bis(4-chlorophenyl)methanone

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:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reaction vessel equipped with a dropping funnel was charged with 40 ml of dehydrated tetrahydrofuran and 2.15 ml (25.9 mmol) of cyclopentadiene under nitrogen atmosphere, and 18.0 ml (28.5 mmol) of a hexane solution of n-butyllithium of 1.58 mol/L was added dropwise and stirred while cooling the above solution at 0° C. Then, a solution prepared by dissolving 5.00 g (19.9 mmol) of 4,4′-dichlorobenzophenone in 30 ml of dehydrated tetrahydrofuran was placed in the dropping funnel and added dropwise while cooling at 0° C., and the solution was allowed to return to room temperature and stirred for one day. This reaction solution was extracted with diethyl ether, and the separated organic layer was washed with 1N hydrochloric acid, a saturated sodium hydrogen carbonate aqueous solution and a saturated salt solution and dried over anhydrous magnesium sulfate. Then, magnesium sulfate was removed by filtration, and the solvent contained in the filtrate was removed by distillation under reduced pressure by means of a rotary evaporator. The residue was purified through a silica gel column to obtain a targeted product (amount obtained: 3.37 g, yield: 57%). The targeted product was identified by means of 1H-NMR. A reaction vessel equipped with a dropping funnel Then, a solution prepared added dropwise while cooling at 0° C. to return to room temperature stirred for one day This reaction solution was extracted with diethyl ether the separated organic layer was washed with 1N hydrochloric acid a saturated sodium hydrogen carbonate aqueous solution and a saturated salt solution and dried over anhydrous magnesium sulfate Then, magnesium sulfate was removed by filtration was removed by distillation under reduced pressure by means of a rotary evaporator The residue was purified through a silica gel column to obtain a targeted product (amount obtained: 3.37 g, yield: 57%)

反応条件: temp:27.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a round bottom flask, (2 g) 4,4′-dichlorobenzophenone in 4 ml methanol was taken. (1.75 ml) (2 equiv.) tri-methyl orthoformate was added into the reaction mixture and stirred at 25-30° C. Then 0.04 ml perchloric acid (as a catalyst) was added and refluxed for 7.5 hrs. After completion of the reaction ethyl acetate and NaHCO3 solution were added and stirred for 10 min. Then layers were separated and washed the organic layer with water. Dry it over sodium sulfate. Concentrate it on rotavapor to obtain yellow colored liquid product refluxed for 7.5 hrs were added stirred for 10 min Then layers were separated washed the organic layer with water Dry it over sodium sulfate Concentrate it on rotavapor to obtain yellow colored liquid product

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

実験手順: 2.19 g (0.09 gr.at.) of magnesium and 10.9 g (0.1 mol) of ethyl bromide were converted into a Grignard compound in 50 ml. of refluxing anhydrous tetrahydrofuran. In the course of 5 minutes a solution of 8.46 g (0.09 mol) of 1-vinylimidazole in 20 ml. of anhydrous tetrahydrofuran was added with stirring to the refluxing mixture, after which the reaction mixture was refluxed for another two hours. A suspension of 22.6 g (0.09 mol) of 4,4'-dichlorobenzophenone in 50 ml. of anhydrous tetrahydrofuran was then added and refluxing was continued for 24 hours. The whole procedure was carried out under a nitrogen atmosphere. After cooling, the reaction mixture was poured into a mixture of ice, water and ammonium chloride. The mixture was then extracted with diethyl ether and the extract was washed with water, dried over sodium sulphate and concentrated. The solid residue was twice crystallized from a mixture of isopropyl alcohol and dimethyl formamide. α,α-Bis(p-chlorophenyl)-1-vinylimidazole-2-methanol was obtained. Melting point 173.5°- 174° C. In the course of 5 minutes after which the reaction mixture was refluxed for another two hours refluxing After cooling The mixture was then extracted with diethyl ether the extract was washed with water dried over sodium sulphate concentrated The solid residue was twice crystallized from a mixture of isopropyl alcohol and dimethyl formamide

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

実験手順: 2.19 g (0.09 gr.at.) of magnesium and 10.9 g (0.1 mol) of ethyl bromide were converted into a Grignard compound in 50 ml. of refluxing anhydrous tetrahydrofuran. In the course of 5 minutes a solution of 8.46 g (0.09 mol) of 1-vinylimidazole in 20 ml. of anhydrous tetrahydrofuran was added with stirring to the refluxing mixture, after which the reaction mixture was refluxed for another two hours. A suspension of 22.6 g (0.09 mol) of 4,4'-dichlorobenzophenone in 50 ml. of anhydrous tetrahydrofuran was then added and refluxing was continued for 24 hours. The whole procedure was carried out under a nitrogen atmosphere. After cooling, the reaction mixture was poured into a mixture of ice, water and ammonium chloride. The mixture was then extracted with diethyl ether and the extract was washed with water, dried over sodium sulphate and concentrated. The solid residue was twice crystallized from a mixture of isopropyl alcohol and dimethyl formamide. α,α-Bis(p-chlorophenyl)-1-vinylimidazole-2-methanol was obtained. Melting point 173.5°- 174° C. In the course of 5 minutes after which the reaction mixture was refluxed for another two hours refluxing After cooling The mixture was then extracted with diethyl ether the extract was washed with water dried over sodium sulphate concentrated The solid residue was twice crystallized from a mixture of isopropyl alcohol and dimethyl formamide

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

実験手順: In the course of one hour, 64 ml. (0.105 mol) of 15% butyl lithium in n-hexane were added dropwise at -65° to -70° C. and under a nitrogen atmosphere, to a solution of 19.3 g (0.1 mol) of 1-(p-chlorobenzyl)imidazole (prepared from the oxalate described under (A) and 12.2 g (0.105 mol) of N,N,N',N'-tetramethylethylenediamine in 150 ml. of anhydrous tetrahydrofuran. The reaction mixture was stirred for one hour and then a suspension of 25.1 g (0.1 mol) of 4,4'-dichlorobenzophenone in 150 ml. of anhydrous tetrahydrofuran was added quickly under the same reaction conditions. Stirring was continued for one hour and then the cooling means was removed and the reaction mixture was kept standing overnight at room temperature. 20 ml. of water were added and the organic phase was separated off and concentrated. The residue was suspended in a mixture of water and diethyl ether. The solid matter formed was filtered off and the ethereal layer was separated off, dried over sodium sulphate and concentrated. The residue was twice crystallised from methanol. 1-(p-Chlorobenzyl)-α,α-bis-(p-chlorophenyl)imidazole-2-methanol was obtained. Melting point 171°-173° C. In the course of one hour, 64 ml Stirring was continued for one hour the cooling means was removed the reaction mixture was kept standing overnight at room temperature of water were added the organic phase was separated off concentrated The residue was suspended in a mixture of water and diethyl ether The solid matter formed was filtered off the ethereal layer was separated off dried over sodium sulphate concentrated The residue was twice crystallised from methanol

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

実験手順: In the course of one hour, 64 ml. (0.105 mol) of 15% butyl lithium in n-hexane were added dropwise at -65° to -70° C. and under a nitrogen atmosphere, to a solution of 19.3 g (0.1 mol) of 1-(p-chlorobenzyl)imidazole (prepared from the oxalate described under (A) and 12.2 g (0.105 mol) of N,N,N',N'-tetramethylethylenediamine in 150 ml. of anhydrous tetrahydrofuran. The reaction mixture was stirred for one hour and then a suspension of 25.1 g (0.1 mol) of 4,4'-dichlorobenzophenone in 150 ml. of anhydrous tetrahydrofuran was added quickly under the same reaction conditions. Stirring was continued for one hour and then the cooling means was removed and the reaction mixture was kept standing overnight at room temperature. 20 ml. of water were added and the organic phase was separated off and concentrated. The residue was suspended in a mixture of water and diethyl ether. The solid matter formed was filtered off and the ethereal layer was separated off, dried over sodium sulphate and concentrated. The residue was twice crystallised from methanol. 1-(p-Chlorobenzyl)-α,α-bis-(p-chlorophenyl)imidazole-2-methanol was obtained. Melting point 171°-173° C. In the course of one hour, 64 ml Stirring was continued for one hour the cooling means was removed the reaction mixture was kept standing overnight at room temperature of water were added the organic phase was separated off concentrated The residue was suspended in a mixture of water and diethyl ether The solid matter formed was filtered off the ethereal layer was separated off dried over sodium sulphate concentrated The residue was twice crystallised from methanol