2,6-dimethylcyclohexan-1-one

反応条件: temp:0.00; pressure:0.00; stir:

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: 5 g of 2,6-dimethylcyclohexanone and 5.51 g of hydroxylamine hydrochloride were suspended to 80 ml of ethanol, then 9.4 g of pyridine was dropped at 0° C. The mixture was stirred at room temperature for 4 hours, then the reaction mixture was concentrated. Water was added to the residue and extracted with ethyl acetate three times. The organic layers were joined, washed with saturated aqueous solution of sodium chloride, dried with anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3.1 g of cis-2,6-dimethylcyclohexanoneoxime and 1.3 g of trans-2,6-dimethylcyclohexanoneoxime. the reaction mixture was concentrated Water was added to the residue extracted with ethyl acetate three times washed with saturated aqueous solution of sodium chloride dried with anhydrous magnesium sulfate concentrated

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: Into 80 ml of ethanol were suspended 5 g of 2,6-dimethylcyclohexanone and 5.51 g of hydroxylamine hydrochloride, 9.4 g of pyridine was added dropwise at 0° C., and the mixture was stirred for 4 hours at room temperature. The reaction mixture was concentrated, water was added to the residue, the mixture was extracted with ethyl acetate three times. The organic layers were washed with a saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to obtain 3.1 g of cis-2,6-dimethyl cyclohexanone oxime and 1.3 g of trans-2,6-dimethylcyclohexanone oxime. was added dropwise at 0° C. The reaction mixture was concentrated water was added to the residue the mixture was extracted with ethyl acetate three times The organic layers were washed with a saturated sodium chloride aqueous solution dried over anhydrous magnesium sulfate concentrated

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

実験手順: Into 80 ml of ethanol were suspended 5 g of 2,6-dimethylcyclohexanone and 5.51 g of hydroxylamine hydrochloride, 9.4 g of pyridine was added dropwise at 0° C., and the mixture was stirred for 4 hours at room temperature. The reaction mixture was concentrated, water was added to the residue, the mixture was extracted with ethyl acetate three times. The organic layers were washed with a saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to obtain 3.1 g of cis-2,6-dimethyl cyclohexanone oxime and 1.3 g of trans-2,6-dimethylcyclohexanone oxime. was added dropwise at 0° C. The reaction mixture was concentrated water was added to the residue the mixture was extracted with ethyl acetate three times The organic layers were washed with a saturated sodium chloride aqueous solution dried over anhydrous magnesium sulfate concentrated

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 1 l of a solution of 25 g of 2,6-dimethylcyclohexanone in acetic acid were added 13.5 g of methylamine hydrochloride and 32.4 g of formalin (37% aqueous solution) and the resulting mixture was heated to 100° C. for 2 hours. After removing the solvent under reduced pressure, the obtained residue was distributed between ethyl acetate and an aqueous solution of potassium carbonate. The organic layer was extracted and dried over anhydrous sodium sulfate. Then the residue was purified by silica gel column chromatography (eluting with ethyl acetate/n-hexane) to thereby give 19 g of the title compound as a colorless oily substance. After removing the solvent under reduced pressure The organic layer was extracted dried over anhydrous sodium sulfate Then the residue was purified by silica gel column chromatography (eluting with ethyl acetate/n-hexane)

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

実験手順: Into 80 ml of ethanol were suspended 5 g of 2,6-dimethylcyclohexanone and 5.51 g of hydroxylamine hydrochloride, 9.4 g of pyridine was added dropwise at 0° C., and the mixture was stirred for 4 hours at room temperature. The reaction mixture was concentrated, water was added to the residue, the mixture was extracted with ethyl acetate three times. The organic layers were washed with a saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to obtain 3.1 g of cis-2,6-dimethyl cyclohexanone oxime and 1.3 g of trans-2,6-dimethylcyclohexanone oxime. was added dropwise at 0° C. The reaction mixture was concentrated water was added to the residue the mixture was extracted with ethyl acetate three times The organic layers were washed with a saturated sodium chloride aqueous solution dried over anhydrous magnesium sulfate concentrated

反応条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of potassium permanganate (195.7 g, 1.24 mol) in water (1390 ml) was added carefully to a mixture of 2,6-dimethylcyclohexanone (120.0 g, 0.95 mol) and water (600 ml) while stirring vigorously the mixture at 30° C. or lower over a period of about 1 hour, and the mixture was stirred at room temperature overnight. The produced manganese dioxide was filtrated, and the filtration cake was washed with methyl tert-butyl ether (250 ml) and water (250 ml). The organic layer of the filtrate was separated, and the aqueous layer was adjusted to pH 1.0 with 35% concentrated hydrochloric acid (about 150 ml), and sodium chloride (400 g) was added and the mixture was extracted with ethyl acetate (300 ml×5), and the organic layer was dried over anhydrous magnesium sulfate, then, the solvent was distilled off under reduced pressure, and the resultant residual oil was distilled under reduced pressure by a vacuum pump. Fractions of boiling points of 130 to 144° C./267 Pa were collected, to obtain 79.92 g (yield 53.2%) of a racemate of 2-methyl-6-oxoheptanoic acid. the mixture was stirred at room temperature overnight The produced manganese dioxide was filtrated the filtration cake was washed with methyl tert-butyl ether (250 ml) and water (250 ml) The organic layer of the filtrate was separated was added the mixture was extracted with ethyl acetate (300 ml×5) the organic layer was dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure the resultant residual oil was distilled under reduced pressure by a vacuum pump Fractions of boiling points of 130 to 144° C./267 Pa were collected

反応条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of potassium permanganate (195.7 g, 1.24 mol) in water (1390 ml) was added carefully to a mixture of 2,6-dimethylcyclohexanone (120.0 g, 0.95 mol) and water (600 ml) while stirring vigorously the mixture at 30° C. or lower over a period of about 1 hour, and the mixture was stirred at room temperature overnight. The produced manganese dioxide was filtrated, and the filtration cake was washed with methyl tert-butyl ether (250 ml) and water (250 ml). The organic layer of the filtrate was separated, and the aqueous layer was adjusted to pH 1.0 with 35% concentrated hydrochloric acid (about 150 ml), and sodium chloride (400 g) was added and the mixture was extracted with ethyl acetate (300 ml×5), and the organic layer was dried over anhydrous magnesium sulfate, then, the solvent was distilled off under reduced pressure, and the resultant residual oil was distilled under reduced pressure by a vacuum pump. Fractions of boiling points of 130 to 144° C./267 Pa were collected, to obtain 79.92 g (yield 53.2%) of a racemate of 2-methyl-6-oxoheptanoic acid. the mixture was stirred at room temperature overnight The produced manganese dioxide was filtrated the filtration cake was washed with methyl tert-butyl ether (250 ml) and water (250 ml) The organic layer of the filtrate was separated was added the mixture was extracted with ethyl acetate (300 ml×5) the organic layer was dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure the resultant residual oil was distilled under reduced pressure by a vacuum pump Fractions of boiling points of 130 to 144° C./267 Pa were collected

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Dimethyl-cyclohexanone (1 kg, 4 mol), trimethyl orthoformate (TMOF, 880 g), and methanol (800 mL) were charged to a 5 L reaction flask. HCl was added quickly. Reaction exothermed and the temperature increased from 14° C. to 20° C. The reaction mixture was heated to 60° C. and aged for 7 hours. When the reaction was about 75% complete, the reaction mixture was quenched with NaOCH3 (25%, 25 g), heated to 90° C., and applied to a Dean-Stark trap. The reaction mixture was then cooled to room temperature followed by sequential addition of methallyl alcohol (1.25 Kg, 8.5 moles), HOAc (50 g), and methane sulfonic acid (MSA, 10 g). The resulting mixture was heated to 110° C., applied to a Bidwell-Sterling trap, and aged for 4 hours until gas chromatograph analysis indicated that the reaction was 95% completed. The reaction mixture was then cooled and washed with saturated sodium carbonate solution (3 L) to provide the crude product 2,6-dimethyl-2-(2-methyl-allyl)-cyclohexanone. Reaction the temperature increased from 14° C. to 20° C the reaction mixture was quenched with NaOCH3 (25%, 25 g) heated to 90° C. The reaction mixture was then cooled to room temperature The resulting mixture was heated to 110° C. The reaction mixture was then cooled washed with saturated sodium carbonate solution (3 L)

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

実験手順: Example 3 was repeated, replacing (-)-menthol by 2,6-dimethylcyclohexanol (6.4 g; 50 mmol), using 5.1 cm3 (60 mmol) of 40% of H2O2, adding 4 g of anhydrous MgSO4 and reducing the reaction time to 30 minutes. 5.61 g (44.5 mmol) of 2,6-dimethyl-cyclohexanone were obtained (GLC purity>99%), which corresponds to a 89% yield. to 30 minutes