2-(1,4-dioxaspiro[4.5]decan-8-ylidene)acetonitrile

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

実験手順: The above nitrile (2.15 g) is treated with platinum oxide (0.1 g) in ethanol (200 ml) and hydrogenated at 3 atmospheres pressure over 4 hours. Removal of the catalyst and concentration of the solvent gives 8-cyanomethyl-1,4-dioxaspiro[4.5]decane as an oil. Removal of the catalyst and concentration of the solvent

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

実験手順: To a suspension of sodium hydride (50% in mineral oil, 1.15 g, washed with hexane) in toluene (50 ml) is added a solution of diethyl cyanomethylphosphonate (4.25 g) in toluene (50 ml) dropwise under nitrogen and the mixture is stirred 30 minutes longer. A solution of 1,4-cyclohexanedione monoethylene ketal (3.12 g) in toluene (50 ml) is added dropwise under nitrogen at room temperature. After 10 minutes, ice water is added under vigorous stirring. The aqueous layer is collected and extracted several times with ether. The combined toluene-ether extracts are washed with water, then brine, dried over sodium sulphate and concentrated to dryness at reduced pressure. The residual oil is chromatographed through a 25×140 mm column of silica gel, using methylene chloride as solvent to afford an oil which gradually crystallizes to give 8-cyanomethylene-1,4-dioxaspiro[4.5]decane. After 10 minutes The aqueous layer is collected extracted several times with ether The combined toluene-ether extracts are washed with water brine, dried over sodium sulphate concentrated to dryness at reduced pressure The residual oil is chromatographed through a 25×140 mm column of silica gel to afford an oil which gradually crystallizes

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

実験手順: To a suspension of sodium hydride (50% in mineral oil, 1.15 g, washed with hexane) in toluene (50 ml) is added a solution of diethyl cyanomethylphosphonate (4.25 g) in toluene (50 ml) dropwise under nitrogen and the mixture is stirred 30 minutes longer. A solution of 1,4-cyclohexanedione monoethylene ketal (3.12 g) in toluene (50 ml) is added dropwise under nitrogen at room temperature. After 10 minutes, ice water is added under vigorous stirring. The aqueous layer is collected and extracted several times with ether. The combined toluene-ether extracts are washed with water, then brine, dried over sodium sulphate and concentrated to dryness at reduced pressure. The residual oil is chromatographed through a 25×140 mm column of silica gel, using methylene chloride as solvent to afford an oil which gradually crystallizes to give 8-cyanomethylene-1,4-dioxaspiro[4.5]decane. After 10 minutes The aqueous layer is collected extracted several times with ether The combined toluene-ether extracts are washed with water brine, dried over sodium sulphate concentrated to dryness at reduced pressure The residual oil is chromatographed through a 25×140 mm column of silica gel to afford an oil which gradually crystallizes

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

実験手順: The above nitrile (2.15 g) is treated with platinum oxide (0.1 g) in ethanol (200 ml) and hydrogenated at 3 atmospheres pressure over 4 hours. Removal of the catalyst and concentration of the solvent gives 8-cyanomethyl-1,4-dioxaspiro[4.5]decane as an oil. Removal of the catalyst and concentration of the solvent

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

実験手順: To a suspension of sodium hydride (50% in mineral oil, 1.15 g, washed with hexane) in toluene (50 ml) is added a solution of diethyl cyanomethylphosphonate (4.25 g) in toluene (50 ml) dropwise under nitrogen and the mixture is stirred 30 minutes longer. A solution of 1,4-cyclohexanedione monoethylene ketal (3.12 g) in toluene (50 ml) is added dropwise under nitrogen at room temperature. After 10 minutes, ice water is added under vigorous stirring. The aqueous layer is collected and extracted several times with ether. The combined toluene-ether extracts are washed with water, then brine, dried over sodium sulphate and concentrated to dryness at reduced pressure. The residual oil is chromatographed through a 25×140 mm column of silica gel, using methylene chloride as solvent to afford an oil which gradually crystallizes to give 8-cyanomethylene-1,4-dioxaspiro[4.5]decane. After 10 minutes The aqueous layer is collected extracted several times with ether The combined toluene-ether extracts are washed with water brine, dried over sodium sulphate concentrated to dryness at reduced pressure The residual oil is chromatographed through a 25×140 mm column of silica gel to afford an oil which gradually crystallizes