Hydrogen Peroxide → HCID 22463279, compound

HRID 133653Notes

Reaction equation

HRID 133653 reaction equation
OO.[C:3]([O:22][CH:23]1[CH2:28][C:27]([CH3:30])([CH3:29])[NH:26][C:25]([CH3:32])([CH3:31])[CH2:24]1)(=[O:21])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].[C:33](=[O:36])(O)[O-].[Na+].S([O-])([O-])=O.[Na+].[Na+]>O.C1CCCCC1.C(#N)C.C(OCC)(=O)C.C(O)(=O)C>[CH:33]1([O:36][N:26]2[C:27]([CH3:30])([CH3:29])[CH2:28][CH:23]([O:22][C:3](=[O:21])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])[CH2:24][C:25]2([CH3:31])[CH3:32])[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3]1

Participants

10

Reactant 4

HCID 784Hydrogen Peroxide2×HCID 24437Sodium SulfiteHCID 516892Sodium BicarbonateHCID 141134162,2,6,6-Tetramethyl-4-piperidinyl octadecanoate

Product 1

HCID 22463279HCID 22463279, compoundYield 846.8%

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolvent4×HCID 962WaterSolvent5×HCID 6342AcetonitrileSolvent2×HCID 8078CyclohexaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

A solution of 2.84 g (41.7 mmol) of 50% aqueous hydrogen peroxide is added dropwise over 3 hours to a mixture of 5.98 g (14.1 mmol) of 4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 0.026 g (0.31 mmol, 2.2 mole percent) of sodium bicarbonate dissolved in 0.6 g of water, 4 ml of cyclohexane, and 4 ml of acetonitrile while the reaction temperature is maintained at 65-68° C. After the peroxide is added, the reaction mixture is stirred at 65° C. for 4.5 hours. The red mixture is cooled, and then diluted with cyclohexane and acetonitrile. The aqueous layer is discarded. The mixture is washed with water, and the wash is extracted with a mixture of cyclohexane and acetonitrile. A total of 25 ml each of cyclohexane and acetonitrile are used in the work up. The organic layers are combined, and more acetonitrile (13 ml) is added. The temperature is brought to 50° C., and a solution of 0.117 g (0.433 mmol) of ferric chloride hexahydrate and 0.096 g (1.60 mmol) of glacial acetic acid in 2 ml of water is added to the reaction mixture. A solution of 4.28 g (63 mmol) of 50% aqueous peroxide is added dropwise over 3 hours to the reaction mixture while the temperature is maintained near 60° C. A solution of 0.042 g of ferric chloride hexahydrate, 0.5 g of water, and 0.044 g of glacial acetic acid is added to the reaction mixture 1.5 hours after the peroxide addition is begun. The mixture is heated at reflux for 4 hours after the peroxide is added, then allowed to stand at room temperature overnight. Glacial acetic acid (0.403 g, 6.7 mmol) and a solution of 0.130 g of ferric chloride hexahydrate in 0.5 g of water are added to the red reaction mixture. The temperature is brought to reflux, and a solution of 4.56 g (67.0 mmol) of 50% aqueous hydrogen peroxide is added dropwise over 2 hours. A solution of 0.070 g of ferric chloride hexahydrate and 0.096 g of glacial acetic acid in 1 ml of water is added to the reaction mixture 1 hour after the peroxide addition is begun. The mixture is heated at reflux for 2.5 hours after the peroxide is added. The mixture is cooled and stirred with 10 ml of 10% aqueous sodium sulfite. Ethyl acetate is added, and the aqueous layer is extracted with ethyl acetate. The organic layers are combined and concentrated. The concentrate is purified by flash chromatography with 20:1 heptane-ethyl acetate to afford a red liquid. A second purification by flash chromatography affords 1.37 g (19% yield) of the title compound as a white solid, mp 42-45. The assay is % by NMR integration.

Workup

  1. temperatureThe red mixture is cooled
  2. washThe mixture is washed with water
  3. extractionthe wash is extracted with a mixture of cyclohexane and acetonitrile
  4. additionmore acetonitrile (13 ml) is added
  5. customis brought to 50° C.
  6. temperatureis maintained near 60° C
  7. temperatureThe mixture is heated
  8. additionis added
  9. waitto stand at room temperature overnight
  10. temperatureto reflux
  11. temperatureThe mixture is heated
  12. additionis added
  13. temperatureThe mixture is cooled
  14. extractionthe aqueous layer is extracted with ethyl acetate
  15. concentrationconcentrated
  16. customThe concentrate is purified by flash chromatography with 20:1 heptane-ethyl acetate
  17. customto afford a red liquid
  18. customA second purification by flash chromatography

Sources & evidence

ORD record
ord-e9dfbb15bb0b4c3aa6cccfd8380b6f4b
Source dataset
uspto-grants-2008_06
Patent number
US07390904B2

Reaction notes

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