Additivity rules using similarity models for chemical reactivity: Calculation and interpretation of electrofugality and nucleofugality

Bentley TW

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Additivity rules using similarity models for chemical reactivity: Calculation and interpretation of electrofugality and nucleofugality

机译：使用相似性模型进行化学反应的加性规则：电逸性和核逸性的计算和解释

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A recently proposed, multiparameter correlation: log k (25 degrees C) = s(f) (E-f + N-f), where E-f is electrofugality and N-f is nucleofugality, for the substituent and solvent effects on the rate constants for solvolyses of benzhydryl and substituted benzhydryl substrates, is re-evaluated. A new formula (E-f = log k (RCl/EtoH/25 degrees C) -1.87), where RCl/EtOH refers to ethanolysis of chlorides, reproduces published values of E-f satisfactorily, avoids multi-parameter optimisations and provides additional values of E-f. From the formula for E-f, it is shown that the term (s(f) x E-f) is compatible with the Hammett-Brown (rho(+) sigma(+)) equation for substituent effects. However, the previously published values of N-f do not accurately account for solvent and leaving group effects (e.g. nucleofuge Cl or X), even for benzhydryl solvolyses; alternatively, if the more exact, two-parameter term, (s(f) x N-f) is used, calculated effects are less accurate. A new formula (N-f = 6.14 + log k(BX/any solvent/25 degrees C)), where BX refers to solvolysis of the parent benzhydryl as electrofuge, defines improved Nf values for benzhydryl substrates. The new formulae for E-f and N-f are consistent with an assumption that s(f) = 1.00, and so improved correlations for benzhydryl substrates can be obtained from the additive formula: log k(RX/any solvent/25 degrees C) = (E-f + N-f). Possible extensions of this approach are also discussed.

机译：最近提出的多参数相关性：log k（25摄氏度）= s（f）（Ef + Nf），其中Ef是电逸性，Nf是核逸性，对于取代基和溶剂对苯甲基和被取代的苯酚溶剂化速率常数的影响重新评估二苯甲基底物。一个新的公式（E-f = log k（RCl / EtoH / 25摄氏度）-1.87），其中RCl / EtOH指氯化物的乙醇化作用，令人满意地重现了E-f的发布值，避免了多参数优化并提供了E-f的其他值。从E-f的公式可以看出，项（s（f）x E-f）与用于取代基效应的Hammett-Brown（rho（+）sigma（+））方程兼容。然而，即使对于苯二甲酰基溶剂解，先前公开的N-f值也不能准确地说明溶剂和离开基团的作用（例如，核仁烃Cl或X）。或者，如果使用更精确的两参数项（s（f）x N-f），则计算出的效果不太准确。一个新的公式（N-f = 6.14 + log k（BX /任何溶剂/ 25摄氏度）），其中BX指的是将母体苯甲基溶剂化为电絮凝剂，它定义了苯甲基底物的改良Nf值。 Ef和Nf的新公式与s（f）= 1.00的假设一致，因此可以从添加公式获得对苯甲基底物的改进相关性：log k（RX /任何溶剂/ 25摄氏度）=（Ef + Nf）。还讨论了这种方法的可能扩展。

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《Chemistry: A European journal》 |2006年第25期|共7页
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Bentley TW;
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正文语种 eng
中图分类化学;
关键词
kinetics; leaving group effects; nucleophilic substitution; solvent effects; substituent effects; MONOSUBSTITUTED BENZHYDRYL CHLORIDES; AROMATIC RING PARAMETER; TERT-BUTYL; BENZYLIC CHLORIDES; SOLVOLYSIS RATES; S(N)1 REACTIONS; Y-SCALE; 1-ADAMANTYL; KINETICS; SOLVENT;

机译：动力学;离去基团效应;亲核取代;溶剂效应;取代基效应;单取代的苄基氯;芳族环参数;叔丁基;苄基氯;溶剂化速率;S（N）1反应;Y-规模;1-ADAMANTYL;动力学溶剂;

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1. Additivity rules using similarity models for chemical reactivity: Calculation and interpretation of electrofugality and nucleofugality [J] . Bentley TW Chemistry: A European journal . 2006,第25期

机译：使用相似性模型进行化学反应的加性规则：电逸性和核逸性的计算和解释
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3. A DFT-based model for calculating solvolytic reactivity. The nucleofugality of aliphatic carboxylates in terms of N_f parameters [J] . Bernard Denegri, Mirela Matic, Olga Kronja Organic & biomolecular chemistry . 2014,第30期

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Additivity rules using similarity models for chemical reactivity: Calculation and interpretation of electrofugality and nucleofugality

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