(44)--10.3重氮和偶氮化合物.ppt

偶氮化合物HaiduCollegeQingdaoAgriculturalUniversity偶氮苯偶氮二异丁腈重氮化合物(Cl,H,N)HaiduCollegeQingdaoAgriculturalUniversity苯重氮氨基苯氯化重氮苯重氮盐的制备——重氮化反应HaiduCollegeQingdaoAgriculturalUniversity芳香伯胺重氮盐低温稳定，高温分解中性或碱性介质，不稳定，爆炸π,π–共轭NN..苯重氮正离子的结构性质活泼：失去氮的取代反应保留氮的偶合反应、还原反应HaiduCollegeQingdaoAgriculturalUniversity取代反应HaiduCollegeQingdaoAgriculturalUniversity(a)重氮基被—OH取代重氮盐的稀酸溶液加热N2酚由胺制备酚的方法HaiduCollegeQingdaoAgriculturalUniversity(b)重氮基被H取代——重氮盐的去氨基反应芳香重氮盐与H3PO2或C2H5OH作用：HaiduCollegeQingdaoAgriculturalUniversity特殊的定位效果(85%)HaiduCollegeQingdaoAgriculturalUniversity(c)重氮基被Cl、Br取代芳香重氮盐CuX/Cu强酸介质卤化物HaiduCollegeQingdaoAgriculturalUniversity(d)重氮基被氰基取代CuCN、KCNHaiduCollegeQingdaoAgriculturalUniversity由重氮盐制备芳香碘代物的方法：KI:(81%)由重氮盐制备芳香碘代物的方法KI:(81%)(e)重氮基被I取代HaiduCollegeQingdaoAgriculturalUniversity重氮盐失去氮的取代反应在合成中的应用价值：在芳环上引入用其它方法难于引入的―F,―I,―CN,―OH等制备不能通过芳环上亲电取代反应得到的化合物HaiduCollegeQingdaoAgriculturalUniversity(100%)(74％-77%)1，3，5-三溴苯的制备HaiduCollegeQingdaoAgriculturalUniversity+-+偶合反应芳香重氮盐弱亲电试剂亲电取代反应被偶合的芳环上有强的斥电子基团HaiduCollegeQingdaoAgriculturalUniversity酚：弱碱性介质,pH=8~10芳胺：弱酸性的介质，pH=5~7偶合反应特点HaiduCollegeQingdaoAgriculturalUniversity萘系化合物偶合反应特点HaiduCollegeQingdaoAgriculturalUniversity取代发生在对位；对位有取代基时，发生在邻位。偶合反应的重要用途是合成偶氮染料,例如：甲基橙HaiduCollegeQingdaoAgriculturalUniversity还原剂：SnCl2+HCl，NaHSO3,Na2SO3,SO2等芳基肼还原反应HaiduCollegeQingdaoAgriculturalUniversity