Problems in Fluorocarbon Chemistry

氟碳化学问题

• 批准号: 0346733
• 负责人: David Lemal
• 金额: --
• 依托单位: Dartmouth College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-01-15 至 2007-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0346733&HistoricalAwards=false
• 关键词: Problems; Fluorocarbon; Chemistry

In extreme bonding situations the contrasts between fluorinated molecules and their hydrocarbon analogues are often especially sharp, resulting in novel properties and reactivity for the fluorocarbons. This project will explore the synthesis and properties of highly strained fluorocarbons - [2.2.2]propellanes, a [2.2.1]propellane, bicyclo[2.1.0]pentanes, bicyclo[1.1.0]butanes and a bicyclo[2.2.0]alkene - as well as highly fluorinated derivatives of an unusual aromatic system, the nonbenzenoid hydrocarbon azulene. These molecules are of interest not only for their reactivity, but especially for their electronic spectra and photophysics, which will be explored collaboratively. Methods for functionalization of fluorocarbon liquids will be applied to fluoropolymer surfaces. In contrast to other methods of functionalizing fluoropolymer surfaces, which are non-selective in nature, the approach to be used will introduce a specific functional group at specific sites on the surface. The result should be novel properties for the polymer, including the ability to chelate metals. Also to be explored is the synthesis of perfluorinated triplet carbenes that should display extraordinary thermal stability without the electron delocalization characteristic of the only known stable triplet carbenes. The synthetic plan is predicated on the size difference between alkyl and perfluoroalkyl groups, together with the great strength of carbon-fluorine bonds.Fluorocarbons and derived materials enjoy an wide variety of uses in our society, for many of which they are without equal. They owe their special character to the fact that substitution of fluorine for the hydrogens in organic molecules results in dramatic changes in properties and chemical behavior. With the support of the Organic and Macromolecular Chemistry Program, Professor David M. Lemal, of the Department of Chemistry at Dartmouth College, is extending what is known regarding the structure, reactivity and synthesis of highly fluorinated molecules. Through these studies, Professor Lemal is enhancing our understanding of the contrasts between these molecules and their better known hydrocarbon counterparts.

在极端成键的情况下，氟化分子和它们的碳氢化合物类似物之间的对比通常特别强烈，导致氟碳化合物具有新的性质和反应性。本项目将探索高应变氟碳化合物的合成和性质--[2.2.2]螺旋烷、[2.2.1]螺旋烷、双环[2.1.0]戊烷、双环[1.1.0]丁烷和双环[2.2.0]烯烃--以及一种不寻常的芳香族体系的高度氟化的衍生物--非苯烃类天青烯。这些分子不仅因为它们的反应性而感兴趣，而且特别是因为它们的电子光谱和光物理，这将被合作探索。氟碳液体的功能化方法将应用于氟聚合物表面。与其他非选择性的氟聚合物表面功能化方法不同，所使用的方法将在表面的特定位置引入特定的官能团。其结果应该是聚合物具有新的性能，包括螯合金属的能力。还需要探索的是全氟三重卡宾的合成，它应该具有非凡的热稳定性，而不会像已知的唯一稳定的三重卡宾那样具有电子离域特性。合成计划是基于烷基和全氟烷基团之间的尺寸差异，以及碳-氟键的巨大强度。氟碳化合物及其衍生材料在我们的社会中有广泛的用途，其中许多用途是无与伦比的。它们之所以具有特殊的性质，是因为有机分子中的氢被氟取代后，其性质和化学行为发生了巨大的变化。在有机化学和高分子化学计划的支持下，达特茅斯学院化学系的大卫·M·莱马尔教授正在扩展关于高度氟化分子的结构、反应性和合成的已知知识。通过这些研究，Lemal教授加深了我们对这些分子与其更知名的碳氢化合物之间的对比的理解。