N-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Lithium aluminum hydride (52.9 mL, 52.9 mmol) in THF (1.0M) was added to a solution of 2-(4-bromophenylamino)-2-(4-chlorophenyl)acetonitrile (20.0 g, 62.2 mmol) in THF (311 mL, 62.2 mmol) at −78° C. The reaction was allowed to stir at −78° C. and gradually warmed to room temperature over 4 hours. The reaction mixture was poured into 1N HCl. The solution was then basified and extracted with ethyl acetate (3×). The combined organic layers were washed with brine, dried and concentrated to give an oil. This residue was purified by column chromatography, eluting first with ethyl acetate/hexanes (2:1) then 5% MeOH/CH2Cl2->10% MeOH/CH2Cl2+1% NH4OH, affording N1-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine as an oil (9.60 g, 49%). 1H NMR (400 MHz, CD3OD) δ □7.38 (d, 2H), 7.34 (d, 2H), 7.15 (d, 2H), 6.53 (d, 2H), 4.59 (dd, J=9.8, 4.7 Hz, 1H), 3.14 (dd, J=12.9, 4.7 Hz, 1H), 3.05 (dd, J=12.9, 9.4 Hz, 1H). gradually warmed to room temperature over 4 hours extracted with ethyl acetate (3×) The combined organic layers were washed with brine dried concentrated to give an oil This residue was purified by column chromatography eluting first with ethyl acetate/hexanes (2:1)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Lithium aluminum hydride (52.9 mL, 52.9 mmol) in THF (1.0M) was added to a solution of 2-(4-bromophenylamino)-2-(4-chlorophenyl)acetonitrile (20.0 g, 62.2 mmol) in THF (311 mL, 62.2 mmol) at −78° C. The reaction was allowed to stir at −78° C. and gradually warmed to room temperature over 4 hours. The reaction mixture was poured into 1N HCl. The solution was then basified and extracted with ethyl acetate (3×). The combined organic layers were washed with brine, dried and concentrated to give an oil. This residue was purified by column chromatography, eluting first with ethyl acetate/hexanes (2:1) then 5% MeOH/CH2Cl2→10% MeOH/CH2Cl2+1% NH4OH, affording N1-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine as an oil (9.60 g, 49%). 1H NMR (400 MHz, CD3OD) δ □7.38 (d, 2H), 7.34 (d, 2H), 7.15 (d, 2H), 6.53 (d, 2H), 4.59 (dd, J=9.8, 4.7 Hz, 1H), 3.14 (dd, J=12.9, 4.7 Hz, 1H), 3.05 (dd, J=12.9, 9.4 Hz, 1H). gradually warmed to room temperature over 4 hours extracted with ethyl acetate (3×) The combined organic layers were washed with brine dried concentrated to give an oil This residue was purified by column chromatography eluting first with ethyl acetate/hexanes (2:1)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Lithium aluminum hydride (52.9 mL, 52.9 mmol) in THF (1.0M) was added to a solution of 2-(4-bromophenylamino)-2-(4-chlorophenyl)acetonitrile (20.0 g, 62.2 mmol) in THF (311 mL, 62.2 mmol) at −78° C. The reaction was allowed to stir at −78° C. and gradually warmed to room temperature over 4 hours. The reaction mixture was poured into 1N HCl. The solution was then basified and extracted with ethyl acetate (3×). The combined organic layers were washed with brine, dried and concentrated to give an oil. This residue was purified by column chromatography, eluting first with ethyl acetate/hexanes (2:1) then 5% MeOH/CH2Cl2->10% MeOH/CH2Cl2+1% NH4OH, affording N1-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine as an oil (9.60 g, 49%). 1H NMR (400 MHz, CD3OD) δ □7.38 (d, 2H), 7.34 (d, 2H), 7.15 (d, 2H), 6.53 (d, 2H), 4.59 (dd, J=9.8, 4.7 Hz, 1H), 3.14 (dd, J=12.9, 4.7 Hz, 1H), 3.05 (dd, J=12.9, 9.4 Hz, 1H). gradually warmed to room temperature over 4 hours extracted with ethyl acetate (3×) The combined organic layers were washed with brine dried concentrated to give an oil This residue was purified by column chromatography eluting first with ethyl acetate/hexanes (2:1)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Lithium aluminum hydride (52.9 mL, 52.9 mmol) in THF (1.0M) was added to a solution of 2-(4-bromophenylamino)-2-(4-chlorophenyl)acetonitrile (20.0 g, 62.2 mmol) in THF (311 mL, 62.2 mmol) at −78° C. The reaction was allowed to stir at −78° C. and gradually warmed to room temperature over 4 hours. The reaction mixture was poured into 1N HCl. The solution was then basified and extracted with ethyl acetate (3×). The combined organic layers were washed with brine, dried and concentrated to give an oil. This residue was purified by column chromatography, eluting first with ethyl acetate/hexanes (2:1) then 5% MeOH/CH2Cl2->10% MeOH/CH2Cl2+1% NH4OH, affording N1-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine as an oil (9.60 g, 49%). 1H NMR (400 MHz, CD3OD) δ □7.38 (d, 2H), 7.34 (d, 2H), 7.15 (d, 2H), 6.53 (d, 2H), 4.59 (dd, J=9.8, 4.7 Hz, 1H), 3.14 (dd, J=12.9, 4.7 Hz, 1H), 3.05 (dd, J=12.9, 9.4 Hz, 1H). gradually warmed to room temperature over 4 hours extracted with ethyl acetate (3×) The combined organic layers were washed with brine dried concentrated to give an oil This residue was purified by column chromatography eluting first with ethyl acetate/hexanes (2:1)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Lithium aluminum hydride (52.9 mL, 52.9 mmol) in THF (1.0M) was added to a solution of 2-(4-bromophenylamino)-2-(4-chlorophenyl)acetonitrile (20.0 g, 62.2 mmol) in THF (311 mL, 62.2 mmol) at −78° C. The reaction was allowed to stir at −78° C. and gradually warmed to room temperature over 4 hours. The reaction mixture was poured into 1N HCl. The solution was then basified and extracted with ethyl acetate (3×). The combined organic layers were washed with brine, dried and concentrated to give an oil. This residue was purified by column chromatography, eluting first with ethyl acetate/hexanes (2:1) then 5% MeOH/CH2Cl2->10% MeOH/CH2Cl2+1% NH4OH, affording N1-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine as an oil (9.60 g, 49%). 1H NMR (400 MHz, CD3OD) δ 7.38 (d, 2H), 7.34 (d, 2H), 7.15 (d, 2H), 6.53 (d, 2H), 4.59 (dd, J=9.8, 4.7 Hz, 1H), 3.14 (dd, J=12.9, 4.7 Hz, 1H), 3.05 (dd, J=12.9, 9.4 Hz, 1H). gradually warmed to room temperature over 4 hours extracted with ethyl acetate (3×) The combined organic layers were washed with brine dried concentrated to give an oil This residue was purified by column chromatography eluting first with ethyl acetate/hexanes (2:1)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Lithium aluminum hydride (52.9 mL, 52.9 mmol) in THF (1.0M) was added to a solution of 2-(4-bromophenylamino)-2-(4-chlorophenyl)acetonitrile (20.0 g, 62.2 mmol) in THF (311 mL, 62.2 mmol) at −78° C. The reaction was allowed to stir at −78° C. and gradually warmed to room temperature over 4 hours. The reaction mixture was poured into 1N HCl. The solution was then basified and extracted with ethyl acetate (3×). The combined organic layers were washed with brine, dried and concentrated to give an oil. This residue was purified by column chromatography, eluting first with ethyl acetate/hexanes (2:1) then 5% MeOH/CH2Cl2→10% MeOH/CH2Cl2+1% NH4OH, affording N1-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine as an oil (9.60 g, 49%). 1H NMR (400 MHz, CD3OD) δ □7.38 (d, 2H), 7.34 (d, 2H), 7.15 (d, 2H), 6.53 (d, 2H), 4.59 (dd, J=9.8, 4.7 Hz, 1H), 3.14 (dd, J=12.9, 4.7 Hz, 1H), 3.05 (dd, J=12.9, 9.4 Hz, 1H). gradually warmed to room temperature over 4 hours extracted with ethyl acetate (3×) The combined organic layers were washed with brine dried concentrated to give an oil This residue was purified by column chromatography eluting first with ethyl acetate/hexanes (2:1)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Lithium aluminum hydride (52.9 mL, 52.9 mmol) in THF (1.0M) was added to a solution of 2-(4-bromophenylamino)-2-(4-chlorophenyl)acetonitrile (20.0 g, 62.2 mmol) in THF (311 mL, 62.2 mmol) at −78° C. The reaction was allowed to stir at −78° C. and gradually warmed to room temperature over 4 hours. The reaction mixture was poured into 1N HCl. The solution was then basified and extracted with ethyl acetate (3×). The combined organic layers were washed with brine, dried and concentrated to give an oil. This residue was purified by column chromatography, eluting first with ethyl acetate/hexanes (2:1) then 5% MeOH/CH2Cl2->10% MeOH/CH2Cl2+1% NH4OH, affording N1-(4-bromophenyl)-1-(4-chlorophenyl)ethane-1,2-diamine as an oil (9.60 g, 49%). 1H NMR (400 MHz, CD3OD) δ □7.38 (d, 2H), 7.34 (d, 2H), 7.15 (d, 2H), 6.53 (d, 2H), 4.59 (dd, J=9.8, 4.7 Hz, 1H), 3.14 (dd, J=12.9, 4.7 Hz, 1H), 3.05 (dd, J=12.9, 9.4 Hz, 1H). gradually warmed to room temperature over 4 hours extracted with ethyl acetate (3×) The combined organic layers were washed with brine dried concentrated to give an oil This residue was purified by column chromatography eluting first with ethyl acetate/hexanes (2:1)