1,1-diethoxy-2-iodoethane

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: To the solution of 11.15 g of 3-hydroxy-3,3-diphenylpropionitrile, 13.4 g of iodo acetaldehyde diethylacetal, and 0.9 g of tetra-n-butylammonium hydrogen sulfate in 40 ml of methylene chloride, 10 ml of 50% aqueous sodium hydroxide are added and the mixture is well stirred at room temperature for 24 hours. It is washed with water, dried and evaporated, to give the 2-(2-cyano-1,1-diphenylethoxy)-acetaldehyde diethylacetal as an oil which is sufficiently pure to be used without purification. It is washed with water dried evaporated

反応条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 31.98 g of (2RS,3RS)-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentan-2-ol [synthesized by the same method as Reference Example 1(1) and (2) using 3,4-methylenedioxyphenylacetone and iodoacetaldehyde diethyl acetal as the starting materials] was dissolved in 320 ml of vinyl acetate, and 15.1 ml of triethylamine was added thereto. Then, 1.0 g of immobilized lipase (Toyothium LIP) was added thereto, followed by stirring at 30° C. for 16 hours. Further, 0.9 g of immobilized lipase was added thereto, followed by stirring at the same temperature for 46 hours. Then, insoluble matters were filtered off. The filtrate was diluted with ethyl acetate, then sequentially washed with 1N hydrochloric acid, a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1) to obtain 16.05 g of the above-identified compound, [α]D20 -31.8° (c 1.0, methanol) as colorless oily substance and 18.40 g of (2R,3S)-2-acetoxy-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentane as colorless oily substance. Further, the absolute configuration of the above-identified compound was determined by Mosher method (J. Am. Chem. Soc., vol. 113, p. 4092 (1991)). Then, 1.0 g of immobilized lipase (Toyothium LIP) was added Further, 0.9 g of immobilized lipase was added by stirring at the same temperature for 46 hours Then, insoluble matters were filtered off The filtrate was diluted with ethyl acetate sequentially washed with 1N hydrochloric acid a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate The drying agent was filtered off the solvent was distilled off under reduced pressure The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1)

反応条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 31.98 g of (2RS,3RS)-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentan-2-ol [synthesized by the same method as Reference Example 1(1) and (2) using 3,4-methylenedioxyphenylacetone and iodoacetaldehyde diethyl acetal as the starting materials] was dissolved in 320 ml of vinyl acetate, and 15.1 ml of triethylamine was added thereto. Then, 1.0 g of immobilized lipase (Toyothium LIP) was added thereto, followed by stirring at 30° C. for 16 hours. Further, 0.9 g of immobilized lipase was added thereto, followed by stirring at the same temperature for 46 hours. Then, insoluble matters were filtered off. The filtrate was diluted with ethyl acetate, then sequentially washed with 1N hydrochloric acid, a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1) to obtain 16.05 g of the above-identified compound, [α]D20 -31.8° (c 1.0, methanol) as colorless oily substance and 18.40 g of (2R,3S)-2-acetoxy-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentane as colorless oily substance. Further, the absolute configuration of the above-identified compound was determined by Mosher method (J. Am. Chem. Soc., vol. 113, p. 4092 (1991)). Then, 1.0 g of immobilized lipase (Toyothium LIP) was added Further, 0.9 g of immobilized lipase was added by stirring at the same temperature for 46 hours Then, insoluble matters were filtered off The filtrate was diluted with ethyl acetate sequentially washed with 1N hydrochloric acid a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate The drying agent was filtered off the solvent was distilled off under reduced pressure The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1)

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

実験手順: To the solution of 11.15 g of 3-hydroxy-3,3-diphenylpropionitrile, 13.4 g of iodo acetaldehyde diethylacetal, and 0.9 g of tetra-n-butylammonium hydrogen sulfate in 40 ml of methylene chloride, 10 ml of 50% aqueous sodium hydroxide are added and the mixture is well stirred at room temperature for 24 hours. It is washed with water, dried and evaporated, to give the 2-(2-cyano-1,1-diphenylethoxy)-acetaldehyde diethylacetal as an oil which is sufficiently pure to be used without purification. The solution of 6.8 g thereof in 100 ml of diethyl ether is added dropwise to the stirred suspension of 1.15 g of lithium aluminum hydride in 20 ml of diethyl ether, while cooling with ice. Upon completion of the addition, the mixture is stirred under reflux for 6 hours. It is cooled and excess hydride is destroyed by successive addition of 1.15 ml of water, 1.15 ml of 15% aqueous sodium hydroxide and 3.45 ml more water. The mixture is filtered, the filtrate is dried and evaporated to give the oily 2-(3-amino-1,1-diphenylpropoxy)-acetaldehyde diethylacetal. It is washed with water dried evaporated

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

実験手順: To the solution of 11.15 g of 3-hydroxy-3,3-diphenylpropionitrile, 13.4 g of iodo acetaldehyde diethylacetal, and 0.9 g of tetra-n-butylammonium hydrogen sulfate in 40 ml of methylene chloride, 10 ml of 50% aqueous sodium hydroxide are added and the mixture is well stirred at room temperature for 24 hours. It is washed with water, dried and evaporated, to give the 2-(2-cyano-1,1-diphenylethoxy)-acetaldehyde diethylacetal as an oil which is sufficiently pure to be used without purification. It is washed with water dried evaporated

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

実験手順: To the solution of 11.15 g of 3-hydroxy-3,3-diphenylpropionitrile, 13.4 g of iodo acetaldehyde diethylacetal, and 0.9 g of tetra-n-butylammonium hydrogen sulfate in 40 ml of methylene chloride, 10 ml of 50% aqueous sodium hydroxide are added and the mixture is well stirred at room temperature for 24 hours. It is washed with water, dried and evaporated, to give the 2-(2-cyano-1,1-diphenylethoxy)-acetaldehyde diethylacetal as an oil which is sufficiently pure to be used without purification. It is washed with water dried evaporated

反応条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 31.98 g of (2RS,3RS)-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentan-2-ol [synthesized by the same method as Reference Example 1(1) and (2) using 3,4-methylenedioxyphenylacetone and iodoacetaldehyde diethyl acetal as the starting materials] was dissolved in 320 ml of vinyl acetate, and 15.1 ml of triethylamine was added thereto. Then, 1.0 g of immobilized lipase (Toyothium LIP) was added thereto, followed by stirring at 30° C. for 16 hours. Further, 0.9 g of immobilized lipase was added thereto, followed by stirring at the same temperature for 46 hours. Then, insoluble matters were filtered off. The filtrate was diluted with ethyl acetate, then sequentially washed with 1N hydrochloric acid, a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1) to obtain 16.05 g of the above-identified compound, [α]D20 -31.8° (c 1.0, methanol) as colorless oily substance and 18.40 g of (2R,3S)-2-acetoxy-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentane as colorless oily substance. Further, the absolute configuration of the above-identified compound was determined by Mosher method (J. Am. Chem. Soc., vol. 113, p. 4092 (1991)). Then, 1.0 g of immobilized lipase (Toyothium LIP) was added Further, 0.9 g of immobilized lipase was added by stirring at the same temperature for 46 hours Then, insoluble matters were filtered off The filtrate was diluted with ethyl acetate sequentially washed with 1N hydrochloric acid a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate The drying agent was filtered off the solvent was distilled off under reduced pressure The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1)

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

実験手順: To 11.7 g of 3,4-methylenedioxyphenylacetone in 100 ml of dimethylformamide, 2.76 g of 60% oily sodium hydride was added under cooling with ice with stirring, and after stirring at the same temperature for 30 minutes, 20.9 g of iodoacetaldehyde diethyl acetal in 20 ml of dimethylformamide was added. The reaction solution was stirred at room temperature for 2 hours and partitioned between water and ethyl ether. The organic layer was washed with saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. The desiccant was filtered off, and the solvent was evaporated in vacuo. The residue was purified by silica gel column chromatography [hexane/ethyl acetate=15/1→10/1] to give 18.3 g of the title compound. under cooling with ice after stirring at the same temperature for 30 minutes The reaction solution was stirred at room temperature for 2 hours partitioned between water and ethyl ether The organic layer was washed with saturated aqueous sodium chloride dried over anhydrous magnesium sulfate The desiccant was filtered off the solvent was evaporated in vacuo The residue was purified by silica gel column chromatography [hexane/ethyl acetate=15/1→10/1]

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

実験手順: To 11.7 g of 3,4-methylenedioxyphenylacetone in 100 ml of dimethylformamide, 2.76 g of 60% oily sodium hydride was added under cooling with ice with stirring, and after stirring at the same temperature for 30 minutes, 20.9 g of iodoacetaldehyde diethyl acetal in 20 ml of dimethylformamide was added. The reaction solution was stirred at room temperature for 2 hours and partitioned between water and ethyl ether. The organic layer was washed with saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. The desiccant was filtered off, and the solvent was evaporated in vacuo. The residue was purified by silica gel column chromatography [hexane/ethyl acetate=15/1→10/1] to give 18.3 g of the title compound. under cooling with ice after stirring at the same temperature for 30 minutes The reaction solution was stirred at room temperature for 2 hours partitioned between water and ethyl ether The organic layer was washed with saturated aqueous sodium chloride dried over anhydrous magnesium sulfate The desiccant was filtered off the solvent was evaporated in vacuo The residue was purified by silica gel column chromatography [hexane/ethyl acetate=15/1→10/1]

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

実験手順: To a cold solution (-5° C. to 0° C.) of sodium hydride in anhydrous dimethylformamide (11.8 g, 245.9 mmol), pyrrole (15.0 g, 223.6 mmol) in dry dimethylformamide was slowly added while stirring vigorously. The reaction was completed, and the temperature raised to room temperature. After hydrogen is fully evolved, iodoacetaldehyde diethyl acetal was added (65.5 g, 268.1 mmol) to the reaction mixture. The reaction mixture was allowed to reflux for 5 hours or until there was no further advance of the reaction. The reaction mixture was cooled to room temperature, poured onto 50 mL of water, extracted with ether, dried over MgSO4, and concentrated. The product was purified by column chromatography [silica gel, hexane] to give the title compound, 1-(2,2-diethoxyethyl)pyrrole, (95%), ms 183 (M+). to reflux for 5 hours or until there no further advance of the reaction The reaction mixture was cooled to room temperature extracted with ether dried over MgSO4 concentrated The product was purified by column chromatography [silica gel, hexane]

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

実験手順: To a cold solution (-5° C. to 0° C.) of sodium hydride in anhydrous dimethylformamide (11.8 g, 245.9 mmol), pyrrole (15.0 g, 223.6 mmol) in dry dimethylformamide was slowly added while stirring vigorously. The reaction was completed, and the temperature raised to room temperature. After hydrogen is fully evolved, iodoacetaldehyde diethyl acetal was added (65.5 g, 268.1 mmol) to the reaction mixture. The reaction mixture was allowed to reflux for 5 hours or until there was no further advance of the reaction. The reaction mixture was cooled to room temperature, poured onto 50 mL of water, extracted with ether, dried over MgSO4, and concentrated. The product was purified by column chromatography [silica gel, hexane] to give the title compound, 1-(2,2-diethoxyethyl)pyrrole, (95%), ms 183 (M+). to reflux for 5 hours or until there no further advance of the reaction The reaction mixture was cooled to room temperature extracted with ether dried over MgSO4 concentrated The product was purified by column chromatography [silica gel, hexane]