(3-oxocyclohexen-1-yl) acetate

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

実験手順: 3-Hydroxy-cyclohex-2-enone (1.08 g, 9.64 mmol) was combined with methylene chloride (10 mL) in a 250 mL flask and acetic acid (1.4 eq, 13.75 mmol, 0.78 mL) was added to the mixture. The mixture was cooled in an ice bath and dicyclohexylcarbodiimide (1.3 eq, 12 mmol, 2.5 g) was added portionwise, followed by the addition of 4-(dimethylamino)pyridine (0.05 eq, 0.45 mmol, 50 mg). A sufficient amount of methylene chloride was added to ensure easy stirring and the reaction was monitored by TLC (silica gel, hexane-ethyl acetate-methylene chloride-acetone (3:3:3:1 v/v)), HPLC and LCMS and the intermediate acetic acid 3-oxo-cyclohex-1-enyl ester was formed. The mixture was stirred overnight at room temperature and then toluene (20 mL) was added. The mixture heated to 60° C. and after 72 hours the mixture was filtered, concentrated and purified by flash column chromatography to provide 2-acetyl-3-hydroxy-cyclohex-2-enone (1.19 g, 80%) as a colorless liquid. LCMS: MH+ 154.8. The mixture was cooled in an ice bath

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

実験手順: 3-Hydroxy-cyclohex-2-enone (1.08 g, 9.64 mmol) was combined with methylene chloride (10 mL) in a 250 mL flask and acetic acid (1.4 eq, 13.75 mmol, 0.78 mL) was added to the mixture. The mixture was cooled in an ice bath and dicyclohexylcarbodiimide (1.3 eq, 12 mmol, 2.5 g) was added portionwise, followed by the addition of 4-(dimethylamino)pyridine (0.05 eq, 0.45 mmol, 50 mg). A sufficient amount of methylene chloride was added to ensure easy stirring and the reaction was monitored by TLC (silica gel, hexane-ethyl acetate-methylene chloride-acetone (3:3:3:1 v/v)), HPLC and LCMS and the intermediate acetic acid 3-oxo-cyclohex-1-enyl ester was formed. The mixture was stirred overnight at room temperature and then toluene (20 mL) was added. The mixture heated to 60° C. and after 72 hours the mixture was filtered, concentrated and purified by flash column chromatography to provide 2-acetyl-3-hydroxy-cyclohex-2-enone (1.19 g, 80%) as a colorless liquid. LCMS: MH+ 154.8. The mixture was cooled in an ice bath

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

実験手順: According to Scheme 4 Step 2: AlCl3 (26.5 mmol, 3.53 g) was added to a solution of 3-oxocyclohex-1-enyl acetate (13.2 mmol, 2.04 g) in dichloroethane (10 mL) and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was poured onto a solution of H2SO4 in ice. The aqueous phase was extracted with CHCl3 (50 mL). The organic phase was washed with water, dried over Na2SO4, was filtered and was concentrated to yield 2-acetylcyclohexane-1,3-dione (7.78 mmol, 1.20 g, 59%) as a yellow oil. The aqueous phase was extracted with CHCl3 (50 mL) The organic phase was washed with water dried over Na2SO4 was filtered was concentrated

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

実験手順: According to Scheme 4 Step 2: AlCl3 (26.5 mmol, 3.53 g) was added to a solution of 3-oxocyclohex-1-enyl acetate (13.2 mmol, 2.04 g) in dichloroethane (10 mL) and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was poured onto a solution of H2SO4 in ice. The aqueous phase was extracted with CHCl3 (50 mL). The organic phase was washed with water, dried over Na2SO4, was filtered and was concentrated to yield 2-acetylcyclohexane-1,3-dione (7.78 mmol, 1.20 g, 59%) as a yellow oil. The aqueous phase was extracted with CHCl3 (50 mL) The organic phase was washed with water dried over Na2SO4 was filtered was concentrated

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

実験手順: According to Scheme 4 Step 1: Acetyl chloride (19.6 mmol, 1.39 mL) was added to a solution of cyclohexane-1,3-dione (17.8 mmol, 2.00 g) and pyridine (17.8 mmol, 1.28 mL) in CHCl3 (60 mL) and the reaction mixture was stirred at room temperature for 2 hours. The reaction was quenched with the addition of water and the organic phase was washed with a solution of HCl (0.1 M, 30 mL), a saturated solution of NaHCO3 (30 mL) and water (30 mL). The organic phase was dried over Na2SO4 and concentrated to yield 3-oxocyclohex-1-enyl acetate (13.2 mmol, 2.04 g, 74%) as a yellow oil. The reaction was quenched with the addition of water the organic phase was washed with a solution of HCl (0.1 M, 30 mL) The organic phase was dried over Na2SO4 concentrated

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

実験手順: According to Scheme 4 Step 1: Acetyl chloride (19.6 mmol, 1.39 mL) was added to a solution of cyclohexane-1,3-dione (17.8 mmol, 2.00 g) and pyridine (17.8 mmol, 1.28 mL) in CHCl3 (60 mL) and the reaction mixture was stirred at room temperature for 2 hours. The reaction was quenched with the addition of water and the organic phase was washed with a solution of HCl (0.1 M, 30 mL), a saturated solution of NaHCO3 (30 mL) and water (30 mL). The organic phase was dried over Na2SO4 and concentrated to yield 3-oxocyclohex-1-enyl acetate (13.2 mmol, 2.04 g, 74%) as a yellow oil. The reaction was quenched with the addition of water the organic phase was washed with a solution of HCl (0.1 M, 30 mL) The organic phase was dried over Na2SO4 concentrated