Acetic Acid → HCID 22463279, compound

HRID 133643Notes

Reaction equation

HRID 133643 reaction equation
[C:1](O)(=O)[CH3:2].[OH:5][N:6]1[C:11]([CH3:13])([CH3:12])[CH2:10][CH:9]([O:14][C:15](=[O:33])[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[CH2:8][C:7]1([CH3:35])[CH3:34].OO.S([O-])([O-])=O.[Na+].[Na+]>O.C(O)(=O)C.C(#N)C.C1CCCCC1>[CH:2]1([O:5][N:6]2[C:11]([CH3:12])([CH3:13])[CH2:10][CH:9]([O:14][C:15](=[O:33])[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[CH2:8][C:7]2([CH3:34])[CH3:35])[CH2:1][CH2:9][CH2:8][CH2:7][CH2:34]1

Participants

9

Reactant 4

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 24437Sodium SulfiteHCID 580171Octadecanoic acid, 1-hydroxy-2,2,6,6-tetramethyl-4-piperidinyl ester

Product 1

HCID 22463279HCID 22463279, compoundYield 511.4%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidCatalyst2×HCID 962WaterSolvent3×HCID 6342AcetonitrileSolventHCID 8078CyclohexaneSolvent

Procedure

A solution of 0.116 g (0.429 mmol) of ferric chloride hexahydrate and 0.096 g (1.60 mmol) of glacial acetic acid in 2 ml of water is added to a mixture of 5.08 g (11.6 mmol) of 1-oxyl-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 40 ml of cyclohexane, and 60 ml of acetonitrile that has been heated to 60°. A solution of 3.36 g (49.4 mmol) of aqueous 50% hydrogen peroxide is added to the reaction mixture dropwise over 2.5 hours at the reflux temperature of 60-62°. A solution of 0.033 g of ferric chloride hexahydrate and 0.040 g of glacial acetic acid in 1 ml of water is added to the reaction mixture 1.5 hours after the peroxide addition is begun. A solution of 0.031 g of ferric chloride and 0.028 g of glacial acetic acid in 1 ml of water is added to the reaction mixture 4 hours after the peroxide addition is begun. After being heated a total of 5 hours at reflux temperature, the reaction mixture is cooled and excess peroxide is decomposed by the addition of aqueous sodium sulfite solution. The organic layer is concentrated and purified by flash chromatography with 20:1 heptane-ethyl acetate to afford 4.27 g (71% yield) of the title compound, a white solid, mp 42-46. The assay is approximately 90% by NMR integration.

Workup

  1. temperaturehas been heated to 60°
  2. temperatureAfter being heated a total of 5 hours
  3. temperatureat reflux temperature
  4. temperaturethe reaction mixture is cooled
  5. concentrationThe organic layer is concentrated
  6. custompurified by flash chromatography with 20:1 heptane-ethyl acetate

Sources & evidence

ORD record
ord-03fabe7367bb4a3fac05e2c7d131743d
Source dataset
uspto-grants-2008_06
Patent number
US07390904B2

Reaction notes

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