Phenol → Cumyl t-amyl peroxide

HRID 1733395Notes

Reaction equation

HRID 1733395 reaction equation
[CH3:1][C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[CH2:3].[C:10]([O:15][OH:16])([CH2:13][CH3:14])([CH3:12])[CH3:11].C1(O)C=CC=CC=1>O>[C:10]([O:15][O:16][C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)([CH3:1])[CH3:3])([CH2:13][CH3:14])([CH3:12])[CH3:11]

Participants

5

Reactant 3

HCID 996PhenolHCID 7407Alpha-MethylstyreneHCID 76962tert-Amyl hydroperoxide

Product 1

HCID 18979329Cumyl t-amyl peroxideYield 60.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
25 °C

Procedure

Into the 200 ml jacketed reactor described in Example II were added 15.0 grams (0.127 m) alpha-methylstyrene, 15.5 grams (0.1 m) 67.3% t-amyl hydroperoxide and 3.8 grams (0.041 m) phenol. The mixture was stirred to obtain a clear solution and the temperature was adjusted to 20° C. by pumping cool water through the reactor jacket. To this solution was added 1.4 grams (0.009 m) of t-cumyl chloride from the addition funnel over 10 minutes while holding the temperature at 21°-22° C. The reaction was stirred 5 minutes at 22° C., the temperature raised to 25° C. and the reaction stirred 1/2 hour at 30° C., 1/2 hour at 35° C., 11/2 hours at 40° C. and 1/2 hour at 45° C. for a total reaction time of 31/2 hours. At this point essentially all the t-amyl hydroperoxide had been consumed. The reaction was terminated by adding 25 mls of water, stirring 5 minutes, adding 5 mls of 50% NaOH, stirring another 5 minutes and then separating the aqueous caustic layer. The organic layer was washed with saturated NaHCO3 solution, water, 15% NaHSO3, saturated NaHCO3 again and water. The dried material weighed 24.6 grams and contained 54.6% cumyl t-amyl peroxide for a corrected yield of 13.4 grams and a 60.5% yield. The pure cumyl t-amyl peroxide was isolated by fractional distillation under vacuum.

Workup

  1. customto obtain a clear solution
  2. customwas adjusted to 20° C.
  3. customat 21°-22° C
  4. stirringThe reaction was stirred 5 minutes at 22° C.
  5. stirringthe reaction stirred 1/2 hour at 30° C., 1/2 hour at 35° C.
  6. custom2 hours
  7. customat 40° C.
  8. custom1/2 hour
  9. customat 45° C.
  10. customAt this point essentially all the t-amyl hydroperoxide had been consumed
  11. customThe reaction was terminated
  12. additionby adding 25 mls of water
  13. stirringstirring 5 minutes
  14. additionadding 5 mls of 50% NaOH
  15. stirringstirring another 5 minutes
  16. customseparating the aqueous caustic layer
  17. washThe organic layer was washed with saturated NaHCO3 solution, water, 15% NaHSO3, saturated NaHCO3 again

Sources & evidence

ORD record
ord-15114492b7f648d4915bc5c505ed5206
Source dataset
uspto-grants-1980_12
Patent number
US04241222

Reaction notes

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