Sodium Chloride → Di-[1-(alpha-methylbenzyloxy)-2,2,6,6-tetramethylpiperidine-4-yl] Sebacate

HRID 1650039Notes

Reaction equation

HRID 1650039 reaction equation
[C:1]([O:5]O)([CH3:4])([CH3:3])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]>C(C1C=CC=CC=1)C.CCCCCCC.[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][CH:1]([CH3:4])[C:3]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[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:5][CH:1]([CH3:4])[C:3]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:23]([CH3:29])([CH3:30])[CH2:22]1)=[O:19]

Participants

7

Reactant 3

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

Product 1

HCID 19768362Di-[1-(alpha-methylbenzyloxy)-2,2,6,6-tetramethylpiperidine-4-yl] SebacateYield 13.3%

Reagents, catalysts & solvents 3

HCID 21801Titanium tetrabutoxideCatalystHCID 7500EthylbenzeneSolvent2×HCID 8900HeptaneSolvent2×

Conditions

Temperature
136 °C

Procedure

A 2-phase mixture of 85.7 g (0.666 mol) of 70% aqueous tert-butyl hydroperoxide, 250 ml of ethylbenzene and 10 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 hydroperoxideethylbenzene solution is heated to reflux (136° C.) under a nitrogen atmosphere. To this mixture is added over a 5-minute period, a solution of 5.0 g of titanium tetrabutoxide in 35 ml of ethylbenzene. The reaction mixture becomes red and water is collected in a Dean-Stark trap. The reaction mixture is heated at reflux for 18 hours. The red color remains. The solids are then removed by filtration, and the filtrate is concentrated under reduced pressure to give a red oil. The oil is dissolved in heptane (100 ml) and passed through a short column of silica gel with additional heptane. Further purification (Waters Prep 500A HPLC; 29:1 heptane:ethyl acetate) affords 4.0 g (7% yield) of the title compound as a cloudy, colorless syrup.

Workup

  1. dry with materialThe organic layer is dried over anhydrous magnesium sulfate
  2. additionTo this mixture is added over a 5-minute period
  3. customwater is collected in a Dean-Stark trap
  4. temperatureThe reaction mixture is heated
  5. temperatureat reflux for 18 hours
  6. customThe solids are then removed by filtration
  7. concentrationthe filtrate is concentrated under reduced pressure
  8. customto give a red oil
  9. customFurther purification (Waters Prep 500A HPLC; 29:1 heptane:ethyl acetate)

Sources & evidence

ORD record
ord-683efc6d25184eebbcb5583d5270875b
Source dataset
uspto-grants-1990_05
Patent number
US04921962

Reaction notes

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