(2,2,6,6-tetramethylpiperidin-4-yl) acetate

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 60 g (301 mmol) of 4-acetoxy-2,2,6,6-tetramethylpiperidine are dissolved in 300 ml of cyclohexane under nitrogen in a 1.5 l sulfonation flask fitted with magnetic stirrer, water separator, thermometer and dropping funnel. 4.3 g (30 mmol) of molybdenum oxide are added. 154 g (1.2 mol) of an aqueous 70% solution of t-butyl hydroperoxide are extracted three times with 35 ml of cyclohexane in each case, and the organic phase is dried over sodium sulfate and transferred into the dropping funnel. The reaction mixture is warmed to reflux, and the t-butyl hydroperoxide solution is added dropwise over the course of 2 hours. After a further 2 hours, the elimination of water is complete. The mixture is held at the reflux temperature overnight and is then cooled to 25° C., and the catalyst is filtered off. Ice is added, a little sodium sulfite is added in order to destroy the excess hydroperoxide, and the organic phase is then separated off, washed with water and dried over sodium sulfate, and the solvent is removed on a Rotavap. fitted with magnetic stirrer 154 g (1.2 mol) of an aqueous 70% solution of t-butyl hydroperoxide are extracted three times with 35 ml of cyclohexane in each case the organic phase is dried over sodium sulfate The reaction mixture is warmed to reflux the t-butyl hydroperoxide solution is added dropwise over the course of 2 hours is held at the reflux temperature overnight the catalyst is filtered off Ice is added a little sodium sulfite is added in order to destroy the excess hydroperoxide the organic phase is then separated off washed with water dried over sodium sulfate the solvent is removed on a Rotavap

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 60 g (301 mmol) of 4-acetoxy-2,2,6,6-tetramethylpiperidine are dissolved in 300 ml of cyclohexane under nitrogen in a 1.5 l sulfonation flask fitted with magnetic stirrer, water separator, thermometer and dropping funnel. 4.3 g (30 mmol) of molybdenum oxide are added. 154 g (1.2 mol) of an aqueous 70% solution of t-butyl hydroperoxide are extracted three times with 35 ml of cyclohexane in each case, and the organic phase is dried over sodium sulfate and transferred into the dropping funnel. The reaction mixture is warmed to reflux, and the t-butyl hydroperoxide solution is added dropwise over the course of 2 hours. After a further 2 hours, the elimination of water is complete. The mixture is held at the reflux temperature overnight and is then cooled to 25° C., and the catalyst is filtered off. Ice is added, a little sodium sulfite is added in order to destroy the excess hydroperoxide, and the organic phase is then separated off, washed with water and dried over sodium sulfate, and the solvent is removed on a Rotavap. fitted with magnetic stirrer 154 g (1.2 mol) of an aqueous 70% solution of t-butyl hydroperoxide are extracted three times with 35 ml of cyclohexane in each case the organic phase is dried over sodium sulfate The reaction mixture is warmed to reflux the t-butyl hydroperoxide solution is added dropwise over the course of 2 hours is held at the reflux temperature overnight the catalyst is filtered off Ice is added a little sodium sulfite is added in order to destroy the excess hydroperoxide the organic phase is then separated off washed with water dried over sodium sulfate the solvent is removed on a Rotavap

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 60 g (301 mmol) of 4-acetoxy-2,2,6,6-tetramethylpiperidine are dissolved in 300 ml of cyclohexane under nitrogen in a 1.5 l sulfonation flask fitted with magnetic stirrer, water separator, thermometer and dropping funnel. 4.3 g (30 mmol) of molybdenum oxide are added. 154 g (1.2 mol) of an aqueous 70% solution of t-butyl hydroperoxide are extracted three times with 35 ml of cyclohexane in each case, and the organic phase is dried over sodium sulfate and transferred into the dropping funnel. The reaction mixture is warmed to reflux, and the t-butyl hydroperoxide solution is added dropwise over the course of 2 hours. After a further 2 hours, the elimination of water is complete. The mixture is held at the reflux temperature overnight and is then cooled to 25° C., and the catalyst is filtered off. Ice is added, a little sodium sulfite is added in order to destroy the excess hydroperoxide, and the organic phase is then separated off, washed with water and dried over sodium sulfate, and the solvent is removed on a Rotavap. fitted with magnetic stirrer 154 g (1.2 mol) of an aqueous 70% solution of t-butyl hydroperoxide are extracted three times with 35 ml of cyclohexane in each case the organic phase is dried over sodium sulfate The reaction mixture is warmed to reflux the t-butyl hydroperoxide solution is added dropwise over the course of 2 hours is held at the reflux temperature overnight the catalyst is filtered off Ice is added a little sodium sulfite is added in order to destroy the excess hydroperoxide the organic phase is then separated off washed with water dried over sodium sulfate the solvent is removed on a Rotavap

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 24.7 g (0.25 mol) of phosgene in about 150 ml of ethyl acetate is added dropwise to a solution of 99.7 g (0.5 mol) of 4-acetoxy-2,2,6,6-tetramethylpiperidine in 400 ml of ethyl acetate at 20°-22° in the course of 6 hours, with stirring. After the reaction mixture has been stirred for another 2 hours at room temperature, 63 ml (0.6 mol) of diethylamine are added dropwise in the course of about 30 minutes. The reaction mixture is stirred at room temperature for another 14 hours and is filtered and the salt residue is washed thoroughly with hexane. The combined filtrates are washed twice with water, three times with ice-cold N hydrochloric acid and again with water and dried over sodium sulfate and the solvent is distilled off in a vacuum rotary evaporator. The crude product is recrystallised from diisopropyl ether to give pure 1-diethylcarbamoyl-4-acetoxy-2,2,6,6-tetramethylpiperidine (Compound No. 1) of melting point 58° -60°. After the reaction mixture has been stirred for another 2 hours at room temperature The reaction mixture is stirred at room temperature for another 14 hours is filtered the salt residue is washed thoroughly with hexane The combined filtrates are washed twice with water, three times with ice-cold N hydrochloric acid and again with water dried over sodium sulfate the solvent is distilled off in a vacuum rotary evaporator The crude product is recrystallised from diisopropyl ether