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重氮化反应

重氮化,是亚硝酸生成重氮盐的反应。反应中一般使用亚硝酸钠与过量无机酸作为亚硝酸供源。通式如下:

R—NH2 + 2HCl + NaNO2 —> R—N2Cl + NaCl + 2H2O

其中R为芳基。反应由 Peter Griess 在1858年发现。

反应中使用大大过量的HCl,常达3摩每摩胺,其中1摩用于产生ON-OH2+离子,1摩用于生成NOCl,另1摩则用于产生重氮盐酸盐R—N≡NCl。重氮化用于众多芳香族化合物(特别是重氮染料)的制取;产物重氮盐可经重氮偶联、水解(成)、脱重氮化Schiemann反应Sandmeyer反应、还原(成芳肼)及Gomberg-Bachmann反应等众多方法转化为其他化合物,在合成上有很多用途。

反应条件

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重氮化多在0-5℃进行,高于此温时重氮盐易分解,导致副产物的生成。与亚硝酸钠的反应是放热的,故在反应中需冷却反应液,确保温度不过高。工业上是用通致冷剂或加入冰块的方法保持低温的,实验室中则一般用冰盐浴。

注意事项

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反应物胺与亚硝酸钠均有毒。产物重氮盐不稳定,在水溶液中逐渐分解。干燥的重氮盐可在震动、摩擦、加热或电击的条件下发生爆炸。实际操作中应避免对重氮盐进行干燥。特别注意不要将反应液洒出,导致干燥重氮盐的产生。

反应机理

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  • 亚硝酸的质子化
HO-N=O + H+ H2O+-N=O
  • 消去一分子水,产生亲电性的亚硝正离子
H2O+-N=O [N=O]+ + H2O
  • 芳胺亲核性的氮进攻亚硝正离子的氮原子
[N=O]+ + Ar-NH2 Ar-NH2+-NO
  • 去质子化,重排,得重氮氢氧化物
Ar-NH2+-NO Ar-N=N-OH + H+
  • 氧原子被质子化,脱去水,得重氮正离子。
Ar-N=N-OH + H+ Ar-N+N + H2O

重氮正离子的四氟硼酸盐或六氟磷酸盐相对较稳定,可以固体形式使用。

重氮化是测定芳香伯胺的标准方法。

参考资料

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  • Rainer Beckert (Bearb.): Organikum. 22. Auflage, Wiley-VCH, Weinheim 2004, ISBN 3-527-31148-3.
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重氮化反应
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