ethyl 2-(5-amino-2-chlorophenyl)acetate

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

Procedure: Iron powder (2.5 g, 44.7 mmol) was added portion wise to a solution of ethyl 2-(2-chloro-5-nitrophenyl)acetate (8 g, 4.68 mmol) and cone. HCl (12 M, 3.9 mL, 46.8 mmol) in EtOH (100 mL). The resultant mixture was heated at 50° C. for 2 hour. The mixture was filtered and the filtrate cake was washed with saturated aqueous Na2CO3 until pH 8. The filter cake was further washed with EtOAc and the combined filtrates were partitioned between EtOAc and water. The organics were dried over Na2SO4 and concentrated in vacuo to provide ethyl 2-(5-amino-2-chlorophenyl)acetate (5.6 g, 56% yield). 1H NMR (400 MHz, DMSO-d6): δ 7.00 (d, J=8.4 Hz, 1 H), 6.50 (s, J=2.8 Hz, 1 H), 6.44 (dd, J=8.4 Hz, 2.8 Hz, 1H), 5.20 (s, 2 H), 4.05 (q, J=7.2 Hz, 2 H), 3.56 (s, 2 H), 1.15 (t, J=7.2 Hz, 3 H). The mixture was filtered the filtrate cake was washed with saturated aqueous Na2CO3 until pH 8 The filter cake was further washed with EtOAc the combined filtrates were partitioned between EtOAc and water The organics were dried over Na2SO4 concentrated in vacuo

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

Procedure: Iron powder (2.5 g, 44.7 mmol) was added portion-wise to a solution of ethyl 2-(2-chloro-5-nitrophenyl)acetate (8 g, 4.68 mmol) and conc. HCl (12 M, 3.9 mL, 46.8 mmol) in EtOH (100 mL). The resultant mixture was heated at 50° C. for 2 h. The mixture was filtered and the filtrate cake was washed with satd. Na2CO3 until pH 8. The filter cake was further washed with EtOAc and the combined filtrates were partitioned between EtOAc and water. The organics were dried over Na2SO4 and concentrated in vacuo to provide ethyl 2-(5-amino-2-chlorophenyl)acetate (5.6 g, 56% yield). 1H NMR (400 MHz, DMSO-d6): δ 7.00 (d, J=8.4 Hz, 1H), 6.50 (s, J=2.8 Hz, 1H), 6.44 (dd, J=8.4 Hz, 2.8 Hz, 1H), 5.20 (s, 2H), 4.05 (q, J=7.2 Hz, 2H), 3.56 (s, 2H), 1.15 (t, J=7.2 Hz, 3H). The mixture was filtered the filtrate cake was washed with satd The filter cake was further washed with EtOAc the combined filtrates were partitioned between EtOAc and water The organics were dried over Na2SO4 concentrated in vacuo

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

Procedure: Iron powder (2.5 g, 44.7 mmol) was added portion-wise to a solution of ethyl 2-(2-chloro-5-nitrophenyl)acetate (8 g, 4.68 mmol) and conc. HCl (12 M, 3.9 mL, 46.8 mmol) in EtOH (100 mL). The resultant mixture was heated at 50° C. for 2 h. The mixture was filtered and the filtrate cake was washed with satd. Na2CO3 until pH 8. The filter cake was further washed with EtOAc and the combined filtrates were partitioned between EtOAc and water. The organics were dried over Na2SO4 and concentrated in vacuo to provide ethyl 2-(5-amino-2-chlorophenyl)acetate (5.6 g, 56% yield). 1H NMR (400 MHz, DMSO-d6): δ 7.00 (d, J=8.4 Hz, 1H), 6.50 (s, J=2.8 Hz, 1H), 6.44 (dd, J=8.4 Hz, 2.8 Hz, 1H), 5.20 (s, 2H), 4.05 (q, J=7.2 Hz, 2H), 3.56 (s, 2H), 1.15 (t, J=7.2 Hz, 3H). The mixture was filtered the filtrate cake was washed with satd The filter cake was further washed with EtOAc the combined filtrates were partitioned between EtOAc and water The organics were dried over Na2SO4 concentrated in vacuo