Wall Leo A, Pummer Walter J, Fearn James E, Antonucci Joseph M
J Res Natl Bur Stand A Phys Chem. 1963 Sep-Oct;67A(5):481-497. doi: 10.6028/jres.067A.050. Epub 1963 Oct 1.
Nucleophilic reactions of hexafluorobenzene and related polyfluorobenzenes were studied in detail. Reaction of hexafluorobenzene with hydroxides, alcoholates, aqueous amines, and organolithium compounds led to the substitution of one or more fluorine atoms. The structures of the products were determined, using near infrared and nuclear magnetic resonance spectra. Fluorine is replaced more readily than chlorine, bromine, iodine, or other groups. In the majority of the products in which two of the fluorines in hexafluorobenzene were replaced, the substituting groups were para to each other. However, depending on the reagents other orientation effects were noted. The reaction mechanisms were a function of reagents and conditions. The most prevalent mechanism is presumably the displacement of a fluoride anion by another anion, probably via the formation of transition complexes of different lifetimes. However, simple ionization or attack by neutral species may occur under some conditions. The diazotization and oxidation of pentafluoroaniline were also investigated.
对六氟苯及相关多氟苯的亲核反应进行了详细研究。六氟苯与氢氧化物、醇盐、胺水溶液和有机锂化合物反应会导致一个或多个氟原子被取代。使用近红外光谱和核磁共振光谱确定了产物的结构。氟比氯、溴、碘或其他基团更容易被取代。在六氟苯中两个氟被取代的大多数产物中，取代基彼此处于对位。然而，根据试剂的不同，也观察到了其他取向效应。反应机理是试剂和条件的函数。最普遍的机理可能是一个氟阴离子被另一个阴离子取代，可能是通过形成不同寿命的过渡络合物。不过，在某些条件下可能会发生简单的离子化或中性物种的进攻。还研究了五氟苯胺的重氮化和氧化反应。
