tert-Butyl hydroperoxide → Di-(1-nonyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate

HRID 1650021Notes

Reaction equation

HRID 1650021 reaction equation
[C:1]([O:5]O)([CH3:4])(C)C.[C:7]([O:30][CH:31]1[CH2:36][C:35]([CH3:38])([CH3:37])[NH:34][C:33]([CH3:40])([CH3:39])[CH2:32]1)(=[O:29])[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([O:18][CH:19]1[CH2:24][C:23]([CH3:26])([CH3:25])[NH:22][C:21]([CH3:28])([CH3:27])[CH2:20]1)=[O:17].[CH3:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH3:49].[CH3:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56].C(OCC)(=[O:59])C>[Mo](=O)(=O)=O>[C:7]([O:30][CH:31]1[CH2:36][C:35]([CH3:38])([CH3:37])[N:34]([O:5][CH2:1][CH2:4][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56])[C:33]([CH3:40])([CH3:39])[CH2:32]1)(=[O:29])[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([O:18][CH:19]1[CH2:24][C:23]([CH3:25])([CH3:26])[N:22]([O:59][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH3:49])[C:21]([CH3:27])([CH3:28])[CH2:20]1)=[O:17]

Participants

7

Reactant 5

HCID 6410tert-Butyl hydroperoxideHCID 8141NonaneHCID 8857Ethyl AcetateHCID 8900HeptaneHCID 164282Tinuvin 770

Product 1

HCID 53886802Di-(1-nonyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate

Reagents, catalysts & solvents 1

HCID 14802Molybdenum trioxideCatalyst

Conditions

Temperature
60 °C

Procedure

A solution of 55 grams (427 mmol) of 70% aqueous tert-butyl hydroperoxide is added over 85 minutes to a mixture of 25 grams (52 mmol) of di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1.5 grams (10.4 mmol) of molybdenum trioxide and 190 ml of a nonane fraction (b.p. 148°-156° C., Fluka) which mixture is first heated to 60° C. During the addition, the reaction temperature is slowly increased till the mixture begins to reflux. Water is collected in a Dean-Stark trap. The reaction mixture is heated at reflux for six hours after the addition of hydroperoxide is complete. The reaction mixture is then cooled to room temperature. The solids present are removed by filtration and washed with 25 ml of heptane. The filtrate is stirred for two hours with a solution of 26 grams of sodium sulfite in 500 ml of water. The resulting thick solution is diluted with ethyl acetate (300 ml) and 100 ml of water. The organic layer is separated, dried over anhydrous magnesium sulfate and concentrated to an oil. Flash chromatography (silica gel; 100:3 heptane:ethyl acetate) affords 26.6 grams (67% yield) of a colorless oil as the title compound.

Workup

  1. additionDuring the addition
  2. temperaturethe reaction temperature is slowly increased till the mixture
  3. temperatureto reflux
  4. customWater is collected in a Dean-Stark trap
  5. temperatureThe reaction mixture is heated
  6. temperatureat reflux for six hours
  7. additionafter the addition of hydroperoxide
  8. temperatureThe reaction mixture is then cooled to room temperature
  9. customThe solids present are removed by filtration
  10. washwashed with 25 ml of heptane
  11. additionThe resulting thick solution is diluted with ethyl acetate (300 ml) and 100 ml of water
  12. customThe organic layer is separated
  13. dry with materialdried over anhydrous magnesium sulfate
  14. concentrationconcentrated to an oil

Sources & evidence

ORD record
ord-e1308e69fe0243f8b5ca9091086d965e
Source dataset
uspto-grants-1990_05
Patent number
US04921962

Reaction notes

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