反应详情

温度

70 °C

Chart A, Step A-1. To a stirred solution of 3,5-dinitroiodobenzene (6.65 g, 22.6 mmol, starting material in CHART A) in ethanol (94 mL) is added stannous chloride (51.0 g, 226 mmol). The reaction mixture is heated at 70° C. for 1 hour. The reaction mixture is cooled and poured onto ice (300 cc) and the pH is adjusted to 8 with 10% aqueous sodium hydroxide. A thick white precipitate forms and the reaction mixture is filtered through a pad of celite. The filter cake is first washed with ethyl acetate and then stirred with ethyl acetate (300 mL) for 30 min. The celitc mixture is filtered again and filtrates are combined. The phases of the filtrates are separated and the aqueous phase is extracted with ethyl acetate (3×400 mL). The combined organics are dried (Na2SO4), filtered and concentrated. The organic residue is purified by flash chromatography using 50% ethyl acetate in hexane to afford 4.53 g of 5-iodo-1,3-phenylenediamine. (A-1, X is I) Mp=125°-127° C. (dec). IR (mull) 3429, 3312, 3206, 2954, 2925, 2868, 2854, 1632, 1607, 1569, 1472, 1462, 1459, 1198, 984, 810, 675 cm-1 ; 1H NMR (CDCl3)δ6.48 (d, 2 H, J=2 Hz), 5.98 (t, 1 H, J=2 Hz), 3.78 (s, 4 H); 13C NMR (CDCl3) δ148.1, 114.6, 101.0, 94.9; Mass Spec (70eV, EI) m/z 234 (parent), 206, 117, 107 (base), 80, 66, 53, 42; Exact Mass calculated for C6H7IN2 : 233.9656. Found: 233.9652. Analysis Calculated for C6H7IN2 : C, 30.79; H, 3.02; N, 11.97; I, 54.22; Found: C, 30.93; H, 2.97; N, 11.71; I, 54.26.

1. temperatureThe reaction mixture is cooled
2. additionpoured onto ice (300 cc)
3. filtrationA thick white precipitate forms and the reaction mixture is filtered through a pad of celite
4. washThe filter cake is first washed with ethyl acetate
5. filtrationThe celitc mixture is filtered again
6. customThe phases of the filtrates are separated
7. extractionthe aqueous phase is extracted with ethyl acetate (3×400 mL)
8. dry with materialThe combined organics are dried (Na2SO4)
9. filtrationfiltered
10. concentrationconcentrated
11. customThe organic residue is purified by flash chromatography