(S)-(+)-2-辛醇

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

实验步骤: Sodium hydride (0.8 g) was decanted twice with n-heptane (20 ml), successively with THF (20 ml) and placed in a flask in the form of a suspension in THF (20 ml), followed by dropwise adding a solution of 4'-hydroxy-4-(1-methylheptyloxy)-biphenyl (IIIa-7) of m.p. 98.1° C. (5.1 g) obtained by reacting 4,4'-dihydroxybiphenyl with a tosylate derived from S-(+)-2-octanol, in THF (30 ml), thereafter dropwise adding DMSO (20 ml), successively dropwise adding a solution of p-heptyloxybenzyl bromide (5.4 g) in DMSO (30 ml), stirring the mixture at room temperature, allowing to stand overnight, adding 6N-HCl (200 ml), extracting with toluene, washing with acid, washing with alkali, washing with water to make it neutral, drying, concentrating, subjecting the concentrate to column chromatography with activated alumina (20 g) to effect separation-concentration using toluene as an elute, and twice recrystallizing from a mixed solvent of ethanol (40 ml) and ethyl acetate (20 ml) to obtain the captioned 4'-(p-(heptyloxy)phenylmethyloxy)-4-(1-methylheptyloxy)biphenyl (3.6 g). Its m.p., etc. are described in Table 2. Further its elementary analysis values accorded well with its calculated values as follows: Sodium hydride (0.8 g) was decanted twice with n-heptane (20 ml), successively with THF (20 ml) placed in a flask in the form of a suspension in THF (20 ml) by dropwise adding a solution of 4'-hydroxy-4-(1-methylheptyloxy)-biphenyl (IIIa-7) of m.p. 98.1° C. (5.1 g) obtained extracting with toluene washing with acid washing with alkali, washing with water drying concentrating concentrate to column chromatography with activated alumina (20 g) separation-concentration twice recrystallizing from a mixed solvent of ethanol (40 ml) and ethyl acetate (20 ml)

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

实验步骤: p-Hydroxy-benzaldehyde (15 g), ethanol (200 ml) and 50% NaOH (12 g) were mixed with stirring, followed by pouring in the mixture, a tosylate (26 g) derived from S-(+)-2-octanol, heating the resulting mixture under reflux for 6 hours, distilling off most of ethanol, adding 6N-HCl (100 ml), extracting with toluene, washing the toluene layer with acid, washing with alkali, washing with water to make it neutral, drying, concentrating, and further concentrating the resulting concentrate according to column chromatography with Al2O3 (40 g) to obtain oily p-(1-methylheptyloxy)benzaldehyde (13.0 g). Next, sodium boron hydride (1.0 g) was suspended in isopropyl alcohol (50 ml), followed by dropwise adding to the suspension, a solution of p-(1-methylheptyloxy)benzaldehyde obtained above in isopropyl alcohol (100 ml) so that the liquid temperature might not exceed 40° C., stirring the mixture at 60° C. for 4 hours, adding 6N-HCl (30 ml) and water (20 ml), further heating with stirring at 60° C., distilling off the solvent, extracting the residue with toluene, washing the toluene layer with acid, washing with alkali, washing with water to make it neutral, drying and concentrating to obtain raw p-(1-methylheptyloxy)benzyl alcohol (13 g), which was then heated together with thionyl chloride for 6 hours, followed by distilling off excess thionyl chloride under reduced pressure to obtain raw p-(1-methylheptyloxy)benzyl chloride (IIIb-2) (13 g), which was used, as it was, in the following reaction. by pouring in the mixture heating the resulting mixture under reflux for 6 hours distilling off most of ethanol adding 6N-HCl (100 ml) extracting with toluene washing the toluene layer with acid washing with alkali, washing with water drying concentrating further concentrating the resulting concentrate

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

实验步骤: p-Benzyloxyphenol (50 g), ethanol (150 ml) and 50% NaOH aqueous solution (25 g) were mixed with stirring, followed by pouring in the mixture, optically active 1-methylheptyl p-toluenesulfonate derived from S-(+)-2-octanol, heating the mixture under reflux for 4 hours, distilling off most of ethanol, extracting with toluene, washing with acid, alkali and water, drying, concentrating and purifying the concentrate according to column chromatography with activated alumina (150 g) to obtain oily p-benzyloxy-(1-methylheptyloxy)benzene (68.6 g), which was then subjected to hydrogenolysis with 5% Pd-C catalyst in ethanol, followed by removing the catalyst, concentrating the solution and subjecting the concentrate to vacuum distillation to obtain oily p-(1-methylheptyloxy)phenol (IIIa-2) (30.7 g) having a b.p. of 129°-130.5° C./0.5 Torr. heating the mixture under reflux for 4 hours distilling off most of ethanol extracting with toluene washing with acid alkali and water, drying concentrating purifying the concentrate

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

实验步骤: Quantities: 2-(hydroxybenzonitrile (38) (9.17 g, 0.077 mol), (S)-(+)-octan-2-ol (10.00 g, 0.077 mol), DEAD (13.41 g, 0.077 mol), triphenylphosphine (20.20 g, 0.077 mol). The experimental procedure was as described for the preparation of compound 5. The crude product was purified by column chromatography (20% petrol/dichloromethane) to give a colourless oil. The crude product was purified by column chromatography (20% petrol/dichloromethane) to give a colourless oil

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

实验步骤: Quantities: 2-(hydroxybenzonitrile (38) (9.17 g, 0.077 mol), (S)-(+)-octan-2-ol (10.00 g, 0.077 mol), DEAD (13.41 g, 0.077 mol), triphenylphosphine (20.20 g, 0.077 mol). The experimental procedure was as described for the preparation of compound 5. The crude product was purified by column chromatography (20% petrol/dichloromethane) to give a colourless oil. The crude product was purified by column chromatography (20% petrol/dichloromethane) to give a colourless oil

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

实验步骤: Sodium hydride (0.8 g) was decanted twice with n-heptane (20 ml), successively with THF (20 ml) and placed in a flask in the form of a suspension in THF (20 ml), followed by dropwise adding a solution of 4'-hydroxy-4-(1-methylheptyloxy)-biphenyl (IIIa-7) of m.p. 98.1° C. (5.1 g) obtained by reacting 4,4'-dihydroxybiphenyl with a tosylate derived from S-(+)-2-octanol, in THF (30 ml), thereafter dropwise adding DMSO (20 ml), successively dropwise adding a solution of p-heptyloxybenzyl bromide (5.4 g) in DMSO (30 ml), stirring the mixture at room temperature, allowing to stand overnight, adding 6N-HCl (200 ml), extracting with toluene, washing with acid, washing with alkali, washing with water to make it neutral, drying, concentrating, subjecting the concentrate to column chromatography with activated alumina (20 g) to effect separation-concentration using toluene as an elute, and twice recrystallizing from a mixed solvent of ethanol (40 ml) and ethyl acetate (20 ml) to obtain the captioned 4'-(p-(heptyloxy)phenylmethyloxy)-4-(1-methylheptyloxy)biphenyl (3.6 g). Its m.p., etc. are described in Table 2. Further its elementary analysis values accorded well with its calculated values as follows: Sodium hydride (0.8 g) was decanted twice with n-heptane (20 ml), successively with THF (20 ml) placed in a flask in the form of a suspension in THF (20 ml) by dropwise adding a solution of 4'-hydroxy-4-(1-methylheptyloxy)-biphenyl (IIIa-7) of m.p. 98.1° C. (5.1 g) obtained extracting with toluene washing with acid washing with alkali, washing with water drying concentrating concentrate to column chromatography with activated alumina (20 g) separation-concentration twice recrystallizing from a mixed solvent of ethanol (40 ml) and ethyl acetate (20 ml)

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

实验步骤: p-Hydroxy-benzaldehyde (15 g), ethanol (200 ml) and 50% NaOH (12 g) were mixed with stirring, followed by pouring in the mixture, a tosylate (26 g) derived from S-(+)-2-octanol, heating the resulting mixture under reflux for 6 hours, distilling off most of ethanol, adding 6N-HCl (100 ml), extracting with toluene, washing the toluene layer with acid, washing with alkali, washing with water to make it neutral, drying, concentrating, and further concentrating the resulting concentrate according to column chromatography with Al2O3 (40 g) to obtain oily p-(1-methylheptyloxy)benzaldehyde (13.0 g). Next, sodium boron hydride (1.0 g) was suspended in isopropyl alcohol (50 ml), followed by dropwise adding to the suspension, a solution of p-(1-methylheptyloxy)benzaldehyde obtained above in isopropyl alcohol (100 ml) so that the liquid temperature might not exceed 40° C., stirring the mixture at 60° C. for 4 hours, adding 6N-HCl (30 ml) and water (20 ml), further heating with stirring at 60° C., distilling off the solvent, extracting the residue with toluene, washing the toluene layer with acid, washing with alkali, washing with water to make it neutral, drying and concentrating to obtain raw p-(1-methylheptyloxy)benzyl alcohol (13 g), which was then heated together with thionyl chloride for 6 hours, followed by distilling off excess thionyl chloride under reduced pressure to obtain raw p-(1-methylheptyloxy)benzyl chloride (IIIb-2) (13 g), which was used, as it was, in the following reaction. by pouring in the mixture heating the resulting mixture under reflux for 6 hours distilling off most of ethanol adding 6N-HCl (100 ml) extracting with toluene washing the toluene layer with acid washing with alkali, washing with water drying concentrating further concentrating the resulting concentrate

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

实验步骤: p-Benzyloxyphenol (50 g), ethanol (150 ml) and 50% NaOH aqueous solution (25 g) were mixed with stirring, followed by pouring in the mixture, optically active 1-methylheptyl p-toluenesulfonate derived from S-(+)-2-octanol, heating the mixture under reflux for 4 hours, distilling off most of ethanol, extracting with toluene, washing with acid, alkali and water, drying, concentrating and purifying the concentrate according to column chromatography with activated alumina (150 g) to obtain oily p-benzyloxy-(1-methylheptyloxy)benzene (68.6 g), which was then subjected to hydrogenolysis with 5% Pd-C catalyst in ethanol, followed by removing the catalyst, concentrating the solution and subjecting the concentrate to vacuum distillation to obtain oily p-(1-methylheptyloxy)phenol (IIIa-2) (30.7 g) having a b.p. of 129°-130.5° C./0.5 Torr. heating the mixture under reflux for 4 hours distilling off most of ethanol extracting with toluene washing with acid alkali and water, drying concentrating purifying the concentrate

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

实验步骤: p-Benzyloxyphenol (50 g), ethanol (150 ml) and 50% NaOH aqueous solution (25 g) were mixed with stirring, followed by pouring in the mixture, optically active 1-methylheptyl p-toluenesulfonate derived from S-(+)-2-octanol, heating the mixture under reflux for 4 hours, distilling off most of ethanol, extracting with toluene, washing with acid, alkali and water, drying, concentrating and purifying the concentrate according to column chromatography with activated alumina (150 g) to obtain oily p-benzyloxy-(1-methylheptyloxy)benzene (68.6 g), which was then subjected to hydrogenolysis with 5% Pd-C catalyst in ethanol, followed by removing the catalyst, concentrating the solution and subjecting the concentrate to vacuum distillation to obtain oily p-(1-methylheptyloxy)phenol (IIIa-2) (30.7 g) having a b.p. of 129°-130.5° C./0.5 Torr. heating the mixture under reflux for 4 hours distilling off most of ethanol extracting with toluene washing with acid alkali and water, drying concentrating purifying the concentrate

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

实验步骤: After (S)-2-octanol (300 mg, 2.30 mmol), triphenylphosphine (726 mg, 2.76 mmol), 4-nitrobenzoic acid (462 mg, 2.76 mmol), and acetonitrile (12 ml) were added to a 50 ml flask, azodicarboxylic acid bis(2-methoxyethyl) ester (648 mg, 2.76 mmol) dissolved in acetonitrile (6 ml) was added dropwise thereto at 20° C., and the reaction was allowed to proceed for 21 hours. Water (0.5 mL) was added, and concentration was carried out. Then, water (10 ml) was added to the solution, and extraction was carried out using diethyl ether (10 ml, ×2). Then, the organic layer was washed with water (10 mL) and saturated salt water (10 ml), and dehumidified with anhydrous magnesium sulfate. Subsequently, a crude product obtained by concentration was purified by column chromatography (silica gel, 10% ethyl acetate-hexane solution) to give (R)-2-(4-nitrobenzoyloxy)octane as a pale yellow liquid substance (349 mg, yield: 54%/(S)-2-octanol). was added dropwise at 20° C. concentration Then, water (10 ml) was added to the solution, and extraction Then, the organic layer was washed with water (10 mL) and saturated salt water (10 ml) Subsequently, a crude product obtained by concentration was purified by column chromatography (silica gel, 10% ethyl acetate-hexane solution)

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

实验步骤: After (S)-2-octanol (300 mg, 2.30 mmol), triphenylphosphine (726 mg, 2.76 mmol), 4-nitrobenzoic acid (462 mg, 2.76 mmol), and acetonitrile (12 ml) were added to a 50 ml flask, azodicarboxylic acid bis(2-methoxyethyl) ester (648 mg, 2.76 mmol) dissolved in acetonitrile (6 ml) was added dropwise thereto at 20° C., and the reaction was allowed to proceed for 21 hours. Water (0.5 mL) was added, and concentration was carried out. Then, water (10 ml) was added to the solution, and extraction was carried out using diethyl ether (10 ml, ×2). Then, the organic layer was washed with water (10 mL) and saturated salt water (10 ml), and dehumidified with anhydrous magnesium sulfate. Subsequently, a crude product obtained by concentration was purified by column chromatography (silica gel, 10% ethyl acetate-hexane solution) to give (R)-2-(4-nitrobenzoyloxy)octane as a pale yellow liquid substance (349 mg, yield: 54%/(S)-2-octanol). was added dropwise at 20° C. concentration Then, water (10 ml) was added to the solution, and extraction Then, the organic layer was washed with water (10 mL) and saturated salt water (10 ml) Subsequently, a crude product obtained by concentration was purified by column chromatography (silica gel, 10% ethyl acetate-hexane solution)

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

实验步骤: After (S)-2-octanol (300 mg, 2.30 mmol), triphenylphosphine (725 mg, 2.76 mmol), 4-nitrobenzoic acid (463 mg, 2.76 mmol), and toluene (12 ml) were added to a 50 ml flask, azodicarboxylic acid bis(2-methoxyethyl) ester (648 mg, 2.76 mmol) dissolved in toluene (6 ml) was added dropwise thereto at 20° C., and the reaction was allowed to proceed for 3.5 hours. Water (10 mL) was added, and separation was carried out. Then, the aqueous layer was extracted using toluene (10 mL, ×1). The resulting organic layer was collectively washed with water (10 mL) and saturated salt water (10 ml), and dehumidified with anhydrous magnesium sulfate. Subsequently, a crude product obtained by concentration was purified by column chromatography (silica gel, 5% ethyl acetate-hexane solution) to give (R)-2-(4-nitrobenzoyloxy)octane as a pale yellow liquid substance (615 mg, yield: 96%/(S)-2-octanol). was added dropwise at 20° C. separation Then, the aqueous layer was extracted The resulting organic layer was collectively washed with water (10 mL) and saturated salt water (10 ml) Subsequently, a crude product obtained by concentration was purified by column chromatography (silica gel, 5% ethyl acetate-hexane solution)