[Cl-].[Cl-].[Ca+2].FC1C=CC(N)=C(N)C=1.[F:13][C:14]1[C:20]([F:21])=[CH:19][C:17]([NH2:18])=[C:16]([N+:22]([O-])=O)[CH:15]=1>CCO.O.[Zn]>[F:13][C:14]1[C:20]([F:21])=[CH:19][C:17]([NH2:18])=[C:16]([NH2:22])[CH:15]=14,5-Difluoro-1,2-diaminobenzene was prepared using an adaptation of the method of Tsuji et al., (Tsuji, Y. et al., J. Org. Chem. 55: 580 (1990)). Zn powder (942 mg, 14.4 mmol), CaCl2 (94.4 mg), H2O (1.0 mL) and 4.0 mL EtOH were combined and brought to reflux as described for 4-fluoro-1,2-diaminobenzene (see Example 11) and to this mixture was added slowly dropwise a solution of 4,5-difluoro-2-nitroaniline (200 mg, 1.15 mmol) in 2 mL EtOH. Analysis and workup were as described for 4-fluoro-1,2-diaminobenzene (Example 11 ) except that the reaction was dissolved in 5 mL H2O and the solution extracted with 3×10 mL Et2O. The organic layers were combined and treated with activated charcoal, dried (MgSO4) and filtered through a pad of Celite. The solvent was evaporated at reduced pressure to yield 111.5 mg (67.3%) of a brown crystalline solid. 1H NMR (CDCl3) δ 3.34 (br s, 4H, NH2), 6.53 (t, 2H, ArH).
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