Octane → N-(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)acetamide

HRID 1756848Notes

Reaction equation

HRID 1756848 reaction equation
[CH3:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[Cl-].[Na+].[CH3:11][C:12]1([CH3:24])[CH2:17][CH:16]([NH:18][C:19](=[O:21])[CH3:20])[CH2:15][C:14]([CH3:23])([CH3:22])[NH:13]1.C([O:29]O)(C)(C)C>[Mo](=O)(=O)=O>[CH2:1]([O:29][N:13]1[C:12]([CH3:24])([CH3:11])[CH2:17][CH:16]([NH:18][C:19](=[O:21])[CH3:20])[CH2:15][C:14]1([CH3:23])[CH3:22])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]

Participants

6

Reactant 4

HCID 356Octane2×HCID 5234Sodium ChlorideHCID 6410tert-Butyl hydroperoxide3×HCID 100241N-(2,2,6,6-Tetramethyl-4-piperidinyl)acetamide

Product 1

HCID 23372128N-(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)acetamideYield 61%

Reagents, catalysts & solvents 1

HCID 14802Molybdenum trioxideCatalyst

Conditions

Temperature
5 °C

Procedure

A two-phase mixture of 260 grams (2.02 mol) of 70% aqueous tert-butyl hydroperoxide, 350 ml of n-octane, and 50 grams of sodium chloride is vigorously stirred. The organic phase is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate is diluted with n-octane to a volume of 580 ml. To a mixture of 100.0 grams (0.504 mol) of N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 1.8 gram of molybdenum trioxide, and 100 ml of n-octane preheated to 120° C. is added 300 ml of tert-butyl hydroperoxide solution over a 15-minute period. The mixture quickly turns red and water is collected in a Dean-Stark trap. The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours. The reaction mixture is heated at reflux for three hours after the addition is complete, then treated with 50.1 grams (0.50 mol) of 90% tert-butyl hydroperoxide and heated at reflux for 2.5 hours to discharge the red color of the N-oxyl intermediate. Solids are removed by filtration, and the filtrate is cooled to 5° C. and stirred with a solution of 40 grams of sodium sulfite in 400 ml of water to decompose unreacted hydroperoxide. The organic layer is dried over anhydrous magnesium sulfate and concentrated to an oil. Purification by flash chromatography (1:1 heptane:ethyl acetate) affords 100.2 grams (61% yield) of the title compound as a waxy solid.

Workup

  1. customThe organic phase is separated
  2. dry with materialdried over anhydrous magnesium sulfate
  3. filtrationfiltered
  4. additionThe filtrate is diluted with n-octane to a volume of 580 ml
  5. custompreheated to 120° C.
  6. customThe mixture quickly turns red and water is collected in a Dean-Stark trap
  7. additionThe remaining tert-butyl hydroperoxide solution (280 ml) is added
  8. customto-the refluxing reaction mixture over a period of 2.5 hours
  9. temperatureThe reaction mixture is heated
  10. temperatureat reflux for three hours
  11. additionafter the addition
  12. temperatureheated
  13. temperatureat reflux for 2.5 hours
  14. customSolids are removed by filtration
  15. stirringstirred with a solution of 40 grams of sodium sulfite in 400 ml of water
  16. dry with materialThe organic layer is dried over anhydrous magnesium sulfate
  17. concentrationconcentrated to an oil
  18. customPurification by flash chromatography (1:1 heptane:ethyl acetate)

Sources & evidence

ORD record
ord-853c3687fb9745f19fa38d8f743613c2
Source dataset
uspto-grants-1995_08
Patent number
US05442071

Reaction notes

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