4-OXO-CYCLOHEXANECARBOXALDEHYDE

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Suspension of 114 g of 4-n-propylbenzyltriphenyl phosphonium bromide in 500 ml of THF was stirred under nitrogen gas stream and 32.3 g of potassium-t-butoxide was added thereto at room temperature. After stirred at room temperature for 1 hour, a solution of 31.2 g of 4-formylcyclohexanone in 200 ml of THF was added dropwise to the suspension. After stirred at room temperature for 2 hours, 1 l of water was added thereto and then it was extracted with 1 l of ethyl acetate. Organic layer was washed with water and dried over anhydrous magnesium sulfate, the solvent was distilled off under a reduced pressure, and then 500 ml of heptane was added thereto. Precipitate thus separated was filtered off and purified by a column chromatography over a silica gel by using ethyl acetate/heptane (1/5) as an eluent, and the solvent was distilled off under a reduced pressure to obtain 42 g of 4-(2-(4-n-propylphenyl)ethenyl)cyclohexanone. was added at room temperature After stirred at room temperature for 2 hours it was extracted with 1 l of ethyl acetate Organic layer was washed with water dried over anhydrous magnesium sulfate the solvent was distilled off under a reduced pressure 500 ml of heptane was added Precipitate thus separated was filtered off purified by a column chromatography over a silica gel the solvent was distilled off under a reduced pressure

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 63.3 g of p-cyanobenzyl-triphenylphosphonium chloride, 17.2 g of potassium t-butylate and 195 ml of ethylene glycol dimethyl ether were placed in a sulphonation flask while stirring and gassing with nitrogen, whereby the internal temperature rose to 44° C. The brown suspension was cooled to 0° C. and treated within 2 minutes with a solution of 16.7 g of 4-formylcyclohexanone in 100 ml of ethylene glycol dimethyl ether. Thereafter, the cooling bath was removed and the reaction mixture was stirred for a further 3.5 hours at room temperature. The suspension was subsequently poured into 500 ml of water and extracted three times with 600 ml of methylene chloride each time. The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium chloride solution each time, dried over sodium sulphate, filtered and concentrated, whereby 76.9 g of a brownish paste remained behind. Chromatographic separation of this crude product on silica gel with methylene chloride as the eluent gave 33.0 g of 4-[ 2-(p-cyanophenyl)vinyl]cyclohexanone as a yellow-brownish oil. rose to 44° C Thereafter, the cooling bath was removed the reaction mixture was stirred for a further 3.5 hours at room temperature The suspension was subsequently poured into 500 ml of water extracted three times with 600 ml of methylene chloride each time The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium chloride solution each time dried over sodium sulphate filtered concentrated Chromatographic separation of this crude product on silica gel with methylene chloride as the eluent

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 63.3 g of p-cyanobenzyl-triphenylphosphonium chloride, 17.2 g of potassium t-butylate and 195 ml of ethylene glycol dimethyl ether were placed in a sulphonation flask while stirring and gassing with nitrogen, whereby the internal temperature rose to 44° C. The brown suspension was cooled to 0° C. and treated within 2 minutes with a solution of 16.7 g of 4-formylcyclohexanone in 100 ml of ethylene glycol dimethyl ether. Thereafter, the cooling bath was removed and the reaction mixture was stirred for a further 3.5 hours at room temperature. The suspension was subsequently poured into 500 ml of water and extracted three times with 600 ml of methylene chloride each time. The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium chloride solution each time, dried over sodium sulphate, filtered and concentrated, whereby 76.9 g of a brownish paste remained behind. Chromatographic separation of this crude product on silica gel with methylene chloride as the eluent gave 33.0 g of 4-[ 2-(p-cyanophenyl)vinyl]cyclohexanone as a yellow-brownish oil. rose to 44° C Thereafter, the cooling bath was removed the reaction mixture was stirred for a further 3.5 hours at room temperature The suspension was subsequently poured into 500 ml of water extracted three times with 600 ml of methylene chloride each time The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium chloride solution each time dried over sodium sulphate filtered concentrated Chromatographic separation of this crude product on silica gel with methylene chloride as the eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 28.2 g of 1,1-ethylenedioxy-4-(methoxymethylene)cyclohexane, 770 ml of glacial acetic acid and 385 ml of water was heated to reflux for 1 hour in a round flask while gassing with nitrogen. Thereafter, the yellowish clear solution was cooled to room temperature, diluted with 800 ml of water and extracted three times with 700 ml of methylene chloride each time. The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium carbonate solution each time, dried over sodium sulphate, filtered and concentrated. Chromatographic separation of the brownish liquid obtained (18.5 g) on silica gel with methylene chloride as the eluent finally gave 16.7 g of 4-formylcyclohexanone as a brownish liquid. was heated to reflux for 1 hour in a round flask extracted three times with 700 ml of methylene chloride each time The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium carbonate solution each time dried over sodium sulphate filtered concentrated Chromatographic separation of the brownish liquid

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 28.2 g of 1,1-ethylenedioxy-4-(methoxymethylene)cyclohexane, 770 ml of glacial acetic acid and 385 ml of water was heated to reflux for 1 hour in a round flask while gassing with nitrogen. Thereafter, the yellowish clear solution was cooled to room temperature, diluted with 800 ml of water and extracted three times with 700 ml of methylene chloride each time. The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium carbonate solution each time, dried over sodium sulphate, filtered and concentrated. Chromatographic separation of the brownish liquid obtained (18.5 g) on silica gel with methylene chloride as the eluent finally gave 16.7 g of 4-formylcyclohexanone as a brownish liquid. was heated to reflux for 1 hour in a round flask extracted three times with 700 ml of methylene chloride each time The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium carbonate solution each time dried over sodium sulphate filtered concentrated Chromatographic separation of the brownish liquid

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 36.72 g of triphenylphosphine in 200 ml of methylene chloride was treated slowly at -20° C. with 23.22 g of carbon tetrabromide and stirred for a further 10 minutes. Subsequently, the mixture was added dropwise by means of a cannula to a solution, cooled to -60° C., of 6.30 g of 4-formylcyclohexanone in 100 ml of methylene chloride. The mixture was stirred at -60° C. for a further 15 minutes and then partitioned in water/methylene chloride. The aqueous phases were extracted a further twice with methylene chloride. The organic phases were washed twice with water, dried over magnesium sulphate and evaporated. Low-pressure chromatography of the resulting, pale yellow oil (16 g) on silica gel with ethyl acetate/petroleum ether (vol. 10:90) gave 12.08 g (85.8%) of 4-(2,2-dibromovinyl)cyclohexanone as a pale yellow liquid. Subsequently, the mixture was added dropwise by means of a cannula to a solution The mixture was stirred at -60° C. for a further 15 minutes partitioned in water/methylene chloride The aqueous phases were extracted a further twice with methylene chloride The organic phases were washed twice with water dried over magnesium sulphate evaporated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 36.72 g of triphenylphosphine in 200 ml of methylene chloride was treated slowly at -20° C. with 23.22 g of carbon tetrabromide and stirred for a further 10 minutes. Subsequently, the mixture was added dropwise by means of a cannula to a solution, cooled to -60° C., of 6.30 g of 4-formylcyclohexanone in 100 ml of methylene chloride. The mixture was stirred at -60° C. for a further 15 minutes and then partitioned in water/methylene chloride. The aqueous phases were extracted a further twice with methylene chloride. The organic phases were washed twice with water, dried over magnesium sulphate and evaporated. Low-pressure chromatography of the resulting, pale yellow oil (16 g) on silica gel with ethyl acetate/petroleum ether (vol. 10:90) gave 12.08 g (85.8%) of 4-(2,2-dibromovinyl)cyclohexanone as a pale yellow liquid. Subsequently, the mixture was added dropwise by means of a cannula to a solution The mixture was stirred at -60° C. for a further 15 minutes partitioned in water/methylene chloride The aqueous phases were extracted a further twice with methylene chloride The organic phases were washed twice with water dried over magnesium sulphate evaporated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 10.55 g of 1,1-ethylenedioxy-4-(methoxymethylene)cyclohexane, 130 ml of water and 200 ml of glacial acetic acid was heated to reflux for 1 hour. The solvent was subsequently distilled off on a rotary evaporator and the distillate was extracted twice with methylene chloride. The distillation residue (a yellow oil) was diluted with 200 ml of water, neutralized with sodium carbonate solution and extracted three times with methylene chloride. The organic phases were washed with saturated sodium carbonate solution and the aqueous phases were back-extracted with methylene chloride. The organic phases were dried over magnesium sulphate and evaporated. Distillation of the residual, yellow oil gave 6.7 g (93%) of 4-formylcyclohexanone at 70° C./0.15 Torr. was heated to reflux for 1 hour The solvent was subsequently distilled off on a rotary evaporator the distillate was extracted twice with methylene chloride The distillation residue (a yellow oil) was diluted with 200 ml of water extracted three times with methylene chloride The organic phases were washed with saturated sodium carbonate solution the aqueous phases were back-extracted with methylene chloride The organic phases were dried over magnesium sulphate evaporated Distillation of the residual, yellow oil

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 63.3 g of p-cyanobenzyl-triphenylphosphonium chloride, 17.2 g of potassium t-butylate and 195 ml of ethylene glycol dimethyl ether were placed while stirring and gassing with nitrogen in a sulphonation flask, whereby the internal temperature rose to 44° C. The brown suspension was cooled to 0° C. and treated within 2 minutes with a solution of 16.7 g of 4-formylcyclohexanone in 100 ml of ethylene glycol dimethyl ether. The cooling bath was then removed and the mixture was stirred at room temperature for a further 3.5 hours. The suspension was subsequently poured into 500 ml of water and extracted three times with 600 ml of methylene chloride each time. The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium chloride solution each time, dried over sodium sulphate, filtered and concentrated, there being obtained 76.9 g of a brownish paste. Chromatographic separation of this crude product on silica gel with methylene chloride as the eluent gave 33.0 g of 4-[2-(p-cyanophenyl)vinyl]cyclohexanone as a yellow-brownish oil. gassing with nitrogen in a sulphonation flask rose to 44° C The cooling bath was then removed the mixture was stirred at room temperature for a further 3.5 hours The suspension was subsequently poured into 500 ml of water extracted three times with 600 ml of methylene chloride each time The organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium chloride solution each time dried over sodium sulphate filtered concentrated there being obtained 76.9 g of a brownish paste Chromatographic separation of this crude product on silica gel with methylene chloride as the eluent