tert-Butyl hydroperoxide → HCID 53631979, compound

HRID 1590935Notes

Reaction equation

HRID 1590935 reaction equation
[C:1]([O:22][CH:23]1[CH2:28][C:27]([CH3:30])([CH3:29])[NH:26][C:25]([CH3:32])([CH3:31])[CH2:24]1)(=[O:21])[C:2]1[C:3](=[CH:17][CH:18]=[CH:19][CH:20]=1)[C:4]([O:6][CH:7]1[CH2:12][C:11]([CH3:14])([CH3:13])[NH:10][C:9]([CH3:16])([CH3:15])[CH2:8]1)=[O:5].[C:33]([O:37]O)([CH3:36])([CH3:35])C>[Mo](=O)(=O)=O.C1CCCCC1>[C:4]([O:6][CH:7]1[CH2:8][C:9]([CH3:16])([CH3:15])[N:10]([O:37][CH:33]2[CH2:36][CH2:17][CH2:3][CH2:4][CH2:35]2)[C:11]([CH3:13])([CH3:14])[CH2:12]1)(=[O:5])[C:3]1[C:2](=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:1]([O:22][CH:23]1[CH2:24][C:25]([CH3:32])([CH3:31])[N:26]([O:37][CH:33]2[CH2:36][CH2:20][CH2:2][CH2:1][CH2:35]2)[C:27]([CH3:30])([CH3:29])[CH2:28]1)=[O:21]

Participants

5

Reactant 2

HCID 6410tert-Butyl hydroperoxide3×HCID 1513129Bis(2,2,6,6-tetramethyl-4-piperidinyl) phthalate

Product 1

HCID 53631979HCID 53631979, compoundYield 143.3%

Reagents, catalysts & solvents 2

HCID 14802Molybdenum trioxideCatalystHCID 8078CyclohexaneSolvent

Conditions

Temperature
140 °C

Procedure

A mixture of 30.0 g (67.5 mmol) of di-(2,2,6,6-tetramethyl-piperidin-4-yl) phthalate, 27.5 g (214 mmol) of 70% aqueous t-butyl hydroperoxide, 2.0 g of molybdenum trioxide, and 200 ml of cyclohexane is heated to reflux. Water is collected in a Dean-Stark trap. After 75 min., the reaction mixture becomes red. Another portion of t-butyl hydroperoxide (42.5 g, 70%, 330 mmol) is added over 30 minutes. After the additional water is collected, the reaction mixture is transferred to a Fischer-Porter bottle and heated at 140° C. for 4.5 hours. The nearly colorless reaction mixture is treated with 6.9 g (90%, 69 mmol) of t-butyl hydroperoxide and heated at 140° C. for 90 minutes to remove the last traces of pink color. The reaction mixture is cooled, filtered, and stirred with a solution of 43 g of sodium sulfite in 530 ml of water for 2 hours. Dichloromethane (600 ml) is added, and the organic layer is separated, dried over magnesium sulfate, and concentrated to obtain a crude solid. Purification (Waters Prep. 500A HPLC, 25:1 heptane:ethyl acetate) affords 31.0 g (72% yield) of a white solid, m.p. 149°-51° C.

Workup

  1. temperatureis heated to reflux
  2. customWater is collected in a Dean-Stark trap
  3. customAfter the additional water is collected
  4. temperatureheated at 140° C. for 90 minutes
  5. customto remove the last traces of pink color
  6. temperatureThe reaction mixture is cooled
  7. filtrationfiltered
  8. additionDichloromethane (600 ml) is added
  9. customthe organic layer is separated
  10. dry with materialdried over magnesium sulfate
  11. concentrationconcentrated
  12. customto obtain a crude solid
  13. customPurification (Waters Prep. 500A HPLC, 25:1 heptane:ethyl acetate)

Sources & evidence

ORD record
ord-4fc763e57fd743adad48425debc9828b
Source dataset
uspto-grants-1993_04
Patent number
US05204473

Reaction notes

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