9H-xanthen-9-ylmethanol

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: A. From 2,7-Dichloroxanthene-9-carboxylic Acid: To a suspension of 0.75 g of LiAlH4 in 90 mL of anhydrous ether was added dropwise a solution of 3.0 g of 2,7-dichloroxanthene-9-carboxylic acid in 45 mL of freshly distilled THF over a period of 25 minutes. The mixture was stirred at room temperature until the color had changed from grey to light brown (ca. 6hr). The excess LiAlH4 was decomposed by the slow addition of 10 mL of methanol and 2 mL of water while stirring. The suspended precipitate was filtered, rinsed with ether (2×30 mL) and discarded. The combined filtrate was washed with water (2×40 mL), dried over MgSO4, and evaporated under reduced pressure to give 1.53 g (53.6%) of the alcohol as a white solid. Recrystallization from Skelly B--EtOAc (4:1) gave 1.21 g (42.36%) of the 2,7-dichloro-9-xanthenemethanol as a white fluffy solid, m.p. 134.5°-136° C.; IR (KBr): 3250 (b, OH) cm-1 ; 1H NMR (CDCl3): δ 1.65 (b, 1H, OH), 3.75 (d, 2H, CH2O), 4.01 (t, 1H, CH), 6.94-7.40 (m, 6H, aryl). Anal. Calcd for C14H10O2Cl2 : C, 59.81; H, 3.59. Found: C, 60.73; H, 3.91. B. From 9-Xanthenemethanol: To a suspension of 3.0 g of 9-xanthenemethanol and 4.2 g of N-chlorosuccinimide in 25 mL of freshly distilled THF and 12.5 mL of water was added dropwise 2.0 mL of conc. HCl over a period of 5 minutes. The mixture was stirred at room temperature for 6 hours and poured into 200 mL of water with stirring. The precipitated solid was filtered, rinsed with water (2×30 mL), and dried in air to afford 3.95 g (100%) of the crude alcohol. Recrystallization from Skelly B--EtOAc (4:1) gave 1.35 g (34%) of 2,7-dichloro-9-xanthenemethanol as a fluffy solid, m.p. 134.5°-136° C., identified by the mixture melting point, IR and NMR spectral comparison with an authentic sample obtained by the reduction of 2,7-dichloroxanthene-9-carboxylic acid. Recrystallization from Skelly B EtOAc (4:1) gave 1.21 g (42.36%) of the 2,7-dichloro-9-xanthenemethanol as a white fluffy solid, m.p. 134.5°-136° C. with stirring The precipitated solid was filtered rinsed with water (2×30 mL) dried in air

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

実験手順: To a mixture of 4.0 g of 9-xanthenemethanol and 3.0 mL of freshly distilled thionyl chloride in 30 mL of freshly distilled THF was added dropwise 1.7 mL of pyridine over a period of 15 minutes. The mixture was heated in an oil bath at 50° C. for 12 hours, cooled to room temperature, and washed with half sat'd brine (30 mL), sat'd NaHCO3 (30 mL) and water (2×30 mL). The organic layer was dried over MgSO4 and the solvent was evaporated in vacuo to give 4.16 g (95.7%) of the crude 9-chloromethylxanthene as an off-white solid. Recrystallization from CH3OH--CH2Cl2 (4:1) gave 3.53g (81.35%) of the pure 9-chloromethylxanthene as white needles, m.p. 104.5°-106° C.; 1H NMR (CDCl3 ):δ 3.67 (d, 2H, CH2), 4.32 (t, 1H, CH), 7.04-7.46 (m, 8H, aryl). cooled to room temperature washed with half sat'd brine (30 mL), sat'd NaHCO3 (30 mL) and water (2×30 mL) The organic layer was dried over MgSO4 the solvent was evaporated in vacuo

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

実験手順: To a mixture of 1.0 g of 9-xanthenemethanol and 0.51 mL of phenyl isocyanate in 5.0 mL of dry benzene was added two drops of triethylamine. The mixture was heated in an oil bath at 80° C. for 20 hours and cooled in an ice bath for 2 hours. The precipitated crystals were filtered and rinsed with Skelly B to give 1.48 g (95.2%) of the crude urethane as white crystals. Recrystallization from EtOAc--Skelly B (5:1) gave 1.37 g (88.1%) of the pure Xmoc-aniline as white needles, m.p. 180°-181° C.; IR (KBr): 3350 (NH), 1705 (C=O) cm-1 ; 1H NMR (CDCl3): δ 4.30 (m, 3H, CHCH2O), 6.55 (b, 1H, NH , 6.90-7.40 (m, 13H, aryl). cooled in an ice bath for 2 hours The precipitated crystals were filtered rinsed with Skelly B

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

実験手順: To a suspension of 7.5 g of lithium aluminum hydride in 360 mL of dry ether was added dropwise a solution of 30 g of xanthene-9-carboxylic acid in 90 mL of freshly distilled THF at 0° C. over a period of 30 minutes. The mixture was stirred at room temperature until the color had changed from grey to brownish red (ca. 1.5 hours) The excess LiAlH4 was decomposed by the slow addition, while stirring, of a mixture of 60 mL of methanol and 25 mL of water at room temperature. The milky white suspension was filtered (sintered glass funnel) and rinsed with ether (3×50 mL). The filtrate was washed with water (2×200 mL), dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure to give 27.5 g (100%) of the crude alcohol as an off-white solid. Recrystallization from Skelly F--ether (2:1) afforded 23.59 g (86.4%) of the pure 9-xanthenemethanol as white crystals, m.p. 66°-68° C.; IR (KBr): 3290 cm-1 (OH); 1H NMR (CDCl3): δ b 1.70 (t, 1H, OH), 3.71 (dt, 2H, CH2), 4.09 (t, 1H, CH), 6.95-7.40 (m, 8H, aryl). grey to brownish red (ca. 1.5 hours) was decomposed by the slow addition The milky white suspension was filtered (sintered glass funnel) rinsed with ether (3×50 mL) The filtrate was washed with water (2×200 mL) dried over anhydrous MgSO4 the solvent was evaporated under reduced pressure

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

実験手順: To a suspension of 7.5 g of lithium aluminum hydride in 360 mL of dry ether was added dropwise a solution of 30 g of xanthene-9-carboxylic acid in 90 mL of freshly distilled THF at 0° C. over a period of 30 minutes. The mixture was stirred at room temperature until the color had changed from grey to brownish red (ca. 1.5 hours) The excess LiAlH4 was decomposed by the slow addition, while stirring, of a mixture of 60 mL of methanol and 25 mL of water at room temperature. The milky white suspension was filtered (sintered glass funnel) and rinsed with ether (3×50 mL). The filtrate was washed with water (2×200 mL), dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure to give 27.5 g (100%) of the crude alcohol as an off-white solid. Recrystallization from Skelly F--ether (2:1) afforded 23.59 g (86.4%) of the pure 9-xanthenemethanol as white crystals, m.p. 66°-68° C.; IR (KBr): 3290 cm-1 (OH); 1H NMR (CDCl3): δ b 1.70 (t, 1H, OH), 3.71 (dt, 2H, CH2), 4.09 (t, 1H, CH), 6.95-7.40 (m, 8H, aryl). grey to brownish red (ca. 1.5 hours) was decomposed by the slow addition The milky white suspension was filtered (sintered glass funnel) rinsed with ether (3×50 mL) The filtrate was washed with water (2×200 mL) dried over anhydrous MgSO4 the solvent was evaporated under reduced pressure