反应详情

N-Methyl-1,2-diaminobenzene was prepared using an adaptation of the method of Tsuji et al. (J. Org. Chem. 55:580 (1990)). Zn powder (8.07 g, 0.123 mol), CaCl2 (807 mg), H2O (9.9 mL) and 30 mL EtOH were combined and brought to reflux as described for 4-fluoro-1,2-diaminobenzene (see Example 10), and to this mixture was added slowly dropwise a solution of N-methyl-2-nitroaniline (1.50 g, 9.86 mmol) in 15 mL EtOH. Analysis and workup were as described for 4-fluoro-1,2-diaminobenzene except that the reaction residue was dissolved in 50 ml Et2O. This Et2O solution was then extracted with 3×25 mL 1N HCl and the aqueous layers combined and basified with 5 g of 50% NaOH solution. This solution was then extracted with 3×25 mL Et2O. These Et2O layers were then combined, dried (MgSO4) and the solvent evaporated at reduced pressure to yield 911.1 mg (76.1%) of a dark brown oil. 1H NMR (CDCl2) δ2.87 (s, 3H, CH3), 3.31 (br s, 3H, NH), 6.67 (m, 3H, ArH), 6.86 (m, 1H, ArH).

1. temperatureto reflux
2. extractionThis Et2O solution was then extracted with 3×25 mL 1N HCl
3. extractionThis solution was then extracted with 3×25 mL Et2O
4. dry with materialdried (MgSO4)
5. customthe solvent evaporated at reduced pressure