[CH3:1][S:2][C:3]1[CH:9]=[CH:8][CH:7]=[CH:6][C:4]=1[NH2:5].[N:10]([O-])=O.[Na+].[Sn](Cl)[Cl:15]>Cl.FC(F)(F)C(O)=O.O>[ClH:15].[CH3:1][S:2][C:3]1[CH:9]=[CH:8][CH:7]=[CH:6][C:4]=1[NH:5][NH2:10]
2-(Methylmercapto)aniline (23.6 g, 169.5 mmol) was suspended in conc. HCl (200 mL) and trifluoroacetic acid (130 mL), and cooled to 0° C. in an ice bath. Sodium nitrite (14.0 g, 203.4 mmol) was dissolved in water (45 mL) and added dropwise to the suspension over 45 minutes. After the addition, the reaction was stirred at 0° C. for 1 h. In a separate flask, tin (II) chloride (76 g, 338.4 mmol) was dissolved in conc. HCl (100 mL) and added slowly over 15 minutes to the reaction mixture. The resultant suspension was warmed to room temperature and stirred for 48 hours. The reaction was filtered, washed with isopropyl alcohol (15 mL), and dried to give 1-[2-(methylsulfanyl)phenyl]hydrazine hydrochloride (30 g, 93%). 1H NMR (CD3OD, 300 MHz) δ 7.44 (d, 1H, J=7.7 Hz), 7.32-7.26 (m, 1H), 7.08-7.00 (m, 2H), 2.39 (s, 3H) ppm.
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