合成对甲氧基苯肼

合成对甲氧基苯肼:

O NHNH2

To a solution of 4-methoxyaniline (2.46 g, 20mmol) in 60 mL of conc. HCl

was added dropwise the solution of NaNO

2

(1.38 g, 20 mmol) in 35 mL of

H

2

O at 0°C. After stirring for 0.5 h at 0°C, the reaction mixture was

added dropwise to a solution of SnCl

2

(9.03 g, 40 mmol) in 3 5 mL of conc. HCl at 0°C, t h en stirring was continued for 1.5 h at 0°C. 2N NaOH was then added to quench the reaction until pH=9 to 10. The aqueous layer was

extracted with DCM (50 mLx3) and the organic layer was dried over Na

2SO

4

.

After filtration and concentration, the desired product,

(4-methoxyphenyl) hydrazine was obtained (0.98 g, 35% yield), which was used directly for next step. (4-methoxyphenyl)hydrazine, yield (0.98 g, 35%),

Synthesis of compound, Bis(pyridin−2−ylmethyl)amine (1)

N

N

N

Into a solution of picolinaldehyde (2.38 g, 22 mmol) in ethanol (15 mL) was added dropwise pyridin−2−ylmethanamine (2.14 g, 20 mmol) in ethanol (5 mL) during 10 min. The reaction mixture was stirred for 6h at room temperature. Sodium borohydride (3.8 g, 100 mmol) was then added slowly in small portions at 0 °C during the period of 5 min. Then, the mixture was warmed up to room temperature and stirred overnight. Ethanol was removed by evaporation and water (20 mL) was added to the residue. The aqueous layer was then extracted with CH2Cl2 (30 mL × 3) and the combined extracts were dried over MgSO4. After concentration under reduced pressure, the residue was purified by flash chromatography on silica gel (eluent: ethanol / ethyl acetate / triethylamine = 10:50:1) to give yellow oil (2.12 g, 53%).1H NMR (CDCl3, ppm), 8.480 (s, 2H,), 7.556 (s, 2H), 7.278 (s, 2H), 7.072 (s, 2H), 3.903(s, 4H), 2.676(s, 1H).