tert-Butyl hydroperoxide → HCID 21386992, compound

HRID 1834327Notes

Reaction equation

HRID 1834327 reaction equation
[OH-].[K+].[C:3]([O:7][OH:8])([CH3:6])([CH3:5])[CH3:4].[CH:9]([N:12]=[N:13][C:14]1(Cl)[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1)([CH3:11])[CH3:10].[OH-].[Na+]>>[CH:9]([N:12]=[N:13][C:14]1([O:8][O:7][C:3]([CH3:6])([CH3:5])[CH3:4])[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1)([CH3:11])[CH3:10]

Participants

5

Reactant 4

HCID 6410tert-Butyl hydroperoxideHCID 14797Potassium HydroxideHCID 14798Sodium HydroxideHCID 21387085HCID 21387085, compound

Product 1

HCID 21386992HCID 21386992, compound

Procedure

To a stirred solution of 24.7 grams (0.11 moles) of 25% potassium hydroxide in an erlenmeyer flask equipped with a magnetic stirrer, thermometer and addition funnel was added 14.0 grams (0.14 moles) of 90% tert.-butylhydroperoxide while holding the temperature below 30° C with a cold water bath. After the addition was complete, the reaction was stirred for 30 minutes at room temperature, cooled to 18° C and with rapid stirring 18.85 grams (0.1 mole) of 1-isopropylazo-1-chlorocyclohexane (from Example 3-2) was added dropwise from the addition funnel over 40 minutes while holding the reaction temperature at 20° C ± 2° C. After the addition was complete, the reaction was stirred for 10 minutes at 15° C, cooled to 0° C and stirred an additional 30 minutes. At this point, 3.2 grams (0.04 mole) of 50% sodium hydroxide was added, the reaction stirred an additional 10 minutes, poured into 100 ml of ice water and the product extracted into 100 ml of pentane. The pentane solution was separated, washed with 50 ml portions of water and saturated sodium bicarbonate, dried over anhydrous sodium sulfate, filtered and the pentane evaporated at 0° C under reduced pressure on a rotating evaporator. The product was a light yellow liquid weighing 18.7 grams (77% crude yield). It was stored in dry ice chest to prevent decomposition and it was not shock sensitive. The infrared spectrum was in agreement with the structure of 1-isopropylazo-1-(tert.-butylperoxy)cyclohexane (absence of the carbon-chlorine band of the starting material at 800-825 cm-1 and the presence of a tert.-butylperoxy band around 885 cm-1.) The presence of a weak OH band at 3350cm-1 indicates that a small amount of 1-isopropylazo-1-hydroxycyclohexane also formed.

Workup

  1. additionthermometer and addition funnel
  2. customthe temperature below 30° C
  3. additionAfter the addition
  4. temperaturecooled to 18° C
  5. additionwas added dropwise from the addition funnel over 40 minutes
  6. customat 20° C ± 2° C
  7. additionAfter the addition
  8. stirringthe reaction was stirred for 10 minutes at 15° C
  9. temperaturecooled to 0° C
  10. stirringstirred an additional 30 minutes
  11. stirringthe reaction stirred an additional 10 minutes
  12. extractionthe product extracted into 100 ml of pentane
  13. customThe pentane solution was separated
  14. washwashed with 50 ml portions of water and saturated sodium bicarbonate
  15. dry with materialdried over anhydrous sodium sulfate
  16. filtrationfiltered
  17. customthe pentane evaporated at 0° C under reduced pressure on a rotating evaporator
  18. customalso formed

Sources & evidence

ORD record
ord-e6b53b874ab64d86a761e164523b40a5
Source dataset
uspto-grants-1978_01
Patent number
US04069377

Reaction notes

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