nonane-1,9-diol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer and stir bar was charged with 1,9-nonanediol (10.00 g, 62.3 mmol) in dimethyl sulfoxide (100 mL) and H2O (100 mL). To this was added slowly a solution of sodium hydroxide (5.0 g, 125.0 mmol) in H2O (10 mL) at room temperature. During addition of sodium hydroxide the reaction mixture generated heat and the temperature rose to ˜40° C. The mixture was stirred for one hour, and then dimethyl sulfate (16.52 g, 131 mmol) was added in four portions while maintaining the temperature of the reaction mixture at ˜40° C. The reaction mixture was stirred at room temperature overnight. Progress of the reaction was monitored by TLC (Note 1). TLC monitoring indicated that the reaction was 25% conversion. At this stage additional dimethyl sulfate (24.78 g, 196.44 mmol) was added and the resulting mixture was stirred at room temperature for an additional 24 h. After completion of the reaction, sodium hydroxide (10% solution in water) was added to the reaction mixture to adjust the pH of the solution to 11-13. The mixture was stirred at room temperature for 2 h and extracted with dichloromethane (3×100 mL). The combined organic layers were washed with H2O (200 mL), brine (150 mL), dried over anhydrous sodium sulfate (20 g), filtered and concentrated in vacuo to obtain a crude product (14 g). The crude product was purified by column chromatography using 250-400 mesh silica gel. A solvent gradient of ethyl acetate in hexanes (10-50%) was used to elute the product from the column. All fractions containing the desired pure product were combined and concentrated in vacuo to give pure 9-methoxy-1-nonanol (lot D-1027-155, 2.38 g, 21.9%). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent: 60% ethyl acetate in hexanes. a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer generated heat rose to ˜40° C The mixture was stirred for one hour The reaction mixture was stirred at room temperature overnight the resulting mixture was stirred at room temperature for an additional 24 h was added to the reaction mixture The mixture was stirred at room temperature for 2 h extracted with dichloromethane (3×100 mL) The combined organic layers were washed with H2O (200 mL), brine (150 mL) dried over anhydrous sodium sulfate (20 g) filtered concentrated in vacuo to obtain a crude product (14 g) The crude product was purified by column chromatography to elute the product from the column All fractions containing the desired pure product concentrated in vacuo

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer and stir bar was charged with 1,9-nonanediol (10.00 g, 62.3 mmol) in dimethyl sulfoxide (100 mL) and H2O (100 mL). To this was added slowly a solution of sodium hydroxide (5.0 g, 125.0 mmol) in H2O (10 mL) at room temperature. During addition of sodium hydroxide the reaction mixture generated heat and the temperature rose to ˜40° C. The mixture was stirred for one hour, and then dimethyl sulfate (16.52 g, 131 mmol) was added in four portions while maintaining the temperature of the reaction mixture at ˜40° C. The reaction mixture was stirred at room temperature overnight. Progress of the reaction was monitored by TLC (Note 1). TLC monitoring indicated that the reaction was 25% conversion. At this stage additional dimethyl sulfate (24.78 g, 196.44 mmol) was added and the resulting mixture was stirred at room temperature for an additional 24 h. After completion of the reaction, sodium hydroxide (10% solution in water) was added to the reaction mixture to adjust the pH of the solution to 11-13. The mixture was stirred at room temperature for 2 h and extracted with dichloromethane (3×100 mL). The combined organic layers were washed with H2O (200 mL), brine (150 mL), dried over anhydrous sodium sulfate (20 g), filtered and concentrated in vacuo to obtain a crude product (14 g). The crude product was purified by column chromatography using 250-400 mesh silica gel. A solvent gradient of ethyl acetate in hexanes (10-50%) was used to elute the product from the column. All fractions containing the desired pure product were combined and concentrated in vacuo to give pure 9-methoxy-1-nonanol (lot D-1027-155, 2.38 g, 21.9%). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent: 60% ethyl acetate in hexanes. a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer generated heat rose to ˜40° C The mixture was stirred for one hour The reaction mixture was stirred at room temperature overnight the resulting mixture was stirred at room temperature for an additional 24 h was added to the reaction mixture The mixture was stirred at room temperature for 2 h extracted with dichloromethane (3×100 mL) The combined organic layers were washed with H2O (200 mL), brine (150 mL) dried over anhydrous sodium sulfate (20 g) filtered concentrated in vacuo to obtain a crude product (14 g) The crude product was purified by column chromatography to elute the product from the column All fractions containing the desired pure product concentrated in vacuo

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

実験手順: 200 g (2.7 mol) of tert-butanol, 100 g (0.625 mol) of 1,9-nonanediol and 2 g of sulfuric aid were placed in a 500 ml round bottomed flask, and refluxed with heat for 5 hours, followed by neutralizing with an aqueous sodium hydroxide solution. After unreacted tert-butanol was evaporated, hexane was added and stirred. The diol insoluble in hexane was discarded by filtration. The hexane layer was washed with water, and dried with anhydrous sodium sulfate. After filtration, the solvent was evaporated and the residue was purified by silica gel column chromatography (hexane/chloroform) to obtain 35 g of 9-tert-butoxy-1-nonanol as a colorless oil. refluxed with heat for 5 hours After unreacted tert-butanol was evaporated hexane was added The diol insoluble in hexane was discarded by filtration The hexane layer was washed with water dried with anhydrous sodium sulfate After filtration the solvent was evaporated the residue was purified by silica gel column chromatography (hexane/chloroform)

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 16 g (100 mmol) of nonane-1,9-diol was dissolved in 150 ml of dimethylformamide and instilled in a suspension of 2.88 g (1.20 mmol) of sodium hydride in 100 ml of DMF. It is stirred for 2 hours at 50° C. It is cooled in an ice bath to 0° C. and 17.1 g (100 mmol) of benzyl bromide is instilled within 3 hours. Then, it is stirred for 5 hours at 60° C. The solution is cooled to room temperature, 1 l of water is added and it is extracted 3 times with 150 ml of ether. The combined organic phases are dried on magnesium sulfate and concentrated by evaporation in a vacuum. The remaining oil is chromatographed on silica gel (mobile solvent: hexane/acetone=15:1). It is cooled in an ice bath to 0° C. Then, it is stirred for 5 hours at 60° C The solution is cooled to room temperature it is extracted 3 times with 150 ml of ether The combined organic phases are dried on magnesium sulfate concentrated by evaporation in a vacuum The remaining oil is chromatographed on silica gel (mobile solvent: hexane/acetone=15:1)

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

実験手順: To a stirred solution of 51.2 grams (0.320 mole) of 1,9-nonanediol in 500 ml of tetrahydrofuran was added one crystal of p-dimethylaminopyridine, and then 8.9 grams (0.088 mole) of triethylamine was added. To this mixture was added dropwise a solution of 11.2 grams (0.08 mole) of benzoyl chloride in 40 ml of methylene chloride. Upon completion of addition, the reaction mixture was stirred at ambient temperature for 18 hours. The reaction mixture was concentrated under reduced pressure to a residue. The residue was dissolved in 200 ml of methylene chloride and was washed with five 75 ml portions of water. The organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. Volatile materials were removed by distillation leaving 11.5 grams of 9-hydroxynonyl benzoate. The nmr spectrum was consistent with the proposed structure. Upon completion of addition The reaction mixture was concentrated under reduced pressure to a residue The residue was dissolved in 200 ml of methylene chloride was washed with five 75 ml portions of water The organic layer was dried with magnesium sulfate filtered The filtrate was concentrated under reduced pressure to a residue Volatile materials were removed by distillation

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

実験手順: To a stirred solution of 51.2 grams (0.320 mole) of 1,9-nonanediol in 500 ml of tetrahydrofuran was added one crystal of p-dimethylaminopyridine, and then 8.9 grams (0.088 mole) of triethylamine was added. To this mixture was added dropwise a solution of 11.2 grams (0.08 mole) of benzoyl chloride in 40 ml of methylene chloride. Upon completion of addition, the reaction mixture was stirred at ambient temperature for 18 hours. The reaction mixture was concentrated under reduced pressure to a residue. The residue was dissolved in 200 ml of methylene chloride and was washed with five 75 ml portions of water. The organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. Volatile materials were removed by distillation leaving 11.5 grams of 9-hydroxynonyl benzoate. The nmr spectrum was consistent with the proposed structure. Upon completion of addition The reaction mixture was concentrated under reduced pressure to a residue The residue was dissolved in 200 ml of methylene chloride was washed with five 75 ml portions of water The organic layer was dried with magnesium sulfate filtered The filtrate was concentrated under reduced pressure to a residue Volatile materials were removed by distillation

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

実験手順: Prepared as in Example 274c (except DBU was replaced with 1,1,3,3-tetramethylguanidine) from 1,9-nonanediol and 2,6-dinitrobenzonitrile in 30.7% yield. MS 307 (MH+).

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

実験手順: Prepared as in Example 274c (except DBU was replaced with 1,1,3,3-tetramethylguanidine) from 1,9-nonanediol and 2,6-dinitrobenzonitrile in 30.7% yield. MS 307 (MH+).

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer and stir bar was charged with 1,9-nonanediol (10.00 g, 62.3 mmol) in dimethyl sulfoxide (100 mL) and H2O (100 mL). To this was added slowly a solution of sodium hydroxide (5.0 g, 125.0 mmol) in H2O (10 mL) at room temperature. During addition of sodium hydroxide the reaction mixture generated heat and the temperature rose to ˜40° C. The mixture was stirred for one hour, and then dimethyl sulfate (16.52 g, 131 mmol) was added in four portions while maintaining the temperature of the reaction mixture at ˜40° C. The reaction mixture was stirred at room temperature overnight. Progress of the reaction was monitored by TLC (Note 1). TLC monitoring indicated that the reaction was 25% conversion. At this stage additional dimethyl sulfate (24.78 g, 196.44 mmol) was added and the resulting mixture was stirred at room temperature for an additional 24 h. After completion of the reaction, sodium hydroxide (10% solution in water) was added to the reaction mixture to adjust the pH of the solution to 11-13. The mixture was stirred at room temperature for 2 h and extracted with dichloromethane (3×100 mL). The combined organic layers were washed with H2O (200 mL), brine (150 mL), dried over anhydrous sodium sulfate (20 g), filtered and concentrated in vacuo to obtain a crude product (14 g). The crude product was purified by column chromatography using 250-400 mesh silica gel. A solvent gradient of ethyl acetate in hexanes (10-50%) was used to elute the product from the column. All fractions containing the desired pure product were combined and concentrated in vacuo to give pure 9-methoxy-1-nonanol (lot D-1027-155, 2.38 g, 21.9%). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent: 60% ethyl acetate in hexanes. a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer generated heat rose to ˜40° C The mixture was stirred for one hour The reaction mixture was stirred at room temperature overnight the resulting mixture was stirred at room temperature for an additional 24 h was added to the reaction mixture The mixture was stirred at room temperature for 2 h extracted with dichloromethane (3×100 mL) The combined organic layers were washed with H2O (200 mL), brine (150 mL) dried over anhydrous sodium sulfate (20 g) filtered concentrated in vacuo to obtain a crude product (14 g) The crude product was purified by column chromatography to elute the product from the column All fractions containing the desired pure product concentrated in vacuo

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer and stir bar was charged with 1,9-nonanediol (10.00 g, 62.3 mmol) in dimethyl sulfoxide (100 mL) and H2O (100 mL). To this was added slowly a solution of sodium hydroxide (5.0 g, 125.0 mmol) in H2O (10 mL) at room temperature. During addition of sodium hydroxide the reaction mixture generated heat and the temperature rose to ˜40° C. The mixture was stirred for one hour, and then dimethyl sulfate (16.52 g, 131 mmol) was added in four portions while maintaining the temperature of the reaction mixture at ˜40° C. The reaction mixture was stirred at room temperature overnight. Progress of the reaction was monitored by TLC (Note 1). TLC monitoring indicated that the reaction was 25% conversion. At this stage additional dimethyl sulfate (24.78 g, 196.44 mmol) was added and the resulting mixture was stirred at room temperature for an additional 24 h. After completion of the reaction, sodium hydroxide (10% solution in water) was added to the reaction mixture to adjust the pH of the solution to 11-13. The mixture was stirred at room temperature for 2 h and extracted with dichloromethane (3×100 mL). The combined organic layers were washed with H2O (200 mL), brine (150 mL), dried over anhydrous sodium sulfate (20 g), filtered and concentrated in vacuo to obtain a crude product (14 g). The crude product was purified by column chromatography using 250-400 mesh silica gel. A solvent gradient of ethyl acetate in hexanes (10-50%) was used to elute the product from the column. All fractions containing the desired pure product were combined and concentrated in vacuo to give pure 9-methoxy-1-nonanol (lot D-1027-155, 2.38 g, 21.9%). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent: 60% ethyl acetate in hexanes. a 500-mL, one-necked, round-bottom flask equipped with a magnetic stirrer generated heat rose to ˜40° C The mixture was stirred for one hour The reaction mixture was stirred at room temperature overnight the resulting mixture was stirred at room temperature for an additional 24 h was added to the reaction mixture The mixture was stirred at room temperature for 2 h extracted with dichloromethane (3×100 mL) The combined organic layers were washed with H2O (200 mL), brine (150 mL) dried over anhydrous sodium sulfate (20 g) filtered concentrated in vacuo to obtain a crude product (14 g) The crude product was purified by column chromatography to elute the product from the column All fractions containing the desired pure product concentrated in vacuo