methyl cyclohexanecarboxylate

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:

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: Prepared according to the method for the preparation of 4-iodomethyltetrahydropyran-4-carboxylic acid methyl ester, from cyclohexane-carboxylic acid methyl ester (10 ml), to give the title compound as a brown gum (20 g, 100%). Prepared

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under anhydrous conditions and a nitrogen atmoshere a solution of 8.7 g (0.086 mole) diisopropylamine in 250 ml tetrahydrofuran was cooled to -78° C. and 1.6M n-butyllithium (53.75 ml, 0.086 mole) was added dropwise over ten minutes. The mixture was stirred for 45 minutes, allowed to warm to 0° C. and 12.2 g (0.086 mole) methyl cyclohexancarboxylate was added. Stirring was continued for 45 minutes and then 20 g (0.086 mole) 2-benzyloxybenzyl chloride in 20 ml tetrahydrofuran was added dropwise. The resulting mixture was stirred at room temperature for 24 hours, quenched by addition of 150 ml 3M acetic acid and stirred at room temperature for one week. The mixture was diluted with ethyl ether, washed with sodium bicarbonate solution, brine, dried (MgSO4) and concentrated to a yellow oil, 29.3 g. This was distilled to obtain 20.23 g (70%) of viscous oil, b.p. 135°-140° C. (0.4 Torr). to warm to 0° C. Stirring was continued for 45 minutes The resulting mixture was stirred at room temperature for 24 hours quenched by addition of 150 ml 3M acetic acid stirred at room temperature for one week The mixture was diluted with ethyl ether washed with sodium bicarbonate solution, brine dried (MgSO4) concentrated to a yellow oil, 29.3 g This was distilled

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under anhydrous conditions and a nitrogen atmoshere a solution of 8.7 g (0.086 mole) diisopropylamine in 250 ml tetrahydrofuran was cooled to -78° C. and 1.6M n-butyllithium (53.75 ml, 0.086 mole) was added dropwise over ten minutes. The mixture was stirred for 45 minutes, allowed to warm to 0° C. and 12.2 g (0.086 mole) methyl cyclohexancarboxylate was added. Stirring was continued for 45 minutes and then 20 g (0.086 mole) 2-benzyloxybenzyl chloride in 20 ml tetrahydrofuran was added dropwise. The resulting mixture was stirred at room temperature for 24 hours, quenched by addition of 150 ml 3M acetic acid and stirred at room temperature for one week. The mixture was diluted with ethyl ether, washed with sodium bicarbonate solution, brine, dried (MgSO4) and concentrated to a yellow oil, 29.3 g. This was distilled to obtain 20.23 g (70%) of viscous oil, b.p. 135°-140° C. (0.4 Torr). to warm to 0° C. Stirring was continued for 45 minutes The resulting mixture was stirred at room temperature for 24 hours quenched by addition of 150 ml 3M acetic acid stirred at room temperature for one week The mixture was diluted with ethyl ether washed with sodium bicarbonate solution, brine dried (MgSO4) concentrated to a yellow oil, 29.3 g This was distilled

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

実験手順: 28 Grams of methyl cyclohexylcarboxylate and 15 g of 85%-NH2NH2.H2O were dissolved in 50 ml of isopropyl alcohol, and the solution was refluxed by heating for 10 hours. The reaction mixture was concentrated, and the crystals precipitated by adding water were collected by filtration, then the crystals were washed with water, then recrystallized from water to yield 20 g of cyclohexanecarbohydrazide in the form of colorless needle-like crystals. the solution was refluxed by heating for 10 hours The reaction mixture was concentrated the crystals precipitated by adding water were collected by filtration the crystals were washed with water recrystallized from water

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of diisopropylamine (879 μL, 6.22 mmol) in anhydrous tetrahydrofuran (12 mL) at −40° C. under nitrogen was added 1.6 M n-butyl lithium in hexane (3.9 mL, 6.22 mmol), followed by hexamethylphosphoramide (4 mL). The mixture was cooled down to −78° C. and added a solution of methyl cyclohexanecarboxylate (80 7 μL, 5.65 mmol) tetrahydrofuran (4 mL) with the temperature maintained below −70° C. throughout the addition. After 15 min, propargyl bromide (80% w/w in xylene, 2.5 mL, 22.6 mmol) was added, and the reaction mixture was allowed to warm to room temperature. After 30 min, it was quenched with saturated ammonium chloride, and extracted with ethyl acetate. The organic phase was washed with water (×4), dried over MgSO4, filtered and concentrated to get 900 mg the title intermediate as a pale brown oil. maintained below −70° C. throughout the addition to warm to room temperature After 30 min it was quenched with saturated ammonium chloride extracted with ethyl acetate The organic phase was washed with water (×4) dried over MgSO4 filtered concentrated

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

実験手順: To a solution of diisopropylamine (10 mL, 72 mmol) in tetrahydrofuran (100 mL) pre-cooled to −69° C. was added a 2.5 M solution of n-butyllithium in hexanes (29 mL, 72 mmol) dropwise. Following addition, the reaction mixture was warmed to 0° C. for 30 min and then re-cooled to −70° C. To the mixture was added a solution of methyl cyclohexane carboxylate (8.9 mL, 60 mmol) in tetrahydrofuran (30 mL) dropwise. After stirring for 30 min, a solution of allyl iodide (7.2 mL, 78 mmol) in HMPA (5 mL) was added dropwise. The cooling bath was removed to allow the mixture to warm to 20° C. After 1.5 h, the reaction mixture was poured into H2O (200 mL). The two layers were separated and the aqueous layer was extracted with Et2O (100 mL). The organic solutions were combined and dried over K2CO3, filtered and concentrated to afford 11 g of the title compound as an oil. addition re-cooled to −70° C The cooling bath was removed to warm to 20° C After 1.5 h the reaction mixture was poured into H2O (200 mL) The two layers were separated the aqueous layer was extracted with Et2O (100 mL) dried over K2CO3 filtered concentrated

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

実験手順: To a solution of diisopropylamine (10 mL, 72 mmol) in tetrahydrofuran (100 mL) pre-cooled to −69° C. was added a 2.5 M solution of n-butyllithium in hexanes (29 mL, 72 mmol) dropwise. Following addition, the reaction mixture was warmed to 0° C. for 30 min and then re-cooled to −70° C. To the mixture was added a solution of methyl cyclohexane carboxylate (8.9 mL, 60 mmol) in tetrahydrofuran (30 mL) dropwise. After stirring for 30 min, a solution of allyl iodide (7.2 mL, 78 mmol) in HMPA (5 mL) was added dropwise. The cooling bath was removed to allow the mixture to warm to 20° C. After 1.5 h, the reaction mixture was poured into H2O (200 mL). The two layers were separated and the aqueous layer was extracted with Et2O (100 mL). The organic solutions were combined and dried over K2CO3, filtered and concentrated to afford 11 g of the title compound as an oil. addition re-cooled to −70° C The cooling bath was removed to warm to 20° C After 1.5 h the reaction mixture was poured into H2O (200 mL) The two layers were separated the aqueous layer was extracted with Et2O (100 mL) dried over K2CO3 filtered concentrated

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

実験手順: Prepared according to the method for the preparation of 4-iodomethyltetrahydropyran-4-carboxylic acid methyl ester, from cyclohexane-carboxylic acid methyl ester (10 ml), to give the title compound as a brown gum (20 g, 100%). Prepared