetate (prepared according to Example 10) were dissolved in 1 l of methanol. The solution was cooled to 0° C. and treated portionwise within 15 minutes with 74.2 g of potassium hydroxide in such a manner that the temperature did not exceed 11° C. The mixture was stirred at 4°-8° C. for a further 15 minutes and then at room temperature for 30 minutes. The reaction mixture was subsequently poured into 2 l of water and 26.5 g of glacial acetic acid. The mixture was extracted three times with 500 ml of methylene chloride each time. The organic phases were washed with 500 ml of saturated sodium chloride solution, and with 600 ml of saturated sodium bicarbonate solution dried over sodium sulphate and filtered. The filtrate was concentrated almost completely in a rotary evaporator under a water-jet vacuum at 30° C. bath temperature. The residual oil was dissolved in 300 ml of pentane and the solution was evaporated completely in a rotary evaporator under a water-jet vacuum at 30° C. bath temperature. The oil obtained was dried at room temperature for 30 minutes in a high vacuum, whereby spontaneous crystalization (strongly exothermic) took place. There were thus obtained 146 g of (R)-4-ethynyl-3,5,5-trimethyl-3-cyclohexen-1-ol (purity 98%, chemical yield 98.8%) as colourless crystals having a pale violet hue; Rf value (diisopropyl ether) 0.40.

Workup

  1. customdid not exceed 11° C
  2. waitat room temperature for 30 minutes
  3. extractionThe mixture was extracted three times with 500 ml of methylene chloride each time
  4. washThe organic phases were washed with 500 ml of saturated sodium chloride solution
  5. dry with materialwith 600 ml of saturated sodium bicarbonate solution dried over sodium sulphate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated almost completely in a rotary evaporator under a water-jet vacuum at 30° C. bath temperature
  8. dissolutionThe residual oil was dissolved in 300 ml of pentane
  9. customthe solution was evaporated completely in a rotary evaporator under a water-jet vacuum at 30° C. bath temperature
  10. customThe oil obtained
  11. customwas dried at room temperature for 30 minutes in a high vacuum, whereby spontaneous crystalization (strongly exothermic)

Sources & evidence

ORD record
ord-59572118338c4b01978e7ac4a153c781
Source dataset
uspto-grants-1993_07
Patent number
US05227507

Reaction notes

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