ethyl 2-chlorobenzenecarboximidate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 2-chlorobenzimidate (2.80 g) and triethylamine (1.70 g) are dissolved in toluene (50 ml), to which is added dropwise (E)-3-chloro-2-methyl-2-butenoyl chloride at 5° C.-10° C. with stirring, and the stirring is continued at room temperature for 4 hours after the completion of the addition. After the completion of the reaction, the reaction mixture is added with toluene (150 ml), washed with a saline solution, dried on anhydrous magnesium sulfate and concentrated under a reduced pressure. The concentrate is purified through a silica gel column chromatography (Wakogel C-200: made by Wako Junyaku Kabushiki Kaisha) using a mixed solution of hexane-ethyl acetate (10:1) as a developing medium to obtain an oily ethyl (E)-N-(3-chloro-1-methyl-2-butenoyl)-2-chlorobenzimidate (2.37 g). after the completion of the addition After the completion of the reaction washed with a saline solution dried on anhydrous magnesium sulfate concentrated under a reduced pressure The concentrate is purified through a silica gel column chromatography (Wakogel C-200: made by Wako Junyaku Kabushiki Kaisha)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 2-chlorobenzimidate (2.80 g) and triethylamine (1.70 g) are dissolved in toluene (50 ml), to which is added dropwise (E)-3-chloro-2-methyl-2-butenoyl chloride at 5° C.-10° C. with stirring, and the stirring is continued at room temperature for 4 hours after the completion of the addition. After the completion of the reaction, the reaction mixture is added with toluene (150 ml), washed with a saline solution, dried on anhydrous magnesium sulfate and concentrated under a reduced pressure. The concentrate is purified through a silica gel column chromatography (Wakogel C-200: made by Wako Junyaku Kabushiki Kaisha) using a mixed solution of hexane-ethyl acetate (10:1) as a developing medium to obtain an oily ethyl (E)-N-(3-chloro-1-methyl-2-butenoyl)-2-chlorobenzimidate (2.37 g). after the completion of the addition After the completion of the reaction washed with a saline solution dried on anhydrous magnesium sulfate concentrated under a reduced pressure The concentrate is purified through a silica gel column chromatography (Wakogel C-200: made by Wako Junyaku Kabushiki Kaisha)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 40 g (22 mmol) of ethyl o-chlorobenzimidate and 22.2 g (21 mmol) of 2,6-lutidine in 500 ml of petroleum ether (b.p. 100°-130° C.) is treated with 27.2 g (25 mmol) of ethyl chloroformate and the whole is then heated at reflux temperature for about 16 hours. The precipitated salt is subsequently filtered off, the filtrate is evaporated under reduced pressure and the residue is recrystallized from diethyl ether. In this manner there is obtained ethyl (o-chloro-α-ethoxybenzylidene)carbamate, m.p. 65°-66° C.; 1H--NMR (CDCl3, 60 MHz): 4.02 (q,OCH2CH3), 4.58 (q, OCH2CH3); mass spectrum: 220(100). the whole is then heated at reflux temperature for about 16 hours The precipitated salt is subsequently filtered off the filtrate is evaporated under reduced pressure the residue is recrystallized from diethyl ether

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 40 g (22 mmol) of ethyl o-chlorobenzimidate and 22.2 g (21 mmol) of 2,6-lutidine in 500 ml of petroleum ether (b.p. 100°-130° C.) is treated with 27.2 g (25 mmol) of ethyl chloroformate and the whole is then heated at reflux temperature for about 16 hours. The precipitated salt is subsequently filtered off, the filtrate is evaporated under reduced pressure and the residue is recrystallized from diethyl ether. In this manner there is obtained ethyl (o-chloro-α-ethoxybenzylidene)carbamate, m.p. 65°-66° C.; 1H--NMR (CDCl3, 60 MHz): 4.02 (q,OCH2CH3), 4.58 (q, OCH2CH3); mass spectrum: 220(100). the whole is then heated at reflux temperature for about 16 hours The precipitated salt is subsequently filtered off the filtrate is evaporated under reduced pressure the residue is recrystallized from diethyl ether

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 41 g (22.3 mmol) of ethyl o-chlorobenzimidate and 25 g (25 mmol) of triethylamine in 500 ml of methylene chloride is treated dropwise with 19.5 g (24.8 mmol) of acetyl chloride, the temperature being held at 40° C. by the use of cooling. The reaction mixture is stirred at room temperature for a further 30 minutes, and the mixture is then washed in sequence with water, 5% sodium bicarbonate solution and semi-saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. After distillation of the crude product at 110° C./0.16 mmHg (21.33 Pa) there is obtained ethyl N-acetyl-o-chlorobenzimidate as a colourless liquid. being held at 40° C. by the use of cooling the mixture is then washed in sequence with water, 5% sodium bicarbonate solution and semi-saturated sodium chloride solution dried over anhydrous magnesium sulfate evaporated under reduced pressure After distillation of the crude product at 110° C./0.16 mmHg (21.33 Pa) there

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Analogously to the procedure described in Example 2, starting from ethyl o-chlorobenzimidate and o-trifluoromethyl-benzoyl chloride there is obtained ethyl N-(o-trifluoromethyl-benzoyl)-o-chlorobenzimidate, m.p. 64°-65° C., and therefrom by means of 2-hydroxyethylhydrazine there is obtained 3-(o-chlorophenyl)-1-(2-hydroxyethyl)-5-(o-trifluoromethyl-phenyl)-1H-1,2,4-triazole, m.p. 115° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: starting from ethyl o-chlorobenzimidate and 4-trifluoromethyl-nicotinoyl chloride there is obtained ethyl N-(4-trifluoromethyl-nicotinoyl)-2-chlorobenzimidate and therefrom with methylhydrazine there is obtained 3-(o-chlorophenyl)-1-methyl-5-(4-trifluoromethyl-3-pyridyl)-1H-1,2,4-triazole, 1H-NMR(CDCl3): 3.85 (s, N-CH3), 7.6-8.1 (5 aromatic H), 8.9-9.2 (2 aromatic H); mass spectrum: 338 (100), 319 (5), 166 (94), 138 (95);

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: starting from ethyl o-chlorobenzimidate and 4-trifluoromethyl-nicotinoyl chloride there is obtained ethyl N-(4-trifluoromethyl-nicotinoyl)-2-chlorobenzimidate and therefrom with methylhydrazine there is obtained 3-(o-chlorophenyl)-1-methyl-5-(4-trifluoromethyl-3-pyridyl)-1H-1,2,4-triazole, 1H-NMR(CDCl3): 3.85 (s, N-CH3), 7.6-8.1 (5 aromatic H), 8.9-9.2 (2 aromatic H); mass spectrum: 338 (100), 319 (5), 166 (94), 138 (95);