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

Participants

Reaction Conditions

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 three hours at 40° C. to a mixture of 1.12 g (4.0 mmol) of ferrous sulfate heptahydrate, 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, 0.145 g (0.5 mmol) of ferrous sulfate heptahydrate, 0.1 mL of 98% sulfuric acid, and 1-2 mL of water are added to the reaction mixture. The remainding one-fourth of the peroxide solution is added over one hour at 40° C. One hour later, a solution of 2.9 g. (40 mmol) of 50% aqueous hydrogen peroxide is added dropwise to the reaction mixture. After another 1.3 hours, a solution of 0.14 g (0.5 mmol) of ferrous sulfate heptahydrate, 0.15 mL of 98% sulfuric acid and 1-2 mL of water are added in one portion. The reaction mixture is stirred an additional 40 minutes at 40° C. After the peroxides are decomposed with sodium sulfite, the reaction mixture is treated with sodium hydroxide and sodium borohydride and concentrated. The residue is dissolved in ethyl acetate and passed through silica gel to afford 20.5 g (84% yield) of the title compound as a white solid.

Provenance & Evidence