[O:1]([C:8]1[CH:9]=[C:10]([NH:14]C2C=CC=CC=2)[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N:21]([O-])=O.[Na+].O.O.[Sn](Cl)(Cl)(Cl)Cl.[OH-].[Na+].C(=O)(O)[O-].[Na+]>CO.O.Cl>[O:1]([C:8]1[CH:9]=[C:10]([NH:14][NH2:21])[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1To a solution of 3-phenoxy-phenylaniline (2.32 g, 12.5 mmol) in methanol (5 mL), water (10 mL) and concentrated HCl (3 mL) at 0° C. was added in rapid drops a solution of sodium nitrite (0.87 g, 12.7 mmol) in water (2 mL). The reaction was stirred 10 min then treated in rapid drops with a 0° C. solution of tin chloride dihydrate (6.77 g, 30 mmol) in concentrated HCl (25 mL). The reaction was stirred for 1 h, then adjusted to ˜pH 7 with 6N NaOH and sodium bicarbonate, then filtered through Celite, washing with 1:3 methanol:dichloromethane. The filtrate was separated, the aqueous phase was extracted with 1:3 methanol:dichloromethane (2×). The combined organic layer was dried over sodium sulfate, evaporated, then purified by flash chromatography (SiO2) eluted with 35:65 ethyl acetate:hexanes to provide (3-phenoxy-phenyl)-hydrazine (1.78 g, 71% yield) as an orange oil. 1H-NMR (CDCl3, 500 MHz) 7.30 (m, 2H), 7.14 (t, 1H), 7.08 (t, 1H), 7.00 (m, 2H), 6.52 (m, 1H), 6.47 (m, 1H), 6.45 (m, 1H) 5.2 (br 1H), 3.5 (br 2H) ppm; MS (FIA) 201.1 (M+H); HPLC (method A) 2.887 min.
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