3-butylcyclohexan-1-one

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A THF (5 mL) suspension of CuBr.Me2S (26.3 mg, 0.128 mmol) was treated with 1.0 equiv of n-BuLi at -78° C. under an argon atmosphere. The mixture was allowed to warm up slightly with the formation of a bright yellow solid. The mixture was again cooled to -78° C. and treated with Li(CHIRAMT) formed from compound 4 (85.8 mg, 0.261 mmol) and n-BuLi (1.0 equiv). The yellow slurry was stirred with gradual warming until a homogeneous burgundy solution was obtained. In the case of R=Me, a homogeneous mixture was not obtained even after prolonged stirring at room temperature, and it was evident that unreacted (CuMe)n was still present. The solution was cooled to -78° C. and THF (8 mL each) solutions of n-BuMgCl (25.0 equiv) and cyclohexenone (0.3068 g, 3.19 mmol) were added dropwise and simultaneously over a 5 min period. The resulting reaction mixture was stirred for an additional 10 min at -78° C., quenched with saturated aqueous NH4Cl solution (7 mL), and worked up as described in the previous section. Pure 3-butylcyclohexanone (0.4617 g, 94%) was obtained as checked by glc. with gradual warming until a homogeneous burgundy solution was obtained In the case of R=Me, a homogeneous mixture was not obtained even after prolonged stirring at room temperature The resulting reaction mixture was stirred for an additional 10 min at -78° C. quenched with saturated aqueous NH4Cl solution (7 mL)

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A THF (5 mL) suspension of CuBr.Me2S (26.3 mg, 0.128 mmol) was treated with 1.0 equiv of n-BuLi at -78° C. under an argon atmosphere. The mixture was allowed to warm up slightly with the formation of a bright yellow solid. The mixture was again cooled to -78° C. and treated with Li(CHIRAMT) formed from compound 4 (85.8 mg, 0.261 mmol) and n-BuLi (1.0 equiv). The yellow slurry was stirred with gradual warming until a homogeneous burgundy solution was obtained. In the case of R=Me, a homogeneous mixture was not obtained even after prolonged stirring at room temperature, and it was evident that unreacted (CuMe)n was still present. The solution was cooled to -78° C. and THF (8 mL each) solutions of n-BuMgCl (25.0 equiv) and cyclohexenone (0.3068 g, 3.19 mmol) were added dropwise and simultaneously over a 5 min period. The resulting reaction mixture was stirred for an additional 10 min at - 78° C., quenched with saturated aqueous NH4Cl solution (7 mL), and worked up as described in the previous section. Pure 3-butylcyclohexanone (0.4617 g, 94%) was obtained as checked by glc. with gradual warming until a homogeneous burgundy solution was obtained In the case of R=Me, a homogeneous mixture was not obtained even after prolonged stirring at room temperature The resulting reaction mixture was stirred for an additional 10 min at - 78° C. quenched with saturated aqueous NH4Cl solution (7 mL)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 30 ml of anhydrous diethyl ether were added 3.8 g (20 mmol) of cuprous iodide and 4.0 g (20 mmol) of tri-n-butylphosphine, and the mixture was stirred for about 1 hour at room temperature in an atmosphere of nitrogen and then cooled to -78° C. Then, 25.6 ml (40 mmol) of a 15 % by weight hexane solution of n-butyllithium was added, and the mixture was stirred for 30 minutes, and 1.92 g (20 mmol) of 2-cyclohexenone was added. The mixture was further stirred for 1 hour at -78° C. Then, 5 ml of hexamethylphosphoric tiramide was added, and the mixture was stirred for about 10 minutes. Phthalic anhydride (2.96 g, 20 mmol) was further added, and the mixture was stirred for 3 hours at room temperature. After the reaction, a solution of 4 g (100 mmol) of sodium hydroxide in 50 ml of water was added, and the mixture was stirred for about 1 hour. It was extracted with ether, washed, and dried to afford 6.22 g of a crude product. The crude product was distilled to afford 1.62 g (10.5 mmol) of 3-n-butylcyclohexanone in a yield of 53%. cooled to -78° C the mixture was stirred for 30 minutes The mixture was further stirred for 1 hour at -78° C Then, 5 ml of hexamethylphosphoric tiramide was added the mixture was stirred for about 10 minutes the mixture was stirred for 3 hours at room temperature After the reaction the mixture was stirred for about 1 hour It was extracted with ether washed dried to afford 6.22 g of a crude product The crude product was distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 30 ml of anhydrous diethyl ether were added 3.8 g (20 mmol) of cuprous iodide and 4.0 g (20 mmol) of tri-n-butylphosphine, and the mixture was stirred for about 1 hour at room temperature in an atmosphere of nitrogen and then cooled to -78° C. Then, 25.6 ml (40 mmol) of a 15 % by weight hexane solution of n-butyllithium was added, and the mixture was stirred for 30 minutes, and 1.92 g (20 mmol) of 2-cyclohexenone was added. The mixture was further stirred for 1 hour at -78° C. Then, 5 ml of hexamethylphosphoric tiramide was added, and the mixture was stirred for about 10 minutes. Phthalic anhydride (2.96 g, 20 mmol) was further added, and the mixture was stirred for 3 hours at room temperature. After the reaction, a solution of 4 g (100 mmol) of sodium hydroxide in 50 ml of water was added, and the mixture was stirred for about 1 hour. It was extracted with ether, washed, and dried to afford 6.22 g of a crude product. The crude product was distilled to afford 1.62 g (10.5 mmol) of 3-n-butylcyclohexanone in a yield of 53%. cooled to -78° C the mixture was stirred for 30 minutes The mixture was further stirred for 1 hour at -78° C Then, 5 ml of hexamethylphosphoric tiramide was added the mixture was stirred for about 10 minutes the mixture was stirred for 3 hours at room temperature After the reaction the mixture was stirred for about 1 hour It was extracted with ether washed dried to afford 6.22 g of a crude product The crude product was distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 30 ml of anhydrous diethyl ether were added 1.5 g (10 mmol) of cuprous bromide and 2.5 g (20 mmol) of trimethyl phosphite, and the mixture stirred for about 1 hour at room temperature in an atmosphere of nitrogen. The mixture was cooled to -78° C, and 12.8 ml (20 mmol) of a 15 % by weight hexane solution of n-butyllithium was added, followed by further stirring the mixture for 30 minutes. Then, 960 mg (10 mmol) of 2-cycohexenone was added and reacted for 1 hour. After the reaction, 5 ml of tetramethylenediamine was added, and the mixture was stirred for about 10 minutes. The resulting solution was added dropwise at 0° C to a solution prepared by adding 2.84 g (20 mmol) of a boron trifluoride-diethyl ether complex and 2.04 g (20 mmol) of acetic anhydride to 20 ml of anhydrous diethyl ether, and stirring the mixture at 0° C for about 30 minutes in an atmosphere of nitrogen. Then, the mixture was stirred for an additional 3 hours at room temperature, and then, post-treated, extracted, washed with dilute hydrochloric acid, and dried in the same way as in Example 4 to afford 5.432 g of a crude product. The crude product was purified by distillation at reduced pressure to afford 370 mg (2.4 mmol) of 3-n-butylcyclohexanone in a yield of 24% and 170 mg (0.9 mmol) of 2-acetyl-3-n-butylcyclohexanone in a yield of 9%. The mixture was cooled to -78° C by further stirring the mixture for 30 minutes reacted for 1 hour was added the mixture was stirred for about 10 minutes The resulting solution was added dropwise at 0° C to a solution prepared stirring the mixture at 0° C for about 30 minutes in an atmosphere of nitrogen Then, the mixture was stirred for an additional 3 hours at room temperature post-treated extracted washed with dilute hydrochloric acid dried in the same way as in Example 4 to afford 5.432 g of a crude product The crude product was purified by distillation at reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In the same way as in Example 4, 12.8 ml (20 mmol) of a 15 % by weight hexane solution of n-butyllithium was reacted with 960 mg (10 mmol) of a solution of 960 mg (10 mmol) of 2-cyclohexenone in 10 ml of ether for one hour in the presence of 1.9 g (10 mmol) of cuprous iodide and 2.0 g (10 mmol) of tri-n-butylphosphone. Then, 5 ml of hexamethylphosphoric triamide was added, and the mixture stirred for about 10 minutes. Furthermore, a solution of 5.1 g (50 mmol) of acetic anhydride in 20 ml of ether was added, and the mixture was stirred for an additional 2.5 hours at room temperature. After the reaction, the reaction product was post-treated, extracted, washed, and dried in the same way as in Example 4 to afford 2.285 g of a crude product. The crude product was purified by column chromatography to afford 81 mg (0.5 mmol) of 3-n-butylcyclohexanone as a by-product in a yield of 5%, and 98 mg (0.5 mmol) of 2-acetyl-3-n-butylcyclohexanone as a product in a yield of 5%. the mixture was stirred for an additional 2.5 hours at room temperature After the reaction the reaction product was post-treated extracted washed dried in the same way as in Example 4 to afford 2.285 g of a crude product The crude product was purified by column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 20 ml of anhydrous diethyl ether was added 1.9 g (10 mmol) of cuprous iodide, and at -78° C in an atmosphere of nitrogen, 12.8 ml (20 mmol) of a 15 % by weight hexane solution of n-butyllithium was added. The mixture was stirred for 30 minutes, and then, 960 mg (10 mmol) of 2-cyclohexenone was added. The mixture was further stirred for one hour. Then, 3.93 g (50 mmol) of acetyl chloride was added, and the mixture was stirred for 2 hours at room temperature. After the reaction, the reaction product was post-treated, extracted, washed, and dried in the same way as in Example 4 to afford 2.662 g of a crude product. The crude product was purified by column chromatography (silica gel) to afford 56 mg (0.4 mmol) of 3-n-butylcyclohexanone as a by-product in a yield of 4% and 1.103 g (5.6 mmol) of 2-acetyl-3-n-butylcyclohexanone as a main product in a yield of 56%. The mixture was further stirred for one hour the mixture was stirred for 2 hours at room temperature After the reaction the reaction product was post-treated extracted washed dried in the same way as in Example 4 to afford 2.662 g of a crude product The crude product was purified by column chromatography (silica gel)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 20 ml of anhydrous diethyl ether was added 1.9 g (10 mmol) of cuprous iodide, and at -78° C in an atmosphere of nitrogen, 12.8 ml (20 mmol) of a 15 % by weight hexane solution of n-butyllithium was added. The mixture was stirred for 30 minutes, and then, 960 mg (10 mmol) of 2-cyclohexenone was added. The mixture was further stirred for one hour. Then, 3.93 g (50 mmol) of acetyl chloride was added, and the mixture was stirred for 2 hours at room temperature. After the reaction, the reaction product was post-treated, extracted, washed, and dried in the same way as in Example 4 to afford 2.662 g of a crude product. The crude product was purified by column chromatography (silica gel) to afford 56 mg (0.4 mmol) of 3-n-butylcyclohexanone as a by-product in a yield of 4% and 1.103 g (5.6 mmol) of 2-acetyl-3-n-butylcyclohexanone as a main product in a yield of 56%. The mixture was further stirred for one hour the mixture was stirred for 2 hours at room temperature After the reaction the reaction product was post-treated extracted washed dried in the same way as in Example 4 to afford 2.662 g of a crude product The crude product was purified by column chromatography (silica gel)

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A THF (5 mL) suspension of CuBr.Me2S (26.3 mg, 0.128 mmol) was treated with 1.0 equiv of n-BuLi at -78° C. under an argon atmosphere. The mixture was allowed to warm up slightly with the formation of a bright yellow solid. The mixture was again cooled to -78° C. and treated with Li(CHIRAMT) formed from compound 4 (85.8 mg, 0.261 mmol) and n-BuLi (1.0 equiv). The yellow slurry was stirred with gradual warming until a homogeneous burgundy solution was obtained. In the case of R=Me, a homogeneous mixture was not obtained even after prolonged stirring at room temperature, and it was evident that unreacted (CuMe)n was still present. The solution was cooled to -78° C. and THF (8 mL each) solutions of n-BuMgCl (25.0 equiv) and cyclohexenone (0.3068 g, 3.19 mmol) were added dropwise and simultaneously over a 5 min period. The resulting reaction mixture was stirred for an additional 10 min at -78° C., quenched with saturated aqueous NH4Cl solution (7 mL), and worked up as described in the previous section. Pure 3-butylcyclohexanone (0.4617 g, 94%) was obtained as checked by glc. with gradual warming until a homogeneous burgundy solution was obtained In the case of R=Me, a homogeneous mixture was not obtained even after prolonged stirring at room temperature The resulting reaction mixture was stirred for an additional 10 min at -78° C. quenched with saturated aqueous NH4Cl solution (7 mL)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The bromination of 3-butylcyclohexanone takes place in a manner similar to that described above for the preparation of 2-bromo-4-isopropyl-cyclohexanone. The title compound is reacted as a crude product without further characterization.

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of copper iodide (6.3 mmol) in dimethyl sulphide (12 ml) is cooled to 50° C. A solution of butyl lithium (6.2 mmol) is added dropwise accompanied by stirring and stirred for a further 5 to 15 mins. The reaction mixture is cooled to −78° C. and then a solution precooled to −78° C. of cyclohex-2-enone (6 mmol), dissolved in dimethyl sulphide (1 ml), is slowly added dropwise. After stirring for one hour at −78° C. the mixture is quenched with saturated aqueous ammonium chloride solution. The reaction mixture which has been heated to room temperature is extracted with diethyl ether. The combined ether phases are washed with saturated aqueous ammonium chloride solution and dried over sodium sulphate. After evaporating-off of the solvent the residue obtained is taken up in hexane, the solution is filtered and concentrated by evaporation. After chromatography of the residue on silica gel with ethyl acetate/hexane 1:4 pure 3-butylcyclohexanone is obtained (Tetrahedron 1989, 45 (2), 425-434). stirred for a further 5 to 15 mins is slowly added dropwise After stirring for one hour at −78° C. the mixture is quenched with saturated aqueous ammonium chloride solution The reaction mixture which has been heated to room temperature is extracted with diethyl ether The combined ether phases are washed with saturated aqueous ammonium chloride solution dried over sodium sulphate After evaporating-off of the solvent the residue obtained the solution is filtered concentrated by evaporation