2-N-benzylbenzene-1,2-diamine

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: The title compound was prepared in accordance with the general method of Example 191(C), from N1-benzylbenzene-1,2-diamine (2.93 g, 14.78 mmol) and 2-chloroacetic acid (2.10 g, 22 mmol). The crude residue was purified over silicagel chromatography (prepacked 70 g silicagel column, Cyclohexane/AcOEt: from 80/20 to 70/30 as eluent) to afford 2.34 g of 1-benzyl-2-(chloromethyl)-1H-benzo[d]imidazole (Yield: 61%) as a yellow oil. The crude residue was purified over silicagel chromatography (prepacked 70 g silicagel column, Cyclohexane/AcOEt: from 80/20 to 70/30 as eluent)

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N-benzyl-o-phenylenediamine (3 g, 15 mmol), which is a known compound, was added to polyphosphoric ester (10 g), to which monochloroacetic acid (1.1 g, 12 mmol) was added and heated at 120° C. for 1 hour. Then water was added to the mixture to decompose remaining polyphosphoric ester. The resultant was refined in a conventional process and the title intermediate (2.25 g, 8.8 mmol) was obtained. was added

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

Procedure: The title compound was prepared in accordance with the general method of Example 191(C), from N1-benzylbenzene-1,2-diamine (2.93 g, 14.78 mmol) and 2-chloroacetic acid (2.10 g, 22 mmol). The crude residue was purified over silicagel chromatography (prepacked 70 g silicagel column, Cyclohexane/AcOEt: from 80/20 to 70/30 as eluent) to afford 2.34 g of 1-benzyl-2-(chloromethyl)-1H-benzo[d]imidazole (Yield: 61%) as a yellow oil. The crude residue was purified over silicagel chromatography (prepacked 70 g silicagel column, Cyclohexane/AcOEt: from 80/20 to 70/30 as eluent)

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: [N-(2-Aminophenyl)]-benzylamine (15.1 mmol, 3.0 g) in dichloromethane (80 ml) is charged with triphosgene (5.3 mmol, 1.57 g) in dichloromethane (40 ml) and is stirred at room temperature over the weekend. The suspension is poured into water (100 g) and is extracted with dichloromethane (2×50 ml). The organic layer is a suspension The colorless solid is filtered off, is dried in vacuo and is recrystallized from ethyl acetate to give the title product (81%)(R1=H, R2=benzyl, n=0). is extracted with dichloromethane (2×50 ml) is filtered off is dried in vacuo is recrystallized from ethyl acetate

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

Procedure: [N-(2-Aminophenyl)]-benzylamine (15.1 mmol, 3.0 g) in dichloromethane (80 ml) is charged with triphosgene (5.3 mmol, 1.57 g) in dichloromethane (40 ml) and is stirred at room temperature over the weekend. The suspension is poured into water (100 g) and is extracted with dichloromethane (2×50 ml). The organic layer is a suspension The colorless solid is filtered off, is dried in vacuo and is recrystallized from ethyl acetate to give the title product (81%)(R1=H, R2=benzyl, n=0). is extracted with dichloromethane (2×50 ml) is filtered off is dried in vacuo is recrystallized from ethyl acetate

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

Procedure: [N-(2-Nitrophenyl)]-benzylamine (21.9 mmol, 5.0 g) in ethyl acetate (150 ml) is charged with SnCl22H2O (131 mmol, 29.55 g) and is refluxed for 3 hours. The mixture is poured into ice water (100 g), sodium bicarbonate is added to achieve pH 7, and the reaction mixture is extracted with ethyl acetate (3×50 ml). The organic layer is dried with MgSO4, is filtered and evaporated to yield a light sensitive oil, which is used as such in the next step. is refluxed for 3 hours is added the reaction mixture is extracted with ethyl acetate (3×50 ml) The organic layer is dried with MgSO4 is filtered evaporated to yield a light sensitive oil, which

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

Procedure: [N-(2-Nitrophenyl)]-benzylamine (21.9 mmol, 5.0 g) in ethyl acetate (150 ml) is charged with SnCl22H2O (131 mmol, 29.55 g) and is refluxed for 3 hours. The mixture is poured into ice water (100 g), sodium bicarbonate is added to achieve pH 7, and the reaction mixture is extracted with ethyl acetate (3×50 ml). The organic layer is dried with MgSO4, is filtered and evaporated to yield a light sensitive oil, which is used as such in the next step. is refluxed for 3 hours is added the reaction mixture is extracted with ethyl acetate (3×50 ml) The organic layer is dried with MgSO4 is filtered evaporated to yield a light sensitive oil, which

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

Procedure: To a solution of benzyl-(2-nitro-phenyl)-amine (1068) (2.5 g, 10.43 mmol) in ethanol (150 mL) and water (10 mL) was added iron (8.7 g, 155.7 mmol) followed by 30 drops of concentrated HCl, and the resulting mixture was heated overnight at reflux. The reaction mixture was quenched with water, diluted with DCM and the layers were separated. The organic layer was washed with saturated sodium bicarbonate solution, brine, dried over sodium sulfate and concentrated to give a brown oily residue. Further purification by column chromatography (SiO2, 20% ethyl acetate/hexanes) afforded N-benzyl-benzene-1,2-diamine (1069) as a dark yellow oil (1.18 g, 57%). 1H NMR (400 MHz, CDCl3)  7.41-7.24 (m, 5H), 6.82-6.67 (m, 4H), 4.32 (s, 2H), 3.56 (b, 3H, NH). the resulting mixture was heated overnight at reflux The reaction mixture was quenched with water diluted with DCM the layers were separated The organic layer was washed with saturated sodium bicarbonate solution, brine dried over sodium sulfate concentrated to give a brown oily residue Further purification by column chromatography (SiO2, 20% ethyl acetate/hexanes)