Sodium Chloride → Di-(1-nonyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate

HRID 1650040Notes

Reaction equation

HRID 1650040 reaction equation
[C:1]([O:5]O)([CH3:4])(C)C.[Cl-].[Na+].[C:9]([O:32][CH:33]1[CH2:38][C:37]([CH3:40])([CH3:39])[NH:36][C:35]([CH3:42])([CH3:41])[CH2:34]1)(=[O:31])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]([O:20][CH:21]1[CH2:26][C:25]([CH3:28])([CH3:27])[NH:24][C:23]([CH3:30])([CH3:29])[CH2:22]1)=[O:19]>CCCCCCCCC.[O-]CCCC.[O-]CCCC.[O-]CCCC.[O-]CCCC.[Ti+4]>[C:9]([O:32][CH:33]1[CH2:38][C:37]([CH3:40])([CH3:39])[N:36]([O:5][CH2:1][CH2:4][CH2:27][CH2:25][CH2:26][CH2:21][CH2:22][CH2:23][CH3:29])[C:35]([CH3:42])([CH3:41])[CH2:34]1)(=[O:31])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]([O:20][CH:21]1[CH2:26][C:25]([CH3:27])([CH3:28])[N:24]([O:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH3:10])[C:23]([CH3:29])([CH3:30])[CH2:22]1)=[O:19]

Participants

6

Reactant 3

HCID 5234Sodium ChlorideHCID 6410tert-Butyl hydroperoxideHCID 164282Tinuvin 770

Product 1

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

Reagents, catalysts & solvents 2

HCID 21801Titanium tetrabutoxideCatalystHCID 8141NonaneSolvent2×

Conditions

Temperature
151 °C

Procedure

A 2-phase mixture of 85.7 g (0.666 mol) of 70% aqueous tert-butyl hydroperoxide, 200 ml of n-nonane and 15 g of sodium chloride is agitated in a separatory funnel. The organic layer is dried over anhydrous magnesium sulfate. A mixture of 40.0 g (0.0832 mol) of bis-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the tert-butyl hydroperoxidenonane solution is heated to reflux (151° C.) under a nitrogen atmosphere. To this mixture is added over a 10-minute period, a solution of 5.0 g of titanium tetrabutoxide in 50 ml of nonane. The reaction mixture turns red. Water is collected in a Dean Stark trap. The reaction mixture is heated at reflux for 17 hours. Another 5.0 g of titanium tetrabutoxide is added, and the reaction mixture is heated at reflux for an additional 7 hours. Solids are removed by filtration, and the filtrate is concentrated under reduced pressure. The crude red oil obtained is purified by chromatography (Waters Prep 500A HPLC; 29:1 heptane:ethyl acetate) to give 3.6 g (6% yield) or the title compound as a light yellow oil.

Workup

  1. dry with materialThe organic layer is dried over anhydrous magnesium sulfate
  2. additionTo this mixture is added over a 10-minute period
  3. customWater is collected in a Dean Stark trap
  4. temperatureThe reaction mixture is heated
  5. temperatureat reflux for 17 hours
  6. additionAnother 5.0 g of titanium tetrabutoxide is added
  7. temperaturethe reaction mixture is heated
  8. temperatureat reflux for an additional 7 hours
  9. customSolids are removed by filtration
  10. concentrationthe filtrate is concentrated under reduced pressure
  11. customThe crude red oil obtained
  12. customis purified by chromatography (Waters Prep 500A HPLC; 29:1 heptane:ethyl acetate)
  13. customto give 3.6 g (6% yield)

Sources & evidence

ORD record
ord-ced0d83a439f497ab88409c2f77ac965
Source dataset
uspto-grants-1990_05
Patent number
US04921962

Reaction notes

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