8-乙炔基-1,4-二氧杂螺[4.5]癸烷

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 3.9 grams (0.022 mole) of 8-ethynyl-1,4-dioxaspiro[4.5]decane, 10.5 grams (0.031 mole) of 3,5-di(trifluoromethyl)phenyl iodide (prepared in Step A of this Example), 10.7 grams (0.077 mole) of triethylamine, 0.5 gram (catalyst) of bis(triphenylphosphine)palladium(II) chloride, and 0.5 gram (catalyst) of copper(I) iodide in 100 mL of acetonitrile is stirred at ambient temperature for about 18 hours. After this time the reaction mixture is concentrated under reduced pressure to a residue. The residue is then stirred for about 2 hours with 150 mL of aqueous 1N hydrochloric acid. After this time the mixture is extracted with three 100 mL portions of ethyl acetate. The combined extracts are washed with an aqueous solution of 10% lithium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 4-[3,5-di(trifluoromethyl)phenylethynyl]cyclohexanone. After this time the reaction mixture is concentrated under reduced pressure to a residue The residue is then stirred for about 2 hours with 150 mL of aqueous 1N hydrochloric acid After this time the mixture is extracted with three 100 mL portions of ethyl acetate The combined extracts are washed with an aqueous solution of 10% lithium chloride The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 3.9 grams (0.022 mole) of 8-ethynyl-1,4-dioxaspiro[4.5]decane, 10.5 grams (0.031 mole) of 3,5-di(trifluoromethyl)phenyl iodide (prepared in Step A of this Example), 10.7 grams (0.077 mole) of triethylamine, 0.5 gram (catalyst) of bis(triphenylphosphine)palladium(II) chloride, and 0.5 gram (catalyst) of copper(I) iodide in 100 mL of acetonitrile is stirred at ambient temperature for about 18 hours. After this time the reaction mixture is concentrated under reduced pressure to a residue. The residue is then stirred for about 2 hours with 150 mL of aqueous 1N hydrochloric acid. After this time the mixture is extracted with three 100 mL portions of ethyl acetate. The combined extracts are washed with an aqueous solution of 10% lithium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 4-[3,5-di(trifluoromethyl)phenylethynyl]cyclohexanone. After this time the reaction mixture is concentrated under reduced pressure to a residue The residue is then stirred for about 2 hours with 150 mL of aqueous 1N hydrochloric acid After this time the mixture is extracted with three 100 mL portions of ethyl acetate The combined extracts are washed with an aqueous solution of 10% lithium chloride The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 16.7 grams (0.07 mole) of 8-trimethylsilylethynyl-1,4-dioxaspiro[4.5]decane and 1.1 grams (0.07 mole) of potassium carbonate in 200 mL of methanol is stirred at ambient temperature for about one hour. The reaction mixture is then concentrated under reduced pressure to a residue. The residue is stirred in about 150 mL of water, and the mixture is extracted with three 150 mL portions of diethyl ether. The combined extracts are dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 8-ethynyl-1,4-dioxaspiro[4.5]decane. The reaction mixture is then concentrated under reduced pressure to a residue The residue is stirred in about 150 mL of water the mixture is extracted with three 150 mL portions of diethyl ether The combined extracts are dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 6.5 g of 4-ethynyl-1,1-ethylenedioxycyclohexane in 40 ml of tetrahydrofuran was treated at -20° C. with 39.1 ml of a 1.4M solution of butyl lithium in hexane. Subsequently, the mixture was treated at 0° C. with 60 ml of hexamethylphosphoric acid triamide (brief temperature rise to 26° C.) and then dropwise with 6.5 ml of propyl iodide. The cooling bath was removed and the mixture was left to warm to room temperature. A white precipitate formed. After 30 minutes, the mixture was treated with 150 ml of water and extracted three times with hexane. The organic phases were washed three times with water and the wash-water was back-extracted with hexane. The organic phases were dried over magnesium sulphate, filtered and freed from solvent on a rotary evaporator. Low-pressure chromatography of the resulting, yellow liquid (9 g) on silica gel with ethyl acetate/petroleum ether (vol. 10:90) and treatment with active carbon gave 6.23 g (76.5%) of 1,1-ethylenedioxy- 4-(1-pentynyl)cyclohexane as a light pale yellow liquid. The cooling bath was removed the mixture was left A white precipitate formed extracted three times with hexane The organic phases were washed three times with water the wash-water was back-extracted with hexane The organic phases were dried over magnesium sulphate filtered freed from solvent on a rotary evaporator

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 6.5 g of 4-ethynyl-1,1-ethylenedioxycyclohexane in 40 ml of tetrahydrofuran was treated at -20° C. with 39.1 ml of a 1.4M solution of butyl lithium in hexane. Subsequently, the mixture was treated at 0° C. with 60 ml of hexamethylphosphoric acid triamide (brief temperature rise to 26° C.) and then dropwise with 6.5 ml of propyl iodide. The cooling bath was removed and the mixture was left to warm to room temperature. A white precipitate formed. After 30 minutes, the mixture was treated with 150 ml of water and extracted three times with hexane. The organic phases were washed three times with water and the wash-water was back-extracted with hexane. The organic phases were dried over magnesium sulphate, filtered and freed from solvent on a rotary evaporator. Low-pressure chromatography of the resulting, yellow liquid (9 g) on silica gel with ethyl acetate/petroleum ether (vol. 10:90) and treatment with active carbon gave 6.23 g (76.5%) of 1,1-ethylenedioxy- 4-(1-pentynyl)cyclohexane as a light pale yellow liquid. The cooling bath was removed the mixture was left A white precipitate formed extracted three times with hexane The organic phases were washed three times with water the wash-water was back-extracted with hexane The organic phases were dried over magnesium sulphate filtered freed from solvent on a rotary evaporator

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 14 g of 1,1-ethylenedioxy-4-(2,2-dibromovinyl)cyclohexane in 70 ml of tetrahydrofuran was cooled to -20° C. and treated slowly at this temperature with 76.62 ml of a 1.4M solution of butyl lithium in hexane (exothermic reaction). The cooling bath was removed and the mixture was left to warm to 20° C. within about 20 minutes. The mixture was subsequently treated with 150 ml of water and extracted three times with diethyl ether. The organic phases were washed twice with water and the wash-water was back-extracted with diethyl ether. The organic phases were dried over magnesium sulphate, filtered and evaporated. Low-pressure chromatography of the resulting, yellow liquid (8 g) on silica gel with ethyl acetate/petroleum ether (vol. 7:93) gave 6.5 g (91%) of 4-ethynyl-1,1-ethylenedioxycyclohexane as a clear liquid. The cooling bath was removed the mixture was left The mixture was subsequently treated with 150 ml of water extracted three times with diethyl ether The organic phases were washed twice with water the wash-water was back-extracted with diethyl ether The organic phases were dried over magnesium sulphate filtered evaporated

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 1.03 g of 8-ethynyl-1,4-dioxaspiro[4.5]decane, 1.197 g 4-bromo-4'-fluorobiphenyl, 0.11 g of tetrakis(triphenylphosphine)palladium, 0.041 g of copper(I) bromide and 45 ml of triethylamine was heated to boiling for 4.5 hours. After cooling the mixture was diluted with diethyl ether, washed twice with water, dried over sodium sulphate, filtered and concentrated. The crude 8-[(4'-fluoro-4-biphenylyl)ethynyl]-1,4-dioxaspiro[4.5]decane (1.82. g) obtained was purified by chromatography on 35 g of silica gel with hexane/ethyl acetate (vol. 9:1). Yield 1.30 g. was heated After cooling the mixture washed twice with water dried over sodium sulphate filtered concentrated

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 14 g of 1,1-ethylenedioxy-4-(2,2-dibromovinyl)cyclohexane in 70 ml of tetrahydrofuran was cooled to -20° C. and treated slowly at this temperature with 76.62 ml of a 1.4M solution of butyl lithium in hexane (exothermic reaction). The cooling bath was removed and the mixture was left to warm to 20° C. within about 20 minutes. The reaction mixture was subsequently treated with 150 ml of water and extracted three times with diethyl ether. The organic phases were washed twice with water and the wash-water was back-extracted with diethyl ether. The organic phases were dried over magnesium sulphate, filtered and evaporated. Low-pressure chromatography of the residual, yellow liquid (8 g) on silica gel with ethyl acetate/petroleum ether (vol. 7:93) gave 6.5 g (91%) of 4-ethynyl-1,1-ethylenedioxycyclohexane as a clear liquid. The cooling bath was removed the mixture was left The reaction mixture was subsequently treated with 150 ml of water extracted three times with diethyl ether The organic phases were washed twice with water the wash-water was back-extracted with diethyl ether The organic phases were dried over magnesium sulphate filtered evaporated

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 14 g of 1,1-ethylenedioxy-4-(2,2-dibromovinyl)cyclohexane in 70 ml of tetrahydrofuran was cooled to -20° C. and treated slowly at this temperature with 76.62 ml of a 1.4M solution of butyl lithium in hexane (exothermic reaction). The cooling bath was removed and the mixture was left to warm to 20° C. within about 20 minutes. The reaction mixture was subsequently treated with 150 ml of water and extracted three times with diethyl ether. The organic phases were washed twice with water and the wash-water was back-extracted with diethyl ether. The organic phases were dried over magnesium sulphate, filtered and evaporated. Low-pressure chromatography of the residual, yellow liquid (8 g) on silica gel with ethyl acetate/petroleum ether (vol. 7:93) gave 6.5 g (91%) of 4-ethynyl-1,1-ethylenedioxycyclohexane as a clear liquid. The cooling bath was removed the mixture was left The reaction mixture was subsequently treated with 150 ml of water extracted three times with diethyl ether The organic phases were washed twice with water the wash-water was back-extracted with diethyl ether The organic phases were dried over magnesium sulphate filtered evaporated

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 14 g of 1,1-ethylenedioxy-4-(2,2-dibromovinyl)cyclohexane in 70 ml of tetrahydrofuran was cooled to -20° C. and treated slowly at this temperature with 76.62 ml of a 1.4M solution of butyl lithium in hexane (exothermic reaction). The cooling bath was removed and the mixture was left to warm to 20° C. within about 20 minutes. The reaction mixture was subsequently treated with 150 ml of water and extracted three times with diethyl ether. The organic phases were washed twice with water and the wash-water was back-extracted with diethyl ether. The organic phases were dried over magnesium sulphate, filtered and evaporated. Low-pressure chromatography of the residual, yellow liquid (8 g) on silica gel with ethyl acetate/petroleum ether (vol. 7:93) gave 6.5 g (91%) of 4-ethynyl-1,1-ethylenedioxycyclohexane as a clear liquid. The cooling bath was removed the mixture was left The reaction mixture was subsequently treated with 150 ml of water extracted three times with diethyl ether The organic phases were washed twice with water the wash-water was back-extracted with diethyl ether The organic phases were dried over magnesium sulphate filtered evaporated