1-(cyclohexen-1-yl)ethanone

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:

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a flask equipped with a stirrer, dropping funnel, condenser and gas inlet tube maintained under a nitrogen atmosphere, there is added 50 g. (0.89) moles of potassium hydroxide in one liter of 2-methoxyethanol. Stirring is initiated and 100 g. (0.79 mole) of anhydrous phloroglucinol is added in three portions, followed by the addition of 100 g. (0.80 mole) of 1-acetyl-cyclohexene while maintaining the temperature at 50° C. The resulting solution is refluxed at 140° C. for 4 hours. After cooling there is then added gradually 53.6 g. of acetic acid while obtaining a pH of approximately 7. The solvent is then removed in vacuo, and the residue is further heated in an oil bath at 70° C., to obtain a viscous residue. The resulting residue is dissolved in ethyl acetate and water washed twice with water, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to obtain a brown solid. The resulting solid is recrystallized from ethyl acetate/cyclohexane to give 2,4-dihydroxy-4b,5,6,7,8,8a,9,10-octahydro-9-oxo-phenanthrene; m.p. 220°-223° C. To a flask equipped with a stirrer maintained under a nitrogen atmosphere there is added 50 g followed by the addition of 100 g After cooling there is then added gradually 53.6 g The solvent is then removed in vacuo the residue is further heated in an oil bath at 70° C. to obtain a viscous residue water washed twice with water dried over anhydrous sodium sulfate filtered evaporated in vacuo to obtain a brown solid The resulting solid is recrystallized from ethyl acetate/cyclohexane

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a flask equipped with a stirrer, dropping funnel, condenser and gas inlet tube maintained under a nitrogen atmosphere, there is added 50 g. (0.89) moles of potassium hydroxide in one liter of 2-methoxyethanol. Stirring is initiated and 100 g. (0.79 mole) of anhydrous phloroglucinol is added in three portions, followed by the addition of 100 g. (0.80 mole) of 1-acetyl-cyclohexene while maintaining the temperature at 50° C. The resulting solution is refluxed at 140° C. for 4 hours. After cooling there is then added gradually 53.6 g. of acetic acid while obtaining a pH of approximately 7. The solvent is then removed in vacuo, and the residue is further heated in an oil bath at 70° C., to obtain a viscous residue. The resulting residue is dissolved in ethyl acetate and water washed twice with water, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to obtain a brown solid. The resulting solid is recrystallized from ethyl acetate/cyclohexane to give 2,4-dihydroxy-4b,5,6,7,8,8a,9,10-octahydro-9-oxo-phenanthrene; m.p. 220°-223° C. To a flask equipped with a stirrer maintained under a nitrogen atmosphere there is added 50 g followed by the addition of 100 g After cooling there is then added gradually 53.6 g The solvent is then removed in vacuo the residue is further heated in an oil bath at 70° C. to obtain a viscous residue water washed twice with water dried over anhydrous sodium sulfate filtered evaporated in vacuo to obtain a brown solid The resulting solid is recrystallized from ethyl acetate/cyclohexane

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

実験手順: Ethyl difluoroacetate (4.71 g, 38 mmol) was placed in a 100 mL round bottom flask and dissolved in ether (20 mL). To the stirred solution was added 25 weight % sodium methoxide (9.68 g, 45 mmol) followed by 1-acetyl-1-cyclohexene (4.27 g, 34 mmol The reaction was stirred at room temperature overnight 17.5 hours), then treated with 3N HCl (20 mL). The organic layer was collected and washed with brine (20 mL), dried over MgSO4, and concentrated in vacuo to give a brown oil (6.48 g, 93%). 1H NMR (CDCl3) 300 MHz 15.00 (br s, 1H), 6.09 (s, 1H), 5.92 (t, J=54.4 Hz, 1H), 2.31 (m, 4H), 1.64 (m, 4H); 19F NMR (CDCl3) 300 MHz: -126.94; M+202. The organic layer was collected washed with brine (20 mL) dried over MgSO4 concentrated in vacuo

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a flask equipped with a stirrer, dropping funnel, condenser and gas inlet tube maintained under a nitrogen atmosphere, there is added 50 g. (0.89) moles of potassium hydroxide in one liter of 2-methoxyethanol. Stirring is initiated and 100 g. (0.79 mole) of anhydrous phloroglucinol is added in three portions, followed by the addition of 100 g. (0.80 mole) of 1-acetyl-cyclohexene while maintaining the temperature at 50° C. The resulting solution is refluxed at 140° C. for 4 hours. After cooling there is then added gradually 53.6 g. of acetic acid while obtaining a pH of approximately 7. The solvent is then removed in vacuo, and the residue is further heated in an oil bath at 70° C., to obtain a viscous residue. The resulting residue is dissolved in ethyl acetate and water washed twice with water, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to obtain a brown solid. The resulting solid is recrystallized from ethyl acetate/cyclohexane to give 2,4-dihydroxy-4b,5,6,7,8,8a,9,10-octahydro-9-oxo-phenanthrene; m.p. 220°-223° C. To a flask equipped with a stirrer maintained under a nitrogen atmosphere there is added 50 g followed by the addition of 100 g After cooling there is then added gradually 53.6 g The solvent is then removed in vacuo the residue is further heated in an oil bath at 70° C. to obtain a viscous residue water washed twice with water dried over anhydrous sodium sulfate filtered evaporated in vacuo to obtain a brown solid The resulting solid is recrystallized from ethyl acetate/cyclohexane

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

実験手順: A mixture of 19.5 g (0.1 mole) of 3,4-dihydro-7-fluoroisoquinoline hydrochloride and 18.6 g (0.15 mole) of 1-cyclohexen-1-yl methyl ketone in 22 ml of ethanol is reluxed with stirring overnight then cooled to room temperature. The solution is poured into water, whereupon a suspension of undissolved material forms, and is extracted with ether. The aqueous layer and its suspended solid is stirred and treated with ammonium hydroxide solution to pH 8.5 to 9.0. The suspended solid is broken up, collected by decantation, washed with water, dissolved in methylene chloride, dried over sodium sulfate and evaporated. The residue is dissolved in benzene and chromatographed on alumina and eluted with benzene. The resulting solid is triturated with hexane and dried to give 2,3,4,4a,6,7,11b,12,13,13a-decahydro-10-fluoro-1H-dibenzo[a,f]quinolizin-13-one, M.P. 130°-136° C. EXAMPLE 35 is extracted with ether is stirred treated with ammonium hydroxide solution to pH 8.5 to 9.0 collected by decantation washed with water dissolved in methylene chloride dried over sodium sulfate evaporated The residue is dissolved in benzene chromatographed on alumina eluted with benzene The resulting solid is triturated with hexane dried

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

実験手順: Ethyl difluoroacetate (4.71 g, 38 mmol) was placed in a 100 mL round bottom flask and dissolved in ether (20 mL). To the stirred solution was added 25 weight % sodium methoxide (9.68 g, 45 mmol) followed by 1-acetyl-1-cyclohexene (4.27 g, 34 mmol). The reaction was stirred at room temperature overnight (17.5 hours), then treated with 3N HCl (20 mL). The organic layer was collected and washed with brine (20 mL), dried over MgSO4, and concentrated in vacuo to give a brown oil (6.48 g, 93%). 1H NMR (CDCl3) 300 MHz 15.00 (br s, 1H), 6.09 (s,1H), 5.92 (t, J=54.4 Hz,1H), 2.31 (m, 4H), 1.64 (m, 4H); 19F NMR (CDCl3) 300 MHz: -126.94; M+ 202. The organic layer was collected washed with brine (20 mL) dried over MgSO4 concentrated in vacuo

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

実験手順: Ethyl difluoroacetate (4.71 g, 38 mmol) was placed in a 100 mL round bottom flask and dissolved in ether (20 mL). To the stirred solution was added 25 weight % sodium methoxide (9.68 g, 45 mmol) followed by 1-acetyl-1-cyclohexene (4.27 g, 34 mmol). The reaction was stirred at room temperature overnight (17.5 hours), then treated with 3N HCl (20 mL). The organic layer was collected and washed with brine (20 mL), dried over MgSO4, and concentrated in vacuo to give a brown oil (6.48 g, 93%). 1H NMR (CDCl3) 300 MHz 15.00 (br s, 1H), 6.09 (s,1H), 5.92 (t, J=54.4 Hz,1H), 2.31 (m, 4H), 1.64 (m, 4H); 19F NMR (CDCl3) 300 MHz: -126.94; M+ 202. The organic layer was collected washed with brine (20 mL) dried over MgSO4 concentrated in vacuo

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

実験手順: Ethyl difluoroacetate (4.71 g, 38 mmol) was placed in a 100 mL round bottom flask and dissolved in ether (20 mL). To the stirred solution was added 25 weight % sodium methoxide (9.68 g, 45 mmol) followed by 1-acetyl-1-cyclohexene (4.27 g, 34 mmol). The reaction was stirred at room temperature overnight (17.5 hours), then treated with 3N HCl (20 mL). The organic layer was collected and washed with brine (20 mL), dried over MgSO4, and concentrated in vacuo to give a brown oil (6.48 g, 93%). 1H NMR (CDCl3) 300 MHz 15.00 (br s, 1H), 6.09 (s, 1H), 5.92 (t, J=54.4 Hz,1H) 2.31 (m, 4H), 1.64 (m, 4H); 19F NMR (CDCl3) 300 MHz: -126.94; M+202. The organic layer was collected washed with brine (20 mL) dried over MgSO4 concentrated in vacuo