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本文在“化学平衡、动力学、机理和结构”的基础上讨论了重氮盐偶合反应。偶合反应大都是在稀水溶液中进行的亲电取代反应,亲电质点是重氮阳离子,它是二元Lewis酸((pK_1+pk_2)/2是其重要参数,亲核质点是酚阴离子(或游离胺)。偶合反应遵循SE2机理,可以用Bodenstein方程描述偶合反应的动力学过程。笼统偶合反应的适宜pH范围是:pKa(酚或胺)~((pK_1+pK_2)/2)(重氮盐)。氨基羟基萘存在多个偶合位置:酸性介质有有利于氮基位置偶合,碱性介质有利于羟基位置偶合:适当降低偶合pH,减小缓冲剂碱浓度,较低的偶合温度和添加少量吡啶碱类催亿剂都有利于提高产物构成中羟基邻位偶合物的比率。水不混溶有机相、无机盐、脲素和水对偶合反应也有一定的影响。
This paper discusses the diazonium salt coupling reaction on the basis of “chemical equilibrium, kinetics, mechanism and structure”. The coupling reaction is mostly electrophilic substitution reaction in dilute aqueous solution. The electrophilic point is diazonium cation, which is the important parameter of binary Lewis acid (pK_1 + pk_2) / 2. The nucleophile is phenolic anion (or Free amine.) The coupling reaction follows the SE2 mechanism and the Bodenstein equation can be used to characterize the kinetics of the coupling reaction. The suitable pH range for the general coupling reaction is: pKa (pK1 + pK2) / 2) Salt) Aminohydroxynaphthalene There are multiple coupling sites: acidic medium is conducive to nitrogen-site coupling, alkaline medium is conducive to the coupling of hydroxyl sites: appropriate reduction of coupling pH, reducing the buffer base concentration, lower coupling temperature and add A small amount of pyridine base catalysis agents are conducive to improve the ratio of hydroxyl ortho-conjugates in the product composition.The water-immiscible organic phase, inorganic salts, urea and water also have some impact on the coupling reaction.