5-bromo-2-phenoxyaniline

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

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

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

Procedure: Iron powder (3 g, 53.4 mmol) and acetic acid (10 mL) were added to a stirred suspension of 4-bromo-2-nitro-1-phenoxybenzene (3.1 g, 9.5 mmol) in water (25 mL) of 60° C. The reaction mixture was heated to 80° C. and stirred for 30 min. After cooling to room temperature the reaction mixture was filtered and extracted with toluene. The toluene solution was washed with water (3×) and brine, dried (Na2SO4) and evaporated to give the crude compound (2.3 g, 87%). Data: (m/z)=264+266 (M+H)+. After cooling to room temperature the reaction mixture was filtered extracted with toluene The toluene solution was washed with water (3×) and brine dried (Na2SO4) evaporated

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

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

Procedure: Iron powder (3 g, 53.4 mmol) and acetic acid (10 mL) were added to a stirred suspension of 4-bromo-2-nitro-1-phenoxybenzene (3.1 g, 9.5 mmol) in water (25 mL) of 60° C. The reaction mixture was heated to 80° C. and stirred for 30 min. After cooling to room temperature the reaction mixture was filtered and extracted with toluene. The toluene solution was washed with water (3×) and brine, dried (Na2SO4) and evaporated to give the crude compound (2.3 g, 87%). Data: (m/z)=264+266 (M+H)+. After cooling to room temperature the reaction mixture was filtered extracted with toluene The toluene solution was washed with water (3×) and brine dried (Na2SO4) evaporated

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

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

Procedure: The product from Example 1d (278 mg, 1.56 mmol) was reacted with the product from Example 124b (412 mg, 1.56 mmol) for 18 h following the procedure from Example 1g giving the crude title compound which was purified by HPLC with TFA providing the product as a trifluoroacetic acid (206 mg, 25%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 2.73 (s, 3 H) 6.69 (d, J=7.35 Hz, 2 H) 6.96 (d, J=7.72 Hz, 2 H) 7.05-7.15 (m, 3 H) 7.24-7.36 (m, 2 H) 7.68 (dd, J=8.82, 2.57 Hz, 1 H) 7.75 (d, J=8.46 Hz, 1 H) 7.82 (d, J=2.21 Hz, 1 H) 8.52 (d, J=6.99 Hz, 1 H) 8.86 (d, J=8.82 Hz, 1 H) 10.93 (s, 1 H) 14.49 (s, 1 H); MS (ESI+) m/z 408 (M+H−TFA)+.

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

Procedure: The product from Example 2g (275 mg, 1.33 mmol) was reacted with the product from Example 124b (351 mg, 1.33 mmol) for 18 h following the procedure from Example 1g giving the crude title compound which was purified by HPLC with TFA providing the product as a trifluoroacetic acid (470 mg, 65%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 0.95 (t, J=7.35 Hz, 3 H) 1.72-1.93 (m, 2 H) 2.91-3.02 (m, 2 H) 6.70 (d, J=6.99 Hz, 1 H) 6.97 (d, J=7.72 Hz, 2 H) 7.10 (t, J=8.27 Hz, 2 H) 7.27-7.36 (m, 2 H) 7.68 (dd, J=8.82, 2.57 Hz, 1 H) 7.78 (d, J=8.46 Hz, 1 H) 7.82 (d, J=2.57 Hz, 1 H) 8.52 (d, J=6.99 Hz, 1 H) 8.89 (d, J=8.82 Hz, 1 H) 10.90 (s, 1 H) 14.49 (s, 1 H); MS (ESI+) m/z 436 (M+H−TFA)+.

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

Procedure: The product from Example 2g (275 mg, 1.33 mmol) was reacted with the product from Example 124b (351 mg, 1.33 mmol) for 18 h following the procedure from Example 1g giving the crude title compound which was purified by HPLC with TFA providing the product as a trifluoroacetic acid (470 mg, 65%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 0.95 (t, J=7.35 Hz, 3 H) 1.72-1.93 (m, 2 H) 2.91-3.02 (m, 2 H) 6.70 (d, J=6.99 Hz, 1 H) 6.97 (d, J=7.72 Hz, 2 H) 7.10 (t, J=8.27 Hz, 2 H) 7.27-7.36 (m, 2 H) 7.68 (dd, J=8.82, 2.57 Hz, 1 H) 7.78 (d, J=8.46 Hz, 1 H) 7.82 (d, J=2.57 Hz, 1 H) 8.52 (d, J=6.99 Hz, 1 H) 8.89 (d, J=8.82 Hz, 1 H) 10.90 (s, 1 H) 14.49 (s, 1 H); MS (ESI+) m/z 436 (M+H−TFA)+.

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

Procedure: The product from Example 124a (6.6 g, 22.5 mmol) was reduced with SnCl2 following the procedure from Example 1f giving the title compound as a brown oil (5.9 g, 100%).

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

Procedure: The product from Example 124a (6.6 g, 22.5 mmol) was reduced with SnCl2 following the procedure from Example 1f giving the title compound as a brown oil (5.9 g, 100%).

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

Procedure: The product from Example 1d (278 mg, 1.56 mmol) was reacted with the product from Example 124b (412 mg, 1.56 mmol) for 18 h following the procedure from Example 1g giving the crude title compound which was purified by HPLC with TFA providing the product as a trifluoroacetic acid (206 mg, 25%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 2.73 (s, 3H) 6.69 (d, J=7.35 Hz, 2H) 6.96 (d, J=7.72 Hz, 2H) 7.05-7.15 (m, 3H) 7.24-7.36 (m, 2H) 7.68 (dd, J=8.82, 2.57 Hz, 1H) 7.75 (d, J=8.46 Hz, 1H) 7.82 (d, J=2.21 Hz, 1H) 8.52 (d, J=6.99 Hz, 1H) 8.86 (d, J=8.82 Hz, 1H) 10.93 (s, 1H) 14.49 (s, 1H); MS (ESI+) m/z 408 (M+H−TFA)+.