N-甲酰基邻甲苯胺

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

实验步骤: 79 g (1.1 moles) of chlorine is introduced into a solution of 135 g (1 mole) of 2 -formylaminotoluene in 500 ml of chloroform at 20° to 25° C. in the course of 2 to 3 hours. After the addition of 28 g (0.88 mole) of methanol, the mixture obtained is stirred for 2 hours at 25° to 30° C., and the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off. There is obtained 130 g (73% of theory relative to 2 -formylaminotoluene) of 2 -amino-5 -chlorotoluene hydrochloride. The content of 2 -amino-5 -chlorotoluene hydrochloride in the product is 98 to 99%. the mixture obtained the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off

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

实验步骤: 79 g (1.1 moles) of chlorine is introduced into a solution of 135 g (1 mole) of 2 -formylaminotoluene in 500 ml of chloroform at 20° to 25° C. in the course of 2 to 3 hours. After the addition of 28 g (0.88 mole) of methanol, the mixture obtained is stirred for 2 hours at 25° to 30° C., and the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off. There is obtained 130 g (73% of theory relative to 2 -formylaminotoluene) of 2 -amino-5 -chlorotoluene hydrochloride. The content of 2 -amino-5 -chlorotoluene hydrochloride in the product is 98 to 99%. the mixture obtained the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off

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

实验步骤: Splitting of the 2-formylamino-5-chlorotoluene, formed on chlorination of 2-formylaminotoluene, with methanol is performed at a temperature of between 20° and 60° C., preferably at between 25° and 30° C. The reaction duration is about 1 to 2 hours.

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

实验步骤: Splitting of the 2-formylamino-5-chlorotoluene, formed on chlorination of 2-formylaminotoluene, with methanol is performed at a temperature of between 20° and 60° C., preferably at between 25° and 30° C. The reaction duration is about 1 to 2 hours.

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

实验步骤: An improved process for the production of 2-amino-chlorotoluene hydrochloride comprising chlorination of 2-formyl-amino-toluene, splitting off the formyl group of the 2-formyl-amino-chlorotoluenes and isolation of crystalline 2-amino-5-chlorotoluene hydrochloride is disclosed, in which process the 2-formylamino-5-chlorotoluene formed by chlorination of 2-formylamino-toluene in an inert solvent is reacted with methanol to form 2-amino-5-chlorotoluene and methyl formate, and the 2-amino-5-chlorotoluene is isolated as hydrochloride.

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

实验步骤: An improved process for the production of 2-amino-chlorotoluene hydrochloride comprising chlorination of 2-formyl-amino-toluene, splitting off the formyl group of the 2-formyl-amino-chlorotoluenes and isolation of crystalline 2-amino-5-chlorotoluene hydrochloride is disclosed, in which process the 2-formylamino-5-chlorotoluene formed by chlorination of 2-formylamino-toluene in an inert solvent is reacted with methanol to form 2-amino-5-chlorotoluene and methyl formate, and the 2-amino-5-chlorotoluene is isolated as hydrochloride.

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

实验步骤: 79 g (1.1 moles) of chlorine is introduced into a solution of 135 g (1 mole) of 2 -formylaminotoluene in 500 ml of chloroform at 20° to 25° C. in the course of 2 to 3 hours. After the addition of 28 g (0.88 mole) of methanol, the mixture obtained is stirred for 2 hours at 25° to 30° C., and the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off. There is obtained 130 g (73% of theory relative to 2 -formylaminotoluene) of 2 -amino-5 -chlorotoluene hydrochloride. The content of 2 -amino-5 -chlorotoluene hydrochloride in the product is 98 to 99%. the mixture obtained the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off

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

实验步骤: Splitting of the 2-formylamino-5-chlorotoluene, formed on chlorination of 2-formylaminotoluene, with methanol is performed at a temperature of between 20° and 60° C., preferably at between 25° and 30° C. The reaction duration is about 1 to 2 hours.

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

实验步骤: An improved process for the production of 2-amino-chlorotoluene hydrochloride comprising chlorination of 2-formyl-amino-toluene, splitting off the formyl group of the 2-formyl-amino-chlorotoluenes and isolation of crystalline 2-amino-5-chlorotoluene hydrochloride is disclosed, in which process the 2-formylamino-5-chlorotoluene formed by chlorination of 2-formylamino-toluene in an inert solvent is reacted with methanol to form 2-amino-5-chlorotoluene and methyl formate, and the 2-amino-5-chlorotoluene is isolated as hydrochloride.

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

实验步骤: A mixture of 8b (4.055 g, 30 mmol) and phosphorus pentasulfide (1.351 g, 3.04 mmol) in dry 1,4-dioxane (4 mL) was stirred at room temperature for 15 min under an argon atmosphere. 4-Chloro-2-butanone (2.131 g, 20 mmol) was added and the resulting slurry was heated at 100° C. The reaction mixture was refluxed for 50 min, initially becoming clear yellow and finally deep red. After cooling at room temperature, the crude mixture was diluted with H2O (20 mL). Na2CO3 was added to the reaction mixture until pH≈7. The solvent was evaporated under reduced pressure and the resulting solid was suspended in CH2Cl2 and purified by column chromatography (column packed with silica gel) eluting with EtOH/CH2Cl2 (15/85). Upon concentration of the last yellowish band, a viscous orange oil was obtained. This was solidified when washed under vigorous stirring with diethyl ether (3×2 mL) to afford 9b as a tan solid (1.20 g, 17%). 1H NMR (CD2Cl2, 300 MHz): δ=11.09 (s, 1H), 7.53-7.31 (m, 4H), 2.57 (s, 3H), 2.08 (s, 3H), 2.04 (s, 3H); 13C{1H} NMR (CD2Cl2, 75 MHz): δ=160.77, 142.05, 136.10, 134.60, 134.30, 132.23, 132.00, 128.08, 126.55, 17.23, 12.90, 11.98; HRMS (FAB+) calculated for C12H14NS [M]+ 204.0847, observed 204.0845. the resulting slurry was heated at 100° C The reaction mixture was refluxed for 50 min After cooling at room temperature The solvent was evaporated under reduced pressure purified by column chromatography (column packed with silica gel) eluting with EtOH/CH2Cl2 (15/85) Upon concentration of the last yellowish band, a viscous orange oil was obtained washed under vigorous stirring with diethyl ether (3×2 mL)

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

实验步骤: A mixture of formic acid (14.361 g, 0.312 mol) and acetic anhydride (12.659 g, 0.124 mol) was stirred at room temperature for 1 h under an argon atmosphere. This mixture was added to a solution of 2-methylaniline (10.710 g, 0.1 mol) in dry dichloromethane (60 ml) at such a rate that the temperature of the reaction mixture was kept between 5 and 10° C. The reaction was stirred at room temperature for 16 h and then refluxed for 4 h. The solvent was evaporated under reduced pressure, the residue was dissolved in CHCl3 (200 mL) and washed with a saturated aqueous NaHCO3 solution (3×200 mL), and water (200 mL). The organic layer was dried over Na2SO4 and the solvent was evaporated under reduced pressure. The remaining yellow solid was washed with a mixture of hexanes/diethyl ether (2×10 mL) and then with hexanes (3×5 mL) to afford N-formyl-2-methylaniline 8b as a white solid (9.70 g, 72%). 1H NMR (CDCl3, 300 MHz): δ=9.03-8.18 (m, 2H, CHO, NH), 7.77-7.03 (m, 4H), 2.30-2.22 (m, 3H); 13C{1H}NMR (CDCl3, 75 MHz): δ=164.41, 160.32, 135.50, 134.99, 131.45, 130.82, 130.50, 129.87, 127.25, 126.80, 126.34, 125.84, 123.75, 121.32, 18.05, 17.99; HRMS (FAB+) calculated for C8H10NO [M]+ 136.0762, observed 136.0783. was kept between 5 and 10° C The reaction was stirred at room temperature for 16 h refluxed for 4 h The solvent was evaporated under reduced pressure the residue was dissolved in CHCl3 (200 mL) washed with a saturated aqueous NaHCO3 solution (3×200 mL), and water (200 mL) The organic layer was dried over Na2SO4 the solvent was evaporated under reduced pressure The remaining yellow solid was washed with a mixture of hexanes/diethyl ether (2×10 mL)

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

实验步骤: 79 g (1.1 moles) of chlorine is introduced into a solution of 135 g (1 mole) of 2 -formylaminotoluene in 500 ml of chloroform at 20° to 25° C. in the course of 2 to 3 hours. After the addition of 28 g (0.88 mole) of methanol, the mixture obtained is stirred for 2 hours at 25° to 30° C., and the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off. There is obtained 130 g (73% of theory relative to 2 -formylaminotoluene) of 2 -amino-5 -chlorotoluene hydrochloride. The content of 2 -amino-5 -chlorotoluene hydrochloride in the product is 98 to 99%. the mixture obtained the formed 2 -amino-5 -chlorotoluene hydrochloride is subsequently filtered off