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首页> 外文学位 >Novel fluorocarbon peroxygen compound derived from difluorodioxirane, bis(fluoroformyl) peroxide and related compounds.
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Novel fluorocarbon peroxygen compound derived from difluorodioxirane, bis(fluoroformyl) peroxide and related compounds.

机译：衍生自二氟二环氧乙烷，双（氟甲酰基）过氧化物和相关化合物的新型碳氟过氧化物。

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摘要

Fluorinated peroxides are a potentially large and interesting class of compounds. They are high-energy oxidizers with remarkable stability compared to hydrocarbon analogous. Research in the preparation of fluorinated peroxides was initially driven by their potential application in rocket propellant technology. Today their use as initiators in the production of fluorinated polymers has made research on their synthesis and reactivity of interest. In this dissertation, the study on the chemistry of difluorodioxirane (the simplest perfluorinated peroxide) and Bis(fluoroformyl) peroxide (the simplest fluorinated diacyl peroxide) will be described.; Dioxiranes are powerful oxygen transfer reagents which have been studied extensively over the last twenty years. Difluorodioxirane is one of the most stable dioxiranes known. The first successful synthesis of difluorodioxirane was based on the reaction of its isomer fluorocarbonyl hypofluorite—FC(O)OF with OF in the presence of CsF. We have improved this method by using Cl 2 and the new catalyst KHF2. A novel reaction associated with difluorodioxirane is the reaction of difluorodioxirane with COF 2 in the presence of CsF which forms CF3OOC(O)F and the new compounds CF3 O(OCF2O)nOC(O)F (n = 1∼3); 13C labeling shows that the difluorodioxirane undergoes ring opening at the O-O bond. This is very surprising result because of the attack of CF 3O− on difluorodioxirane at oxygen and not at the more electropositive carbon. The reaction has been extended to prepare other fluoroformyl peroxy esters FC(O)OORf which are precursors to functionalized fluoroxy compounds. Fluoroxy compounds are very useful in the production of fuorovinyl ethers, a family of monomers suitable for the preparation of both crystalline and amorphous polymers.; Difluorodioxirane is also involved as an intermediate in other reactions. For example, the reaction of CF2(OF)2 with COF 2 in the presence of CsF formed CF3OOC(O)F in excellent to moderate yields. Our 13C labeling study indicates difluorodioxirane is probably an intermediate in the reaction.; Bis(fluoroformyl) peroxide FC(O)OOC(O)F is a highly reactive but easily prepared peroxide. Much of the chemistry of FC(O)OOC(O)F has been devoted to the elucidation of its reaction chemistry as a radical source. One of the more interesting early reactions of FC(O)OOC(O)F was the formation of fluoroformyl trifluoromethyl peroxide CF3OOC(O)F and bis(trifluoromethyl) bis(peroxy)carbonate (CF3OO)2C=O in the presence of CsF. In our study of the chemistry of difluorodioxirane we reinvestigated this reaction and found two new compounds FC(O)OOCF2OOC(O)F and 4,4-difluoro2,3,5,6-tetraoxacylohexanone. We proposed a new mechanism to explain the generation of the products. In order to synthesize new functionalized fluoroxy compounds, the reactions of FC(O)OOC(O)F with F2 in the presence of several metal florides were also studied. We found FOCF2OOC(O)F can be prepared by using KHF2 or CSHF2 as a catalyst. FOCF2OOC(O)F is an interesting example of a functionalized fluoroxy compound carrying the peroxide, fluorooxy and carbonyl function groups. Its reaction chemistry to other noval fluoroxy compounds such like FOCF2OOH and (FOCF2OO)2C=O is discussed.
机译：氟化过氧化物是一类潜在的大而有趣的化合物。与类似烃相比，它们是高能氧化剂，具有出色的稳定性。氟化过氧化物的制备研究最初是由其在火箭推进剂技术中的潜在应用推动的。如今，它们在氟化聚合物生产中用作引发剂的用途已引起人们对其合成和反应活性的研究。本文将介绍二氟二环氧乙烷（最简单的全氟过氧化物）和双（氟甲酰基）过氧化物（最简单的氟化二酰基过氧化物）的化学研究。二恶英是一种强大的氧转移试剂，在过去的二十年中已经进行了广泛的研究。二氟二环氧乙烷是已知的最稳定的二环氧乙烷。二氟二环氧乙烷的第一个成功合成是基于其异构体氟羰基次萤石-FC（O）OF与OF在CsF存在下的反应。我们通过使用Cl 2 和新型催化剂KHF 2 改进了该方法。与二氟二环氧乙烷有关的新反应是在CsF存在下二氟二环氧乙烷与COF 2 的反应，形成CF 3 OOC（O）F和新的化合物CF 3 O（OCF 2 O） n OC（O）F（n = 1〜3）; 13 C标记表明二氟二环氧乙烷在O-O键处开环。这是非常令人惊讶的结果，因为CF 3 O -会在氧气处而不是在更正电的碳上攻击二氟二环氧乙烷。该反应已扩展到制备其他氟甲酰基过氧酯FC（O）OOR f ，它们是官能化氟代化合物的前体。氟氧基化合物在生产氟乙烯醚中是非常有用的，氟乙烯醚是适用于制备结晶和无定形聚合物的一族单体。二氟二环氧乙烷也作为中间体参与其他反应。例如，在CsF存在下CF 2 （OF） 2 与COF 2 的反应形成CF 3 OOC（O）F，具有极好的中度收率。我们的 13 C标记研究表明，二氟二环氧乙烷可能是反应的中间体。双（氟甲酰基）过氧化物FC（O）OOC（O）F是高反应性但易于制备的过氧化物。 FC（O）OOC（O）F的许多化学性质都致力于阐明其作为自由基源的反应化学性质。 FC（O）OOC（O）F最有趣的早期反应之一是形成氟甲酰三氟甲基过氧化物CF 3 OOC（O）F和双（三氟甲基）双（过氧）碳酸酯（CF CsF存在下 3 OO） 2 C = O在对二氟二环氧乙烷的化学研究中，我们对这一反应进行了重新研究，发现了两个新的化合物FC（O）OOCF 2 OOC（O）F和4,4-二氟2,3,5,6-四氧杂六环酮。我们提出了一种新的机制来解释产品的产生。为了合成新的官能化氟代化合物，还研究了FC（O）OOC（O）F与F 2 在几种金属氟化物存在下的反应。我们发现可以使用KHF2 或CSHF 2 作为催化剂制备FOCF 2 OOC（O）F。 FOCF 2 OOC（O）F是带有过氧化物，氟氧基和羰基官能团的官能化氟氧基化合物的一个有趣例子。讨论了其与其他酚醛新化合物如FOCF 2 OOH和（FOCF 2 OO） 2 C = O的反应化学。

著录项

  • 作者

    Huang, Qun.;

  • 作者单位

    Clemson University.;

  • 授予单位 Clemson University.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2000
  • 页码 p.5327
  • 总页数 191
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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