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本文成果可以归纳为:(1)将σ~*值较严格地给予了与芳香系σ值相仿的工作定义。即同是将其与羧酸在一定温度和溶剂系中的pK_a值联系起来,并计算了脂肪系中千余个取代基的数千个不同种类的σ值。(2)增加了模型反应系的种类,使最后有可能达到直线自由能的定量关系在脂防系中普遍应用。但σ~*值仍保持原有标度,因而与其它类型σ值能有简单的数学关系。与历史较早的Branch和Calvin的诱导常数有优良标准的直线关系。(3)将相互关联的取代基数目扩大,增加了统计上的可靠程。(4)使烷基与取代烷基的σ值归于一致的标度线商不要求烷基值都固定为零。(5)阐明了σ~*值与构型、构象、内氢键的形成、溶剂化作用、分子间和分子内的Lewis酸碱作用、静电场力效应、动电分散效应等复杂因素密切相关,远不仅限于代表诱导效应。(6)用氨基酸中的σ~*与ρ~*值与其它羧酸系作比较而证实了烷基的σ~*值主要取决于分子内的动电效应。举例说明带电荷基出偏差的问题在原则上是可以解决的。(7)尝试建立一个氨基酸的模型反应系,其中具有一个带正式电荷的独特传导结构,因而必需有一套全新的σ~*值,烷基成为拉电子取代基。
The results of this paper can be summarized as follows: (1) The working definition of σ ~ * is given more strictly to the value of aromatic σ. That is to say, it is related to the pKa value of carboxylic acid at a certain temperature and solvent system, and thousands of different kinds of σ values of more than a thousand substituents in the fat system are calculated. (2) The type of reaction system is increased, and finally the quantitative relationship of linear free energy can be finally applied in lipid defense system. However, the value of σ ~ * remains the original scale, so it has a simple mathematical relationship with other types of σ values. There is a good standard linear relationship with the inducing constants of earlier Branch and Calvin. (3) Expanding the number of interrelated substituents and increasing the reliability of statistics. (4) The systolic quotients that align the sigma values of the alkyl groups with those of the substituted alkyl groups do not require that the alkyl groups be fixed to zero. (5) It is clarified that the σ ~ * values are closely related to the conformational, conformational, formation of hydrogen bonds, solvation, intramolecular and intramolecular Lewis acid-base interactions, electrostatic force effects and electrokinetic dispersion effects , Far more than the representative induction effect. (6) The σ ~ * and p ~ * values of amino acids were compared with those of other carboxylic acids to confirm that the σ ~ * value of alkyl mainly depends on the intramolecular electrokinetic effect. An illustration of the problem of deviations from charge bases can be solved in principle. (7) An attempt was made to establish an amino acid model reaction system with a uniquely conductive, formally charged conductive structure that necessitated a whole new set of σ ~ * values and alkyl groups as electron-withdrawing substituents.