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

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Reaction Steps

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.

Provenance & Evidence