2-acetyl-4-methylcyclohexan-1-one

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

実験手順: 40% Boron trifluoride-acetic acid complex, 24 g, was chilled with ice and a mixture of 5.6 g of 4-methylcyclohexanone and acetic anhydride was dropwise added to the complex. After stirring at room temperature for 4 hours, approximately 50 ml of saturated sodium acetate aqueous solution was added to the mixture followed by heating to reflux for 1 hour. After cooling, the reaction mixture was extracted with ether and the extract was washed with a sodium bicarbonate aqueous solution and then water. Thereafter, the system was dried and ether was removed by distillation. The obtained 2-acetyl-4-methylcyclohexanone was used in the whole amount at the following step in a crude state thereof. 40% Boron trifluoride-acetic acid complex, 24 g, was chilled with ice was dropwise added to the complex by heating to reflux for 1 hour After cooling the reaction mixture was extracted with ether the extract was washed with a sodium bicarbonate aqueous solution Thereafter, the system was dried ether was removed by distillation

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

実験手順: The crude product of the step (1) above, 2-acetyl-4-methylcyclohexanone, was dissolved in 35 ml of ethanol. To the resultant solution, there were added 3.36 g of cyanoacetamide and a small amount of piperidine, and the mixture was heated under reflux for 4 hours. Deposited crystals were filtered out and recrystallized from a mixed solvent of methanol and water. There was obtained 4.22 g of 4-cyano-2,3,5,6,7,8-hexahydro-1,7-dimethyl-3-oxoisoquinoline. under reflux for 4 hours Deposited crystals were filtered out recrystallized from a mixed solvent of methanol and water

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

実験手順: To 24 g of 40% boron trifluoride acetate complex cooled on ice, a mixture of 5.6 g of 4-methylcyclohexanone and 10.5 g of acetic anhydride was dropwise added. The resultant mixture was then stirred at room temperature for 4 hours. To the mixture there was added 50 ml of a saturated aqueous solution of sodium acetate, and then the mixture was heated under reflux for one hour. After cooling, the reaction mixture was extracted with ether to obtain 2-acetyl-4-methylcyclohexanone, which was directly used in the following step without further purifying. To 24 g of 40% boron trifluoride acetate complex cooled on ice was dropwise added the mixture was heated under reflux for one hour After cooling the reaction mixture was extracted with ether

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

実験手順: To 24 g of 40% boron trifluoride acetate complex cooled on ice, a mixture of 5.6 g of 4-methylcyclohexanone and 10.5 g of acetic anhydride was dropwise added. The resultant mixture was then stirred at room temperature for 4 hours. To the mixture there was added 50 ml of a saturated aqueous solution of sodium acetate, and then the mixture was heated under reflux for one hour. After cooling, the reaction mixture was extracted with ether to obtain 2-acetyl-4-methylcyclohexanone, which was directly used in the following step without further purifying. To 24 g of 40% boron trifluoride acetate complex cooled on ice was dropwise added the mixture was heated under reflux for one hour After cooling the reaction mixture was extracted with ether

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

実験手順: To the total amount of the crude 2-acetyl-4methylcyclohexanone prepared in (1), 35 ml of ethanol, 3.36 g of cyanoacetamide and a small amount of piperidine were added and the obtained reaction mixture was heated under reflux for four hours. The crystals thus precipitated were filtered and recrystallized from a mixture of methanol and water to give 4.22 g of 4-cyano-1,7-dimethyl-2,3,5,6,7,8hexahydro-3-oxoisoquinoline. m.p. >290° C. NMRδTMSCF3COOH : 1.23 (3H, d), 2.60 (3H, s) and 1.8-3.3 (7H,m). the obtained reaction mixture was heated under reflux for four hours The crystals thus precipitated were filtered recrystallized from a mixture of methanol and water

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

実験手順: 24 g of 40% boron trifluoride/acetic acid complex was cooled with ice and a mixture of 5.6 g of 4-methylcyclohexanone and acetic anhydride was added dropwise thereto. After stirring at room temperature for four hours, approximately 50 ml of a saturated aqueous solution of sodium acetate was added thereto and the obtained reaction mixture was heated under reflux for one hour. After cooling, the reaction mixture was extracted with ether, washed with an aqueous solution of sodium hydrogencarbonate and water and dried, and ether was distilled off. The total amount of the crude 2-acetyl-4-methylcyclohexanone thus obtained was subjected to the subsequent step as such. 24 g of 40% boron trifluoride/acetic acid complex was cooled with ice was added dropwise the obtained reaction mixture was heated under reflux for one hour After cooling the reaction mixture was extracted with ether washed with an aqueous solution of sodium hydrogencarbonate and water dried ether was distilled off

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

実験手順: 24 g of 40% boron trifluoride/acetic acid complex was cooled with ice and a mixture of 5.6 g of 4-methylcyclohexanone and acetic anhydride was added dropwise thereto. After stirring at room temperature for four hours, approximately 50 ml of a saturated aqueous solution of sodium acetate was added thereto and the obtained reaction mixture was heated under reflux for one hour. After cooling, the reaction mixture was extracted with ether, washed with an aqueous solution of sodium hydrogencarbonate and water and dried, and ether was distilled off. The total amount of the crude 2-acetyl-4-methylcyclohexanone thus obtained was subjected to the subsequent step as such. 24 g of 40% boron trifluoride/acetic acid complex was cooled with ice was added dropwise the obtained reaction mixture was heated under reflux for one hour After cooling the reaction mixture was extracted with ether washed with an aqueous solution of sodium hydrogencarbonate and water dried ether was distilled off

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

実験手順: 40% Boron trifluoride-acetic acid complex, 24 g, was chilled with ice and a mixture of 5.6 g of 4-methylcyclohexanone and acetic anhydride was dropwise added to the complex. After stirring at room temperature for 4 hours, approximately 50 ml of saturated sodium acetate aqueous solution was added to the mixture followed by heating to reflux for 1 hour. After cooling, the reaction mixture was extracted with ether and the extract was washed with a sodium bicarbonate aqueous solution and then water. Thereafter, the system was dried and ether was removed by distillation. The obtained 2-acetyl-4-methylcyclohexanone was used in the whole amount at the following step in a crude state thereof. 40% Boron trifluoride-acetic acid complex, 24 g, was chilled with ice was dropwise added to the complex by heating to reflux for 1 hour After cooling the reaction mixture was extracted with ether the extract was washed with a sodium bicarbonate aqueous solution Thereafter, the system was dried ether was removed by distillation

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

実験手順: The crude product of the step (1) above, 2-acetyl-4-methylcyclohexanone, was dissolved in 35 ml of ethanol. To the resultant solution, there were added 3.36 g of cyanoacetamide and a small amount of piperidine, and the mixture was heated under reflux for 4 hours. Deposited crystals were filtered out and recrystallized from a mixed solvent of methanol and water. There was obtained 4.22 g of 4-cyano-2,3,5,6,7,8-hexahydro-1,7-dimethyl-3-oxoisoquinoline. under reflux for 4 hours Deposited crystals were filtered out recrystallized from a mixed solvent of methanol and water

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

実験手順: To 24 g of 40% boron trifluoride acetate complex cooled on ice, a mixture of 5.6 g of 4-methylcyclohexanone and 10.5 g of acetic anhydride was dropwise added. The resultant mixture was then stirred at room temperature for 4 hours. To the mixture there was added 50 ml of a saturated aqueous solution of sodium acetate, and then the mixture was heated under reflux for one hour. After cooling, the reaction mixture was extracted with ether to obtain 2-acetyl-4-methylcyclohexanone, which was directly used in the following step without further purifying. To 24 g of 40% boron trifluoride acetate complex cooled on ice was dropwise added the mixture was heated under reflux for one hour After cooling the reaction mixture was extracted with ether

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

実験手順: To the total amount of the crude 2-acetyl-4methylcyclohexanone prepared in (1), 35 ml of ethanol, 3.36 g of cyanoacetamide and a small amount of piperidine were added and the obtained reaction mixture was heated under reflux for four hours. The crystals thus precipitated were filtered and recrystallized from a mixture of methanol and water to give 4.22 g of 4-cyano-1,7-dimethyl-2,3,5,6,7,8hexahydro-3-oxoisoquinoline. m.p. >290° C. NMRδTMSCF3COOH : 1.23 (3H, d), 2.60 (3H, s) and 1.8-3.3 (7H,m). the obtained reaction mixture was heated under reflux for four hours The crystals thus precipitated were filtered recrystallized from a mixture of methanol and water

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

実験手順: 24 g of 40% boron trifluoride/acetic acid complex was cooled with ice and a mixture of 5.6 g of 4-methylcyclohexanone and acetic anhydride was added dropwise thereto. After stirring at room temperature for four hours, approximately 50 ml of a saturated aqueous solution of sodium acetate was added thereto and the obtained reaction mixture was heated under reflux for one hour. After cooling, the reaction mixture was extracted with ether, washed with an aqueous solution of sodium hydrogencarbonate and water and dried, and ether was distilled off. The total amount of the crude 2-acetyl-4-methylcyclohexanone thus obtained was subjected to the subsequent step as such. 24 g of 40% boron trifluoride/acetic acid complex was cooled with ice was added dropwise the obtained reaction mixture was heated under reflux for one hour After cooling the reaction mixture was extracted with ether washed with an aqueous solution of sodium hydrogencarbonate and water dried ether was distilled off