1,1,1-TRIFLUORO-2-OCTANOL

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

实验步骤: Into 200 ml of dry DMF containing 2.0 g of sodium hydride (purity 60%), were added dropwise 9.2 g of S-form oa 1-trifluoromethyl-heptanol, at room temperature with such a speed not causing too rapid generation of hydrogen, to prepare sodium salt (alkoxide) of S-form oa 1-trifluoromethyl-heptanol. After the addition was over, stirring was continued further an hour at room temperature, followed by adding thereto 12.4 g of p-iodo-nitro-benzene and then refluxing for 2 hours. After cooling, the product was introduced into iced water, and extracted with hexane. The hexane phase was washed subsequently with water, 1N-hydrochloric acid aqueous solution and then water, followed by purifying with silica gell column to obtain 7.7 g of oily oa p-(1-trifluoromethylheptyloxy)- nitrobenzene. at room temperature After the addition was continued further an hour at room temperature by adding After cooling extracted with hexane The hexane phase was washed subsequently with water, 1N-hydrochloric acid aqueous solution by purifying with silica gell column

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

实验步骤: Into 100 ml of dry DMF containing 0.86 g of sodium hydride (purity 60%), were added dropwise 3.9 g of R-form oa 1-trifluoromethyl-heptanol, at room temperature with such a speed not causing too rapid generation of hydrogen, to prepare sodium salt (alkoxide) of R-form oa 1-trifluoromethyl-heptanol. After addition was over, stirring was continued further an hour at room temperature, followed by adding thereto 4.80 g of p-iodo-benzonitrile and then refluxing for 2 hours. After cooling, the product was introduced into iced water, and extracted with hexane. The hexane phase was washed subsequently with water, 1N-HCl aqueous solution and then water, followed by purifying with silica gel column to obtain 5.16 g of oily oa p-(1-trifluoromethyl-heptyloxy)- benzonitrile. at room temperature After addition was continued further an hour at room temperature by adding After cooling extracted with hexane The hexane phase was washed subsequently with water, 1N-HCl aqueous solution by purifying with silica gel column

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

实验步骤: To a solution of 2-hydroxy-6-carboxynaphthalene (2 g) and optically active 1,1,1-trifluoro-2-octyl alcohol (2.2 g) in ethylene chloride (50 ml) was added a few drops of conc. sulfuric acid, and the solution was refluxed under stirring for about two days. The solution obtained was poured in water in order to collect the organic layer. The layer was washed with aqueous sodium hydroxide solution and water, in this order, and dried over anhydrous magnesium sulfate. The solution was distilled to remove the solvent. The residue was purified by silica-gel column chromatography (developer : chloroform) to obtain the titled compound (1.2 g). the solution was refluxed The solution obtained to collect the organic layer The layer was washed with aqueous sodium hydroxide solution and water, in this order dried over anhydrous magnesium sulfate The solution was distilled to remove the solvent The residue was purified by silica-gel column chromatography (developer : chloroform)

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

实验步骤: To a solution of 2-hydroxy-6-carboxynaphthalene (2 g) and optically active 1,1,1-trifluoro-2-octyl alcohol (2.2 g) in ethylene chloride (50 ml) was added a few drops of conc. sulfuric acid, and the solution was refluxed under stirring for about two days. The solution obtained was poured in water in order to collect the organic layer. The layer was washed with aqueous sodium hydroxide solution and water, in this order, and dried over anhydrous magnesium sulfate. The solution was distilled to remove the solvent. The residue was purified by silica-gel column chromatography (developer : chloroform) to obtain the titled compound (1.2 g). the solution was refluxed The solution obtained to collect the organic layer The layer was washed with aqueous sodium hydroxide solution and water, in this order dried over anhydrous magnesium sulfate The solution was distilled to remove the solvent The residue was purified by silica-gel column chromatography (developer : chloroform)

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

实验步骤: To a solution of 2-hydroxy-6-carboxynaphthalene (1 g) and optically active 1,1,1-trifluoro-2-octanol (1.1 g) in methylene chloride (50 ml) was added a few drops of conc. sulfuric acid and the mixture was refluxed under stirring for about two days. the mixture was refluxed

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

实验步骤: To a solution of 2-hydroxy-6-carboxynaphthalene (1 g) and optically active 1,1,1-trifluoro-2-octanol (1.1 g) in methylene chloride (50 ml) was added a few drops of conc. sulfuric acid and the mixture was refluxed under stirring for about two days. the mixture was refluxed

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

实验步骤: To a solution of 4-benzyloxybenzoic acid chloride (4.3 g) in methylene chloride (50 ml) was slowly added under ice cooling a solution of optically active 1,1,1-trifluoro-2-octanol (2.9 g), dimethylaminopyridine (0.6 g) and triethylamine (1.7 g) in methylene chloride (50 ml). The mixture was left to stand until it reached room temperature and allowed to react overnight. The mixture was poured in ice water and extracted with methylene chloride. The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in this order, and dried over anhydrous magesium sulfate. After the solution was distilled to remove the solvent, the crude product obtained was purified by silica-gel column chromatography and recrystallized from ethanol to obtain the titled compound (3.8 g). The mixture was left reached room temperature to react overnight extracted with methylene chloride The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in this order dried over anhydrous magesium sulfate After the solution was distilled to remove the solvent the crude product obtained was purified by silica-gel column chromatography recrystallized from ethanol

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

实验步骤: To a solution of 4-benzyloxybenzoic acid chloride (4.3 g) in methylene chloride (50 ml) was slowly added under ice cooling a solution of optically active 1,1,1-trifluoro-2-octanol (2.9 g), dimethylaminopyridine (0.6 g) and triethylamine (1.7 g) in methylene chloride (50 ml). The mixture was left to stand until it reached room temperature and allowed to react overnight. The mixture was poured in ice water and extracted with methylene chloride. The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in this order, and dried over anhydrous magesium sulfate. After the solution was distilled to remove the solvent, the crude product obtained was purified by silica-gel column chromatography and recrystallized from ethanol to obtain the titled compound (3.8 g). The mixture was left reached room temperature to react overnight extracted with methylene chloride The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in this order dried over anhydrous magesium sulfate After the solution was distilled to remove the solvent the crude product obtained was purified by silica-gel column chromatography recrystallized from ethanol

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

实验步骤: To a solution of 4-benzyloxybenzoic acid chloride (1.1 g) in methylene chloride (20 ml) was slowly added under ice cooling a solution of optically active 1,1,1-trifluoro-2-octanol (0.74 g, [α]D20 =+25.2) and triethylamine (0.4 g) in methylene chloride (10 ml). After the solution was left to stand to reach room temperature, it was stirred for 12 hours. The solution was poured in ice water and was extracted with methylene chloride. The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in the order, and dehydrated over anhydrous magnesium sulfate. The solution was distilled under reduced pressure to remove the solvent until a crude product was obtained. The product was subjected to silica-gel column chromatography to obtain 1,1,1-trifluoro-2-octyl 4-benzyloxybenzoate (0.73 g). After the solution was left to reach room temperature was extracted with methylene chloride The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in the order The solution was distilled under reduced pressure to remove the solvent until a crude product was obtained

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

实验步骤: To a solution of 4-benzyloxybenzoic acid chloride (1.1 g) in methylene chloride (20 ml) was slowly added under ice cooling a solution of optically active 1,1,1-trifluoro-2-octanol (0.74 g, [α]D20 =+25.2) and triethylamine (0.4 g) in methylene chloride (10 ml). After the solution was left to stand to reach room temperature, it was stirred for 12 hours. The solution was poured in ice water and was extracted with methylene chloride. The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in the order, and dehydrated over anhydrous magnesium sulfate. The solution was distilled under reduced pressure to remove the solvent until a crude product was obtained. The product was subjected to silica-gel column chromatography to obtain 1,1,1-trifluoro-2-octyl 4-benzyloxybenzoate (0.73 g). After the solution was left to reach room temperature was extracted with methylene chloride The extracted layer was washed with dilute aqueous hydrochloric acid solution, water, 1N aqueous sodium carbonate solution and water, in the order The solution was distilled under reduced pressure to remove the solvent until a crude product was obtained

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

实验步骤: Optically active 1,1,1-trifluoro-2-octanol (0.5 g), dimethylformamide (0.35 g) and triethylamine (0.64 g) were dissolved in 20 ml of methylene chloride. To this solution was added in small portions a solution of 4,4'-biphenyldicarboxylic acid dichloride (1.6 g) obtained in 2) of Example 7 in 50 ml of methylene chloride under ice-cooling, and the mixture was stirred for about 20 hours. Next, 2-hydroxy-6-octyloxycarbonylnaphthalene (0.86 g) obtained in 1) was dissolved in 30 ml of methylene chloride and added in small portions to the reaction mixture. The resulting mixture was stirred for about 20 hours. cooling

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

实验步骤: Into 200 ml of dry DMF containing 2.0 g of sodium hydride (purity 60%), were added dropwise 9.2 g of S-form oa 1-trifluoromethyl-heptanol, at room temperature with such a speed not causing too rapid generation of hydrogen, to prepare sodium salt (alkoxide) of S-form oa 1-trifluoromethyl-heptanol. After the addition was over, stirring was continued further an hour at room temperature, followed by adding thereto 12.4 g of p-iodo-nitro-benzene and then refluxing for 2 hours. After cooling, the product was introduced into iced water, and extracted with hexane. The hexane phase was washed subsequently with water, 1N-hydrochloric acid aqueous solution and then water, followed by purifying with silica gell column to obtain 7.7 g of oily oa p-(1-trifluoromethylheptyloxy)nitrobenzene. at room temperature After the addition was continued further an hour at room temperature by adding After cooling extracted with hexane The hexane phase was washed subsequently with water, 1N-hydrochloric acid aqueous solution by purifying with silica gell column