Hydrogen Peroxide → 4-Piperidinol, 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-

HRID 1276644Notes

Reaction equation

HRID 1276644 reaction equation
[OH:1][CH:2]1[CH2:7][C:6]([CH3:9])([CH3:8])[N:5]([OH:10])[C:4]([CH3:12])([CH3:11])[CH2:3]1.OO.S(=O)(=O)(O)O.N=O.[OH2:22]>C(O)(C)(C)C>[OH:1][CH:2]1[CH2:7][C:6]([CH3:8])([CH3:9])[N:5]([O:10][CH2:3][C:4]([OH:22])([CH3:12])[CH3:11])[C:4]([CH3:12])([CH3:11])[CH2:3]1

Participants

7

Reactant 5

HCID 784Hydrogen Peroxide2×HCID 945Nitroxyl2×HCID 962Water2×HCID 1118Sulfuric Acid2×HCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidine

Product 1

HCID 68508284-Piperidinol, 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-Yield 74%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40 mL of water and three-fourths of a solution of 25.0 g (0.37 mol) of 50% aqueous hydrogen peroxide are added simultaneously over 2.5 hours to 40° C. to a mixture of 1.46 g (4.1 mmol) of ferric acetylacetonate, 25 mL of water, 0.5 mL of 98% sulfuric acid and 200 mL of tert-butyl alcohol. At the conclusion of the nitroxyl addition, 0.18 g (0.5 mmol) of ferric acetylacetonate is added to the reaction mixture. The remaining one-fourth of the peroxide solution is added over one hour at 40° C. After heating for two hours, gas chromatography shows less than 10% nitroxyl compound remaining in the reaction mixture. Sulfuric acid (0.3 mL) and a solution of 4.9 g (72 mmol) of 50% aqueous hydrogen peroxide are added to the reaction mixture at 40° C., and the reaction mixture is stirred overnight at room temperature. Work-up as in Example 20 affords 18.1 g (74% yield) of the title compound as a white solid.

Workup

  1. additionis added to the reaction mixture
  2. temperatureAfter heating for two hours

Sources & evidence

ORD record
ord-598dd6d1cf634bc6893c6172301a5ca5
Source dataset
uspto-grants-2000_12
Patent number
US06166212

Reaction notes

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