4,5-dichloro-2-iodoaniline

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

Procedure: Iodine monochloride (1.39 mL; 27.77 mmol) was added to a solution of 3,4-dichloroaniline (4.50 g; 27.77 mmol) in acetic acid (15 mL) and the resulting mixture was stirred 30 minutes at room temperature. The solution was concentrated to dryness, neutralized with sodium bicarbonate and extracted with dichloromethane. The combined organic layers were washed with a saturated solution of sodium thiosulphate, dried over magnesium sulphate and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane) to afford 3.46 g (43%) of 4,5-dichloro-2-iodoaniline as a brown solid. The solution was concentrated to dryness extracted with dichloromethane The combined organic layers were washed with a saturated solution of sodium thiosulphate dried over magnesium sulphate concentrated under reduced pressure The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane)

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

Procedure: Iodine monochloride (1.39 mL; 27.77 mmol) was added to a solution of 3,4-dichloroaniline (4.50 g; 27.77 mmol) in acetic acid (15 mL) and the resulting mixture was stirred 30 minutes at room temperature. The solution was concentrated to dryness, neutralized with sodium bicarbonate and extracted with dichloromethane. The combined organic layers were washed with a saturated solution of sodium thiosulphate, dried over magnesium sulphate and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane) to afford 3.46 g (43%) of 4,5-dichloro-2-iodoaniline as a brown solid. The solution was concentrated to dryness extracted with dichloromethane The combined organic layers were washed with a saturated solution of sodium thiosulphate dried over magnesium sulphate concentrated under reduced pressure The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane)

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

Procedure: A mixture of 4,5-dichloro-2-iodobenzenamine (6 g, 20.8 mmol), tributyl(vinyl)stannane (6.6 g, 20.8 mmol), Pd(PPh3)4 (2.4 g, 2.1 mmol) in toluene (60 mL) was stirred at reflux under argon for 6 h. The mixture was allowed to cool to room temperature, quenched with aqueous KF solution and then extracted with ethyl acetate. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=4:1) to afford the desired product (3.0 g, 76.7% yield) as a colorless oil. at reflux under argon for 6 h quenched with aqueous KF solution extracted with ethyl acetate The organic layer was washed with brine dried over Na2SO4 filtered concentrated in vacuo The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=4:1)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,5-Dichloro-2-iodoaniline (1.50 g; 5.21 mmol), 4-(triethylsilyl)but-3-yn-1-ol (1.65 mL; 7.81 mmol), bis(diphenylphosphino)ferrocene]palladium(II) chloride (0.212 g; 0.260 mmol), lithium chloride (0.221 g; 5.21 mmol) and sodium carbonate (1.10 g; 10.42 mmol) were suspended in DMF (14 mL) and the mixture was stirred at 100° C. for 15 hours. The solution was concentrated under reduced pressure and diluted with ethyl acetate. The organic layer was successively washed with brine, sodium thiosulfate, dried and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane) to afford 2.0 g (quantitative yield) of the title compound as a brown oil. The solution was concentrated under reduced pressure diluted with ethyl acetate The organic layer was successively washed with brine, sodium thiosulfate dried concentrated under reduced pressure The crude residue was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane)

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

Procedure: Iodine monochloride (1.39 mL; 27.77 mmol) was added to a solution of 3,4-dichloroaniline (4.50 g; 27.77 mmol) in acetic acid (15 mL) and the resulting mixture was stirred for 30 minutes at room temperature. The solution was concentrated to dryness, neutralized with sodium bicarbonate and extracted with dichloromethane. The combined organic layers were washed with a saturated solution of sodium thiosulfate, dried and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane) to afford 3.46 g (43%) of the title compound as a brown solid. The solution was concentrated to dryness extracted with dichloromethane The combined organic layers were washed with a saturated solution of sodium thiosulfate dried concentrated under reduced pressure The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane)

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

Procedure: Iodine monochloride (1.39 mL; 27.77 mmol) was added to a solution of 3,4-dichloroaniline (4.50 g; 27.77 mmol) in acetic acid (15 mL) and the resulting mixture was stirred 30 minutes at room temperature. The solution was concentrated to dryness, neutralized with sodium bicarbonate and extracted with dichloromethane. The combined organic layers were washed with a saturated solution of sodium thiosulphate, dried over magnesium sulphate and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane) to afford 3.46 g (43%) of 4,5-dichloro-2-iodoaniline as a brown solid. The solution was concentrated to dryness extracted with dichloromethane The combined organic layers were washed with a saturated solution of sodium thiosulphate dried over magnesium sulphate concentrated under reduced pressure The crude material was purified by flash chromatography on silica gel (eluent 2 to 20% ethyl acetate in heptane)

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

Procedure: A mixture of 4,5-dichloro-2-iodobenzenamine (6 g, 20.8 mmol), tributyl(vinyl)stannane (6.6 g, 20.8 mmol), Pd(PPh3)4 (2.4 g, 2.1 mmol) in toluene (60 mL) was stirred at reflux under argon for 6 h. The mixture was allowed to cool to room temperature, quenched with aqueous KF solution and then extracted with ethyl acetate. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=4:1) to afford the desired product (3.0 g, 76.7% yield) as a colorless oil. at reflux under argon for 6 h quenched with aqueous KF solution extracted with ethyl acetate The organic layer was washed with brine dried over Na2SO4 filtered concentrated in vacuo The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=4:1)