2-oxocycloheptane-1-carbaldehyde

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

Procedure: In an argon atmosphere, sodium hydride (60%; 55.2 g, 1.38 mol) was suspended in ether (2 L), and ethanol (2.5 mL) was added thereto at room temperature. Then, a liquid mixture of cycloheptanone (141 g, 1.26 mol) and ethyl formate (152 mL, 1.84 mol) was added dropwise to the mixture over 2 hours, and the resulting mixture was stirred at the same temperature for 20 hours. Ethanol (25 mL) was added to the reaction solution, subsequently water (1.2 L) was added, and the mixture was separated. The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide, and then the aqueous layers were combined and washed with ether. 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling to adjust the aqueous layer to pH 3 to 4, and then the mixture was extracted twice with ether, washed with saturated solution of sodium chloride, and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and thus the title compound (174 g, 99%) was obtained as a pale orange oil. at room temperature was added dropwise to the mixture over 2 hours was added the mixture was separated The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide washed with ether 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling the mixture was extracted twice with ether washed with saturated solution of sodium chloride dried over anhydrous sodium sulfate The solvent was evaporated under reduced pressure

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

Procedure: In an argon atmosphere, sodium hydride (60%; 55.2 g, 1.38 mol) was suspended in ether (2 L), and ethanol (2.5 mL) was added thereto at room temperature. Then, a liquid mixture of cycloheptanone (141 g, 1.26 mol) and ethyl formate (152 mL, 1.84 mol) was added dropwise to the mixture over 2 hours, and the resulting mixture was stirred at the same temperature for 20 hours. Ethanol (25 mL) was added to the reaction solution, subsequently water (1.2 L) was added, and the mixture was separated. The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide, and then the aqueous layers were combined and washed with ether. 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling to adjust the aqueous layer to pH 3 to 4, and then the mixture was extracted twice with ether, washed with saturated solution of sodium chloride, and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and thus the title compound (174 g, 99%) was obtained as a pale orange oil. at room temperature was added dropwise to the mixture over 2 hours was added the mixture was separated The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide washed with ether 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling the mixture was extracted twice with ether washed with saturated solution of sodium chloride dried over anhydrous sodium sulfate The solvent was evaporated under reduced pressure

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

Procedure: In an argon atmosphere, sodium hydride (60%; 55.2 g, 1.38 mol) was suspended in ether (2 L), and ethanol (2.5 mL) was added thereto at room temperature. Then, a liquid mixture of cycloheptanone (141 g, 1.26 mol) and ethyl formate (152 mL, 1.84 mol) was added dropwise to the mixture over 2 hours, and the resulting mixture was stirred at the same temperature for 20 hours. Ethanol (25 mL) was added to the reaction solution, subsequently water (1.2 L) was added, and the mixture was separated. The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide, and then the aqueous layers were combined and washed with ether. 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling to adjust the aqueous layer to pH 3 to 4, and then the mixture was extracted twice with ether, washed with saturated solution of sodium chloride, and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and thus the title compound (174 g, 99%) was obtained as a pale orange oil. at room temperature was added dropwise to the mixture over 2 hours was added the mixture was separated The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide washed with ether 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling the mixture was extracted twice with ether washed with saturated solution of sodium chloride dried over anhydrous sodium sulfate The solvent was evaporated under reduced pressure

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

Procedure: 2-Formylcycloheptanone (1.70 g, 12.1 mmol) and ethyl 3-aminocrotonate (1.58 g, 12.1 mmol) were stirred at 100° C. for 15 hours. After cooling, the reaction solution was purified by a silica gel column chromatography (ether/hexane=1:3) to obtain the title compound (1.35 g, 46.1%) as pale yellow powder. After cooling the reaction solution was purified by a silica gel column chromatography (ether/hexane=1:3)

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

Procedure: In an argon atmosphere, sodium hydride (60%; 55.2 g, 1.38 mol) was suspended in ether (2 L), and ethanol (2.5 mL) was added thereto at room temperature. Then, a liquid mixture of cycloheptanone (141 g, 1.26 mol) and ethyl formate (152 mL, 1.84 mol) was added dropwise to the mixture over 2 hours, and the resulting mixture was stirred at the same temperature for 20 hours. Ethanol (25 mL) was added to the reaction solution, subsequently water (1.2 L) was added, and the mixture was separated. The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide, and then the aqueous layers were combined and washed with ether. 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling to adjust the aqueous layer to pH 3 to 4, and then the mixture was extracted twice with ether, washed with saturated solution of sodium chloride, and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and thus the title compound (174 g, 99%) was obtained as a pale orange oil. at room temperature was added dropwise to the mixture over 2 hours was added the mixture was separated The resultant was extracted with a 10% (w/v) aqueous solution of sodium hydroxide washed with ether 15% (v/v) hydrochloric acid was added to the aqueous layer under ice cooling the mixture was extracted twice with ether washed with saturated solution of sodium chloride dried over anhydrous sodium sulfate The solvent was evaporated under reduced pressure