3,5-dichloro-4-methoxyaniline

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: Acetylsalicylic acid (1.8 g.) was converted to its acid chloride by conventional method using thionyl chloride and dissolved in acetone (30 ml.). 4-Amino-2,6-dichloroanisole (2.13 g.) with N,N-dimethylaniline (1.27 ml.) was dissolved in acetone (25 ml.) to which, with stirring in the cold at 0°-10° C., the above acetone solution of acetylsalicyloyl chloride was added dropwise over 20-30 minutes. Reaction continued for 1-2 hours, then the solution was evaporated to dryness under reduced pressure, the residue being put in sodium hydroxide solution and gently agitated for 1-2 hours for cleavage of the acetyl group. After reaction was complete the solution was made acidic by the addition of 2 N hydrochloric acid and the precipitate which formed was collected by filtration and recrystallized from aqueous acetone to give needle-like crystals (2.0 g.) of 3,5-dichloro-2'-hydroxy-4-methoxybenzanilide. Yield 64%. The melting point of the product is 226° - 228° C. Reaction the solution was evaporated to dryness under reduced pressure gently agitated for 1-2 hours for cleavage of the acetyl group After reaction the precipitate which formed was collected by filtration recrystallized from aqueous acetone

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: Acetylsalicylic acid (1.8 g.) was converted to its acid chloride by conventional method using thionyl chloride and dissolved in acetone (30 ml.). 4-Amino-2,6-dichloroanisole (2.13 g.) with N,N-dimethylaniline (1.27 ml.) was dissolved in acetone (25 ml.) to which, with stirring in the cold at 0°-10° C., the above acetone solution of acetylsalicyloyl chloride was added dropwise over 20-30 minutes. Reaction continued for 1-2 hours, then the solution was evaporated to dryness under reduced pressure, the residue being put in sodium hydroxide solution and gently agitated for 1-2 hours for cleavage of the acetyl group. After reaction was complete the solution was made acidic by the addition of 2 N hydrochloric acid and the precipitate which formed was collected by filtration and recrystallized from aqueous acetone to give needle-like crystals (2.0 g.) of 3,5-dichloro-2'-hydroxy-4-methoxybenzanilide. Yield 64%. The melting point of the product is 226° - 228° C. Reaction the solution was evaporated to dryness under reduced pressure gently agitated for 1-2 hours for cleavage of the acetyl group After reaction the precipitate which formed was collected by filtration recrystallized from aqueous acetone

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

実験手順: Acetylsalicylic acid (1.8 g.) was converted to its acid chloride by conventional method using thionyl chloride and dissolved in acetone (30 ml.). 4-Amino-2,6-dichloroanisole (2.13 g.) with N,N-dimethylaniline (1.27 ml.) was dissolved in acetone (25 ml.) to which, with stirring in the cold at 0°-10° C., the above acetone solution of acetylsalicyloyl chloride was added dropwise over 20-30 minutes. Reaction continued for 1-2 hours, then the solution was evaporated to dryness under reduced pressure, the residue being put in sodium hydroxide solution and gently agitated for 1-2 hours for cleavage of the acetyl group. After reaction was complete the solution was made acidic by the addition of 2 N hydrochloric acid and the precipitate which formed was collected by filtration and recrystallized from aqueous acetone to give needle-like crystals (2.0 g.) of 3,5-dichloro-2'-hydroxy-4-methoxybenzanilide. Yield 64%. The melting point of the product is 226° - 228° C. Reaction the solution was evaporated to dryness under reduced pressure gently agitated for 1-2 hours for cleavage of the acetyl group After reaction the precipitate which formed was collected by filtration recrystallized from aqueous acetone

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

実験手順: A stirred mixture of 2,6-dichloro-4-nitroanisole (4.6 g, 21 mM) and tin(II) dichloride dihydrate (23.4 g, 104 mM) in ethanol (72 mL) was refluxed for 3 hr. After cooling to room temperature, the reaction mixture was poured into ice water which was then treated with 2N sodium hydroxide until the solution became basic. The resulting mixture was filtered through diatomaceous earth and the filtrate was extracted with ethyl acetate. The combined ethyl acetate extracts were dried (MgSO4), filtered and concentrated to obtain (3.33 g, 83.7%) the title compound as a yellow-brown solid, mp 80°-81° C.; MS(CI): 192 (M+H). was refluxed for 3 hr The resulting mixture was filtered through diatomaceous earth the filtrate was extracted with ethyl acetate The combined ethyl acetate extracts were dried (MgSO4) filtered concentrated

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

実験手順: A stirred mixture of 2,6-dichloro-4-nitroanisole (4.6 g, 21 mM) and tin(II) dichloride dihydrate (23.4 g, 104 mM) in ethanol (72 mL) was refluxed for 3 hr. After cooling to room temperature, the reaction mixture was poured into ice water which was then treated with 2N sodium hydroxide until the solution became basic. The resulting mixture was filtered through diatomaceous earth and the filtrate was extracted with ethyl acetate. The combined ethyl acetate extracts were dried (MgSO4), filtered and concentrated to obtain (3.33 g, 83.7%) the title compound as a yellow-brown solid, mp 80°-81° C.; MS(CI): 192 (M+H). was refluxed for 3 hr The resulting mixture was filtered through diatomaceous earth the filtrate was extracted with ethyl acetate The combined ethyl acetate extracts were dried (MgSO4) filtered concentrated

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

実験手順: Acetylsalicyclic acid (1.8 g.) was converted to its acid chloride by conventional method using thionyl chloride and dissolved in acetone (30 ml.). 4-Amino-2,6-dichloroanisole (2.13 g.) with N,N-dimethylaniline (1.27 ml.) was dissolved in acetone (25 ml.) to which, with stirring in the cold at 0°-10° C., the above acetone solution of acetylsalicyloyl chloride was added dropwise over 20-30 minutes. Reaction continued for 1-2 hours, then the solution was evaporated to dryness under reduced pressure, the residue being put in sodium hydroxide solution and gently agitated for 1-2 hours for cleavage of the acetyl group. After reaction was complete the solution was made acidic by the addition of 2 N hydrochloric acid and the precipitate which formed was collected by filtration and recrystallized from aqueous acetone to give needle-like crystals (2.0 g.) of 3,5-dichloro-2'-hydroxy-4-methoxybenzanilide. Yield 64%. The melting point of the product is 226°-228° C. Reaction the solution was evaporated to dryness under reduced pressure gently agitated for 1-2 hours for cleavage of the acetyl group After reaction the precipitate which formed was collected by filtration recrystallized from aqueous acetone

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

実験手順: Acetylsalicyclic acid (1.8 g.) was converted to its acid chloride by conventional method using thionyl chloride and dissolved in acetone (30 ml.). 4-Amino-2,6-dichloroanisole (2.13 g.) with N,N-dimethylaniline (1.27 ml.) was dissolved in acetone (25 ml.) to which, with stirring in the cold at 0°-10° C., the above acetone solution of acetylsalicyloyl chloride was added dropwise over 20-30 minutes. Reaction continued for 1-2 hours, then the solution was evaporated to dryness under reduced pressure, the residue being put in sodium hydroxide solution and gently agitated for 1-2 hours for cleavage of the acetyl group. After reaction was complete the solution was made acidic by the addition of 2 N hydrochloric acid and the precipitate which formed was collected by filtration and recrystallized from aqueous acetone to give needle-like crystals (2.0 g.) of 3,5-dichloro-2'-hydroxy-4-methoxybenzanilide. Yield 64%. The melting point of the product is 226°-228° C. Reaction the solution was evaporated to dryness under reduced pressure gently agitated for 1-2 hours for cleavage of the acetyl group After reaction the precipitate which formed was collected by filtration recrystallized from aqueous acetone

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

実験手順: Acetylsalicyclic acid (1.8 g.) was converted to its acid chloride by conventional method using thionyl chloride and dissolved in acetone (30 ml.). 4-Amino-2,6-dichloroanisole (2.13 g.) with N,N-dimethylaniline (1.27 ml.) was dissolved in acetone (25 ml.) to which, with stirring in the cold at 0°-10° C., the above acetone solution of acetylsalicyloyl chloride was added dropwise over 20-30 minutes. Reaction continued for 1-2 hours, then the solution was evaporated to dryness under reduced pressure, the residue being put in sodium hydroxide solution and gently agitated for 1-2 hours for cleavage of the acetyl group. After reaction was complete the solution was made acidic by the addition of 2 N hydrochloric acid and the precipitate which formed was collected by filtration and recrystallized from aqueous acetone to give needle-like crystals (2.0 g.) of 3,5-dichloro-2'-hydroxy-4-methoxybenzanilide. Yield 64%. The melting point of the product is 226°-228° C. Reaction the solution was evaporated to dryness under reduced pressure gently agitated for 1-2 hours for cleavage of the acetyl group After reaction the precipitate which formed was collected by filtration recrystallized from aqueous acetone

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

実験手順: 3,5-Dichloro-4-methoxyaniline (1.8 g) and diethylaniline (1.5 g) were dissolved in benzene (20 ml). To the resultant solution was dropwise added isopropyl chloroformate (1.2 g) in 5 minutes under ice-cooling. After being allowed to stand at room temperature for 12 hours, the reaction mixture was poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of benzene and tetrahydrofuran as the eluent to give isopropyl N-(3,5-dichloro-4-methoxyphenyl)carbamate (Compound No. 2) (2.4 g) in a yield of 91.8%. M.P., 107.5°-108° C. in 5 minutes cooling extracted with ethyl acetate The extract was washed with water dried over magnesium sulfate concentrated under reduced pressure The residue was purified by silica gel chromatography a mixture of benzene and tetrahydrofuran as the eluent

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

実験手順: A stirred mixture of 2,6-dichloro-4-nitroanisole (4.6 g, 21 mM) and tin(II) dichloride dihydrate (23.4 g, 104 mM) in ethanol (72 mL) was refluxed for 3 hr. After cooling to room temperature, the reaction mixture was poured into ice water which was then treated with 2N sodium hydroxide until the solution became basic. The resulting mixture was filtered through diatomaceous earth and the filtrate was extracted with ethyl acetate. The combined ethyl acetate extracts were dried (MgSO4), filtered and concentrated to obtain (3.33 g, 83.7%) the title compound as a yellow-brown solid, mp 80°-81° C.; MS(CI): 192 (M+H). was refluxed for 3 hr The resulting mixture was filtered through diatomaceous earth the filtrate was extracted with ethyl acetate The combined ethyl acetate extracts were dried (MgSO4) filtered concentrated