2-heptylpropane-1,3-diol

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: In anhydrous diethyl ether was dissolved 100 g of the obtained diethyl heptylmalonate, and the mixture was added dropwise to a solution of 28.7 g of lithium aluminum hydride dispersed in 270 ml of diethyl ether. The mixture was stirred for 15 hours. Then, to the reaction mixture was added gradually 3N hydrochloric acid to make excess lithium aluminum hydride inactive. After washing with 10% aqueous solution of sodium carbonate, then water, the resulting ether layer dried with anhydrous magnesium sulfate. After distilling ether under reduced pressure, the residue was purified by silica gel chromatography (developing solvent: hexane/ethyl acetate=4/1) and distilled under reduced pressure to give 41.2 of 2-heptyl-1,3-propanediol (yield: 6%). After washing with 10% aqueous solution of sodium carbonate water, the resulting ether layer dried with anhydrous magnesium sulfate After distilling ether under reduced pressure the residue was purified by silica gel chromatography (developing solvent: hexane/ethyl acetate=4/1) distilled under reduced pressure

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

実験手順: A mixture of 3.0 g of 4-cyano-3-fluorobenzaldehyde obtainable from 2-fluoro-4-nitrotoluene by oxidation to the corresponding benzoic acid, conversion into the corresponding nitrile, reduction to 2-fluoro-4-aminobenzonitrile and conversion of the corresponding diazonium salt with formaldoxime into the aldehyde in accordance with the method of Beech (J. Chem. Soc. 1297 (1954)); the target product is also obtainable from 2-fluoro-4-aminotoluene by conversion into 3-fluoro-4-methylbenzonitrile by the Sandmeyer method, hydrolysis of the nitrile, bromination of the side chain of the ethyl 3-fluoro-4-methylbenzoate obtainable, conversion into the aldehyde by the Sommelet method, conversion of the resulting oxime into ethyl 3-fluoro-4-cyanobenzoate, reduction to 3-fluoro-4-cyanobenzyl alcohol and subsequent oxidation to the target product) and 3.5 g of 2-n-heptylpropane-1,3-diol is heated together with 1 g of strongly acid cation exchanger in 100 ml of toluene for 8 hours using a water separator. The catalyst is then filtered off and the toluene is removed. After customary working-up, 2-(4-cyano-3-fluorophenyl)-5-n-heptyl-1,3-dioxane is obtained. The catalyst is then filtered off the toluene is removed

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

実験手順: A mixture of 3.0 g of 4-cyano-3-fluorobenzaldehyde obtainable from 2-fluoro-4-nitrotoluene by oxidation to the corresponding benzoic acid, conversion into the corresponding nitrile, reduction to 2-fluoro-4-aminobenzonitrile and conversion of the corresponding diazonium salt with formaldoxime into the aldehyde in accordance with the method of Beech (J. Chem. Soc. 1297 (1954)); the target product is also obtainable from 2-fluoro-4-aminotoluene by conversion into 3-fluoro-4-methylbenzonitrile by the Sandmeyer method, hydrolysis of the nitrile, bromination of the side chain of the ethyl 3-fluoro-4-methylbenzoate obtainable, conversion into the aldehyde by the Sommelet method, conversion of the resulting oxime into ethyl 3-fluoro-4-cyanobenzoate, reduction to 3-fluoro-4-cyanobenzyl alcohol and subsequent oxidation to the target product) and 3.5 g of 2-n-heptylpropane-1,3-diol is heated together with 1 g of strongly acid cation exchanger in 100 ml of toluene for 8 hours using a water separator. The catalyst is then filtered off and the toluene is removed. After customary working-up, 2-(4-cyano-3-fluorophenyl)-5-n-heptyl-1,3-dioxane is obtained. The catalyst is then filtered off the toluene is removed

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

実験手順: 6 g of 3-(4'-pentyl-2-fluorobiphenyl-4-yl)-propionaldehyde (obtainable by reaction of 4-(2-fluoro-4'-pentylbiphenylyl)-magnesium bromide with ethylene oxide and subsequent oxidation of the resulting alcohol with pyridinium chlorochromate) and 3.5 g of 2-heptylpropane-1,3-diol are heated with a spatula tip of p-toluenesulfonic acid in 100 ml of toluene, using a water separator, until no further water is foamed. After cooling, the mixture is washed with bicarbonate solution and water until neutral and dried over sodium sulfate and the toluene is distilled off. After customary working-up, 1-(4'-pentyl-2-fluorobiphenyl-4-yl)-2-(5-heptyl-1,3-dioxan-2-yl)-ethane is obtained. After cooling the mixture is washed with bicarbonate solution and water until neutral and dried over sodium sulfate the toluene is distilled off

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

実験手順: 6 g of 3-(4'-pentyl-2-fluorobiphenyl-4-yl)-propionaldehyde (obtainable by reaction of 4-(2-fluoro-4'-pentylbiphenylyl)-magnesium bromide with ethylene oxide and subsequent oxidation of the resulting alcohol with pyridinium chlorochromate) and 3.5 g of 2-heptylpropane-1,3-diol are heated with a spatula tip of p-toluenesulfonic acid in 100 ml of toluene, using a water separator, until no further water is foamed. After cooling, the mixture is washed with bicarbonate solution and water until neutral and dried over sodium sulfate and the toluene is distilled off. After customary working-up, 1-(4'-pentyl-2-fluorobiphenyl-4-yl)-2-(5-heptyl-1,3-dioxan-2-yl)-ethane is obtained. After cooling the mixture is washed with bicarbonate solution and water until neutral and dried over sodium sulfate the toluene is distilled off

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

実験手順: 20 g of dimethoxy-(2-propylpyrimidin-5-yl)-borane (obtained from 2-propylpyrimidin-5-ylmagnesium chloride and trimethoxyborane) and 30 g of 2-hydroxymethylnonan-1-ol are heated at 100° for 12 hours, the methanol formed being removed continuously by distillation. When the reaction is complete, excess nonanol is removed under reduced pressure, and 2-(2-propylpyrimidin-5-yl)-5-heptyl-1,3,2-dioxaborinane is obtained. being removed continuously by distillation excess nonanol is removed under reduced pressure

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

実験手順: 20 g of dimethoxy-(2-propylpyrimidin-5-yl)-borane (obtained from 2-propylpyrimidin-5-ylmagnesium chloride and trimethoxyborane) and 30 g of 2-hydroxymethylnonan-1-ol are heated at 100° for 12 hours, the methanol formed being removed continuously by distillation. When the reaction is complete, excess nonanol is removed under reduced pressure, and 2-(2-propylpyrimidin-5-yl)-5-heptyl-1,3,2-dioxaborinane is obtained. being removed continuously by distillation excess nonanol is removed under reduced pressure

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

実験手順: In anhydrous diethyl ether was dissolved 100 g of the obtained diethyl heptylmalonate, and the mixture was added dropwise to a solution of 28.7 g of lithium aluminum hydride dispersed in 270 ml of diethyl ether. The mixture was stirred for 15 hours. Then, to the reaction mixture was added gradually 3N hydrochloric acid to make excess lithium aluminum hydride inactive. After washing with 10% aqueous solution of sodium carbonate, then water, the resulting ether layer dried with anhydrous magnesium sulfate. After distilling ether under reduced pressure, the residue was purified by silica gel chromatography (developing solvent: hexane/ethyl acetate=4/1) and distilled under reduced pressure to give 41.2 of 2-heptyl-1,3-propanediol (yield: 6%). After washing with 10% aqueous solution of sodium carbonate water, the resulting ether layer dried with anhydrous magnesium sulfate After distilling ether under reduced pressure the residue was purified by silica gel chromatography (developing solvent: hexane/ethyl acetate=4/1) distilled under reduced pressure

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

実験手順: In anhydrous diethyl ether was dissolved 100 g of the obtained diethyl heptylmalonate, and the mixture was added dropwise to a solution of 28.7 g of lithium aluminum hydride dispersed in 270 ml of diethyl ether. The mixture was stirred for 15 hours. Then, to the reaction mixture was added gradually 3N hydrochloric acid to make excess lithium aluminum hydride inactive. After washing with 10% aqueous solution of sodium carbonate, then water, the resulting ether layer dried with anhydrous magnesium sulfate. After distilling ether under reduced pressure, the residue was purified by silica gel chromatography (developing solvent: hexane/ethyl acetate=4/1) and distilled under reduced pressure to give 41.2 of 2-heptyl-1,3-propanediol (yield: 6%). After washing with 10% aqueous solution of sodium carbonate water, the resulting ether layer dried with anhydrous magnesium sulfate After distilling ether under reduced pressure the residue was purified by silica gel chromatography (developing solvent: hexane/ethyl acetate=4/1) distilled under reduced pressure

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

実験手順: A mixture of 3.0 g of 4-cyano-3-fluorobenzaldehyde obtainable from 2-fluoro-4-nitrotoluene by oxidation to the corresponding benzoic acid, conversion into the corresponding nitrile, reduction to 2-fluoro-4-aminobenzonitrile and conversion of the corresponding diazonium salt with formaldoxime into the aldehyde in accordance with the method of Beech (J. Chem. Soc. 1297 (1954)); the target product is also obtainable from 2-fluoro-4-aminotoluene by conversion into 3-fluoro-4-methylbenzonitrile by the Sandmeyer method, hydrolysis of the nitrile, bromination of the side chain of the ethyl 3-fluoro-4-methylbenzoate obtainable, conversion into the aldehyde by the Sommelet method, conversion of the resulting oxime into ethyl 3-fluoro-4-cyanobenzoate, reduction to 3-fluoro-4-cyanobenzyl alcohol and subsequent oxidation to the target product) and 3.5 g of 2-n-heptylpropane-1,3-diol is heated together with 1 g of strongly acid cation exchanger in 100 ml of toluene for 8 hours using a water separator. The catalyst is then filtered off and the toluene is removed. After customary working-up, 2-(4-cyano-3-fluorophenyl)-5-n-heptyl-1,3-dioxane is obtained. The catalyst is then filtered off the toluene is removed

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

実験手順: 6 g of 3-(4'-pentyl-2-fluorobiphenyl-4-yl)-propionaldehyde (obtainable by reaction of 4-(2-fluoro-4'-pentylbiphenylyl)-magnesium bromide with ethylene oxide and subsequent oxidation of the resulting alcohol with pyridinium chlorochromate) and 3.5 g of 2-heptylpropane-1,3-diol are heated with a spatula tip of p-toluenesulfonic acid in 100 ml of toluene, using a water separator, until no further water is foamed. After cooling, the mixture is washed with bicarbonate solution and water until neutral and dried over sodium sulfate and the toluene is distilled off. After customary working-up, 1-(4'-pentyl-2-fluorobiphenyl-4-yl)-2-(5-heptyl-1,3-dioxan-2-yl)-ethane is obtained. After cooling the mixture is washed with bicarbonate solution and water until neutral and dried over sodium sulfate the toluene is distilled off