tert-Butyl hydroperoxide → Tinuvin 123

HRID 2050992Notes

Reaction equation

HRID 2050992 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]>[Mo](=O)(=O)=O.CCCCCCCC>[C:7]([O:30][CH:31]1[CH2:36][C:35]([CH3:38])([CH3:37])[N:34]([O:5][CH2:1][CH2:4][CH2:27][CH2:21][CH2:20][CH2:19][CH2:24][CH3:23])[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:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH3:9])[C:21]([CH3:27])([CH3:28])[CH2:20]1)=[O:17]

Participants

5

Reactant 2

HCID 6410tert-Butyl hydroperoxideHCID 164282Tinuvin 770

Product 1

HCID 3592789Tinuvin 123Yield 160.5%

Reagents, catalysts & solvents 2

HCID 14802Molybdenum trioxideCatalystHCID 356OctaneSolvent

Conditions

Temperature
115 °C

Procedure

70% Aqueous t-butyl hydroperoxide (140 g, 1.09 mol) is added over a 6 hour period to a mixture of 75.4 g (0.157 mol) of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1.25 g (8.7 mmol) of molybdenum trioxide, and 570 ml of n-octane that has been heated to 115° C. under a nitrogen atmosphere. During the addition, the reaction is maintained at reflux. Water is collected in a Dean-Stark trap. Upon completion of the addition, the red reaction mixture is heated at reflux (95-97° C.) for seven hours to discharge the red color. The molybdenum trioxide is removed by filtration. The yellow filtrate is stirred at ambient temperature for 30 minutes with 15 g of activated charcoal (DARCO) to remove some of the yellow color, and then concentrated at reduced pressure. The crude product is purified by flash chromatography on silica gel (100:3 heptane: ethyl acetate) to afford 92.9 g (80% yield) of di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, a colorless oil. The column is then eluted with 10:1 heptane:ethyl acetate to obtain the title compound as a mixture of octandiyl isomers. The title compound is a colorless oil.

Workup

  1. additionDuring the addition
  2. temperaturethe reaction is maintained
  3. temperatureat reflux
  4. customWater is collected in a Dean-Stark trap
  5. additionUpon completion of the addition
  6. customthe red reaction mixture
  7. temperatureis heated
  8. temperatureat reflux (95-97° C.) for seven hours
  9. customThe molybdenum trioxide is removed by filtration
  10. customto remove some of the yellow color
  11. concentrationconcentrated at reduced pressure
  12. customThe crude product is purified by flash chromatography on silica gel (100:3 heptane: ethyl acetate)

Sources & evidence

ORD record
ord-41d72f12867a4827ab36118f78a2183d
Source dataset
uspto-grants-1991_05
Patent number
US05015682

Reaction notes

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