2-(3-chlorophenyl)-2-morpholin-4-ylacetonitrile

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

実験手順: To a solution of 11.8 g. of α-(m-chlorophenyl)-4-morpholineacetonitrile in 50 ml. of tetrahydrofuran is added 60 drops of a 30% solution of KOH in methanol. To the solution is added 4.62 ml. of methacrylonitrile (temperature rose to 42° C.). After stirring for 1 hr., the mixture is concentrated to dryness and the residue dissolved in methylene chloride. The solution is passed through a short column of hydrous magnesium silicate and the eluent concentrated to give 15.5 g. of a yellow oil. The oil is heated (steam bath) with a mixture of 75 ml. of acetic acid and 5 ml. of water for 1 hr. and the solvent removed under vacuum. Addition of water to the residue gives 11.2 g. of crystals, m.p. 72°-75° C. Recrystallization from methylene chloride-hexane gives 8.95 g. of crystals, m.p. 79.5°-80.5° C. To the solution is added 4.62 ml , the mixture is concentrated to dryness the residue dissolved in methylene chloride the eluent concentrated to give 15.5 g The oil is heated (steam bath) with a mixture of 75 ml and the solvent removed under vacuum Addition of water to the residue gives 11.2 g Recrystallization from methylene chloride-hexane gives 8.95 g

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

実験手順: To a solution of 23.6 g. of α-(m-chlorophenyl)-4-morpholineacetonitrile in 100 ml. of tetrahydrofuran is added 120 drops of a 30% solution of KOH in methanol. To the mixture is added 4.1 ml. of acrylonitrile (temperature rose to 45° C.). After stirring 1 hr., the mixture is concentrated to dryness under vacuum. The residue is dissolved in methylene chloride and passed through a short column of hydrous magnesium silicate. The eluent is concentrated under vacuum to give 36.6 g. of a yellow oil. The oil is heated (steam bath) with a mixture of 150 ml. of acetic acid and 10 ml. of water for 1 hr. The solvent is removed under vacuum and the residue treated with water. The mixture is filtered to give 18.8 g. of crystals, m.p. 49°-51° C. To the mixture is added 4.1 ml , the mixture is concentrated to dryness under vacuum The residue is dissolved in methylene chloride The eluent is concentrated under vacuum to give 36.6 g The oil is heated (steam bath) with a mixture of 150 ml The solvent is removed under vacuum the residue treated with water The mixture is filtered to give 18.8 g