1,4-Dihydroxy-2,2,6,6-tetramethylpiperidine → Bis(1-oxyl-2,2,6,6-tetramethyl-pieridin-4-yl)adipate

HRID 1900225Notes

Reaction equation

HRID 1900225 reaction equation
[OH:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH:5]([OH:10])[CH2:4][C:3]1([CH3:12])[CH3:11].[C:13]([O:23]C)(=O)[CH2:14][CH2:15][CH2:16][CH2:17][C:18]([O:20][CH3:21])=[O:19]>CCCCCCC>[C:18]([O:20][CH:21]1[CH2:6][C:7]([CH3:9])([CH3:8])[N:2]([OH:1])[C:3]([CH3:12])([CH3:11])[CH2:4]1)(=[O:19])[CH2:17][CH2:16][CH2:15][CH2:14][C:13]([O:10][CH:5]1[CH2:6][C:7]([CH3:8])([CH3:9])[N:2]([OH:1])[C:3]([CH3:12])([CH3:11])[CH2:4]1)=[O:23]

Participants

4

Reactant 2

HCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidineHCID 12329Dimethyladipate

Product 1

HCID 57039687Bis(1-oxyl-2,2,6,6-tetramethyl-pieridin-4-yl)adipate

Reagents, catalysts & solvents 1

HCID 8900HeptaneSolvent

Conditions

Temperature
75 °C

Procedure

Following the general procedure of Example 1, 20.8 g (0.119 mol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 10.3 g (0.06 mol) of dimethyl adipate and 70 ml of heptane are heated to reflux and 15 ml of slightly turbid distillate is removed from the Dean-Stark trap. The mixture is cooled to about 75° C. and 0.3 g of tetraisopropyl orthotitanate in 15 ml of heptane is added to the flask. The mixture is heated to reflux and heating at reflux temperature 100°-105° C. is continued for 7 hours. Heating is stopped and the reaction mixture is cooled to room temperature. Another 0.3 g of tetraisopropyl orthotitanate in 15 ml of heptane is added to the flask. The mixture is heated to reflux and heating at reflux temperature 100°-105° C. is again continued for 6 hours. Water (2 ml) and 50 ml of toluene are then added to the reaction mixture and heating is continued till the water is removed. The reaction mixture is then filtered and washed with toluene. The filtrate is vacuum stripped and the residue is recrystallized from heptane. Orange crystals form on standing, are collected by filtration and are washed with heptane. The crystals melt at 121°-122° C.

Workup

  1. temperatureare heated
  2. temperatureto reflux
  3. custom15 ml of slightly turbid distillate is removed from the Dean-Stark trap
  4. addition0.3 g of tetraisopropyl orthotitanate in 15 ml of heptane is added to the flask
  5. temperatureThe mixture is heated
  6. temperatureto reflux
  7. temperatureheating
  8. temperatureat reflux temperature 100°-105° C.
  9. temperatureHeating
  10. temperaturethe reaction mixture is cooled to room temperature
  11. additionAnother 0.3 g of tetraisopropyl orthotitanate in 15 ml of heptane is added to the flask
  12. temperatureThe mixture is heated
  13. temperatureto reflux
  14. temperatureheating
  15. temperatureat reflux temperature 100°-105° C.
  16. waitis again continued for 6 hours
  17. additionWater (2 ml) and 50 ml of toluene are then added to the reaction mixture
  18. temperatureheating
  19. customis removed
  20. filtrationThe reaction mixture is then filtered
  21. washwashed with toluene
  22. customthe residue is recrystallized from heptane
  23. customOrange crystals form on standing
  24. filtrationare collected by filtration
  25. washare washed with heptane
  26. custommelt at 121°-122° C.

Sources & evidence

ORD record
ord-1628a7478572406096d3bf869959c784
Source dataset
uspto-grants-1996_11
Patent number
US05574163

Reaction notes

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