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为研究膦酸二烷基酯的化学牿构及其物理及化学性能,合成一系列具不同电子效应取代基的对位取代苯基膦酸酯(Ⅰ)及相应的苯甲基膦酸酯(Ⅱ)。应用乙酰化滤祗及相应的展开剂,可顺利进行对位取代苯基及苯甲基膦酸酯的纸层析鉴定与分离。对位取代苯基及苯甲基膦酸酯均有相似的超加克分子折射现象。这些膦酸酯的化学结构与超加折射度的关系,可以用苯环取代基的不同电子效应解释。取代基团σ值与磷-氧键频率及氘-氧键频率或氘-氧键频率变化(Lewis碱性)均能符合Hammett方程式的自由能直线关系。不同烷基酯所形成的直线斜率也不同,但它们之间似无定量规则。对位取代苯甲基膦酸酯的取代基性质与其磷-氧键特征频率及Lewis碱性均无定量规则。对位取代苯基及苯甲基膦酸酯的碱性水解反应速度常数的对数值与取代基团σ值符合Hammett方程式的直线关系。对位取代苯基膦酸酯的碱性水解速度较相应的苯甲基膦酸酯快很多。对位取代苯基及苯甲基膦酸酯的酯烷基诱导效应指数与水解速度也有较好的定量关系。实验结果有助于说明膦酸酯在碱性水解过程中,磷原子为亲核进攻中心。就对位取代苯基膦酸酯的苯环取代基性质与其物理及化学性能的定量关系而言,这类分子内部的影响既可用苯环与磷-氧键共轭,磷-氧属双键结构;也可用取代基团的诱导效应而磷-氧为重键结构以解释,但后一种结构似更为合理。
In order to study the chemical structures of dialkyl phosphonates and their physical and chemical properties, a series of p-substituted phenylphosphonates (Ⅰ) with the corresponding substituents of different electronic effects and the corresponding benzylphosphonates Ⅱ). Application acetylation filter only and the corresponding developing agent, can be carried out on the para-substituted phenyl and benzyl phosphonate paper chromatography identification and separation. Para-substituted phenyl and benzyl phosphonate have similar supergalactur refractive phenomena. The chemical structure of these phosphonates and hyperrefractivity can be explained by the different electronic effects of benzene ring substituents. The σ value of the substituent, the frequency of phosphorus-oxygen bond, the frequency of deuterium-oxygen bond or the frequency of deuterium-oxygen bond (Lewis basicity) all fit the free energy linear relationship of Hammett’s equation. Different alkyl esters formed by the slope of the line is also different, but there may be no quantitative rules between them. Substitution of p-substituted benzylphosphonates has no quantitative rules with respect to the nature of its phosphorus-oxygen bond and Lewis basicity. The linear relationship between the logarithm of the basic hydrolysis rate constant and the σ value of the para-substituted phenyl and benzyl phosphonates is in accordance with the Hammett equation. The basic hydrolysis of p-substituted phenylphosphonates is much faster than the corresponding benzylphosphonates. The para-substituted phenyl and benzyl phosphonate ester alkyl induced effect index and the hydrolysis rate also has a good quantitative relationship. The experimental results help to explain that phosphonate is a nucleophilic attack center during alkaline hydrolysis. In terms of the quantitative relationship between the properties of the benzene ring substituents of the substituted phenylphosphonates and their physical and chemical properties, the influence of such molecules inside can be either conjugated with a benzene ring and a phosphorus-oxygen bond, Structure; also can use the induction of substituent groups and phosphorus - oxygen as the key structure to explain, but the latter seems more reasonable structure.