The kinetics of the reactions of 4‐nitrobenzofurazane 1a, 4‐nitrobenzothiadiazole 1b, and 4‐nitrobenzoselenadiazole 1c with a series of 4‐Y‐substituted phenoxide anions 2a‐e (Y = OMe, Me, H, Cl, and CN) in aqueous solution at 20°C were investigated photometrically. The derived second‐order rate constants (k₂) have been combined with the nucleophilicity parameters values of these series of anions 2a‐e to determine the electrophilicity parameters E of electrophiles 1a‐c according to the linear free‐energy relationship (log k₂)/s versus N. General reactivity of these electrophiles 1a‐c is found to be fairly similar with E values ranging in −10.77 ± 0.61 < E < −7.53 ± 0.29. The comparison with structurally related neutral electron‐deficient heteroaromatic and aromatic compounds revealed that 1a‐c are more reactive than 1,3,5‐trinitrobenzene, as benchmark aromatic electrophile used in nucleophilic addition or substitution processes. The rate constants for the reactions of 4‐nitrobenzochalcogenadiazoles 1a‐c with some other nucleophiles were measured and found to agree with those calculated from Mayr's equation. Finally, analysis of the rate data in terms of the Brønsted approach reveals that 1a‐c exhibits especially low intrinsic reactivity in σ‐adducts 3 forming reactions.

中文翻译：

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4-硝基苯并硫属元素二唑的亲电子亲和力：动力学研究和结构反应关系

4-硝基苯并呋喃烷1a，4-硝基苯并噻二唑1b和4-硝基苯并硒二唑1c与一系列4-Y-取代的酚盐阴离子2a-e（Y = OMe，Me，H，Cl和CN）在水中的反应动力学用光度法研究了20℃下的水溶液。已将导出的二阶速率常数（k ₂）与这些系列阴离子2a-e的亲核参数值组合，以根据线性自由能关系（log k _2）确定亲电子1a-c的亲电子参数E）/ s与N。这些亲电子试剂1a-c的一般反应性非常相似，E值范围为 −10.77± 0.61 <  E <−7.53±0.29。与结构相关的中性电子不足的杂芳族化合物和芳族化合物的比较表明，作为亲核加成或取代过程中使用的基准芳族亲电子试剂，1a - c比1,3,5-三硝基苯更具反应性。测量了4-硝基苯并硫属元素二唑1a-c与其他一些亲核试剂反应的速率常数，发现该常数与根据Mayr方程计算的常数一致。最后，根据布朗斯台德（Brønsted）方法对利率数据进行分析后发现1a-c在σ加合物3形成反应中表现出特别低的固有反应性。