New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion nucleophile was investigated. It was found that independent on the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho-position of the aryl ring slowers the reaction, while the presence of a moderately electron-withdrawing bromine substituent in the para-position to iodine in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para-position to iodine in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.

中文翻译：

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1-Arylbenziodoxolones 与叠氮阴离子的反应：取代基效应的实验和计算研究

制备了新的取代的 1-芳基苯并恶酮并研究了它们与叠氮阴离子亲核试剂的反应性。发现独立于取代基的存在，1-芳基苯并多索酮的所有反应都以缺电子苯并多索酮苯环中碘鎓离去基团的亲核取代进行。在芳环的邻位存在庞大的取代基会减慢反应速度，而在苯并氧酮环中碘的对位存在适度吸电子的溴取代基会适度提高取代率。在苯并多索隆环中碘的对位存在强吸电子硝基，显着提高了取代率。这些观察结果与苯并恶唑环中内部亲核取代的电子要求一致。可能的反应路径的量子化学计算研究与观察到的取代基对该反应中芳基苯并恶酮的反应性的影响一致。