9-methyl-9H-fluorene-2,7-diol

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

実験手順: In a nitrogen atmosphere, concentrated sulfuric acid (0.2 mL) was added to a mixture of 4-hydroxybenzoic acid (13.0 g), 2,7-dihydroxy-9-methylfluorene (10.0 g), boric acid (0.3 g) and xylene (120 mL), and the mixture was heated under reflux for 6 hours while removing water. A solid matter thus deposited was collected by filtration under reduced pressure, and rinsed with toluene. The solid matter was recrystallized from a mixed solvent of ethanol (75 mL) and acetone (75 mL) to provide 2,7-bis(4-hydroxybenzoyloxy)-9-methylfluorene (compound [H1]) (14.9 g) in the form of pale rose crystals. the mixture was heated under reflux for 6 hours while removing water A solid matter thus deposited was collected by filtration under reduced pressure rinsed with toluene The solid matter was recrystallized from a mixed solvent of ethanol (75 mL) and acetone (75 mL)

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

実験手順: Octyloxybenzoic acid chloride 12.5 g was added dividing into several times to a tetrahydrofuran (100 ml) solution of 2,7-dihydroxy-9-methylfluorene 10 g and pyridine 8 g, and the solution was refluxed for 5 hours. 5% hydrochloric acid 50 ml was added to the reaction mixture, and the solution was extracted with methylene chloride. The extract was washed with 5% hydrochloric acid until pH became acidic, and then it was washed with a saturated sodium hydrogencarbonate aqueous solution and dried on anhydrous magnesium sulfate. A residue obtained by distilling the solvent off was refined by silica gel column chromatography (eluent solvent: methylene chloride) to obtain 10 g of 2-(4-octyloxybenzoyloxy)-7-hydroxy-9-methylfluorene (J1). Melting point: 140 to 143° C. the solution was refluxed for 5 hours the solution was extracted with methylene chloride The extract was washed with 5% hydrochloric acid until pH it was washed with a saturated sodium hydrogencarbonate aqueous solution dried on anhydrous magnesium sulfate A residue obtained by distilling the solvent

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

実験手順: Octyloxybenzoic acid chloride 12.5 g was added dividing into several times to a tetrahydrofuran (100 ml) solution of 2,7-dihydroxy-9-methylfluorene 10 g and pyridine 8 g, and the solution was refluxed for 5 hours. 5% hydrochloric acid 50 ml was added to the reaction mixture, and the solution was extracted with methylene chloride. The extract was washed with 5% hydrochloric acid until pH became acidic, and then it was washed with a saturated sodium hydrogencarbonate aqueous solution and dried on anhydrous magnesium sulfate. A residue obtained by distilling the solvent off was refined by silica gel column chromatography (eluent solvent: methylene chloride) to obtain 10 g of 2-(4-octyloxybenzoyloxy)-7-hydroxy-9-methylfluorene (J1). Melting point: 140 to 143° C. the solution was refluxed for 5 hours the solution was extracted with methylene chloride The extract was washed with 5% hydrochloric acid until pH it was washed with a saturated sodium hydrogencarbonate aqueous solution dried on anhydrous magnesium sulfate A residue obtained by distilling the solvent

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

実験手順: A mixture of 2,7-dihydroxy-9-methylfluorene (0.5 g), 4-(6-acryloyloxyhexyloxy)benzoic acid (1.52 g), EDC (0.99 g), DMAP (5.76 mg) and dichloromethane (30 mL) was stirred at a room temperature for 12 hours. Water was added to the reaction mixture, and the separated organic layer was washed with water and dried on anhydrous magnesium sulfate. The solvent was distilled off from this organic layer under reduced pressure, and the resulting residue was purified by means of column chromatography (silica gel, eluting solvent: toluene/ethyl acetate [95/5]) and recrystallization (ethanol/ethyl acetate) to obtain 2,7-bis(4-(6-acryloyloxyhexyl)oxybenzoyloxy)-9-methylfluorene (0.19 g) of a white solid matter. the separated organic layer was washed with water dried on anhydrous magnesium sulfate The solvent was distilled off from this organic layer under reduced pressure the resulting residue was purified by means of column chromatography (silica gel, eluting solvent: toluene/ethyl acetate [95/5]) and recrystallization (ethanol/ethyl acetate)

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

実験手順: A mixture of 2,7-diacetyloxy-9-methylfluorene (12 g), lithium hydroxide monohydrate (3.42 g) and ethylene glycol (120 mL) was refluxed for one hour by heating. The reaction mixture was poured into 6M-hydrochloric acid and extracted with ethyl acetate. The organic layer was sufficiently washed with water and then dried on anhydrous magnesium sulfate. The solvent was distilled off from this organic layer under reduced pressure to obtain 2,7-dihydroxy-9-methylfluorene (7.24 g) of light brown crystal. Melting point: 191.5-196.3° C. was refluxed for one hour by heating extracted with ethyl acetate The organic layer was sufficiently washed with water dried on anhydrous magnesium sulfate The solvent was distilled off from this organic layer under reduced pressure

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

実験手順: A mixture of 2,7-diacetyloxy-9-methylfluorene (12 g), lithium hydroxide monohydrate (3.42 g) and ethylene glycol (120 mL) was refluxed for one hour by heating. The reaction mixture was poured into 6M-hydrochloric acid and extracted with ethyl acetate. The organic layer was sufficiently washed with water and then dried on anhydrous magnesium sulfate. The solvent was distilled off from this organic layer under reduced pressure to obtain 2,7-dihydroxy-9-methylfluorene (7.24 g) of light brown crystal. Melting point: 191.5-196.3° C. was refluxed for one hour by heating extracted with ethyl acetate The organic layer was sufficiently washed with water dried on anhydrous magnesium sulfate The solvent was distilled off from this organic layer under reduced pressure

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-(4-Allyloxybutyloxy)benzoic acid 1.34 g and 2,7-dihydroxy-9-methylfluorene 0.46 g were dissolved in 30 ml of methylene chloride and cooled down to 5° C., and 0.01 g of dimethylaminopyridine and 1.15 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added thereto, followed by stirring the solution at a room temperature for 12 hours. Water 50 ml was added to separate the solution, and the organic layer was dried on anhydrous magnesium sulfate. A residue obtained after distilling the solvent off was refined by means of silica gel chromatography and recrystallized from a mixed solvent of ethanol and ethyl acetate to obtain 0.6 g of 2,7-di[4-(4-allyloxybutyloxy)benzoyloxy]-9-methylfluorene. Phase transition temperature: C 107 N 222 I to separate the solution the organic layer was dried on anhydrous magnesium sulfate A residue obtained after distilling the solvent recrystallized from a mixed solvent of ethanol and ethyl acetate

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-(4-Allyloxybutyloxy)benzoic acid 1.34 g and 2,7-dihydroxy-9-methylfluorene 0.46 g were dissolved in 30 ml of methylene chloride and cooled down to 5° C., and 0.01 g of dimethylaminopyridine and 1.15 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added thereto, followed by stirring the solution at a room temperature for 12 hours. Water 50 ml was added to separate the solution, and the organic layer was dried on anhydrous magnesium sulfate. A residue obtained after distilling the solvent off was refined by means of silica gel chromatography and recrystallized from a mixed solvent of ethanol and ethyl acetate to obtain 0.6 g of 2,7-di[4-(4-allyloxybutyloxy)benzoyloxy]-9-methylfluorene. Phase transition temperature: C 107 N 222 I to separate the solution the organic layer was dried on anhydrous magnesium sulfate A residue obtained after distilling the solvent recrystallized from a mixed solvent of ethanol and ethyl acetate

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1.34 g of 4-(4-allyloxybutyloxy)benzoic acid and 0.46 g of 2,7-dihydroxy-9-methylfluorene were dissolved in 30 ml of methylene chloride and cooled to 5° C. 0.01 g of dimethylaminopyridine and 1.15 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added to it, and stirred at room temperature for 12 hours. 50 ml of water was added to it for liquid-liquid separation, and the organic layer was dried with anhydrous magnesium sulfate. The solvent was evaporated away, and the resulting residue was purified through silica gel chromatography, and recrystallized from a mixed solvent of ethanol and ethyl acetate to obtain 0.6 g of 2,7-di[4-(4-allyloxybutyloxy)benzoyloxy]-9-methylfluorene. the organic layer was dried with anhydrous magnesium sulfate The solvent was evaporated away the resulting residue was purified through silica gel chromatography recrystallized from a mixed solvent of ethanol and ethyl acetate

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

実験手順: Acryloyl chloride (55.4 g, 612.1 mmol) was added dropwise to a mixture of dichloromethane (500 mL), 2,7-dihydroxy-9-methylfluorene (T-11) (50.0 g, 235.6 mmol), triethylamine (61.7 g, 609.7 mmol) and 2,6-di-tert-butyl-p-cresol (52.0 mg, 0.24 mmol) in an ice bath under an atmosphere of nitrogen, and then the mixture was warmed slowly to room temperature. The stirring was continued at room temperature for 16 hours, and the reaction mixture was poured into water. The organic layer was wished with 1M-hydrochloric acid, aqueous 1M-sodium hydroxide solution and water. After the organic layer had been dried over anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (eluent: toluene), and then by recrystallization from a mixed solvent of dichloromethane and ethanol to give colorless crystals (34.2 g) of 2,7-bis(acryloyloxy)-9-methylfluorene (1-3-4). After the organic layer had been dried over anhydrous magnesium sulfate the organic solvent was distilled off under reduced pressure The residue was purified by silica gel chromatography (eluent: toluene) by recrystallization from a mixed solvent of dichloromethane and ethanol

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

実験手順: In a nitrogen atmosphere, concentrated sulfuric acid (0.2 mL) was added to a mixture of 4-hydroxybenzoic acid (13.0 g), 2,7-dihydroxy-9-methylfluorene (10.0 g), boric acid (0.3 g) and xylene (120 mL), and the mixture was heated under reflux for 6 hours while removing water. A solid matter thus deposited was collected by filtration under reduced pressure, and rinsed with toluene. The solid matter was recrystallized from a mixed solvent of ethanol (75 mL) and acetone (75 mL) to provide 2,7-bis(4-hydroxybenzoyloxy)-9-methylfluorene (compound [H1]) (14.9 g) in the form of pale rose crystals. the mixture was heated under reflux for 6 hours while removing water A solid matter thus deposited was collected by filtration under reduced pressure rinsed with toluene The solid matter was recrystallized from a mixed solvent of ethanol (75 mL) and acetone (75 mL)

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

実験手順: Octyloxybenzoic acid chloride 12.5 g was added dividing into several times to a tetrahydrofuran (100 ml) solution of 2,7-dihydroxy-9-methylfluorene 10 g and pyridine 8 g, and the solution was refluxed for 5 hours. 5% hydrochloric acid 50 ml was added to the reaction mixture, and the solution was extracted with methylene chloride. The extract was washed with 5% hydrochloric acid until pH became acidic, and then it was washed with a saturated sodium hydrogencarbonate aqueous solution and dried on anhydrous magnesium sulfate. A residue obtained by distilling the solvent off was refined by silica gel column chromatography (eluent solvent: methylene chloride) to obtain 10 g of 2-(4-octyloxybenzoyloxy)-7-hydroxy-9-methylfluorene (J1). Melting point: 140 to 143° C. the solution was refluxed for 5 hours the solution was extracted with methylene chloride The extract was washed with 5% hydrochloric acid until pH it was washed with a saturated sodium hydrogencarbonate aqueous solution dried on anhydrous magnesium sulfate A residue obtained by distilling the solvent