4-heptylbenzaldehyde

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 9.4 g of p-butoxyphenylacetonitrile and 10.2 g of p-heptylbenzaldehyde are dissolved in 30 ml of methanol. 5 ml of a 40% solution of benzyltrimethylammoniumhydrate in water are added to the solution. The whole is heated at 70° C for 30 minutes and then cooled. The precipitate is sucked off and recrystallized from successively methanol and petroleum ether (60 : 80). Melting point of the resulting compound is 34.5°-35.5.° C. cooled recrystallized from successively methanol and petroleum ether (60 : 80) is 34.5°

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

実験手順: 88 g of n-heptylbenzene are taken up in 50 ml of trifluoroacetic acid and 70 g of hexamethylenetetramine. The whole is refluxed for 12 hours after which the excess of trifluoroacetic acid is distilled off by means of a water jet airpump. The mixture is then poured in ice water and neutralized with soda. After extraction with ether the resulting ether solution is evaporated and the resulting 4-heptylbenzaldehyde is used for the following process step. is distilled off by means of a water jet airpump The mixture is then poured in ice water and neutralized with soda After extraction with ether the resulting ether solution is evaporated

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

実験手順: To a stirred solution of 6.60 g (30 mmol) of 4-heptylbenzoic acid (obtained from Aldrich Chemical Company (#23,064-2) and used without purification) in 50 mL of dichloromethane at room temperature under nitrogen was added 4.0 mL (45 mmol, 1.5 equivalents) of oxalyl chloride and then 0.1 mL (1.3 mmol) of DMF. The resulting vigorously bubbling solution was stirred for 1 h and then evaporated. The semi-solid residue was dissolved in 40 mL of benzene under argon and 350 mg (0.31 mmol) of tetrakis(triphenylphosphine)palladium was added. To this stirring solution at room temperature was added 11.1 mL (34 mmol) of tributyltin hydride over 20 min. The solution turns yellow and warms autogenously to 40° C. After 1 h, the reaction was treated with 100 mL of 10% aqueous potassium fluoride and stirred vigorously for 30 min. The reaction mass was filtered, the filtrate diluted with ether, washed with water, and the organic layer separated, dried (MgSO4) and evaporated onto 10 g of silica gel. Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield, of title compound as a colorless oil. evaporated The semi-solid residue was dissolved in 40 mL of benzene under argon autogenously to 40° C After 1 h stirred vigorously for 30 min The reaction mass was filtered the filtrate diluted with ether washed with water the organic layer separated dried (MgSO4) evaporated onto 10 g of silica gel Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield

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

実験手順: To a stirred solution of 6.60 g (30 mmol) of 4-heptylbenzoic acid (obtained from Aldrich Chemical Company (#23,064-2) and used without purification) in 50 mL of dichloromethane at room temperature under nitrogen was added 4.0 mL (45 mmol, 1.5 equivalents) of oxalyl chloride and then 0.1 mL (1.3 mmol) of DMF. The resulting vigorously bubbling solution was stirred for 1 h and then evaporated. The semi-solid residue was dissolved in 40 mL of benzene under argon and 350 mg (0.31 mmol) of tetrakis(triphenylphosphine)palladium was added. To this stirring solution at room temperature was added 11.1 mL (34 mmol) of tributyltin hydride over 20 min. The solution turns yellow and warms autogenously to 40° C. After 1 h, the reaction was treated with 100 mL of 10% aqueous potassium fluoride and stirred vigorously for 30 min. The reaction mass was filtered, the filtrate diluted with ether, washed with water, and the organic layer separated, dried (MgSO4) and evaporated onto 10 g of silica gel. Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield, of title compound as a colorless oil. evaporated The semi-solid residue was dissolved in 40 mL of benzene under argon autogenously to 40° C After 1 h stirred vigorously for 30 min The reaction mass was filtered the filtrate diluted with ether washed with water the organic layer separated dried (MgSO4) evaporated onto 10 g of silica gel Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield

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

実験手順: To a stirred solution of 6.60 g (30 mmol) of 4-heptylbenzoic acid (obtained from Aldrich Chemical Company (#23,064-2) and used without purification) in 50 mL of dichloromethane at room temperature under nitrogen was added 4.0 mL (45 mmol, 1.5 equivalents) of oxalyl chloride and then 0.1 mL (1.3 mmol) of DMF. The resulting vigorously bubbling solution was stirred for 1 h and then evaporated. The semi-solid residue was dissolved in 40 mL of benzene under argon and 350 mg (0.31 mmol) of tetrakis(triphenylphosphine)palladium was added. To this stirring solution at room temperature was added 11.1 mL (34 mmol) of tributyltin hydride over 20 min. The solution turns yellow and warms autogenously to 40° C. After 1 h, the reaction was treated with 100 mL of 10% aqueous potassium fluoride and stirred vigorously for 30 min. The reaction mass was filtered, the filtrate diluted with ether, washed with water, and the organic layer separated, dried (MgSO4) and evaporated onto 10 g of silica gel. Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield, of title compound as a colorless oil. evaporated The semi-solid residue was dissolved in 40 mL of benzene under argon autogenously to 40° C After 1 h stirred vigorously for 30 min The reaction mass was filtered the filtrate diluted with ether washed with water the organic layer separated dried (MgSO4) evaporated onto 10 g of silica gel Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield

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

実験手順: 8.8 G. of p-n-heptylbenzaldehyde and 8.74 g. of malonic acid are dissolved in 7 ml. of absolute pyridine, treated with 8 drops of piperidine and heated at 90°-100° C. for 68 hours. The mixture is then taken up in ether and washed with dilute hydrochloric acid. After recrystallization from ether/hexane, there are obtained 7.5 g. of p-n-heptylcinnamic acid having a melting point of 121°-122° C. and a clearing point of 150°-153° C. 8.2 G. of this acid are boiled at reflux in 120 ml. of thionyl chloride for 30 minutes. The excess thionyl chloride is removed by distillation, the residue taken up three times in absolute toluene, concentrated and dried. The p-n-heptylcinnamic acid chloride obtained can be used in the process directly. heated at 90°-100° C. for 68 hours washed with dilute hydrochloric acid After recrystallization from ether/hexane, there are obtained 7.5 g a clearing point of 150°-153° C at reflux in 120 ml The excess thionyl chloride is removed by distillation concentrated dried

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

実験手順: 8.8 G. of p-n-heptylbenzaldehyde and 8.74 g. of malonic acid are dissolved in 7 ml. of absolute pyridine, treated with 8 drops of piperidine and heated at 90°-100° C. for 68 hours. The mixture is then taken up in ether and washed with dilute hydrochloric acid. After recrystallization from ether/hexane, there are obtained 7.5 g. of p-n-heptylcinnamic acid having a melting point of 121°-122° C. and a clearing point of 150°-153° C. 8.2 G. of this acid are boiled at reflux in 120 ml. of thionyl chloride for 30 minutes. The excess thionyl chloride is removed by distillation, the residue taken up three times in absolute toluene, concentrated and dried. The p-n-heptylcinnamic acid chloride obtained can be used in the process directly. heated at 90°-100° C. for 68 hours washed with dilute hydrochloric acid After recrystallization from ether/hexane, there are obtained 7.5 g a clearing point of 150°-153° C at reflux in 120 ml The excess thionyl chloride is removed by distillation concentrated dried

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 9.4 g of p-butoxyphenylacetonitrile and 10.2 g of p-heptylbenzaldehyde are dissolved in 30 ml of methanol. 5 ml of a 40% solution of benzyltrimethylammoniumhydrate in water are added to the solution. The whole is heated at 70° C for 30 minutes and then cooled. The precipitate is sucked off and recrystallized from successively methanol and petroleum ether (60 : 80). Melting point of the resulting compound is 34.5°-35.5.° C. cooled recrystallized from successively methanol and petroleum ether (60 : 80) is 34.5°

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 9.4 g of p-butoxyphenylacetonitrile and 10.2 g of p-heptylbenzaldehyde are dissolved in 30 ml of methanol. 5 ml of a 40% solution of benzyltrimethylammoniumhydrate in water are added to the solution. The whole is heated at 70° C for 30 minutes and then cooled. The precipitate is sucked off and recrystallized from successively methanol and petroleum ether (60 : 80). Melting point of the resulting compound is 34.5°-35.5.° C. cooled recrystallized from successively methanol and petroleum ether (60 : 80) is 34.5°

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

実験手順: 88 g of n-heptylbenzene are taken up in 50 ml of trifluoroacetic acid and 70 g of hexamethylenetetramine. The whole is refluxed for 12 hours after which the excess of trifluoroacetic acid is distilled off by means of a water jet airpump. The mixture is then poured in ice water and neutralized with soda. After extraction with ether the resulting ether solution is evaporated and the resulting 4-heptylbenzaldehyde is used for the following process step. is distilled off by means of a water jet airpump The mixture is then poured in ice water and neutralized with soda After extraction with ether the resulting ether solution is evaporated

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

実験手順: To a stirred solution of 6.60 g (30 mmol) of 4-heptylbenzoic acid (obtained from Aldrich Chemical Company (#23,064-2) and used without purification) in 50 mL of dichloromethane at room temperature under nitrogen was added 4.0 mL (45 mmol, 1.5 equivalents) of oxalyl chloride and then 0.1 mL (1.3 mmol) of DMF. The resulting vigorously bubbling solution was stirred for 1 h and then evaporated. The semi-solid residue was dissolved in 40 mL of benzene under argon and 350 mg (0.31 mmol) of tetrakis(triphenylphosphine)palladium was added. To this stirring solution at room temperature was added 11.1 mL (34 mmol) of tributyltin hydride over 20 min. The solution turns yellow and warms autogenously to 40° C. After 1 h, the reaction was treated with 100 mL of 10% aqueous potassium fluoride and stirred vigorously for 30 min. The reaction mass was filtered, the filtrate diluted with ether, washed with water, and the organic layer separated, dried (MgSO4) and evaporated onto 10 g of silica gel. Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield, of title compound as a colorless oil. evaporated The semi-solid residue was dissolved in 40 mL of benzene under argon autogenously to 40° C After 1 h stirred vigorously for 30 min The reaction mass was filtered the filtrate diluted with ether washed with water the organic layer separated dried (MgSO4) evaporated onto 10 g of silica gel Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield

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

実験手順: To a stirred solution of 6.60 g (30 mmol) of 4-heptylbenzoic acid (obtained from Aldrich Chemical Company (#23,064-2) and used without purification) in 50 mL of dichloromethane at room temperature under nitrogen was added 4.0 mL (45 mmol, 1.5 equivalents) of oxalyl chloride and then 0.1 mL (1.3 mmol) of DMF. The resulting vigorously bubbling solution was stirred for 1 h and then evaporated. The semi-solid residue was dissolved in 40 mL of benzene under argon and 350 mg (0.31 mmol) of tetrakis(triphenylphosphine)palladium was added. To this stirring solution at room temperature was added 11.1 mL (34 mmol) of tributyltin hydride over 20 min. The solution turns yellow and warms autogenously to 40° C. After 1 h, the reaction was treated with 100 mL of 10% aqueous potassium fluoride and stirred vigorously for 30 min. The reaction mass was filtered, the filtrate diluted with ether, washed with water, and the organic layer separated, dried (MgSO4) and evaporated onto 10 g of silica gel. Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield, of title compound as a colorless oil. evaporated The semi-solid residue was dissolved in 40 mL of benzene under argon autogenously to 40° C After 1 h stirred vigorously for 30 min The reaction mass was filtered the filtrate diluted with ether washed with water the organic layer separated dried (MgSO4) evaporated onto 10 g of silica gel Purification by flash chromatography (5×20 cm column, 3:7 dichloromethane/hexanes as elutent) gave 5.95 g, 97% yield