2,6,6-三甲基环己-2-烯-1-one

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: 15.4 g of 1,3,3-trimethyl-7-oxabicyclo-[4.1.0]heptan-2-one, 1.8 g of triphenylphosphine and 2.76 g of 1,2-bis-(diphenylphosphino)-ethane were placed under argon gasification in a round flask equipped with a thermometer and a reflux condenser and the mixture was treated with 2.0 g of bis-(dibenzylidene acetone)palladium(O). The reaction vessel was then immersed in an oil-bath preheated to 150° C. and the reaction mixture was stirred at this temperature with a magnetic stirrer for 1 hour under continued argon gasification. A gas-chromatographical analysis of the mixture obtained without an internal standard gave peaks for 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one (81.9 area %) and 2,6,6-trimethyl-2-cyclohexen-1-one (18 area %). For the working-up, the reaction mixture, cooled to room temperature, was taken up in 20 ml of ethyl acetate and filtered over silica gel in a sintered glass suction filter. The content of the suction filter was rinsed three times with 150 ml of ethyl acetate each time. The filtrate was evaporated to constant weight in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. The residue (21.5 g of a yellowish oil) was dissolved in 100 ml of diethyl ether and the solution was added to a separating funnel S1. Two further separating funnels S2 and S3 were each charged with 100 ml of diethyl ether. Then, three 150 ml portions of 3N sodium hydroxide solution were passed in succession and with good intermixing through the three extraction vessels S1 -S3. The ether phases were discarded. The combined alkaline extracts were acidified cautiously (pH about 1) with about 300 ml of concentrated hydrochloric acid while cooling with ice and then saturated with 500 g of sodium chloride while stirring. Three separating funnels S4 -S6 were each charged with 200 ml of ethyl acetate. Thereafter, the aqueous product solution and subsequently three 150 ml portions of saturated sodium chloride solution were passed in succession and with good intermixing through the three extraction vessels S4 -S6. The combined organic phases were dried over sodium sulphate. The drying agent was filtered off under suction and rinsed on the suction filter twice with 100 ml of ethyl acetate each time. The filtrate was evaporated in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. and the residue was dried in a high vacuum. There were obtained 10.1 g (65.6%) of 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one in the form of colourless crystals with a purity of 99.6%: m.p. 112°-114° C. after recrystallization from diisopropyl ether. equipped with a thermometer and a reflux condenser The reaction vessel was then immersed in an oil-bath preheated to 150° C. A gas-chromatographical analysis of the mixture obtained without an internal

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

实验步骤: Prepared under the conditions described in a., starting from 25.0 g (181 mmol) of 2,6,6-trimethyl-2-cyclohexen-1-one, 31.9 g (253 mmol) of (CH3)2SO4, 17.0 g (274 mmol) of (CH3)2S and 43.0 g (1086 mmol) of NaOH in 60 ml of DMSO. 22.09 G of the desired product, 91% pure, were obtained. Prepared under the conditions

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

实验步骤: Prepared under the conditions described in a., starting from 25.0 g (181 mmol) of 2,6,6-trimethyl-2-cyclohexen-1-one, 31.9 g (253 mmol) of (CH3)2SO4, 17.0 g (274 mmol) of (CH3)2S and 43.0 g (1086 mmol) of NaOH in 60 ml of DMSO. 22.09 G of the desired product, 91% pure, were obtained. Prepared under the conditions

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

实验步骤: 15.4 g of 1,3,3-trimethyl-7-oxabicyclo-[4.1.0]heptan-2-one, 1.8 g of triphenylphosphine and 2.76 g of 1,2-bis-(diphenylphosphino)-ethane were placed under argon gasification in a round flask equipped with a thermometer and a reflux condenser and the mixture was treated with 2.0 g of bis-(dibenzylidene acetone)palladium(O). The reaction vessel was then immersed in an oil-bath preheated to 150° C. and the reaction mixture was stirred at this temperature with a magnetic stirrer for 1 hour under continued argon gasification. A gas-chromatographical analysis of the mixture obtained without an internal standard gave peaks for 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one (81.9 area %) and 2,6,6-trimethyl-2-cyclohexen-1-one (18 area %). For the working-up, the reaction mixture, cooled to room temperature, was taken up in 20 ml of ethyl acetate and filtered over silica gel in a sintered glass suction filter. The content of the suction filter was rinsed three times with 150 ml of ethyl acetate each time. The filtrate was evaporated to constant weight in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. The residue (21.5 g of a yellowish oil) was dissolved in 100 ml of diethyl ether and the solution was added to a separating funnel S1. Two further separating funnels S2 and S3 were each charged with 100 ml of diethyl ether. Then, three 150 ml portions of 3N sodium hydroxide solution were passed in succession and with good intermixing through the three extraction vessels S1 -S3. The ether phases were discarded. The combined alkaline extracts were acidified cautiously (pH about 1) with about 300 ml of concentrated hydrochloric acid while cooling with ice and then saturated with 500 g of sodium chloride while stirring. Three separating funnels S4 -S6 were each charged with 200 ml of ethyl acetate. Thereafter, the aqueous product solution and subsequently three 150 ml portions of saturated sodium chloride solution were passed in succession and with good intermixing through the three extraction vessels S4 -S6. The combined organic phases were dried over sodium sulphate. The drying agent was filtered off under suction and rinsed on the suction filter twice with 100 ml of ethyl acetate each time. The filtrate was evaporated in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. and the residue was dried in a high vacuum. There were obtained 10.1 g (65.6%) of 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one in the form of colourless crystals with a purity of 99.6%: m.p. 112°-114° C. after recrystallization from diisopropyl ether. equipped with a thermometer and a reflux condenser The reaction vessel was then immersed in an oil-bath preheated to 150° C. A gas-chromatographical analysis of the mixture obtained without an internal

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

实验步骤: 15.4 g of 1,3,3-trimethyl-7-oxabicyclo-[4.1.0]heptan-2-one, 1.8 g of triphenylphosphine and 2.76 g of 1,2-bis-(diphenylphosphino)-ethane were placed under argon gasification in a round flask equipped with a thermometer and a reflux condenser and the mixture was treated with 2.0 g of bis-(dibenzylidene acetone)palladium(O). The reaction vessel was then immersed in an oil-bath preheated to 150° C. and the reaction mixture was stirred at this temperature with a magnetic stirrer for 1 hour under continued argon gasification. A gas-chromatographical analysis of the mixture obtained without an internal standard gave peaks for 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one (81.9 area %) and 2,6,6-trimethyl-2-cyclohexen-1-one (18 area %). For the working-up, the reaction mixture, cooled to room temperature, was taken up in 20 ml of ethyl acetate and filtered over silica gel in a sintered glass suction filter. The content of the suction filter was rinsed three times with 150 ml of ethyl acetate each time. The filtrate was evaporated to constant weight in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. The residue (21.5 g of a yellowish oil) was dissolved in 100 ml of diethyl ether and the solution was added to a separating funnel S1. Two further separating funnels S2 and S3 were each charged with 100 ml of diethyl ether. Then, three 150 ml portions of 3N sodium hydroxide solution were passed in succession and with good intermixing through the three extraction vessels S1 -S3. The ether phases were discarded. The combined alkaline extracts were acidified cautiously (pH about 1) with about 300 ml of concentrated hydrochloric acid while cooling with ice and then saturated with 500 g of sodium chloride while stirring. Three separating funnels S4 -S6 were each charged with 200 ml of ethyl acetate. Thereafter, the aqueous product solution and subsequently three 150 ml portions of saturated sodium chloride solution were passed in succession and with good intermixing through the three extraction vessels S4 -S6. The combined organic phases were dried over sodium sulphate. The drying agent was filtered off under suction and rinsed on the suction filter twice with 100 ml of ethyl acetate each time. The filtrate was evaporated in a rotary evaporator under a water-jet vacuum at a bath temperature of 40° C. and the residue was dried in a high vacuum. There were obtained 10.1 g (65.6%) of 3-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one in the form of colourless crystals with a purity of 99.6%: m.p. 112°-114° C. after recrystallization from diisopropyl ether. equipped with a thermometer and a reflux condenser The reaction vessel was then immersed in an oil-bath preheated to 150° C. A gas-chromatographical analysis of the mixture obtained without an internal

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: 150 g of 2,6,6-trimethyl-cyclohex-2-en-1-one and 15 g of aluminium isopropylate were heated at 160° under argon atmosphere until obtention of a clear solution, in a reaction vessel fitted with a fractioning device. The clear mixture was then progressively heated to 190° and kept at this temperature for 60 hours, under vigorous stirring, the formed 2,6,6-trimethyl-cyclohex-3-en-1-one being directly distilled from the reaction mixture. During this period, a further amount of 300 g of starting ketone was added to the reaction mixture. 285 g of a distillate containing 40% of the desired product and 60% of unreacted starting material were thus obtained. After further distillation of the above 285 g there were finally isolated 105 g of the desired ketone having b.p. 62°/15 Torr (yield: 92%-conversion rate of 25%). fitted with a fractioning device The clear mixture was then progressively heated to 190° the formed 2,6,6-trimethyl-cyclohex-3-en-1-one being directly distilled from the reaction mixture During this period a further amount of 300 g of starting ketone was added to the reaction mixture 285 g of a distillate containing 40% of the desired product and 60% were thus obtained After further distillation of the above 285 g

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

实验步骤: 150 g of 2,6,6-trimethyl-cyclohex-2-en-1-one and 15 g of aluminium isopropylate were heated at 160° under argon atmosphere until obtention of a clear solution, in a reaction vessel fitted with a fractioning device. The clear mixture was then progressively heated to 190° and kept at this temperature for 60 hours, under vigorous stirring, the formed 2,6,6-trimethyl-cyclohex-3-en-1-one being directly distilled from the reaction mixture. During this period, a further amount of 300 g of starting ketone was added to the reaction mixture. 285 g of a distillate containing 40% of the desired product and 60% of unreacted starting material were thus obtained. After further distillation of the above 285 g there were finally isolated 105 g of the desired ketone having b.p. 62°/15 Torr (yield: 92%-conversion rate of 25%). fitted with a fractioning device The clear mixture was then progressively heated to 190° the formed 2,6,6-trimethyl-cyclohex-3-en-1-one being directly distilled from the reaction mixture During this period a further amount of 300 g of starting ketone was added to the reaction mixture 285 g of a distillate containing 40% of the desired product and 60% were thus obtained After further distillation of the above 285 g

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

实验步骤: 30 g of acrolein (boiling point about 105° C) are added dropwise in the course of 60 minutes to 150 g of ethyl isopropyl ketone and 2 g of p-toluenesulfonic acid, under reflux. The water formed is removed. After 3 hours, the unconverted starting materials are distilled off through a short column under atmospheric pressure at from 40° to 112° C. The reaction mixture ist then kept for 1 hour at an internal temperature of 200° C and is thereafter distilled under reduced pressure. 7 g of water, 3 g of acrolein, 122 g of ethyl isopropyl ketone, 22 g of 2,6,6-trimethyl-cyclohex-2-en-1-one (free from isomers) and 28 g of residue are obtained. This amounts to a yield of 57%, based on ethyl isopropyl ketone employed. under reflux is removed the unconverted starting materials are distilled off through a short column under atmospheric pressure at from 40° to 112° C The reaction mixture ist then kept for 1 hour at an internal temperature of 200° C is thereafter distilled under reduced pressure

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

实验步骤: 150 g of 2,6,6-trimethyl-cyclohex-2-en-1-one and 15 g of aluminium isopropylate were heated at 160° under argon atmosphere until obtention of a clear solution, in a reaction vessel fitted with a fractioning device. The clear mixture was then progressively heated to 190° and kept at this temperature for 60 hours, under vigorous stirring, the formed 2,6,6-trimethyl-cyclohex-3-en-1-one being directly distilled from the reaction mixture. During this period, a further amount of 300 g of starting ketone was added to the reaction mixture. 285 g of a distillate containing 40% of the desired product and 60% of unreacted starting material were thus obtained. After further distillation of the above 285 g there were finally isolated 105 g of the desired ketone having b.p. 62°/15 Torr (yield: 92%--conversion rate of 25%). fitted with a fractioning device The clear mixture was then progressively heated to 190° the formed 2,6,6-trimethyl-cyclohex-3-en-1-one being directly distilled from the reaction mixture During this period a further amount of 300 g of starting ketone was added to the reaction mixture 285 g of a distillate containing 40% of the desired product and 60% were thus obtained After further distillation of the above 285 g

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

实验步骤: Prepared under the conditions described in a., starting from 25.0 g (181 mmol) of 2,6,6-trimethyl-2-cyclohexen-1-one, 31.9 g (253 mmol) of (CH3)2SO4, 17.0 g (274 mmol) of (CH3)2S and 43.0 g (1086 mmol) of NaOH in 60 ml of DMSO. 22.09 G of the desired product, 91% pure, were obtained. Prepared under the conditions