2-(9H-fluoren-9-yl)ethanol

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: Diethyl azodicarboxylate (0.235 ml, 1.49 mmol) was added at 0° C. to a stirred solution of triphenylphosphine (0.392 g, 1.49 mmol) and 2-(9H-fluoren-9-yl)-ethanol (0.208 g, 1.0 mmol) in dry THF (5 ml) and the mixture stirred for 5 min. A solution of ethyl 2-ethoxy-3-(4-hydroxy-phenyl)-propionate (0.356 g, 1.49 mmol) in dry THF (5 ml) was then added, the mixture allowed to warm to room temperature and stirring continued for 20 h. The resulting mixture was treated with water (50 ml), and the products extracted into dichloromethane (4×50 ml). The extracts were combined, washed with brine, dried (Na2SO4) and evaporated to a colourless gum. This was then purified by column chromatography on SiO2 (15% Et2O in petroleum eluent) to give the title compound as a colourless gum; 0.20 g (47%). stirring continued for 20 h the products extracted into dichloromethane (4×50 ml) washed with brine dried (Na2SO4) evaporated to a colourless gum This was then purified by column chromatography on SiO2 (15% Et2O in petroleum eluent)

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

実験手順: Diethyl azodicarboxylate (0.235 ml, 1.49 mmol) was added at 0° C. to a stirred solution of triphenylphosphine (0.392 g, 1.49 mmol) and 2-(9H-fluoren-9-yl)-ethanol (0.208 g, 1.0 mmol) in dry THF (5 ml) and the mixture stirred for 5 min. A solution of ethyl 2-ethoxy-3-(4-hydroxy-phenyl)-propionate (0.356 g, 1.49 mmol) in dry THF (5 ml) was then added, the mixture allowed to warm to room temperature and stirring continued for 20 h. The resulting mixture was treated with water (50 ml), and the products extracted into dichloromethane (4×50 ml). The extracts were combined, washed with brine, dried (Na2SO4) and evaporated to a colourless gum. This was then purified by column chromatography on SiO2 (15% Et2O in petroleum eluent) to give the title compound as a colourless gum; 0.20 g (47%). stirring continued for 20 h the products extracted into dichloromethane (4×50 ml) washed with brine dried (Na2SO4) evaporated to a colourless gum This was then purified by column chromatography on SiO2 (15% Et2O in petroleum eluent)

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

実験手順: To a stirred, cooled (-78° C.) solution of 6.00 g (36.1 mmol) of fluorene in 75 mL of THF was added 15.4 mL (36.2 mmol) of 2.35 M n-BuLi in hexanes dropwise. The resulting dark orange mixture was stirred for 1.5 h and 26.0 mL (36.4 mmol) of 1.4 M ethylene oxide in Et2O was added. The resulting bright orange mixture was warmed slowly to room temperature over 3.5 h, quenched with saturated aqueous NH4Cl and concentrated at reduced pressure. The residue was poured into water and extracted twice with Et2O. The combined organic layers were washed with brine and dried over magnesium sulfate. Solvent was removed at reduced pressure and the crude product was chromatographed on 150 g of flash silica gel eluting with 25% EtOAc in hexane to afford 5.05 g (67%) of the desired alcohol as a white solid, mp 98°-99° C. quenched with saturated aqueous NH4Cl concentrated at reduced pressure The residue was poured into water extracted twice with Et2O The combined organic layers were washed with brine dried over magnesium sulfate Solvent was removed at reduced pressure the crude product was chromatographed on 150 g of flash silica gel eluting with 25% EtOAc in hexane

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

実験手順: 2-(9-Fluorenyl)ethyl chloroformate was prepared from a solution of 2-(9-fluorenyl)ethanol (1.26 g, 6.0 mmol) in 10 ml of toluene and 4 ml of tetrahydrofuran, which was added to 12 ml of phosgene solution (12.4 mol, [1.93M in toluene). The solution was stirred for 1 hour and put under vacuum to remove the phosgene. Concentration yielded 2-(9-fluorenyl)ethyl chloroformate (1.64 g, 6.0 mmol). to remove the phosgene Concentration

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

実験手順: To a solution of 2-(9-fluorenyl)ethanol 1.26 g, 6 mmol) in 10 ml of toluene and 4 ml of tetrahydrofuran (THF), was added dropwise with stirring phosgene (12.4 ml, 1.93M solution in toluene). The solution was stirred for 0.5 hours, then put under vacuum to remove the phosgene. Concentration yielded 2-(9-fluorenyl)ethyl chloroformate (6 mmol, 1.64 g). to remove the phosgene Concentration

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

実験手順: To a solution of 2-(9-fluorenyl)ethanol 1.26 g, 6 mmol) in 10 ml of toluene and 4 ml of tetrahydrofuran (THF), was added dropwise with stirring phosgene (12.4 ml, 1.93M solution in toluene). The solution was stirred for 0.5 hours, then put under vacuum to remove the phosgene. Concentration yielded 2-(9-fluorenyl)ethyl chloroformate (6 mmol, 1.64 g). to remove the phosgene Concentration

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

実験手順: A phosgene solution (12.4 ml of a 1.93M solution in toluene) was added dropwise with stirring to a solution of 2-(9-fluorenyl)ethanol (1.26 g, 6 mmol). After 0.5 hours the solution was put under vacuum to remove the phosgene, and concentrated to give 2-(9-fluorenyl)ethyl chloroformate (1.64 g, 6 mmol). This was dissolved in 10 ml dioxane, and to it added dropwise a solution of anthranilic acid (0.85 g, 6.2 mmol) and potassium carbonate (0.86 g, 6.2 mmol) in 15 ml water. After 3 hours, the dioxane was evaporated, and the solution diluted with an equal amount of water. Acidification with 10% HCl yielded a white precipitate which was washed with water and dried. (1.98 g, 88%), mp 177° C. IR(KBr) 3175, 1709, 1684, 1594, 1537, 1450, 1380, 1301, 1259, 1205, 1146, 1049, 753, 740 cm-1. 1H NMR (300 MHz, CDCl3) δ 2.46 (q, 2H, J=6.8), 4.14 (t, 3H, J=6.8), 7.10 (t, 1H, J=6.5), 8.46 (m, 13H), 10.13 (s, 1H). Anal. calcd for C23H19NO4 : C, 73.98; H, 5.13; N, 3.75. Found: C, 73.87; H, 5.19; N, 3.73. to remove the phosgene concentrated

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

実験手順: N-[9H-(Fluorenyl-9-ethoxycarbonyl)]amino-4-benzoic acid was prepared from a solution of 2-(9-fluorenyl) ethanol (1.5 g, 7.1 mmol) in 10 ml of toluene to which was added dropwise with stirring a solution of phosgene in toluene (12.4 ml, 1.93M). After 0.5 hours, the solution was put under vacuum to remove excess phosgene, and concentrated to yield 2-(9-fluorenyl)ethyl chloroformate. This was then dissolved in 10 ml of dioxane and add to a solution of 4-aminobenzoic acid (1.0 g, 7.3 mmol) in 15 ml water. After 5 hours, the dioxane was evaporated, the solution diluted with an equal amount of water, rendered basic with sodium carbonate solution, and filtered to remove insoluble materials. Acidification with 10% HCl yielded a white precipitate, which was filtered and dried. Crystallization from aqueous DMF gave a white solid (1.22 g, 46%), mp 202° C. IR(KBr) 3342, 2964, 2666, 2543, 2363, 1699, 1676, 1609, 1594, 1524, 1509, 1477, 1414, 1313, 1293, 1266, 1177, 1069, 1049, 938, 853, 768, 750, 735 cm-1. 1H NMR (300 MHz, DMSO) δ 2.3(q, 2H, J=7.0), 400(t, 2H, J=7.0), 4.12(t, 1H, J=6.0), 7.29-7.88(m, 13H, 9.97(s, 1H). Anal. calcd for C23H19NO4 0.25H2O: C, 73:10; H, 5.20; N, 3.71. Found: C, 73.32; H, 5.23; H, 3.70. was added dropwise to remove excess phosgene concentrated

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

実験手順: 2-(9-Fluorenyl) ethanol was prepared from a solution of fluorene (116.35 g, 0.7 mmol) in 800 ml of dry THF at -20° C. which was added n-Buli in hexane (0.7 mol) keeping the temperature below -10° C. To the clear solution was rapidly added 357 ml of 1.4M ethylene oxide in ether (0.5 mol) keeping the temperature below 5° C. The reaction mixture was stirred for 5 hours, then quenched with 50 ml of saturated ammonium chloride solution. The THF was removed at a rotary evaporator. The residue was partitioned between water and ethyl acetate. The organic layer was separated, dried with MgSO4 and concentrated in vacuo until crystallization began. The solution was allowed to stand overnight and the crystals were collected and dried (mp 97° C.) (85.5 g, (81%)). the temperature below -10° C the temperature below 5° C quenched with 50 ml of saturated ammonium chloride solution The THF was removed at a rotary evaporator The residue was partitioned between water and ethyl acetate The organic layer was separated dried with MgSO4 concentrated in vacuo until crystallization to stand overnight the crystals were collected dried (mp 97° C.) (85.5 g, (81%))

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

実験手順: N-[9H-(Fluorenyl-9-ethoxycarbonyl)]amino-4-benzoic acid was prepared from a solution of 2-(9-fluorenyl) ethanol (1.5 g, 7.1 mmol) in 10 ml of toluene to which was added dropwise with stirring a solution of phosgene in toluene (12.4 ml, 1.93M). After 0.5 hours, the solution was put under vacuum to remove excess phosgene, and concentrated to yield 2-(9-fluorenyl)ethyl chloroformate. This was then dissolved in 10 ml of dioxane and add to a solution of 4-aminobenzoic acid (1.0 g, 7.3 mmol) in 15 ml water. After 5 hours, the dioxane was evaporated, the solution diluted with an equal amount of water, rendered basic with sodium carbonate solution, and filtered to remove insoluble materials. Acidification with 10% HCl yielded a white precipitate, which was filtered and dried. Crystallization from aqueous DMF gave a white solid (1.22 g, 46%), mp 202° C. IR(KBr) 3342, 2964, 2666, 2543, 2363, 1699, 1676, 1609, 1594, 1524, 1509, 1477, 1414, 1313, 1293, 1266, 1177, 1069, 1049, 938, 853, 768, 750, 735 cm-1. 1H NMR (300 MHz, DMSO) δ 2.3(q, 2H, J=7.0), 400(t, 2H, J=7.0), 4.12(t, 1H, J=6.0), 7.29-7.88(m, 13H, 9.97(s, 1H). Anal. calcd for C23H19NO4 0.25H2O: C, 73:10; H, 5.20; N, 3.71. Found: C, 73.32; H, 5.23; H, 3.70. was added dropwise to remove excess phosgene concentrated

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

実験手順: To a solution of 21.0 g 2-(9-fluorenyl)ethanol, in 495 mL toluene was added dropwise with stirring 40 mL of a 2.5M solution of n-butyllithium in hexane. The resulting solution of Li{flu-CH2—CH2—O} was cooled to below −25° C. Then, 16.7 g CF3SO2F was condensed into the reaction mixture. Tile temperature was allowed to rise to 25° C. and the reaction mixture was stirred for 6 h. Unreacted CF3SO2F was removed by pumping about 10 mL of liquid into a dry ice-cooled trap. To the solution of flu-CH2—CH2—OSO2CF3 thus obtained was added a solution of 0.1 mole indenyllithium in 100 mL diethyl ether. After stirring for 12 h, solvents were removed under vacuum and the residue recrystallized in air from boiling heptane. The yield of white microcrystalline solid, mp 79-80° C., was 8.9 g (29%). Spectroscopic and chemical analysis confirmed the identity of the desired compound. condensed into the reaction mixture to rise to 25° C. was removed cooled trap To the solution of flu-CH2—CH2—OSO2CF3 thus obtained After stirring for 12 h solvents were removed under vacuum the residue recrystallized in air