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Sandmeyer 反应—— 重氮化碘代

1927 年,同样是德国的化学家G.Balz和G.Schiemann发现直接 加热苯胺的硼氟酸重氮盐能得到氟苯,这就是Balz-Schiemann反应。1935 年, F.B.Dains 和 F.Eberly用KI去处理重氮盐,成功合成了碘代苯。随后重氮化羟基取代和重氮化去胺反应也相继被发现,加上偶氮反应,形成了比较完善的芳香重氮化合物反应体系

在芳香重氮盐的碘代反应中,可不必加入铜盐作催化剂,只需和KI或NaI直 接反应。因为I- 的氧化还原电位(E0 = 1.3 V)足以促使电子向重氮离子转移,而使反应顺利进行。这个反应实际上Griess早在 1864 年就发现了。反应产率一般比氯代和溴代都高,反应也容易,重氮化完成后直接加入KI在室温下就能发生反应。

     In a 600-ml. beaker fitted with a thermometer and mechanical stirrer are placed 150 ml. of concentrated hydrochloric acid and 55 g. (0.32 mole) of o-bromoaniline. After brief stirring, 100 g. of ice is added and the beaker is surrounded by an ice-salt bath. The solution is then diazotized by the dropwise addition with stirring of a solution of 24.3 g. (0.35 mole) of sodium nitrite in 100 ml. of water, the temperature being kept at 0–5°c. 

    After stirring the diazotized solution for 15 minutes, it is slowly poured through a glass-wool filter into a solution of 180 g. (3.4 moles) of potassium iodide in 600 ml. of water. After standing overnight, the heavy dark oil is separated, washed successively with 10% aqueous sodium hydroxide, water, 5% aqueous sodium bisulfite and water, and then dried over magnesium sulfate. 

     Distillation under reduced pressure gives o-bromoiodobenzene as a nearly colorless liquid, b.p. 120–121° at 15 mm. Yield 65–75 g. (72–83%). 




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