首页> 外文期刊>Petroleum Chemistry >Chemical Behavior of 5-Vinyl-2-Norbornene,5-Ethylidene-2-Norbornene,and Related Compounds as a Key to Understanding Specifics of Radiation-Chemical Processes:3.The Structure of 5-Vinyl-2-Norbornene and 2-Vinylnorbornane Radical Cations
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Chemical Behavior of 5-Vinyl-2-Norbornene,5-Ethylidene-2-Norbornene,and Related Compounds as a Key to Understanding Specifics of Radiation-Chemical Processes:3.The Structure of 5-Vinyl-2-Norbornene and 2-Vinylnorbornane Radical Cations

机译:5-乙烯基-2-降冰片烯,5-乙叉基-2-降冰片烯及相关化合物的化学行为是了解辐射化学过程的关键:3.5-乙烯基-2-降冰片烯和2-乙烯基降冰片烷的结构自由基阳离子

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Cyclic and distonic forms of radical cations were recorded by ESR in x-ray irradiated frozen solutions(1.0 vol%)of 5-vinyl-2-norbornene(VNB)and 2-vinylnorbornane in Freon 113(CFCL2CF2CL).In both cases,mixtures of isomers in a ratio of endo-:exo-=66:34 were used.It was shown that,in the general case,the endo-VNB radical cation rearranges into the radical cation of cis-3a,4,7,7a-tetrahydroindene through a multistage mechanism involving the intermediate formation of the distonic radical cation,not via the earlier suggested one-stage concerted mechanism.The interconversions of endo-and exo-VNB in y-irradiated solutions of VNB in CCl4 were studied chromatographically.A general scheme of VNB transformations with allowance for the intermediate formation of the cyclic and distonic forms of the VNB radical cations is proposed.It was found that the structures of the radical cation distonic form and VNB homopolymer are identical,a resemblance.that indicates the occurrence of VNB polymerization via the radical cation mechanism during its gamma-irradiation.
机译:ESR在氟利昂113(CFCL2CF2CL)中的5-乙烯基-2-降冰片烯(VNB)和2-乙烯基降冰片烷的X射线冷冻溶液(1.0%(体积))中通过ESR记录了自由基阳离子的循环和扭曲形式。异构体以endo-:exo- = 66:34的比例使用。结果表明,在通常情况下,endo-VNB自由基阳离子重排为cis-3a,4,7,7a-四氢茚烯是通过多阶段机制参与到间位自由基自由基的中间形成,而不是通过较早提出的一阶协同机制。色谱法研究了VNB在CCl4的y辐射溶液中内-和外-VNB的相互转化。提出了VNB转化方案,考虑到中间形式的VNB自由基阳离子的环状和扭曲形式的形成。发现自由基阳离子扭曲形式和VNB均聚物的结构相同,相似,表明发生了VNB自由基。 VNB聚合vi在其γ辐射过程中的自由基阳离子机理。

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