3-methoxy-4-tri(propan-2-yl)silyloxyaniline

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

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

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

Procedure: Dissolve triisopropyl-(2-methoxy-4-nitro-phenoxy)-silane (95.7 g, 294.0 mmol) in EtOH (1800 mL) and add 5% Pd/C (10.0 g). Hydrogenate the slurry at room temperature under 50 psi hydrogen for 8 h. Filter the slurry through a pad of Celite® and rinse with EtOH. Concentrate the filtrate in vacuo to give a brown oil. Purify by flash chromatography, using a gradient from 100% hexanes to 20% EtOAc/hexanes, to give the title compound as a brown solid (67.4 g, 77.6% yield). MS (ES+) 296.2 (M+1)+. Filter the slurry through a pad of Celite® rinse with EtOH Concentrate the filtrate in vacuo to give a brown oil Purify by flash chromatography

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

Procedure: Dissolve triisopropyl-(2-methoxy-4-nitro-phenoxy)-silane (95.7 g, 294.0 mmol) in EtOH (1800 mL) and add 5% Pd/C (10.0 g). Hydrogenate the slurry at room temperature under 50 psi hydrogen for 8 h. Filter the slurry through a pad of Celite® and rinse with EtOH. Concentrate the filtrate in vacuo to give a brown oil. Purify by flash chromatography, using a gradient from 100% hexanes to 20% EtOAc/hexanes, to give the title compound as a brown solid (67.4 g, 77.6% yield). MS (ES+) 296.2 (M+1)+. Filter the slurry through a pad of Celite® rinse with EtOH Concentrate the filtrate in vacuo to give a brown oil Purify by flash chromatography

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

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

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

Procedure: Suspend 5-(4-chloro-phenyl)-3-methyl-thiophene-2-carboxylic acid (2.13 g, 8.44 mmol) in CH2Cl2 (15 mL) and treat with oxalyl chloride (1.5 mL, 16.87 mmol), followed by the addition of DMF (2 drops). Stir the mixture at RT for 2 h and then evaporate down in vacuo. Dissolve the resulting solid material in CH2Cl2 (30 mL) and cool to 0° C. Add 3-methoxy-4-triisopropylsilanyloxy-phenylamine (2.62 g, 8.86 mmol) and Et3N (1.8 mL, 12.66 mol) in CH2Cl2 (10 mL) dropwise at 0° C. Stir the reaction at 0° C. for 10 min and at RT for 30 min. Dilute the reaction with CH2Cl2 (100 mL), wash with 0.1 M HCl (2×30 mL), 1.0 M NaOH (2×30 mL), dry over Na2SO4, filter, and concentrate. Purify the crude material by chromatography, eluting with 20% EtOAc/hexane to give 3.53 g (79%) of the title compound. LC-MS/ES m/z (37Cl) 531.2 [M+]. evaporate down in vacuo Dissolve the resulting solid material in CH2Cl2 (30 mL) cool to 0° C dropwise at 0° C Stir the reaction at 0° C. for 10 min at RT for 30 min Dilute wash with 0.1 M HCl (2×30 mL), 1.0 M NaOH (2×30 mL) dry over Na2SO4 filter concentrate Purify the crude material by chromatography eluting with 20% EtOAc/hexane

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

Procedure: Suspend 5-(4-chloro-phenyl)-3-methyl-thiophene-2-carboxylic acid (2.13 g, 8.44 mmol) in CH2Cl2 (15 mL) and treat with oxalyl chloride (1.5 mL, 16.87 mmol), followed by the addition of DMF (2 drops). Stir the mixture at RT for 2 h and then evaporate down in vacuo. Dissolve the resulting solid material in CH2Cl2 (30 mL) and cool to 0° C. Add 3-methoxy-4-triisopropylsilanyloxy-phenylamine (2.62 g, 8.86 mmol) and Et3N (1.8 mL, 12.66 mol) in CH2Cl2 (10 mL) dropwise at 0° C. Stir the reaction at 0° C. for 10 min and at RT for 30 min. Dilute the reaction with CH2Cl2 (100 mL), wash with 0.1 M HCl (2×30 mL), 1.0 M NaOH (2×30 mL), dry over Na2SO4, filter, and concentrate. Purify the crude material by chromatography, eluting with 20% EtOAc/hexane to give 3.53 g (79%) of the title compound. LC-MS/ES m/z (37Cl) 531.2 [M+]. evaporate down in vacuo Dissolve the resulting solid material in CH2Cl2 (30 mL) cool to 0° C dropwise at 0° C Stir the reaction at 0° C. for 10 min at RT for 30 min Dilute wash with 0.1 M HCl (2×30 mL), 1.0 M NaOH (2×30 mL) dry over Na2SO4 filter concentrate Purify the crude material by chromatography eluting with 20% EtOAc/hexane

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

Procedure: Dissolve triisopropyl-(2-methoxy-4-nitro-phenoxy)-silane (95.7 g, 294.0 mmol) in EtOH (1800 mL) and add 5% Pd/C (10.0 g). Hydrogenate the slurry at RT under 50 psi hydrogen for 8 h. Filter the slurry through a pad of Celite® and rinse with EtOH. Concentrate the filtrate in vacuo to give a brown oil. Purify the oil by flash chromatography, using a gradient from 100% hexanes to 20% EtOAc/hexanes, to provide 67.4 g (77.6%) of the title compound as a brown solid. MS/ES m/z 296.2 [M+H]+. Filter the slurry through a pad of Celite® rinse with EtOH Concentrate the filtrate in vacuo to give a brown oil Purify the oil by flash chromatography

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

Procedure: Dissolve triisopropyl-(2-methoxy-4-nitro-phenoxy)-silane (95.7 g, 294.0 mmol) in EtOH (1800 mL) and add 5% Pd/C (10.0 g). Hydrogenate the slurry at RT under 50 psi hydrogen for 8 h. Filter the slurry through a pad of Celite® and rinse with EtOH. Concentrate the filtrate in vacuo to give a brown oil. Purify the oil by flash chromatography, using a gradient from 100% hexanes to 20% EtOAc/hexanes, to provide 67.4 g (77.6%) of the title compound as a brown solid. MS/ES m/z 296.2 [M+H]+. Filter the slurry through a pad of Celite® rinse with EtOH Concentrate the filtrate in vacuo to give a brown oil Purify the oil by flash chromatography

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

Procedure: Dissolve triisopropyl-(2-methoxy-4-nitro-phenoxy)-silane (95.7 g, 294.0 mmol) in EtOH (1800 mL) and add 5% Pd/C (10.0 g). Hydrogenate the slurry at room temperature under 50 psi hydrogen for 8 h. Filter the slurry through a pad of Celite® and rinse with EtOH. Concentrate the filtrate in vacuo to give a brown oil. Purify by flash chromatography, using a gradient from 100% hexanes to 20% EtOAc/hexanes, to give the title compound as a brown solid (67.4 g, 77.6% yield). MS (ES+) 296.2 (M+1)+. Filter the slurry through a pad of Celite® rinse with EtOH Concentrate the filtrate in vacuo to give a brown oil Purify by flash chromatography