(E)-1-chlorobut-2-ene

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

実験手順: The N-methoxycarbonyl-3-hydroxy-4-methoxyaniline (34.0 g) was dissolved in dimethylformamide (200 ml). Potassium carbonate (29.0 g) and trans-crotyl chloride (32.2 g) were added to the solution, and the mixture was stirred at room temperature for 5 hours. Water was added to the reaction mixture, and extraction was carried out with ethyl acetate. The extract was washed with saturated saline and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The crude crystal thus obtained was recrystallized from ethyl acetate-n-hexane to obtain N-methoxycarbonyl-3-(2-trans-butenyl)oxy-4-methoxyaniline (39.5 g). The extract was washed with saturated saline dried over sodium sulfate the solvent was distilled off under reduced pressure The crude crystal thus obtained was recrystallized from ethyl acetate-n-hexane

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

実験手順: The N-methoxycarbonyl-3-hydroxy-4-methoxyaniline (34.0 g) was dissolved in dimethylformamide (200 ml). Potassium carbonate (29.0 g) and trans-crotyl chloride (32.2 g) were added to the solution, and the mixture was stirred at room temperature for 5 hours. Water was added to the reaction mixture, and extraction was carried out with ethyl acetate. The extract was washed with saturated saline and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The crude crystal thus obtained was recrystallized from ethyl acetate-n-hexane to obtain N-methoxycarbonyl-3-(2-trans-butenyl)oxy-4-methoxyaniline (39.5 g). The extract was washed with saturated saline dried over sodium sulfate the solvent was distilled off under reduced pressure The crude crystal thus obtained was recrystallized from ethyl acetate-n-hexane

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

実験手順: In accordance with the process of Reference 1, sodium hydride (1.20 g; 50 m mol), methyl acetoacetate (5.70 g; 50 m mol), n-butyl lithium (50 m mol) and trans-crotyl chloride (4.43 g; 50 m mol) were used to obtain 3.60 g of (E)-3-oxo-6-octenoic acid methyl ester.

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

実験手順: A Grignard mixture containing 3 moles of 8-chloro-1-octynyl magnesium chloride in 900 g of tetrahydrofuran was introduced into a reaction vessel and agitated for several minutes with addition of 3 g of copper (I) chloride. Thereafteer, 271.5 g (3 moles) of (E)-2-butenyl chloride were added dropwise to the mixture which was kept at a temperature not to exceed 65° C. followed by further continued agitation for 1.5 hours to complete the reaction. Thereafter, 800 g of an aqueous solution containing 5% ammonium chloride and 5% hydrogen chloride were added to the reaction mixture to effect the hydrolysis. The mixture was then subjected to phase separation and the organic phase was freed from tetrahydrofuran and then to rectification distillation to give 451 g of 1-chloro-(E)-10-dodecen-7-yne having a purity of 95%. The yield of this compound was 72% of the theoretical value. was introduced into a reaction vessel to exceed 65° C. the reaction were added to the reaction mixture the hydrolysis The mixture was then subjected to phase separation to rectification distillation

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

実験手順: There were put 2.5 g of 9-allylfluorene and 31.3 mL of dry tetrahydrofuran manufactured by Kanto Chemical Co., Inc. in a 100 mL-three necked flask. There were added dropwise thereto at 0° C. over 30 minutes 9 mL of a hexane solution of n-butyllithium (concentration: 1.6 M) manufactured by Kanto Chemical Co., Inc. The resultant mixture was stirred for 2 hours at room temperature, and then 1.4 mL of trans-crotyl chloride manufactured by Aldrich Chemical Company was added dropwise thereto at 0° C. The temperature of the mixture was raised gradually up to room temperature, and then the mixture was stirred for 6 hours at room temperature. Water was added to the reaction mixture, and the obtained mixture was subjected to extraction with ether. The extract was washed with water and with a saline solution in this order. The washed extract was dried over anhydrous magnesium sulfate manufactured by Nacalai Tesque, Inc. The dried extract was subjected to removal of the solvent by distillation, and the resultant liquid was distilled in vacuo, thereby obtaining 2.43 g of 9-allyl-9-((2E)-2-butenyl)-fluorene at 155° C. under 4 mmHg. There were added dropwise was added dropwise at 0° C the obtained mixture was subjected to extraction with ether The extract was washed with water and with a saline solution in this order The washed extract was dried over anhydrous magnesium sulfate The dried extract was subjected to removal of the solvent by distillation the resultant liquid was distilled in vacuo

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

実験手順: There were put 2.5 g of 9-allylfluorene and 31.3 mL of dry tetrahydrofuran manufactured by Kanto Chemical Co., Inc. in a 100 mL-three necked flask. There were added dropwise thereto at 0° C. over 30 minutes 9 mL of a hexane solution of n-butyllithium (concentration: 1.6 M) manufactured by Kanto Chemical Co., Inc. The resultant mixture was stirred for 2 hours at room temperature, and then 1.4 mL of trans-crotyl chloride manufactured by Aldrich Chemical Company was added dropwise thereto at 0° C. The temperature of the mixture was raised gradually up to room temperature, and then the mixture was stirred for 6 hours at room temperature. Water was added to the reaction mixture, and the obtained mixture was subjected to extraction with ether. The extract was washed with water and with a saline solution in this order. The washed extract was dried over anhydrous magnesium sulfate manufactured by Nacalai Tesque, Inc. The dried extract was subjected to removal of the solvent by distillation, and the resultant liquid was distilled in vacuo, thereby obtaining 2.43 g of 9-allyl-9-((2E)-2-butenyl)-fluorene at 155° C. under 4 mmHg. There were added dropwise was added dropwise at 0° C the obtained mixture was subjected to extraction with ether The extract was washed with water and with a saline solution in this order The washed extract was dried over anhydrous magnesium sulfate The dried extract was subjected to removal of the solvent by distillation the resultant liquid was distilled in vacuo

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

実験手順: The N-methoxycarbonyl-3-hydroxy-4-methoxyaniline (34.0 g) was dissolved in dimethylformamide (200 ml). Potassium carbonate (29.0 g) and trans-crotyl chloride (32.2 g) were added to the solution, and the mixture was stirred at room temperature for 5 hours. Water was added to the reaction mixture, and extraction was carried out with ethyl acetate. The extract was washed with saturated saline and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The crude crystal thus obtained was recrystallized from ethyl acetate-n-hexane to obtain N-methoxycarbonyl-3-(2-trans-butenyl)oxy-4-methoxyaniline (39.5 g). The extract was washed with saturated saline dried over sodium sulfate the solvent was distilled off under reduced pressure The crude crystal thus obtained was recrystallized from ethyl acetate-n-hexane

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

実験手順: In accordance with the process of Reference 1, sodium hydride (1.20 g; 50 m mol), methyl acetoacetate (5.70 g; 50 m mol), n-butyl lithium (50 m mol) and trans-crotyl chloride (4.43 g; 50 m mol) were used to obtain 3.60 g of (E)-3-oxo-6-octenoic acid methyl ester.