5-(2-methylphenyl)cyclohexane-1,3-dione

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5-(2-methylphenyl)cyclohexane-1,3-dione (1.3 g) and ammonium acetate (0.49 g) in ethanol (30 ml) was stirred at room temperature for 30 minutes, and to the mixture was added 3-butyn-2-one (0.44 g). The reaction solution was stirred at room temperature for 1.5 hours and refluxed for 27 hours. Under reduced pressure, the solvent was evaporated, and the residue was dissolved in ethyl acetate. The solution was washed with sodium hydrogen carbonate solution, water and saturated brine, dried with magnesium sulfate and concentrated under reduced pressure, and the residue was purified with silica gel column chromatography (EtOAc/hexane) to give colorless crystals of 2-methyl-7-(2-methylphenyl)-5,6,7,8-tetrahydroquinolin-5-one (0.88 g). The reaction solution was stirred at room temperature for 1.5 hours refluxed for 27 hours Under reduced pressure, the solvent was evaporated the residue was dissolved in ethyl acetate The solution was washed with sodium hydrogen carbonate solution, water and saturated brine dried with magnesium sulfate concentrated under reduced pressure the residue was purified with silica gel column chromatography (EtOAc/hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5-(2-methylphenyl)cyclohexane-1,3-dione (1.0 g) and ammonium acetate (0.42 g) in ethanol (20 ml) was stirred at room temperature for 15 minutes. To the mixture was added 3-butyn-2-one (0.54 g), and the mixture was refluxed for 16 hours. Under reduced pressure, the solvent was evaporated, and the residue was dissolved in ethyl acetate. The solution was washed with sodium hydrogen carbonate solution, water and saturated brine, dried with magnesium sulfate and concentrated under reduced pressure, and the residue was purified with silica gel column chromatography (EtOAc/hexane) to give colorless crystals of 2,4-dimethyl-7-(2-methylphenyl)-5,6,7,8-tetrahydroquinolin-5-one (0.50 g). the mixture was refluxed for 16 hours Under reduced pressure, the solvent was evaporated the residue was dissolved in ethyl acetate The solution was washed with sodium hydrogen carbonate solution, water and saturated brine dried with magnesium sulfate concentrated under reduced pressure the residue was purified with silica gel column chromatography (EtOAc/hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 5-(2-methylphenyl)cyclohexane-1,3-dione (1.5 g), 1-amino-2-butyne hydrochloride (0.86 g), molecular sieves 4A (2 g) and tetrahydrofuran (20 ml) was added triethylamine (0.74 g), and the mixture was stirred at room temperature for 1 hour and then refluxed for 17 hours and cooled. Insoluble materials were filtered off. Under reduced pressure, the solvent was evaporated, and the residue was stirred at 220° C. for 4 hours, to which were added ethyl acetate and sodium hydrogen carbonate solution. The organic layer was washed with water and saturated brine, dried with magnesium sulfate and concentrated under reduced pressure, and the residue was purified with silica gel column chromatography (EtOAc/hexane). The resulting crystals were recrystallized from ethyl acetate-hexane to give colorless crystals of 4-methyl-7-(2-methylphenyl)-5,6,7,8-tetrahydroquinolin-5-one (0.52 g). refluxed for 17 hours cooled Insoluble materials were filtered off Under reduced pressure, the solvent was evaporated the residue was stirred at 220° C. for 4 hours, to which were added ethyl acetate and sodium hydrogen carbonate solution The organic layer was washed with water and saturated brine dried with magnesium sulfate concentrated under reduced pressure the residue was purified with silica gel column chromatography (EtOAc/hexane) The resulting crystals were recrystallized from ethyl acetate-hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5-(2-methylphenyl)cyclohexane-1,3-dione (2.0 g), 1-bromo-3,3,3-trifluoroacetone (1.9 g), potassium carbonate (2.7 g) and dimethylformamide (30 ml) was stirred at room temperature for 2 hours, and then at 150° C. for 12 hours. Under reduced pressure, the solvent was evaporated, and to the residue was added ethyl acetate. The mixture was washed with water and saturated brine, dried with magnesium sulfate and concentrated under reduced pressure, and the residue was purified with silica gel column chromatography (EtOAc/hexane). The resulting crystals were recrystallized from isopropylether and hexane to give colorless crystals of 3-trifluoromethyl-6-(2-methylphenyl)-4,5,6,7-tetrahydrobenzofuran-4-one (0.26 g). at 150° C. for 12 hours Under reduced pressure, the solvent was evaporated to the residue was added ethyl acetate The mixture was washed with water and saturated brine dried with magnesium sulfate concentrated under reduced pressure the residue was purified with silica gel column chromatography (EtOAc/hexane) The resulting crystals were recrystallized from isopropylether and hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 60% sodium hydride (0.21 g, washed with hexane thrice) was added ethanol (30 ml), and to the mixture was added 5-(2-methylphenyl)cyclohexane-1,3-dione (1.0 g) and then was added chloroacetone (0.45 g) at 0° C. The mixture was stirred at room temperature for 20 minutes and was refluxed for 24 hours. Under reduced pressure, the solvent was evaporated, and the residue was dissolved in ethyl acetate. The solution was washed with water and saturated brine, dried with magnesium sulfate and concentrated under reduced pressure, and the residue was purified with silica gel column chromatography (EtOAc/hexane) to give oil of 3-methyl-6-(2-methylphenyl)-4,5,6,7-tetrahydrobenzofuran-4-one (0.18 g). was refluxed for 24 hours Under reduced pressure, the solvent was evaporated the residue was dissolved in ethyl acetate The solution was washed with water and saturated brine dried with magnesium sulfate concentrated under reduced pressure the residue was purified with silica gel column chromatography (EtOAc/hexane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 5-(2-methylphenyl)cyclohexane-1,3-dione (1.0 g), acetic acid (0.27 g) and dimethylaminopyridine (0.60 g) in dimethylformamide (45 ml) was added dicyclohexylcarbodiimide (1.0 g), and the mixture was stirred at room temperature for 12 hours. Under reduced pressure, the solvent was evaporated, and to the residue was added ethyl acetate. The organic layer was washed with potassium hydrogensulfate aqueous solution, and insoluble materials were filtered, to which was added 1N sodium hydroxide solution. The aqueous layer was neutralized with 1N hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried with magnesium sulfate and concentrated under reduced pressure to give, the residue was recrystallized from ethyl acetate-hexane to give colorless crystals of 2-(1-hydroxyethylidene)-5-(2-methylphenyl)cyclohexane-1,3-dione (0.69 g). Under reduced pressure, the solvent was evaporated to the residue was added ethyl acetate The organic layer was washed with potassium hydrogensulfate aqueous solution, and insoluble materials were filtered, to which was added 1N sodium hydroxide solution extracted with ethyl acetate The organic layer was washed with water and saturated brine dried with magnesium sulfate concentrated under reduced pressure to give the residue was recrystallized from ethyl acetate-hexane