[CH3:1][C:2]1[CH:3]=[C:4]([S:9][C:10]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-])=O)[C:11]=2[C:12]#[N:13])[CH:5]=[C:6]([CH3:8])[CH:7]=1.[OH-].[Na+]>COCCOCCOC.Cl.O>[NH2:18][C:14]1[CH:15]=[CH:16][CH:17]=[C:10]([S:9][C:4]2[CH:3]=[C:2]([CH3:1])[CH:7]=[C:6]([CH3:8])[CH:5]=2)[C:11]=1[C:12]#[N:13]2-[(3,5-Dimethylphenyl)thio]-6-nitrobenzonitrile (Example 5) (1.0 g, 0.0035 mol) was dissolved in 50 ml of diglyme. A solution of stannous chloride-2H2O (3.16 g, 0.014 mol) in 15 ml of concentrated HCl was added dropwise with stirring. After stirring 1 h and 15 min, the reaction mixture was poured into a solution of 12 g NaOH in 100 ml of water with ice added to bring the total volume to 300 ml. The mixture was stirred for 1 h and the solid was collected by vacuum filtration. Chromatography on silica gel (flash; Hex/EtOAc 1:1) provided 0.57 g (64%) of 2-amino-6-[(3,5-dimethylphenyl)thio]benzonitrile: mp 124°-125° C.; NMR (Me2SO-d6, 300 MHz) δ 2.23 (s, H), 6.17 (br, 2H), 6.24 (apparent d, 1H), 7.00 (m, 3H), 7.09 (apparent t, 1H); mass spec (CI) 255 (M+ +1, 100%). Anal. Calc. for C15H14N2S: C, 70.83; H, 5.55; N, 11.01; S, 12.61. Found: C, 70.84; H, 5.60; N, 10.98; S, 12.53.
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