Reactions of aniline derivatives in dimethyl sulfoxide with phenyl 1‐(2,4‐dinitronaphthyl) ether yield aryl 1‐(2,4‐dinitronaphthyl) amine, which results in substitution of the phenoxy groups at the naphthyl ipso carbon atom. Rate constants were measured spectrophotometrically, and reaction proton transfer was rate limiting. The values of the rate coefficients indicate a rate‐limiting proton transfer mechanism with significant substituent effects. The calculated activation parameters were of regular variation with substituents in 4‐ and 3‐position in the aniline nucleophile, and the reaction proceeded through a common mechanism. Hammett's reaction constant showed that the reaction rate constants depend on the electron density of the nitrogen atom of aniline derivative, whereas the coefficient value obtained from the Brönsted relation indicated that the reaction was significantly associative and quite zwitterion like. Computational studies of the substitution were carried out based on density functional theory, and theoretical to the experimental agreement was achieved.

中文翻译：

---

研究苯1–（2,4-二硝基萘基）醚被苯胺衍生物取代的反应性和机理的实验和理论方法

二甲基亚砜中的苯胺衍生物与苯基1-（2,4-二硝基萘基）醚反应生成芳基1-（2,4-二硝基萘基）胺，从而导致萘基ipso碳原子上的苯氧基取代。用分光光度法测量速率常数，反应质子转移是速率限制。速率系数的值表示具有明显取代基效应的限速质子转移机制。计算得出的活化参数在苯胺亲核试剂中的4位和3位有取代基，并且有规律的变化，反应是通过共同的机理进行的。哈米特的反应常数表明，反应速率常数取决于苯胺衍生物氮原子的电子密度，而从布朗斯台德关系式获得的系数值表明该反应是显着缔合的，且两性离子类似。基于密度泛函理论对取代基进行了计算研究，获得了与实验吻合的理论。