9-methyl-9H-fluorene

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: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: Fluorene (15.0 g, 90.4 mmol), n-BuLi (48.1 ml, 120 mmol, 2.5 M in hexane), RX=iodomethane (19.3 g, 136 mmol). 40 was isolated as a yellowish waxy solid (16.2 g, quant.). The analytical data were identical to those in the literature (M. A. Schmidt, H. G. Alt, W. Milius, J. Organomet. Chem. 1996, 525, 15). 40 was isolated as a yellowish waxy solid (16.2 g, quant.)

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:0.00; pressure:0.00; stir:

反応条件: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of fluorene (78.3 g) and THF (700 mL) was cooled down to −70° C., and n-BuLi (300 mL, corresponding to 0.48 mol) was dropwise added thereto while maintaining −60° C. or lower. Then, methyl iodide (66.8 g) was added, and the temperature was allowed to slowly go back to a room temperature. The mixture was cooled again down to 0° C. to add 3M-hydrochloric acid (300 mL), and the reaction mixture was extracted with toluene. The organic layer obtained was washed well in order with saturated sodium hydrogencarbonate, saturated sodium hydrogensulfite and water, and then dried on anhydrous magnesium sulfate. The solvent was distilled off from this organic layer under reduced pressure, and the residue was purified by means of column chromatography (silica gel, eluting solvent: toluene/heptane [40/60]) and recrystallization (ethanol) to obtain 9-methylfluorene (57.4 g) of pale yellow crystal. Melting point: 47.3-48.8° C. while maintaining −60° C. to slowly go back to a room temperature The mixture was cooled again down to 0° C. the reaction mixture was extracted with toluene The organic layer obtained was washed well in order with saturated sodium hydrogencarbonate, saturated sodium hydrogensulfite and water dried on anhydrous magnesium sulfate The solvent was distilled off from this organic layer under reduced pressure the residue was purified by means of column chromatography (silica gel, eluting solvent: toluene/heptane [40/60]) and recrystallization (ethanol)

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

実験手順: 9-Methylfluorene (43.6 g, 0.24 mol) and N-chlorosuccinimide (64.5 g, 0.48 mol) were suspended in 25 mL of acetonitrile and cooled in an ice-water bath. Then 20 mL of concentrated HCl was added dropwise and the solution was stirred at room temperature overnight. The precipitate was filtered and dried. Recrystallization from EtOH and water gave 24 g (41%) of 2,7-dichloro-9-methylfluorene as white crystals, mp 110°-112° C. FT IR: 3425, 1450, 1407, 1273, 1167, 1070, 851,818 cm-1 ; H1NMR (CDCl3, 300 MHz) δ 7.3-7.8 (m, 6H, 3.9-4.1 (q, 1H), 1.2-1.3 (d, 2H). cooled in an ice-water bath The precipitate was filtered dried Recrystallization from EtOH and water

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

実験手順: 9-Methylfluorene (43.6 g, 0.24 mol) and N-chlorosuccinimide (64.5 g, 0.48 mol) were suspended in 25 mL of acetonitrile and cooled in an ice-water bath. Then 20 mL of concentrated HCl was added dropwise and the solution was stirred at room temperature overnight. The precipitate was filtered and dried. Recrystallization from EtOH and water gave 24 g (41%) of 2,7-dichloro-9-methylfluorene as white crystals, mp 110°-112° C. FT IR: 3425, 1450, 1407, 1273, 1167, 1070, 851,818 cm-1 ; H1NMR (CDCl3, 300 MHz) δ 7.3-7.8 (m, 6H, 3.9-4.1 (q, 1H), 1.2-1.3 (d, 2H). cooled in an ice-water bath The precipitate was filtered dried Recrystallization from EtOH and water

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

実験手順: 9-Methylfluorene (43.6 g, 0.24 mol) and N-chlorosuccinimide (64.5 g, 0.48 mol) were suspended in 25 mL of acetonitrile and cooled in an ice-water bath. Then 20 mL of concentrated HCl was added dropwise and the solution was stirred at room temperature overnight. The precipitate was filtered and dried. Recrystallization from EtOH and water gave 24 g (41%) of 2,7-dichloro-9-methylfluorene as white crystals, mp 110°-112° C. FT IR: 3425, 1450, 1407, 1273, 1167, 1070, 851,818 cm-1 ; H1NMR (CDCl3, 300 MHz) δ 7.3-7.8 (m, 6H, 3.9-4.1 (q, 1H), 1.2-1.3 (d, 2H). cooled in an ice-water bath The precipitate was filtered dried Recrystallization from EtOH and water

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 9-methylfluorene (10.0 g, 55.5 mmol) in 100 mL of THF was added n-BuLi (61.0 mmol) at -10° C., then a solution of ethylene oxide (61.0 mmol) in THF was added in one portion. The reaction mixture was stirred at -20° C., then allowed to warm to room temperature, quenched with NH4Cl solution and evaporated to a residue. This was then partitioned between ethyl acetate and water, the organic layer was washed with brine, dried with MgSO4 and evaporated to get the product which was purified by chromatography using 10% ethyl acetate/hexane mixture to provide a pure sample of 9-methylfluorene-9-ethanol, m.p. 84°-85° C. to warm to room temperature quenched with NH4Cl solution evaporated to a residue This was then partitioned between ethyl acetate and water the organic layer was washed with brine dried with MgSO4 evaporated to get the product which was purified by chromatography