3-氨基-5-氯-2-羟基苯甲酸甲酯

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 100 ml of an aqueous 0.78N ammonium chloride solution (with heating at 85° C.) is added 33.4 g of powdery iron with stirring followed by addition of a solution of 49.1 g of methyl 5-chloro-3-nitrosalicylate in 500 ml of toluene over 30 minutes. The reaction temperature rises to 95° C. The resultant solution is stirred at 80°-90° C. for an hour, and filtered with suction through hot celite. The mother liquor is poured into 1 l of ice-cold water, and the toluene layer is separated, washed with water and dried over magnesium sulfate. The solvent is distilled off and the residue is recrystallized from ethanol to give 25.4 g of methyl 3-amino -5-chlorosalicylate, melting at 65°-67° C. rises to 95° C filtered with suction through hot celite The mother liquor is poured into 1 l of ice-cold water the toluene layer is separated washed with water dried over magnesium sulfate The solvent is distilled off the residue is recrystallized from ethanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 100 ml of an aqueous 0.78N ammonium chloride solution (with heating at 85° C.) is added 33.4 g of powdery iron with stirring followed by addition of a solution of 49.1 g of methyl 5-chloro-3-nitrosalicylate in 500 ml of toluene over 30 minutes. The reaction temperature rises to 95° C. The resultant solution is stirred at 80°-90° C. for an hour, and filtered with suction through hot celite. The mother liquor is poured into 1 l of ice-cold water, and the toluene layer is separated, washed with water and dried over magnesium sulfate. The solvent is distilled off and the residue is recrystallized from ethanol to give 25.4 g of methyl 3-amino -5-chlorosalicylate, melting at 65°-67° C. rises to 95° C filtered with suction through hot celite The mother liquor is poured into 1 l of ice-cold water the toluene layer is separated washed with water dried over magnesium sulfate The solvent is distilled off the residue is recrystallized from ethanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Amino-5-chloro-2-hydroxy-benzoic acid methyl ester 8 g (39.6 mmol) is dissolved in tetrahydrofuran 100 mL and carbonyl diimidazole (12.9 g, 79.3 mmol) is added. The reaction is heated to reflux for 2 hours and then cooled to room temperature. The reaction is evaporated in vacuo and then taken up in dichloromethane (200 mL) and then washed with HCl (2N, 50 mL 2×) and water (2×50 mL). The organic layer is dried (Na2SO4) filtered and evaporated in vacuo to give the title compound (8.2 g, 36 mmol, 91%). LCMS (ESMS): m/z 228.9 (M+H+). The reaction is heated to reflux for 2 hours The reaction is evaporated in vacuo washed with HCl (2N, 50 mL 2×) and water (2×50 mL) The organic layer is dried (Na2SO4) filtered evaporated in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 5-Chloro-2-hydroxy-3-nitro-benzoic acid methyl ester 1 g (4.31 mmol) is dissolved in methanol (30 mL) and acetic acid (30 mL) and then iron powder is added (4.8 g, 86 mmol) at room temperature. The resulting suspension is stirred and heated to reflux for 1 hour. The reaction is allowed to cool to room temperature and then gravity filtered though a pad of celite. The celite cake is washed 3× with ethyl acetate (50 mL) and then the combined washings evaporated in vacuo. The oil is then taken up in ethyl acetate (250 mL) and washed with water (100 mL) and saturated sodium bicarbonate (100 mL). The organic layer is dried (MgSO4), decolorized with charcoal, filtered and evaporated to give the title compound that is used without further purification (730 mg, 3.6 mmol, 84%). LCMS (ESMS): m/z 202.5 (M+H+). heated to reflux for 1 hour gravity filtered though a pad of celite The celite cake is washed 3× with ethyl acetate (50 mL) the combined washings evaporated in vacuo washed with water (100 mL) and saturated sodium bicarbonate (100 mL) The organic layer is dried (MgSO4) filtered evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 100 ml of an aqueous 0.78N ammonium chloride solution (with heating at 85° C.) is added 33.4 g of powdery iron with stirring followed by addition of a solution of 49.1 g of methyl 5-chloro-3-nitrosalicylate in 500 ml of toluene over 30 minutes. The reaction temperature rises to 95° C. The resultant solution is stirred at 80°-90° C. for an hour, and filtered with suction through hot celite. The mother liquor is poured into 1 l of ice-cold water, and the toluene layer is separated, washed with water and dried over magnesium sulfate. The solvent is distilled off and the residue is recrystallized from ethanol to give 25.4 g of methyl 3-amino -5-chlorosalicylate, melting at 65°-67° C. rises to 95° C filtered with suction through hot celite The mother liquor is poured into 1 l of ice-cold water the toluene layer is separated washed with water dried over magnesium sulfate The solvent is distilled off the residue is recrystallized from ethanol