1,2,3,4,5,6-hexafluorobenzene

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:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of sodium hydride (2.2 g, 60% in oil) in 20 ml of dimethylformamide, was added a solution of 11.0 g of 4-hydroxy-4-(4-methylphenyl)-1-methylpiperidine in 50 ml of dimethylformamide. After heating to 85° C. for thirty minutes, the mixture was cooled with an ice-bath, and treated over a period of ten minutes with a solution of 7 ml of hexafluorobenzene in 20 ml of dimethylformamide. After stirring at ambient temperature for twenty hours, the mixture was poured into 200 ml water, stirred for five minutes, then extracted with ethyl acetate (2×). The organic layer was washed with water (2×), followed by a saturated solution of sodium chloride, and dried over anhydrous magnesium sulfate. After filtering, evaporation of the solvent afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 10% methanol/dichloromethane). The desired fractions were combined, and evaporated to yield 13 g of (4-(4-methylphenyl)-1-methyl-4-(2,3,4,5,6-pentafluorophenoxy)piperidine as an oil. the mixture was cooled with an ice-bath stirred for five minutes extracted with ethyl acetate (2×) The organic layer was washed with water (2×) dried over anhydrous magnesium sulfate After filtering evaporation of the solvent afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 10% methanol/dichloromethane) evaporated

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

実験手順: To a suspension of sodium hydride (60% in oil, 6.4 g) in 50 ml of dry dimethylformamide was added, over a period of ten minutes, a solution of 25 g of 4-hydroxy-4-phenylpiperidine in 100 ml of dry dimethylformamide. After stirring at 50° C., for thirty minutes, the reaction mixture was cooled to ice bath temperature (5° C.). A solution of 18.6 ml of hexafluorobenzene in 100 ml of dry dimethylformamide was then added over a period of thirty minutes, and the resulting mixture stirred at ambient temperature for twenty hours. The mixture was poured into 500 ml water, stirred for five minutes, and extracted with ethyl acetate. The organic layer was washed with water followed by a saturated sodium chloride solution and dried over anhydrous magnesium sulfate. After filtering, evaporation of the solvents afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 20% methanol/dichloromethane) to afford 21 g (44%) of 4-(2,3,4,5,6-pentafluorophenoxy)-4-phenylpiperidine as an oil. was added, over a period of ten minutes the reaction mixture was cooled to ice bath temperature (5° C.) the resulting mixture stirred at ambient temperature for twenty hours stirred for five minutes extracted with ethyl acetate The organic layer was washed with water dried over anhydrous magnesium sulfate After filtering evaporation of the solvents afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 20% methanol/dichloromethane)

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The monomer 1,4-bis(1-naphthoxy)tetrafluorobenzene (4FNE) was prepared as follows. A 100 mL round bottom flask equipped with a magnetic stirrer was charged with hexafluorobenzene (3.53 g, 0.0190 mole), 1-naphthol, and DMAc (50 mL). After the solids dissolved, potassium carbonate (6.50 g, 0.048 mole) was added and the mixture was heated at about 140° C. for 2 hr. The mixture was then cooled to room temperature, filtered, and poured into toluene (150 mL). The toluene solution was washed twice with water (2×150 mL) and concentrated by rotary evaporation to yield an off-white powder (7.91 g). Analysis of the powder by GC showed a mixture of isomers (2% ortho, 8% meta, and 90% para). The powder was recrystallized from a mixture of N,N-dimethylformamide (DMF) and water to yield the desired all-para 4FNE, GC/MS (m+ /e 434). A 100 mL round bottom flask equipped with a magnetic stirrer After the solids dissolved The mixture was then cooled to room temperature filtered poured into toluene (150 mL) The toluene solution was washed twice with water (2×150 mL) concentrated by rotary evaporation

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The monomer 1,4-bis(1-naphthoxy)tetrafluorobenzene (4FNE) was prepared as follows. A 100 mL round bottom flask equipped with a magnetic stirrer was charged with hexafluorobenzene (3.53 g, 0.0190 mole), 1-naphthol, and DMAc (50 mL). After the solids dissolved, potassium carbonate (6.50 g, 0.048 mole) was added and the mixture was heated at about 140° C. for 2 hr. The mixture was then cooled to room temperature, filtered, and poured into toluene (150 mL). The toluene solution was washed twice with water (2×150 mL) and concentrated by rotary evaporation to yield an off-white powder (7.91 g). Analysis of the powder by GC showed a mixture of isomers (2% ortho, 8% meta, and 90% para). The powder was recrystallized from a mixture of N,N-dimethylformamide (DMF) and water to yield the desired all-para 4FNE, GC/MS (m+ /e 434). A 100 mL round bottom flask equipped with a magnetic stirrer After the solids dissolved The mixture was then cooled to room temperature filtered poured into toluene (150 mL) The toluene solution was washed twice with water (2×150 mL) concentrated by rotary evaporation

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 50.0 g (0.36 mol) of 2-isopropylphenol, 137 g (0.72 mol) of hexafluorobenzene, 50.4 g (0.90 mol) of KOH powder, and 1000 ml of DMSO was stirred for 48 h at 80° C. This mixture was cooled to room temperature and then poured in 3000 ml of water. The product was extracted with 4×500 ml of dichloromethane. The combined organic extract was dried over Na2SO4 and then evaporated on Rotavap. The residue was distilled in vacuum, 130-140° C./13 mm Hg. This mixture was cooled to room temperature The product was extracted with 4×500 ml of dichloromethane The combined organic extract was dried over Na2SO4 evaporated on Rotavap The residue was distilled in vacuum, 130-140° C./13 mm Hg

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: A solution of sec-butyl lithium (350 ml; 12% in cyclohexane) was added over a period of 1 hour to a stirred mixture of hexafluorobenzene (80 g) in cyclohexane (750 ml) at a temperature of 0° C. On warming the reaction above 0° C. a violently exothermic reaction took place which was brought under control by external cooling (Cardice-acetone). The reaction mixture was subsequently brought to room temperature (no further reaction occurred) and was quenched with water (600 ml). The organic layer was separated, washed with dilute hydrochloric acid (2N; 2×200 ml) and water (2×200 ml) and dried over anhydrous magnesium sulphate and distilled through a 15 cm vigreux column. The fraction distilling at 160°-170° C. was collected to give sec-butylpentafluorobenzene (50.3 g), b.p. 162°-164° C. (760 mm), in the form of a colourless liquid. Hexafluorobenzene is a known compound and is readily available. On warming the reaction above 0° C. a violently exothermic reaction was subsequently brought to room temperature no further reaction was quenched with water (600 ml) The organic layer was separated washed with dilute hydrochloric acid (2N; 2×200 ml) and water (2×200 ml) dried over anhydrous magnesium sulphate distilled through a 15 cm vigreux column The fraction distilling at 160°-170° C. was collected

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

実験手順: A solution of sec-butyl lithium (350 ml; 12% in cyclohexane) was added over a period of 1 hour to a stirred mixture of hexafluorobenzene (80 g) in cyclohexane (750 ml) at a temperature of 0° C. On warming the reaction above 0° C. a violently exothermic reaction took place which was brought under control by external cooling (Cardice-acetone). The reaction mixture was subsequently brought to room temperature (no further reaction occurred) and was quenched with water (600 ml). The organic layer was separated, washed with dilute hydrochloric acid (2N; 2×200 ml) and water (2×200 ml) and dried over anhydrous magnesium sulphate and distilled through a 15 cm vigreux column. The fraction distilling at 160°-170° C. was collected to give sec-butylpentafluorobenzene (50.3 g), b.p. 162°-164° C. (760 mm), in the form of a colourless liquid. Hexafluorobenzene is a known compound and is readily available. On warming the reaction above 0° C. a violently exothermic reaction was subsequently brought to room temperature no further reaction was quenched with water (600 ml) The organic layer was separated washed with dilute hydrochloric acid (2N; 2×200 ml) and water (2×200 ml) dried over anhydrous magnesium sulphate distilled through a 15 cm vigreux column The fraction distilling at 160°-170° C. was collected

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

実験手順: To a stirred suspension of sodium hydride (60% in oil, 4.0 g) in 75 ml of dimethylformamide was added a solution of 22.69 g of 1-benzyl-4-hydroxy-4-phenyl piperidine in 100 ml of dimethylformamide. The mixture was heated with a heat gun to initiate evolution of gas. When evolution had ceased, the mixture was cooled to ice bath temperature and 18.61 g of hexafluorobenzene was added, dropwise, and the reaction was allowed to proceed for 20 hours. The reaction mixture was then poured into 500 ml of iced water and the aqueous suspension extracted with ethyl acetate. The organic layer was washed with water, followed by a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. After filtering, evaporation of the solvent afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 10% ethyl acetate/dichloromethane) to yield 5.36 g, (14.53%) of 1-benzyl-4-(2,3,4,5,6,-pentafluorophenoxy)-4-phenyl piperidine, m.p. 80°-83° C. The mixture was heated with a heat gun was added the aqueous suspension extracted with ethyl acetate The organic layer was washed with water dried over anhydrous magnesium sulfate After filtering evaporation of the solvent afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 10% ethyl acetate/dichloromethane)

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of sodium hydride (2.2 g, 60% in oil) in 20 ml of dimethylformamide, was added a solution of 11.0 g of 4-hydroxy-4-(4-methylphenyl)-1-methylpiperidine in 50 ml of dimethylformamide. After heating to 85° C. for thirty minutes, the mixture was cooled with an ice-bath, and treated over a period of ten minutes with a solution of 7 ml of hexafluorobenzene in 20 ml of dimethylformamide. After stirring at ambient temperature for twenty hours, the mixture was poured into 200 ml water, stirred for five minutes, then extracted with ethyl acetate (2×). The organic layer was washed with water (2×), followed by a saturated solution of sodium chloride, and dried over anhydrous magnesium sulfate. After filtering, evaporation of the solvent afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 10% methanol/dichlormethane). The desired fractions were combined, and evaporated to yield 13 g of (4-(4-methylphenyl)-1-methyl-4-(2,3,4,5,6-pentafluorophenoxy) piperidine as an oil. the mixture was cooled with an ice-bath stirred for five minutes extracted with ethyl acetate (2×) The organic layer was washed with water (2×) dried over anhydrous magnesium sulfate After filtering evaporation of the solvent afforded a residue which was purified by means of high pressure liquid chromatography (silica gel; elution with 10% methanol/dichlormethane) evaporated