4-oxocyclohexane-1-carbonitrile

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:

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:

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.6 g of triphenyl(methoxymethyl)phosphonium chloride were suspended in 50 ml of t-butyl methyl ether under argon gasification and treated portionwise at -10° C. with 3.39 g of solid potassium t-butylate. After completion of the addition, the mixture was stirred at 0° to 5° C. for a further 30 minutes and then the deep orange, partially heterogeneous mixture was treated dropwise within 10 minutes with a solution of 2.30 g of 4-cyanocyclohexanone in 20 ml of t-butyl methyl ether. In so doing the internal temperature should not exceed 5° C. After completion of the addition, the now yellow-orange mixture was warmed to 25° C. and stirred for a further 2 hours. 50 ml of a 2% sodium hydrogen carbonate solution were subsequently added and the separated aqueous phase was extracted twice with 50 ml of diethyl ether each time. The organic phases were washed with 50 ml of saturated sodium chloride solution, dried over potassium carbonate and concentrated. The residual semi-crystalline orange oil was triturated with 400 ml of hexane, cooled to -20° C. and freed from precipitated triphenylphosphine oxide by filtration (rinsing with cold hexane). Low-pressure chromatography (0.4 bar) of the concentrated residue on silica gel using 10% ethyl acetate/petroleum ether as the eluant gave 1.60 g (56%) of 4-(methoxymethylene)cyclohexanecarbonitrile as a colourless oil (purity 97%). After completion of the addition exceed 5° C After completion of the addition stirred for a further 2 hours the separated aqueous phase was extracted twice with 50 ml of diethyl ether each time The organic phases were washed with 50 ml of saturated sodium chloride solution dried over potassium carbonate concentrated The residual semi-crystalline orange oil was triturated with 400 ml of hexane cooled to -20° C. from precipitated triphenylphosphine oxide by filtration (rinsing with cold hexane)

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.6 g of triphenyl(methoxymethyl)phosphonium chloride were suspended in 50 ml of t-butyl methyl ether under argon gasification and treated portionwise at -10° C. with 3.39 g of solid potassium t-butylate. After completion of the addition, the mixture was stirred at 0° to 5° C. for a further 30 minutes and then the deep orange, partially heterogeneous mixture was treated dropwise within 10 minutes with a solution of 2.30 g of 4-cyanocyclohexanone in 20 ml of t-butyl methyl ether. In so doing the internal temperature should not exceed 5° C. After completion of the addition, the now yellow-orange mixture was warmed to 25° C. and stirred for a further 2 hours. 50 ml of a 2% sodium hydrogen carbonate solution were subsequently added and the separated aqueous phase was extracted twice with 50 ml of diethyl ether each time. The organic phases were washed with 50 ml of saturated sodium chloride solution, dried over potassium carbonate and concentrated. The residual semi-crystalline orange oil was triturated with 400 ml of hexane, cooled to -20° C. and freed from precipitated triphenylphosphine oxide by filtration (rinsing with cold hexane). Low-pressure chromatography (0.4 bar) of the concentrated residue on silica gel using 10% ethyl acetate/petroleum ether as the eluant gave 1.60 g (56%) of 4-(methoxymethylene)cyclohexanecarbonitrile as a colourless oil (purity 97%). After completion of the addition exceed 5° C After completion of the addition stirred for a further 2 hours the separated aqueous phase was extracted twice with 50 ml of diethyl ether each time The organic phases were washed with 50 ml of saturated sodium chloride solution dried over potassium carbonate concentrated The residual semi-crystalline orange oil was triturated with 400 ml of hexane cooled to -20° C. from precipitated triphenylphosphine oxide by filtration (rinsing with cold hexane)

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

Procedure: A solution of 6 g of 4-cyanocyclohexanone in 50 ml of diethyl ether is added dropwise, while stirring, at room temperature and during the course of 1.5 hours, to a Grignard solution prepared from 13 g of 1-(4-n-pentylphenyl)-2-bromoethane and 1.3 g of magnesium turnings in 200 ml of diethyl ether. The reaction mixture is then heated under reflux to the boil for 2 hours, and, after it has cooled, 150 ml of 10% aqueous ammonium chloride solution is added to it, while stirring. The ether phase is separated off, dried over sodium sulfate and evaporated. The residual 1-(4-n-pentylphenyl)-2-(4-cyano-1-hydroxycyclohex-1-yl)-ethane is dissolved in 40 ml of acetone and this solution is heated to the boil for 1 hour with 0.5 g of p-toluenesulfonic acid. The solvent is then distilled off and the residue is taken up in 100 ml of ethanol. After the addition of 20 mg of copper (II) sulfate, 23 g of hydrazine hydrate and 40 ml of 30% aqueous hydrogen peroxide solution are added successively to the mixture at 0°. The reaction mixture is stirred for 1 hour at room temperature and poured into 500 ml of water, and the 1-(4-n-pentylphenyl)-2-(trans-4-cyanocyclohexyl)-ethane thus obtained is extracted with diethyl ether; the extracts are dried with sodium sulfate and evaporated, and the residue is recrystallized from isopropanol. The reaction mixture is then heated under reflux to the boil for 2 hours after it has cooled while stirring The ether phase is separated off dried over sodium sulfate evaporated The residual 1-(4-n-pentylphenyl)-2-(4-cyano-1-hydroxycyclohex-1-yl)-ethane is dissolved in 40 ml of acetone this solution is heated to the boil for 1 hour with 0.5 g of p-toluenesulfonic acid The solvent is then distilled off After the addition of 20 mg of copper (II) sulfate, 23 g of hydrazine hydrate and 40 ml of 30% aqueous hydrogen peroxide solution are added successively to the mixture at 0° The reaction mixture is stirred for 1 hour at room temperature poured into 500 ml of water

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

Procedure: A solution of 6 g of 4-cyanocyclohexanone in 50 ml of diethyl ether is added dropwise, while stirring, at room temperature and during the course of 1.5 hours, to a Grignard solution prepared from 13 g of 1-(4-n-pentylphenyl)-2-bromoethane and 1.3 g of magnesium turnings in 200 ml of diethyl ether. The reaction mixture is then heated under reflux to the boil for 2 hours, and, after it has cooled, 150 ml of 10% aqueous ammonium chloride solution is added to it, while stirring. The ether phase is separated off, dried over sodium sulfate and evaporated. The residual 1-(4-n-pentylphenyl)-2-(4-cyano-1-hydroxycyclohex-1-yl)-ethane is dissolved in 40 ml of acetone and this solution is heated to the boil for 1 hour with 0.5 g of p-toluenesulfonic acid. The solvent is then distilled off and the residue is taken up in 100 ml of ethanol. After the addition of 20 mg of copper (II) sulfate, 23 g of hydrazine hydrate and 40 ml of 30% aqueous hydrogen peroxide solution are added successively to the mixture at 0°. The reaction mixture is stirred for 1 hour at room temperature and poured into 500 ml of water, and the 1-(4-n-pentylphenyl)-2-(trans-4-cyanocyclohexyl)-ethane thus obtained is extracted with diethyl ether; the extracts are dried with sodium sulfate and evaporated, and the residue is recrystallized from isopropanol. The reaction mixture is then heated under reflux to the boil for 2 hours after it has cooled while stirring The ether phase is separated off dried over sodium sulfate evaporated The residual 1-(4-n-pentylphenyl)-2-(4-cyano-1-hydroxycyclohex-1-yl)-ethane is dissolved in 40 ml of acetone this solution is heated to the boil for 1 hour with 0.5 g of p-toluenesulfonic acid The solvent is then distilled off After the addition of 20 mg of copper (II) sulfate, 23 g of hydrazine hydrate and 40 ml of 30% aqueous hydrogen peroxide solution are added successively to the mixture at 0° The reaction mixture is stirred for 1 hour at room temperature poured into 500 ml of water