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研究了异—丙硫醇、正—己硫醇、正—丁硫醇、正—丙硫醇、3—苯基丙硫醇—[1]、苄硫醇、硫醇乙酸正丙酯和苯硫酚对3—苯基丙烯—[1]的自由基加成反应,讨论了硫醇的结构与反应性能间的关系。受诱导放应支配的硫中心自由基(RS.)加成时,3—苯基丙烯—[1]的百分转化率与RS.中取代基(R)的诱导放应指数(I值)和Taft基团常数(σ~*值)间均有“正S型”曲线关系,因此,硫中心自由基具有亲电子性能。但是受共轭效应支配的苯硫基自由基的反应性能与其他硫自由基不在同一系列。加成产物的结构用与对照物进行比较或以红外光谱,核磁共振谱分析等方法鉴定表明硫醇对3—苯茎丙烯—[1]加成时皆为1:1未端加成物。 苯硫酚与3—苯基丙烯—[1]加成时反应产物中除主要的1:1未端加成物外,可能还存在着少量由于自由基中间体发生苯基1.2—迁移所形成的产物或按Markownikoff规则加成的产物。
The effects of iso-propanethiol, n-hexanethiol, n-butanethiol, n-propanethiol, 3- phenylpropanethiol- [1], benzyl mercaptan, n-propyl mercaptan acetate and benzene Thiophenol on the 3-phenylpropylene - [1] free radical addition reaction, the relationship between the structure of thiols and the reaction performance was discussed. The percent conversion of 3-phenylpropylene- [1] to the inducing excretory index (I value) of the substituent (R) in RS. At the sulfur center radical (RS) And Taft group constant (σ ~ * value) have “positive S-type” curve relationship, therefore, sulfur center free radical electrophilic properties. However, the reaction performance of phenylthio radicals dominated by the conjugation effect is not in the same series as other sulfur free radicals. The structure of the addition product was compared with the control or identified by infrared spectroscopy, nuclear magnetic resonance spectroscopy and the like, indicating that the mercaptan had a 1: 1 unadministered adduct to 3-phenylpropylene- [1]. In addition to the major 1: 1 end-adduct of the thiophenol and 3-phenylpropen- [1] addition products, there may also be small amounts of phenyl 1.2-migrating free radical intermediates Or products that follow the Markownikoff rules.