2,5,5-trimethylcyclohexan-1-one

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A mixture of crude racemic 2,5,5-trimethyl-cyclohexanone (theoretically 31.7 mmol) and benzylamine (3.8 mL, 34.79 mmol) in 50 mL of toluene was stirred for 45 minutes at reflux with continuous removal of H2O. The reaction mixture was cooled to RT and evaporated. The residue was taken into 50 mL of DCM and sodium triacetoxyborohydride (8.1 g, 38.22 mmol) was added, followed by acetic acid (2 mL, 34.94 mmol). The resulting mixture was stirred at RT overnight before being diluted with DCM and washed with saturated aqueous NaHCO3. The aqueous layer was back extracted twice with DCM. The combined organic layers were dried (Na2SO4), filtered, and evaporated. The residue was purified (DCM/(DCM:MeOH:NH4OH 60:10:1] 90% DCM) to give 3.84 g of racemic benzyl-(2,5,5-trimethyl-cyclohexyl)-amine. NMR showed the presence of about 5% of the trans isomer. evaporated was added The resulting mixture was stirred at RT overnight washed with saturated aqueous NaHCO3 The aqueous layer was back extracted twice with DCM The combined organic layers were dried (Na2SO4) filtered evaporated The residue was purified (DCM/(DCM:MeOH:NH4OH 60:10:1] 90% DCM)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 g of magnesium shavings are suspended in 100 ml of absolute ether and treated dropwise with 13.5 ml of methyl iodide. After the addition of 100 ml of ether, the mixture is boiled at reflux for a further 3 hours until all magnesium has dissolved. The mixture is cooled to 0° C. and treated with 20.7 g of finely powdered copper (I) iodide. After stirring at 0° C. for 15 minutes, a solution of 10 g of 3,6,6-trimethyl-2-cyclohexanone in 40 ml of ether is added dropwise thereto and the mixture is stirred at 0° C. for a further 4 hours. Thereafter, the yellow suspension is poured into ice/2N hydrochloric acid, extracted several times with ether, the organic phase is dried and evaporated. The residue is distilled in a water-jet vacuum. There are obtained 9 g of 2,2,5,5-tetramethylcyclohexanone as a colorless liquid, b.p. 71°-74° C./15 mm. has dissolved the mixture is stirred at 0° C. for a further 4 hours extracted several times with ether the organic phase is dried evaporated The residue is distilled in a water-jet vacuum

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 g of magnesium shavings are suspended in 100 ml of absolute ether and treated dropwise with 13.5 ml of methyl iodide. After the addition of 100 ml of ether, the mixture is boiled at reflux for a further 3 hours until all magnesium has dissolved. The mixture is cooled to 0° C. and treated with 20.7 g of finely powdered copper (I) iodide. After stirring at 0° C. for 15 minutes, a solution of 10 g of 3,6,6-trimethyl-2-cyclohexanone in 40 ml of ether is added dropwise thereto and the mixture is stirred at 0° C. for a further 4 hours. Thereafter, the yellow suspension is poured into ice/2N hydrochloric acid, extracted several times with ether, the organic phase is dried and evaporated. The residue is distilled in a water-jet vacuum. There are obtained 9 g of 2,2,5,5-tetramethylcyclohexanone as a colorless liquid, b.p. 71°-74° C./15 mm. has dissolved the mixture is stirred at 0° C. for a further 4 hours extracted several times with ether the organic phase is dried evaporated The residue is distilled in a water-jet vacuum

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 g of magnesium shavings are suspended in 100 ml of absolute ether and treated dropwise with 13.5 ml of methyl iodide. After the addition of 100 ml of ether, the mixture is boiled at reflux for a further 3 hours until all magnesium has dissolved. The mixture is cooled to 0° C. and treated with 20.7 g of finely powdered copper (I) iodide. After stirring at 0° C. for 15 minutes, a solution of 10 g of 3,6,6-trimethyl-2-cyclohexanone in 40 ml of ether is added dropwise thereto and the mixture is stirred at 0° C. for a further 4 hours. Thereafter, the yellow suspension is poured into ice/2N hydrochloric acid, extracted several times with ether, the organic phase is dried and evaporated. The residue is distilled in a water-jet vacuum. There are obtained 9 g of 2,2,5,5-tetramethylcyclohexanone as a colorless liquid, b.p. 71°-74° C./15 mm. has dissolved the mixture is stirred at 0° C. for a further 4 hours extracted several times with ether the organic phase is dried evaporated The residue is distilled in a water-jet vacuum

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 g of magnesium shavings are suspended in 100 ml of absolute ether and treated dropwise with 13.5 ml of methyl iodide. After the addition of 100 ml of ether, the mixture is boiled at reflux for a further 3 hours until all magnesium has dissolved. The mixture is cooled to 0° C. and treated with 20.7 g of finely powdered copper (I) iodide. After stirring at 0° C. for 15 minutes, a solution of 10 g of 3,6,6-trimethyl-2-cyclohexanone in 40 ml of ether is added dropwise thereto and the mixture is stirred at 0° C. for a further 4 hours. Thereafter, the yellow suspension is poured into ice/2N hydrochloric acid, extracted several times with ether, the organic phase is dried and evaporated. The residue is distilled in a water-jet vacuum. There are obtained 9 g of 2,2,5,5-tetramethylcyclohexanone as a colorless liquid, b.p. 71°-74° C./15 mm. has dissolved the mixture is stirred at 0° C. for a further 4 hours extracted several times with ether the organic phase is dried evaporated The residue is distilled in a water-jet vacuum

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 g of magnesium shavings are suspended in 100 ml of absolute ether and treated dropwise with 13.5 ml of methyl iodide. After the addition of 100 ml of ether, the mixture is boiled at reflux for a further 3 hours until all magnesium has dissolved. The mixture is cooled to 0° C. and treated with 20.7 g of finely powdered copper (I) iodide. After stirring at 0° C. for 15 minutes, a solution of 10 g of 3,6,6-trimethyl-2-cyclohexanone in 40 ml of ether is added dropwise thereto and the mixture is stirred at 0° C. for a further 4 hours. Thereafter, the yellow suspension is poured into ice/2N hydrochloric acid, extracted several times with ether, the organic phase is dried and evaporated. The residue is distilled in a water-jet vacuum. There are obtained 9 g of 2,2,5,5-tetramethylcyclohexanone as a colorless liquid, b.p. 71°-74° C./15 mm. has dissolved the mixture is stirred at 0° C. for a further 4 hours extracted several times with ether the organic phase is dried evaporated The residue is distilled in a water-jet vacuum

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

実験手順: A mixture of crude racemic 2,5,5-trimethyl-cyclohexanone (theoretically 31.7 mmol) and benzylamine (3.8 mL, 34.79 mmol) in 50 mL of toluene was stirred for 45 minutes at reflux with continuous removal of H2O. The reaction mixture was cooled to RT and evaporated. The residue was taken into 50 mL of DCM and sodium triacetoxyborohydride (8.1 g, 38.22 mmol) was added, followed by acetic acid (2 mL, 34.94 mmol). The resulting mixture was stirred at RT overnight before being diluted with DCM and washed with saturated aqueous NaHCO3. The aqueous layer was back extracted twice with DCM. The combined organic layers were dried (Na2SO4), filtered, and evaporated. The residue was purified (DCM/(DCM:MeOH:NH4OH 60:10:1] 90% DCM) to give 3.84 g of racemic benzyl-(2,5,5-trimethyl-cyclohexyl)-amine. NMR showed the presence of about 5% of the trans isomer. evaporated was added The resulting mixture was stirred at RT overnight washed with saturated aqueous NaHCO3 The aqueous layer was back extracted twice with DCM The combined organic layers were dried (Na2SO4) filtered evaporated The residue was purified (DCM/(DCM:MeOH:NH4OH 60:10:1] 90% DCM)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 g of magnesium shavings are suspended in 100 ml of absolute ether and treated dropwise with 13.5 ml of methyl iodide. After the addition of 100 ml of ether, the mixture is boiled at reflux for a further 3 hours until all magnesium has dissolved. The mixture is cooled to 0° C. and treated with 20.7 g of finely powdered copper (I) iodide. After stirring at 0° C. for 15 minutes, a solution of 10 g of 3,6,6-trimethyl-2-cyclohexanone in 40 ml of ether is added dropwise thereto and the mixture is stirred at 0° C. for a further 4 hours. Thereafter, the yellow suspension is poured into ice/2N hydrochloric acid, extracted several times with ether, the organic phase is dried and evaporated. The residue is distilled in a water-jet vacuum. There are obtained 9 g of 2,2,5,5-tetramethylcyclohexanone as a colorless liquid, b.p. 71°-74° C./15 mm. has dissolved the mixture is stirred at 0° C. for a further 4 hours extracted several times with ether the organic phase is dried evaporated The residue is distilled in a water-jet vacuum

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 g of magnesium shavings are suspended in 100 ml of absolute ether and treated dropwise with 13.5 ml of methyl iodide. After the addition of 100 ml of ether, the mixture is boiled at reflux for a further 3 hours until all magnesium has dissolved. The mixture is cooled to 0° C. and treated with 20.7 g of finely powdered copper (I) iodide. After stirring at 0° C. for 15 minutes, a solution of 10 g of 3,6,6-trimethyl-2-cyclohexanone in 40 ml of ether is added dropwise thereto and the mixture is stirred at 0° C. for a further 4 hours. Thereafter, the yellow suspension is poured into ice/2N hydrochloric acid, extracted several times with ether, the organic phase is dried and evaporated. The residue is distilled in a water-jet vacuum. There are obtained 9 g of 2,2,5,5-tetramethylcyclohexanone as a colorless liquid, b.p. 71°-74° C./15 mm. has dissolved the mixture is stirred at 0° C. for a further 4 hours extracted several times with ether the organic phase is dried evaporated The residue is distilled in a water-jet vacuum