3-bromo-5-chlorobenzene-1,2-diamine

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 109b (4.3 g, 19.5 mmol) in formic acid (10 mL) was heated at 80° C. for 1 h. After cooled to room temperature, the reaction mixture was poured into aqueous Na2CO3 (30 mL) and the mixture was extracted with ethyl acetate (30 mL×3). The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure to afford 109c as a brown solid (3.5 g, 77%). LCMS: [M+H]+ 233. 1H NMR (500 MHz, CDCl3) δ 10.05 (bs, 1H), 8.18 (s, 1H), 7.64 (bs, 1H), 7.50 (s, 1H). After cooled to room temperature the mixture was extracted with ethyl acetate (30 mL×3) The combined organic phase was dried over anhydrous Na2SO4 filtered evaporated under reduced pressure

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 109b (4.3 g, 19.5 mmol) in formic acid (10 mL) was heated at 80° C. for 1 h. After cooled to room temperature, the reaction mixture was poured into aqueous Na2CO3 (30 mL) and the mixture was extracted with ethyl acetate (30 mL×3). The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure to afford 109c as a brown solid (3.5 g, 77%). LCMS: [M+H]+ 233. 1H NMR (500 MHz, CDCl3) δ 10.05 (bs, 1H), 8.18 (s, 1H), 7.64 (bs, 1H), 7.50 (s, 1H). After cooled to room temperature the mixture was extracted with ethyl acetate (30 mL×3) The combined organic phase was dried over anhydrous Na2SO4 filtered evaporated under reduced pressure

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

Procedure: To a solution of 109a (5.0 g, 20 mmol) in ethyl acetate (100 mL) was added SnCl2.2H2O (22.6 g, 100 mmol). The reaction was heated at reflux for 2 h. After cooled to room temperature, the reaction mixture was poured into aqueous Na2CO3 (200 mL) and the mixture was extracted with ethyl acetate (200 mL×3). The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure to afford 109b as a dark red liquid (4.3 g, 97%). LCMS: [M+H]+ 223. 1H NMR (500 MHz, CDCl3) δ 6.97 (d, J=2.5 Hz, 1H), 6.65 (d, J=2.5 Hz, 1H), 3.67 (bs, 4H). The reaction was heated at reflux for 2 h the mixture was extracted with ethyl acetate (200 mL×3) The combined organic phase was dried over anhydrous Na2SO4 filtered evaporated under reduced pressure

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 109b (4.3 g, 19.5 mmol) in formic acid (10 mL) was heated at 80° C. for 1 h. After cooled to room temperature, the reaction mixture was poured into aqueous Na2CO3 (30 mL) and the mixture was extracted with ethyl acetate (30 mL×3). The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure to afford 109c as a brown solid (3.5 g, 77%). LCMS: [M+H]+ 233. 1H NMR (500 MHz, CDCl3) δ 10.05 (bs, 1H), 8.18 (s, 1H), 7.64 (bs, 1H), 7.50 (s, 1H). After cooled to room temperature the mixture was extracted with ethyl acetate (30 mL×3) The combined organic phase was dried over anhydrous Na2SO4 filtered evaporated under reduced pressure

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

Procedure: To a solution of 109a (5.0 g, 20 mmol) in ethyl acetate (100 mL) was added SnCl2.2H2O (22.6 g, 100 mmol). The reaction was heated at reflux for 2 h. After cooled to room temperature, the reaction mixture was poured into aqueous Na2CO3 (200 mL) and the mixture was extracted with ethyl acetate (200 mL×3). The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure to afford 109b as a dark red liquid (4.3 g, 97%). LCMS: [M+H]+ 223. 1H NMR (500 MHz, CDCl3) δ 6.97 (d, J=2.5 Hz, 1H), 6.65 (d, J=2.5 Hz, 1H), 3.67 (bs, 4H). The reaction was heated at reflux for 2 h the mixture was extracted with ethyl acetate (200 mL×3) The combined organic phase was dried over anhydrous Na2SO4 filtered evaporated under reduced pressure