1,4-dioxaspiro[4.5]decan-8-ylmethanamine

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

実験手順: Paraformaldehyde (2.2 g), in 320 ml 2% v/v H2SO4, is heated to boiling and 2.7 g (0.016 mole) of 8-aminomethyl-1,4-dioxaspiro[4,5]decane in 20 ml EtOH, is added over 4 hours. This mixture is then heated at reflux for 24 hours. The cooled reaction is washed with dichloromethane, then basified with 10N NaOH and extracted with dichloromethane. The combined extracts are dried over MgSO4 and stripped to dryness, giving 1.68 g (69%) of product. This mixture is then heated at reflux for 24 hours The cooled reaction is washed with dichloromethane extracted with dichloromethane The combined extracts are dried over MgSO4

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

実験手順: To 1.4 g (0.037 mole) of lithium aluminum hydride in 100 ml dry THF is added, portionwise, 4.9 g (0.026 mole) of 1,4-dioxaspiro[4,5]decane-8-carboxamide over one-half hour. This mixture is then refluxed 2 hours, then allowed to cool to room temperature. About 5 ml water is added cautiously and then stirred 15 minutes. Dichloromethane is then added and the insolubles filtered off. The organic layer is dried over MgSO4 and stripped to dryness, giving 3.48 g crude product. This material is vacuum-distilled to obtain 8-aminomethyl-1,4-dioxaspiro[4,5]decane (b.p. 84°-101° C. at 0.7 mm Hg.) This mixture is then refluxed 2 hours the insolubles filtered off The organic layer is dried over MgSO4 giving 3.48 g crude product This material is vacuum-distilled

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

実験手順: Paraformaldehyde (2.2 g), in 320 ml 2% v/v H2SO4, is heated to boiling and 2.7 g (0.016 mole) of 8-aminomethyl-1,4-dioxaspiro[4,5]decane in 20 ml EtOH, is added over 4 hours. This mixture is then heated at reflux for 24 hours. The cooled reaction is washed with dichloromethane, then basified with 10N NaOH and extracted with dichloromethane. The combined extracts are dried over MgSO4 and stripped to dryness, giving 1.68 g (69%) of product. This mixture is then heated at reflux for 24 hours The cooled reaction is washed with dichloromethane extracted with dichloromethane The combined extracts are dried over MgSO4

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of (1,4-dioxaspiro[4,5]dec-8-yl)methylamine (11.0 g) in pyridine (64 ml) were added 4-dimethylaminopyridine (catalyst quantity) and pivalic acid anhydride (26.0 ml), and stirred at 90° C. for 2 hours. After completion of the reaction, the solvent was evaporated, ethyl acetate was added thereto, and sequentially washed with 1 N hydrochloric acid aqueous solution, 1 N aqueous solution of sodium hydroxide, and saturated brine. The organic layer was dried over sodium sulfate, then the solvent was evaporated, and the obtained residue was purified with silica gel column chromatography (n-hexane/ethyl acetate) to give the titled compound (12.9 g) as a pale brown oil. MS (ESI) m/z: 256 (M+H)+. After completion of the reaction the solvent was evaporated ethyl acetate was added sequentially washed with 1 N hydrochloric acid aqueous solution, 1 N aqueous solution of sodium hydroxide, and saturated brine The organic layer was dried over sodium sulfate the solvent was evaporated the obtained residue was purified with silica gel column chromatography (n-hexane/ethyl acetate)

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

実験手順: To a solution of 1,4-dioxaspiro[4,5]decan-8-one (10.0 g) and acetic acid (4.4 ml) in dichloromethane (128 ml) were added methylamine hydrochloride (5.19 g) and sodium triacetoxyborohydride (16.3 g), and stirred at room temperature for 2.5 hours. After completion of the reaction, 4 N aqueous solution of sodium hydroxide (90 ml) was added thereto, and extracted with dichloromethane. The organic layer was dried over sodium sulfate, and then the solvent was evaporated to give (1,4-dioxaspiro[4,5]dec-8-yl)methylamine as an orange oil (11.0 g). was added extracted with dichloromethane The organic layer was dried over sodium sulfate the solvent was evaporated