1-Hydroxy-2,2,6,6-tetramethyl-4-piperidinone

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:85.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 25.0 g (0.15 mol) of 1-oxyl-4-oxo-2,2,6,6-tetramethylpiperidine and 162.2 g (1.97 mol) of cyclohexene is heated under a nitrogen atmosphere at 85-86° C. for 56 hours. The reaction mixture is filtered to remove the hydroxylamine, and the solvent is removed in vacuo. The residue is dissolved in heptane and washed with 5% ascorbic acid (2×50 mL) and distilled water (2×50 mL). The organic phase is dried over anhydrous magnesium sulfate and the volatiles removed in vacuo. The residue is eluted through a silica gel column with heptane/ethyl acetate (9/1) to give 3.9 g (21% yield) of the title compound as a yellow oil. The reaction mixture is filtered to remove the hydroxylamine the solvent is removed in vacuo The residue is dissolved in heptane washed with 5% ascorbic acid (2×50 mL) distilled water (2×50 mL) The organic phase is dried over anhydrous magnesium sulfate the volatiles removed in vacuo The residue is eluted through a silica gel column with heptane/ethyl acetate (9/1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in tert-butyl alcohol at 30-60° C. Excess peroxide is decomposed with aqueous sodium sulfite. The organic layer is concentrated and the residue is purified by flash chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one. The organic layer is concentrated the residue is purified by flash chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in tert-butyl alcohol at 30-60° C. Excess peroxide is decomposed with aqueous sodium sulfite. The organic layer is concentrated and the residue is purified by flash chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one. The organic layer is concentrated the residue is purified by flash chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A Parr shaker bottle containing 20.0 g (0.117 mol) 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 6.0 g (0.058 mol) diethylenetriamine, 0.5 g 8% Pt/2% Pd on Carbon and 120 mL methanol is pressurized with hydrogen and shaken for 2 hours. The catalyst is removed by filtration and the solution is concentrated to 40 mL. The product is precipitates as a white solid with the addition of 200 mL of ethyl ether: mp 118-124° C. The catalyst is removed by filtration the solution is concentrated to 40 mL The product is precipitates as a white solid with the addition of 200 mL of ethyl ether

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in tert-butyl alcohol at 30-60° C. Excess peroxide is decomposed with aqueous sodium sulfite. The organic layer is concentrated and the residue is purified by flash chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one. The organic layer is concentrated the residue is purified by flash chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in tert-butyl alcohol at 30-60° C. Excess peroxide is decomposed with aqueous sodium sulfite. The organic layer is concentrated and the residue is purified by flash chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one. The organic layer is concentrated the residue is purified by flash chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in tert-butyl alcohol at 30-60° C. Excess peroxide is decomposed with aqueous sodium sulfite. The organic layer is concentrated and the residue is purified by flash chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-one. The organic layer is concentrated the residue is purified by flash chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in tert-butyl alcohol at 30-60° C. Excess peroxide is decomposed with aqueous sodium sulfite. The organic layer is concentrated and the residue is purified by flash chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one. The organic layer is concentrated the residue is purified by flash chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of cyclohexane (215 ml, 2.0 moles), t-butyl hydroperoxide, 70% aqueous (77.1 g, 0.6 moles), molybdenum trioxide (1.44 g, 0.01 moles) and 1-oxyl-2,2,6,6-tetramethyl-4-piperidone (34 g, 0.2 moles) is charged into a 500 ml flask equipped with a Barrett trap. The mixture is stirred at reflux (80° C.) for two hours until no more water is collected. Then, the mixture is filtered by gravity into a pressure bottle and molybdenum trioxide (1.44 g, 0.01 mole) is added. Subsequently, the mixture is heated under stirring to 105° C. (2.34 bar) and held for 5 hours, until the color changes from deep orange to pale yellow. The mixture is filtered and the clear solution is washed with 10% aqueous sodium sulfite (100 ml) and subsequently with water (2×50 ml). The obtained clear solution is dried over sodium sulfate and then concentrated to give 50 g of the desired material as a clear yellow oil (Mass spectrum: m/e=253) is charged into a 500 ml flask equipped with a Barrett trap is collected is added Subsequently, the mixture is heated under stirring to 105° C. (2.34 bar) The mixture is filtered the clear solution is washed with 10% aqueous sodium sulfite (100 ml) and subsequently with water (2×50 ml) The obtained clear solution is dried over sodium sulfate concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of cyclohexane (215 ml, 2.0 moles), t-butyl hydroperoxide, 70% aqueous (77.1 g, 0.6 moles), molybdenum trioxide (1.44 g, 0.01 moles) and 1-oxyl-2,2,6,6-tetramethyl-4-piperidone (34 g, 0.2 moles) is charged into a 500 ml flask equipped with a Barrett trap. The mixture is stirred at reflux (80° C.) for two hours until no more water is collected. Then, the mixture is filtered by gravity into a pressure bottle and molybdenum trioxide (1.44 g, 0.01 mole) is added. Subsequently, the mixture is heated under stirring to 105° C. (2.34 bar) and held for 5 hours, until the color changes from deep orange to pale yellow. The mixture is filtered and the clear solution is washed with 10% aqueous sodium sulfite (100 ml) and subsequently with water (2×50 ml). The obtained clear solution is dried over sodium sulfate and then concentrated to give 50 g of the desired material as a clear yellow oil (Mass spectrum: m/e=253) is charged into a 500 ml flask equipped with a Barrett trap is collected is added Subsequently, the mixture is heated under stirring to 105° C. (2.34 bar) The mixture is filtered the clear solution is washed with 10% aqueous sodium sulfite (100 ml) and subsequently with water (2×50 ml) The obtained clear solution is dried over sodium sulfate concentrated