2-N-(2-methoxyethyl)benzene-1,2-diamine

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

Procedure: The residue 109B (422 mg, 2.54 mmol) was dissolved in THF (7.5 mL). CDI (494 mg, 3.05 mmol) in THF (7.6 mL) was added slowly via addition funnel. After addition the mixture was stirred overnight at room temperature, solvent was removed under vacuum. The residue was purified by column chromatography (5% MeOH/DCM) to give the product 1-(2-methoxyethyl)-1H-benzo[d]imidazol-2(3H)-one (109C) as an orange solid (449 mg, 92%). ESI-MS:m/z 193.3 (M+H)+. After addition the mixture solvent was removed under vacuum The residue was purified by column chromatography (5% MeOH/DCM)

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

Procedure: The residue 109A was dissolved in methanol (60 mL) and acetic acid (4 mL). Zinc metal (3.24 g, 49.6 mmol) was added and the mixture was stirred overnight at room temperature. The reaction was decanted off from unreacted zinc metal. The solvent was removed under vacuum and resuspended in ethyl acetate (30 mL). The precipitate was removed by filtration on a Buchner funnel with Celite. Solvent was removed from the filtrate and the residue was purified by column chromatography (2% MeOH/DCM) to give the product N1-(2-methoxyethyl)benzene-1,2-diamine (109B) as a red oil (422 mg, 72% yield over two steps). ESI-MS:m/z 167.4 (M+H)+. The reaction was decanted off from unreacted zinc metal The solvent was removed under vacuum The precipitate was removed by filtration on a Buchner funnel with Celite Solvent was removed from the filtrate the residue was purified by column chromatography (2% MeOH/DCM)

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

Procedure: The residue 109A was dissolved in methanol (60 mL) and acetic acid (4 mL). Zinc metal (3.24 g, 49.6 mmol) was added and the mixture was stirred overnight at room temperature. The reaction was decanted off from unreacted zinc metal. The solvent was removed under vacuum and resuspended in ethyl acetate (30 mL). The precipitate was removed by filtration on a Buchner funnel with Celite. Solvent was removed from the filtrate and the residue was purified by column chromatography (2% MeOH/DCM) to give the product N1-(2-methoxyethyl)benzene-1,2-diamine (109B) as a red oil (422 mg, 72% yield over two steps). ESI-MS:m/z 167.4 (M+H)+. The reaction was decanted off from unreacted zinc metal The solvent was removed under vacuum The precipitate was removed by filtration on a Buchner funnel with Celite Solvent was removed from the filtrate the residue was purified by column chromatography (2% MeOH/DCM)

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

Procedure: N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide (EDC, 791 mg) is added to a solution of N1-(2-methoxyethyl)benzene-1,2-diamine (311 mg, 1.87 mmol) and methyl 4-isothiocyanatobenzoate (328 mg, 1.70 mmol) in tetrahydrofuran. The reaction may be heated to reflux for 2 hr and cooled to room temperature. The mixture may be diluted in an appropriate solvent such as ethyl acetate, filtered and concentrated. The residue may be purified by any appropriate method, including Biotage column chromatography to give methyl 4-(1-(2-methoxyethyl)-1H-benzo[d]imidazol-2-ylamino)benzoate (381 mg). The reaction may be heated to reflux for 2 hr filtered concentrated The residue may be purified by any appropriate method

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

Procedure: Ammonium formate (727 mg, 11.3 mmol) followed by a catalytic amount of palladium on carbon (5%) is added to a solution of N-(2-methoxyethyl)-2-nitroaniline (426 mg, 2.17 mmol) in methanol. The mixture may be refluxed for an appropriate time period (such as overnight), cooled to an appropriate temperature (such as room temperature) and filtered. The filtrate may be concentrated and the residue may purified by Biotage column chromatography to give N1-(2-methoxyethyl)benzene-1,2-diamine (319 mg) The mixture may be refluxed for an appropriate time period (such as overnight) filtered The filtrate may be concentrated the residue may purified by Biotage column chromatography

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

Procedure: Ammonium formate (727 mg, 11.3 mmol) followed by a catalytic amount of palladium on carbon (5%) is added to a solution of N-(2-methoxyethyl)-2-nitroaniline (426 mg, 2.17 mmol) in methanol. The mixture may be refluxed for an appropriate time period (such as overnight), cooled to an appropriate temperature (such as room temperature) and filtered. The filtrate may be concentrated and the residue may purified by Biotage column chromatography to give N1-(2-methoxyethyl)benzene-1,2-diamine (319 mg) The mixture may be refluxed for an appropriate time period (such as overnight) filtered The filtrate may be concentrated the residue may purified by Biotage column chromatography

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

Procedure: The residue 109B (422 mg, 2.54 mmol) was dissolved in THF (7.5 mL). CDI (494 mg, 3.05 mmol) in THF (7.6 mL) was added slowly via addition funnel. After addition the mixture was stirred overnight at room temperature, solvent was removed under vacuum. The residue was purified by column chromatography (5% MeOH/DCM) to give the product 1-(2-methoxyethyl)-1H-benzo[d]imidazol-2(3H)-one (109C) as an orange solid (449 mg, 92%). ESI-MS:m/z 193.3 (M+H)+. After addition the mixture solvent was removed under vacuum The residue was purified by column chromatography (5% MeOH/DCM)

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

Procedure: The residue 109A was dissolved in methanol (60 mL) and acetic acid (4 mL). Zinc metal (3.24 g, 49.6 mmol) was added and the mixture was stirred overnight at room temperature. The reaction was decanted off from unreacted zinc metal. The solvent was removed under vacuum and resuspended in ethyl acetate (30 mL). The precipitate was removed by filtration on a Buchner funnel with Celite. Solvent was removed from the filtrate and the residue was purified by column chromatography (2% MeOH/DCM) to give the product N1-(2-methoxyethyl)benzene-1,2-diamine (109B) as a red oil (422 mg, 72% yield over two steps). ESI-MS:m/z 167.4 (M+H)+. The reaction was decanted off from unreacted zinc metal The solvent was removed under vacuum The precipitate was removed by filtration on a Buchner funnel with Celite Solvent was removed from the filtrate the residue was purified by column chromatography (2% MeOH/DCM)