ethyl 4-bromobenzenecarboximidate

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

Procedure: Into a 1000 mL 3-necked flask, was placed a solution of ethyl 4-bromobenzenecarboximidoate (54.0 g, 237 mmol) in xylene (500 mL) To the mixture was added NH2NHCHO (14.22 g, 237 mmol). The resulting solution was heated to reflux overnight. The reaction mixture was cooled in an ice bath and filtered. The solid was washed with 700 mL of petroleum ether and dried in an oven under reduced pressure to afford 3-(4-bromophenyl)-1H-1,2,4-triazole (crude) as a white solid. Into a 1000 mL 3-necked flask, was placed The resulting solution was heated to reflux overnight The reaction mixture was cooled in an ice bath filtered The solid was washed with 700 mL of petroleum ether dried in an oven under reduced pressure

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

Procedure: Into a 3000 mL 3-necked flask was placed EtOH (2000 mL). To this was added sequentially Na (7.13 g, 310 mmol) and ethyl 4-bromobenzimidate hydrochloride (82 g, 310 mmol). The resulting solution was allowed to stir for two hours at room temperature, and filtered. The filtrate was evaporated to afford ethyl 4-bromobenzenecarboximidoate as a white solid. Into a 3000 mL 3-necked flask was placed filtered The filtrate was evaporated

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-benzonitrile (5 g) was suspended in absolute EtOH (100 ml) and cooled to 0-5° C. HCl gas was bubbled through, initially vigorously for several minutes and later slowly for 5 hours. The resulting solution was allowed to stir overnight. Most of solvent was removed and the precipitate was filtered, washed with EtOH twice and dried to afford compound 2BO (4.1 g) as white solid. HCl gas was bubbled through, initially vigorously for several minutes Most of solvent was removed the precipitate was filtered washed with EtOH twice dried to afford compound 2BO (4.1 g) as white solid

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-benzonitrile (5 g) was suspended in absolute EtOH (100 ml) and cooled to 0-5° C. HCl gas was bubbled through, initially vigorously for several minutes and later slowly for 5 hours. The resulting solution was allowed to stir overnight. Most of solvent was removed and the precipitate was filtered, washed with EtOH twice and dried to afford compound 2BO (4.1 g) as white solid. HCl gas was bubbled through, initially vigorously for several minutes Most of solvent was removed the precipitate was filtered washed with EtOH twice dried to afford compound 2BO (4.1 g) as white solid

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-benzonitrile (5 g) was suspended in absolute EtOH (100 ml) and cooled to 0-5° C. HCl gas was bubbled through, initially vigorously for several minutes and later slowly for 5 hours. The resulting solution was allowed to stir overnight. Most of solvent was removed and the precipitate was filtered, washed with EtOH twice and dried to afford compound 2BN (4.1 g) as white solid. (Note: large scale synthesis may take longer time to get reaction complete. It is better to monitor the disappearance of starting material to get reaction end point.) HCl gas was bubbled through, initially vigorously for several minutes Most of solvent was removed the precipitate was filtered washed with EtOH twice dried to afford compound 2BN (4.1 g) as white solid (Note: large scale synthesis to get reaction complete to get reaction end point

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-benzonitrile (5 g) was suspended in absolute EtOH (100 ml) and cooled to 0-5° C. HCl gas was bubbled through, initially vigorously for several minutes and later slowly for 5 hours. The resulting solution was allowed to stir overnight. Most of solvent was removed and the precipitate was filtered, washed with EtOH twice and dried to afford compound 2BN (4.1 g) as white solid. (Note: large scale synthesis may take longer time to get reaction complete. It is better to monitor the disappearance of starting material to get reaction end point.) HCl gas was bubbled through, initially vigorously for several minutes Most of solvent was removed the precipitate was filtered washed with EtOH twice dried to afford compound 2BN (4.1 g) as white solid (Note: large scale synthesis to get reaction complete to get reaction end point

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-benzonitrile (5 g) was suspended in absolute EtOH (100 ml) and cooled to 0-5° C. HCl gas was bubbled through, initially vigorously for several minutes and later slowly for 5 hours. The resulting solution was allowed to stir overnight. Most of solvent was removed and the precipitate was filtered, washed with EtOH twice and dried to afford compound 2BM (4.1 g) as white solid. HCl gas was bubbled through, initially vigorously for several minutes Most of solvent was removed the precipitate was filtered washed with EtOH twice dried to afford compound 2BM (4.1 g) as white solid

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-benzonitrile (5 g) was suspended in absolute EtOH (100 ml) and cooled to 0-5° C. HCl gas was bubbled through, initially vigorously for several minutes and later slowly for 5 hours. The resulting solution was allowed to stir overnight. Most of solvent was removed and the precipitate was filtered, washed with EtOH twice and dried to afford compound 2BH (4.1 g) as white solid. HCl gas was bubbled through, initially vigorously for several minutes Most of solvent was removed the precipitate was filtered washed with EtOH twice dried to afford compound

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

Procedure: A solution of 4-bromo-benzonitrile (58 mmol) in ethanol (200 mL) at 0° C. was bubbled through with HCl gas for 30 min and the resulting solution was stirred from 0° C. to room temperature over the weekend. After the reaction mixture was concentrated in vacuo, the residue was suspended in ether and the solid was filtered to give of 4-bromo-benzimidic acid ethyl ester as HCl salt (47 mmol). After the reaction mixture was concentrated in vacuo the solid was filtered

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

Procedure: Into a 1000 mL 3-necked flask, was placed a solution of ethyl 4-bromobenzenecarboximidoate (54.0 g, 237 mmol) in xylene (500 mL) To the mixture was added NH2NHCHO (14.22 g, 237 mmol). The resulting solution was heated to reflux overnight. The reaction mixture was cooled in an ice bath and filtered. The solid was washed with 700 mL of petroleum ether and dried in an oven under reduced pressure to afford 3-(4-bromophenyl)-1H-1,2,4-triazole (crude) as a white solid. Into a 1000 mL 3-necked flask, was placed The resulting solution was heated to reflux overnight The reaction mixture was cooled in an ice bath filtered The solid was washed with 700 mL of petroleum ether dried in an oven under reduced pressure

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

Procedure: Into a 1000 mL 3-necked flask, was placed a solution of ethyl 4-bromobenzenecarboximidoate (54.0 g, 237 mmol) in xylene (500 mL) To the mixture was added NH2NHCHO (14.22 g, 237 mmol). The resulting solution was heated to reflux overnight. The reaction mixture was cooled in an ice bath and filtered. The solid was washed with 700 mL of petroleum ether and dried in an oven under reduced pressure to afford 3-(4-bromophenyl)-1H-1,2,4-triazole (crude) as a white solid. Into a 1000 mL 3-necked flask, was placed The resulting solution was heated to reflux overnight The reaction mixture was cooled in an ice bath filtered The solid was washed with 700 mL of petroleum ether dried in an oven under reduced pressure

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

Procedure: Into a 3000 mL 3-necked flask was placed EtOH (2000 mL). To this was added sequentially Na (7.13 g, 310 mmol) and ethyl 4-bromobenzimidate hydrochloride (82 g, 310 mmol). The resulting solution was allowed to stir for two hours at room temperature, and filtered. The filtrate was evaporated to afford ethyl 4-bromobenzenecarboximidoate as a white solid. Into a 3000 mL 3-necked flask was placed filtered The filtrate was evaporated