1-cyclohexylethanol

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: Into a two-liter, round bottom, three-necked flask equipped with a condenser, a mechanical stirrer, thermometer and a liquid addition funnel were placed 900 ml. of water, 200 g. (0.67 mole) of technical grade sodium dichromate followed by 176 g. (1.8 mole) of concentrated sulfuric acid. The contents were cooled to 55°-60° C. and 120 g. (0.94 mole) of 1-hydroxyethylcyclohexane was added over a period of 1 hour, holding the temperature between 55°-50° C. by means of external cooling. After the alcohol had been added, the reaction mixture was allowed to stir for an additional 30 minutes and then 600 ml. of water was added and the contents heated to remove the ketone by steam distillation. When no more ketone was being steam distilled, the heat was removed, the distillate of water and ketone separated and the upper organic layer was distilled under vacuum collecting the fraction boiling at 115°-116° C. There was obtained 76 g. of ketone representing a 64% yield. Into a two-liter, round bottom, three-necked flask equipped with a condenser, a mechanical stirrer thermometer and a liquid addition funnel The contents were cooled to 55°-60° C. between 55°-50° C. the contents heated to remove the ketone by steam distillation distilled the heat was removed the distillate of water and ketone separated the upper organic layer was distilled under vacuum collecting the fraction boiling at 115°-116° C There was obtained 76 g

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

実験手順: Into a two-liter, round bottom, three-necked flask equipped with a condenser, a mechanical stirrer, thermometer and a liquid addition funnel were placed 900 ml. of water, 200 g. (0.67 mole) of technical grade sodium dichromate followed by 176 g. (1.8 mole) of concentrated sulfuric acid. The contents were cooled to 55°-60° C. and 120 g. (0.94 mole) of 1-hydroxyethylcyclohexane was added over a period of 1 hour, holding the temperature between 55°-50° C. by means of external cooling. After the alcohol had been added, the reaction mixture was allowed to stir for an additional 30 minutes and then 600 ml. of water was added and the contents heated to remove the ketone by steam distillation. When no more ketone was being steam distilled, the heat was removed, the distillate of water and ketone separated and the upper organic layer was distilled under vacuum collecting the fraction boiling at 115°-116° C. There was obtained 76 g. of ketone representing a 64% yield. Into a two-liter, round bottom, three-necked flask equipped with a condenser, a mechanical stirrer thermometer and a liquid addition funnel The contents were cooled to 55°-60° C. between 55°-50° C. the contents heated to remove the ketone by steam distillation distilled the heat was removed the distillate of water and ketone separated the upper organic layer was distilled under vacuum collecting the fraction boiling at 115°-116° C There was obtained 76 g

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A three liter, three necked round bottom flask was equipped with a thermometer, magnetic stirrer, argon inlet and outlet adapters and a one liter addition funnel containing 922 ml of 1.0 molar BH3.THF. 1-Methyl cyclohexanecarboxylic acid (119.2 g; 0.84 m) was added to the reaction vessel and dissolved in 100 ml of THF. The reaction mixture was cooled with an ice bath to 5° C. and the BH3.THF was added dropwise over 25 min maintaining the temperature between 5°-15° C. After the addition was complete, the ice bath was removed. After about five min, the reaction exothermed and foamed violently. A much slower addition rate and constant cooling should help to avoid this exotherm. The reaction was allowed to stir for two hr at RT under nitrogen, then 150 ml of methanol was added cautiously. When the foaming ceased, the reaction was concentrated in vacuo using low heat and the residue was treated with 100 ml of 5% acetic acid. After stirring for thirty min, the reaction was transferred to a one liter separatory funnel, diluted with water (slurry dissolved) and extracted three times with ether. The combined ether extracts were washed twice with saturated sodium bicarbonate, twice with brine, dried over anhydrous magnesium sulfate, filtered through celite and concentrated in vacuo (low heat) to give 79.09 g of a clear water-white oil. The oil was distilled on a Kugelrohr apparatus at 75°-130° C. (25 mm of Hg). Most distilled at 90° C. to give 72.11 g of 1-methyl-1-cyclohexylmethanol. A three liter, three necked round bottom flask was equipped with a thermometer, magnetic stirrer, argon inlet and outlet adapters and a one liter addition funnel maintaining the temperature between 5°-15° C After the addition the ice bath was removed A much slower addition rate constant cooling should 150 ml of methanol was added cautiously the reaction was concentrated in vacuo using low heat the residue was treated with 100 ml of 5% acetic acid After stirring for thirty min the reaction was transferred to a one liter separatory funnel diluted with water (slurry dissolved) extracted three times with ether The combined ether extracts were washed twice with saturated sodium bicarbonate, twice with brine dried over anhydrous magnesium sulfate filtered through celite and concentrated in vacuo (low heat) to give 79.09 g of a clear water-white oil The oil was distilled on a Kugelrohr apparatus at 75°-130° C. (25 mm of Hg) Most distilled at 90° C.

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

実験手順: 1-cyclohexylethan-1-yl acetate; 1-cyclohexylethan-1-ol;

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

実験手順: 1-cyclohexylethan-1-yl acetate; 1-cyclohexylethan-1-ol;

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A two liter three necked round bottom flask was equipped with a mechanical stirrer, condenser, thermometer, two neck adapter, drying tube and a nitrogen inlet. 1-Methyl-1-cyclohexylmethanol (71.2 g; 0.555 mole) (the compound of Example 7a) was added to the reaction vessel followed by 100 ml of xylene and 43.4 ml (0.555 mole) of epichlorohydrin. The reaction was heated to 50° C. while stirring under nitrogen. 1.45 g (0.0056 mole) of SnCl4 was added. The reaction exothermed suddenly to 140° C. and slowly cooled to 50° C. The reaction was kept at 50° C. in a water bath for 1.5 hr, then cooled to 5°C. with an ice bath. Cold 20% sodium hydroxide (prepared from 40 g of 50% NaOH) was added followed by 47.4 g (0.666 mole) of pyrrolidine. The ice bath was removed, the reaction was heated to reflux for one hr, cooled to RT, diluted with about one liter of water and extracted twice with ether. The combined ether extracts were washed with water, brine, dried over anhydrous potassium carbonate, filtered through dicalite and concentrated in vacuo to give 143.39 g of crude product a light yellow viscous oil. The crude oil was distilled twice to yield 7.6 g (55%) of the title compound, bp 139°-154° C. (0.025 mm). thermometer, two neck adapter, drying tube and a nitrogen inlet exothermed suddenly to 140° C. slowly cooled to 50° C cooled to 5°C. with an ice bath The ice bath was removed the reaction was heated to reflux for one hr cooled to RT diluted with about one liter of water extracted twice with ether The combined ether extracts were washed with water, brine dried over anhydrous potassium carbonate filtered through dicalite concentrated in vacuo to give 143.39 g of crude product a light yellow viscous oil The crude oil was distilled twice

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A two liter three necked round bottom flask was equipped with a mechanical stirrer, condenser, thermometer, two neck adapter, drying tube and a nitrogen inlet. 1-Methyl-1-cyclohexylmethanol (71.2 g; 0.555 mole) (the compound of Example 7a) was added to the reaction vessel followed by 100 ml of xylene and 43.4 ml (0.555 mole) of epichlorohydrin. The reaction was heated to 50° C. while stirring under nitrogen. 1.45 g (0.0056 mole) of SnCl4 was added. The reaction exothermed suddenly to 140° C. and slowly cooled to 50° C. The reaction was kept at 50° C. in a water bath for 1.5 hr, then cooled to 5°C. with an ice bath. Cold 20% sodium hydroxide (prepared from 40 g of 50% NaOH) was added followed by 47.4 g (0.666 mole) of pyrrolidine. The ice bath was removed, the reaction was heated to reflux for one hr, cooled to RT, diluted with about one liter of water and extracted twice with ether. The combined ether extracts were washed with water, brine, dried over anhydrous potassium carbonate, filtered through dicalite and concentrated in vacuo to give 143.39 g of crude product a light yellow viscous oil. The crude oil was distilled twice to yield 7.6 g (55%) of the title compound, bp 139°-154° C. (0.025 mm). thermometer, two neck adapter, drying tube and a nitrogen inlet exothermed suddenly to 140° C. slowly cooled to 50° C cooled to 5°C. with an ice bath The ice bath was removed the reaction was heated to reflux for one hr cooled to RT diluted with about one liter of water extracted twice with ether The combined ether extracts were washed with water, brine dried over anhydrous potassium carbonate filtered through dicalite concentrated in vacuo to give 143.39 g of crude product a light yellow viscous oil The crude oil was distilled twice

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

実験手順: A three liter three necked round bottom flask was equipped with a thermometer, magnetic stirrer, argon inlet and outlet adapters and a one liter addition funnel containing 922 ml of 1.0 molar BH3 ·THF. 1-Methyl cyclohexanecarboxylic acid (119.2 g; 0.84 mole) was added to the reaction vessel and dissolved in 100 ml of THF. The reaction mixture was cooled with an ice bath to 5° C. the BH3 ·THF was added dropwise over 25 min maintaining the temperature between 5°-15° C. After the addition was complete, the ice bath was removed. After about 5 min, the reaction exothermed and foamed violently. A much slower addition rate and constant cooling should help to avoid this exotherm. The reaction was allowed to stir for 2 hr at room temperature under nitrogen, then 150 ml of methanol was added cautiously. When the foaming ceased, the reaction was concentrated in vacuo using low heat and the residue was treated with 100 ml of 5% acetic acid. After stirring for 30 min, the reaction was transferred to a one liter separatory funnel, diluted with water (slurry dissolved) and extracted three times with ether. The combined ether extracts were washed twice with saturated sodium bicarbonate, twice with brine, dried over anhydrous magnesium sulfate, filtered through celite and concentrated in vacuo (low heat) to give 79.09 g of a clear water-white oil. The oil was distilled on a Kugelrohr apparatus at 75°-130° C. (25 mm of Hg). Most distilled at 90° C. to give 72.11 g of 1-methyl-1-cyclohexylmethanol. was added dropwise over 25 min maintaining the temperature between 5°-15° C After the addition the ice bath was removed A much slower addition rate constant cooling should 150 ml of methanol was added cautiously the reaction was concentrated in vacuo using low heat the residue was treated with 100 ml of 5% acetic acid After stirring for 30 min the reaction was transferred to a one liter separatory funnel diluted with water (slurry dissolved) extracted three times with ether The combined ether extracts were washed twice with saturated sodium bicarbonate, twice with brine dried over anhydrous magnesium sulfate filtered through celite and concentrated in vacuo (low heat) to give 79.09 g of a clear water-white oil The oil was distilled on a Kugelrohr apparatus at 75°-130° C. (25 mm of Hg) Most distilled at 90° C.