methyl 3-chlorobenzoate

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:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of n-butyl lithium in hexane (1.63N, 45 ml, 73.3 mmol) was added dropwise to a solution of dimethyl methylphosphonate (9.1 g, 73.3 mmol) in 100 ml of anhydrous THF with stirring at -78° C. under argon atmosphere, and the mixture was stirred for 30 minutes. Then, methyl m-chlorobenzoate (5.0 g, 29.3 mmol) in 10 ml of anhydrous THF was further added dropwise and the mixture was stirred for 30 minutes. This reaction mixture was allowed to warm to 0° C., diluted with 4.4 ml of acetic acid and 10 ml of water, and concentrated. 30 ml of water was added to the residue and the mixture was extracted with ethyl acetate (50 ml×2). The combined ethyl acetate layers were washed with water (30 ml×1) and brine (30 ml×1), dried over anhydrous sodium sulfate, and concentrated. The residue was distilled under reduced pressure to give a colorless transparent oil of dimethyl 2-m-chlorophenyl-2-oxoethylphosphonate (6.5 g, 24.8 mmol, yield 84%, b.p. 144°-146° C./0.06 mmHg), which was assigned the structure by the following data: the mixture was stirred for 30 minutes the mixture was stirred for 30 minutes to warm to 0° C. concentrated 30 ml of water was added to the residue the mixture was extracted with ethyl acetate (50 ml×2) The combined ethyl acetate layers were washed with water (30 ml×1) and brine (30 ml×1) dried over anhydrous sodium sulfate concentrated The residue was distilled under reduced pressure

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

実験手順: An excess solution of diazomethane in ether was added to an ice-cooled and stirred solution of m-chlorobenzoic acid (8.26 g, 52.8 mmol) in 50 ml of ether. The mixture was concentrated and distilled under reduced pressure to give a colorless transparent oil of methyl m-chlorobenzoate (6.1 g, 35.8 mmol, yield 67.8%, b.p. 116°-121° C./21 mmHg), which was assigned the structure by the following data: cooled The mixture was concentrated distilled under reduced pressure

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

実験手順: Sodium (11 g, spheres) was added to 200 ml ethanol with stirring. When the gas evolution ceased, methyl 3-chlorobenzoate (10 g, 0.057 mole) and dimethyl succinate (9.0 g, 0.615 mole) were added rapidly and the mixture was stirred for 5 minutes at room temperature. The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which was slurried in 100 ml ether and an additional 2 ml of dimethyl succinate was added. The reaction was evaporated to a paste, quenched with water and extracted with ether. The ether extracts were washed with water and brine, dried and evaporated in vacuo. the mixture was stirred for 5 minutes at room temperature The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which The reaction was evaporated to a paste quenched with water extracted with ether The ether extracts were washed with water and brine dried evaporated in vacuo

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5,6-Dihydro-cyclopenta[b]thiophen-4-one (2.1 g, 15.0 mmol) in 10 mL of THF was treated with NaH (60 percent, 0.73 g, 18 mmol). After the addition of 3-Chloro-benzoic acid methyl ester, the reaction mixture was heated at 100° C. for 8 hr. The solution was cooled to room temperature and poured into water. The resulting mixture was acidified with concentrated HCl and was added with ethyl acetate (80 mL). The organic layer was collected, brined, dried over MgSO4(s), and concentrated under reduced pressure. The resultant precipitate was collected and recrystallized from ethanol to provide the corresponding 5-(4-Chloro-benzoyl)-5,6-dihydro-cyclopenta[b]thiophen-4-one (0.9 g, 3.3 mmol) as brown solid in 45% yield. The solution was cooled to room temperature The organic layer was collected dried over MgSO4(s) concentrated under reduced pressure The resultant precipitate was collected recrystallized from ethanol

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

実験手順: Sodium (11 g, spheres) was added to 200 ml ethanol with stirring. When the gas evolution ceased, methyl 3-chlorobenzoate (10 g, 0.057 mole) and dimethyl succinate (9.0 g, 0.615 mole) were added rapidly and the mixture was stirred for 5 minutes at room temperature. The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which was slurried in 100 ml ether and an additional 2 ml of dimethyl succinate was added. The reaction was evaporated to a paste, quenched with water and extracted with ether. The ether extracts were washed with water and brine, dried and evaporated in vacuo. the mixture was stirred for 5 minutes at room temperature The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which The reaction was evaporated to a paste quenched with water extracted with ether The ether extracts were washed with water and brine dried evaporated in vacuo

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

実験手順: Sodium (11 g, spheres) was added to 200 ml ethanol with stirring. When the gas evolution ceased, methyl 3-chlorobenzoate (10 g, 0.057 mole) and dimethyl succinate (9.0 g, 0.615 mole) were added rapidly and the mixture was stirred for 5 minutes at room temperature. The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which was slurried in 100 ml ether and an additional 2 ml of dimethyl succinate was added. The reaction was evaporated to a paste, quenched with water and extracted with ether. The ether extracts were washed with water and brine, dried and evaporated in vacuo. the mixture was stirred for 5 minutes at room temperature The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which The reaction was evaporated to a paste quenched with water extracted with ether The ether extracts were washed with water and brine dried evaporated in vacuo

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

実験手順: Sodium (11 g, spheres) was added to 200 ml ethanol with stirring. When the gas evolution ceased, methyl 3-chlorobenzoate (10 g, 0.057 mole) and dimethyl succinate (9.0 g, 0.615 mole) were added rapidly and the mixture was stirred for 5 minutes at room temperature. The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which was slurried in 100 ml ether and an additional 2 ml of dimethyl succinate was added. The reaction was evaporated to a paste, quenched with water and extracted with ether. The ether extracts were washed with water and brine, dried and evaporated in vacuo. the mixture was stirred for 5 minutes at room temperature The mixture was slowly concentrated on a rotary evaporator to yield a greenish paste which The reaction was evaporated to a paste quenched with water extracted with ether The ether extracts were washed with water and brine dried evaporated in vacuo