2-fluorofluoren-9-one

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 mixture of commercially available (Aldrich Chemical, Inc.) 2-fluoro-9-fluorenone (11) (10 g, 50.5 mmoL) and hydrazine monohydrate (10 mL , 200 mmoL, 4 eq) in ethanol (250 mL ) was refluxed for 1.5 h. The solution was then reduced in volume (to about a 100 mL) and chilled. The solid that separated was collected by filtration, washing with cold ethanol to provide 6.5 g (60%) of product (12): mp 161°-165° C.; IR (KBr) 3390, 3310, 3200, 1450 cm-1 ; 1H NMR (CDCl3, 200 MHz) 7.85 (bd, 1H, J=7.3Hz), 7.69 (bd, 1H, J=7.1Hz), 7.57 (dd, 1H, J=4.8, 8.1Hz), 7.36 (m, 3H), 7.02 (ddd, 1H, J=2.5, 8.3, 9.2Hz), 6.48 (bs, 2H); MS m/z 212 (M+), 183 (base peak). was refluxed for 1.5 h chilled The solid that separated was collected by filtration washing with cold ethanol

反応条件: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Fluoro-9-fluorenone, 20 (1.78 gms, 8.9 mmol) was dissolved in ethylene glycol(60 mL) under a nitrogen atmosphere. Hydrazine hydrate(1.8 mL) was added and the mixture was heated at 180° C. for two hours. The mixture was then cooled and poured into water. The aqueous layer was extracted with ethyl acetate and the organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated to yield the title compound. The mixture was then cooled The aqueous layer was extracted with ethyl acetate the organic layer was washed with brine dried over sodium sulfate filtered concentrated

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

実験手順: 2-Fluorofluorene (824.7 g, 4.48 mol) was dissolved in pyridine (4 L) and stirred. A 40% solution of Triton B (100 mL of benzyltrimethylammonium hydroxide 40% in pyridine according to a general procedure of U. Sprinzak, J. Amer. Chem. Soc. 80 (1958) 5449) was added and oxygen was bubbled into the vigorously stirred solution. This exothermic reaction was run for 20 hours whereupon an additional portion of the Triton B solution (50 mL) was added with continued stirring and oxygen addition for an additional 24 hours. The resulting dark green reaction mixture was treated with Norite (100 g, neutralized charcoal), stirred for 30 minutes and filtered through a Celite pad (diatomaceous earth filter aid). The filter pad was then washed with pyridine (1 L). The combined filtrates were concentrated to a small volume in vacuo with heat. A 5% solution of hydrochloric acid in water (1 L) was added and the pyridine was azeotrophed in vacuo with heat. This process was repeated until a total of 6-8 L of water were evaporated. The granular product was filtered and washed with water (4 L) and air dried. The yellow-orange product was distilled through a large bore short path distillation apparatus (bp 167°-170° C.; 1.5 mm Hg) to yield into a chilled receiving flask the bright yellow 2-fluoro-9-fluorenone (600 g) with a m.p. 113°-115° C. and m/e+. 198 for C13H7FO. 80 (1958) 5449) was added oxygen was bubbled into the vigorously stirred solution This exothermic reaction was added with continued stirring stirred for 30 minutes filtered through a Celite pad (diatomaceous earth filter aid) The filter pad was then washed with pyridine (1 L) The combined filtrates were concentrated to a small volume in vacuo with heat A 5% solution of hydrochloric acid in water (1 L) was added with heat were evaporated The granular product was filtered washed with water (4 L) and air dried The yellow-orange product was distilled through path distillation apparatus (bp 167°-170° C.; 1.5 mm Hg)

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

実験手順: A mixture of commercially available (Aldrich Chemical, Inc.) 2-fluoro-9-fluorenone (11) (10 g, 50.5 mmoL) and hydrazine monohydrate (10 mL , 200 mmoL, 4 eq) in ethanol (250 mL ) was refluxed for 1.5 h. The solution was then reduced in volume (to about a 100 mL) and chilled. The solid that separated was collected by filtration, washing with cold ethanol to provide 6.5 g (60%) of product (12): mp 161°-165° C.; IR (KBr) 3390, 3310, 3200, 1450 cm-1 ; 1H NMR (CDCl3, 200 MHz) 7.85 (bd, 1H, J=7.3Hz), 7.69 (bd, 1H, J=7.1Hz), 7.57 (dd, 1H, J=4.8, 8.1Hz), 7.36 (m, 3H), 7.02 (ddd, 1H, J=2.5, 8.3, 9.2Hz), 6.48 (bs, 2H); MS m/z 212 (M+), 183 (base peak). was refluxed for 1.5 h chilled The solid that separated was collected by filtration washing with cold ethanol