Tuning the Reactivity of ortho-, meta- and para- Benzyne Analogs and Releated Polyradicals in the Gas Phase

调节邻位、间位和对位苯炔类似物及相关多自由基在气相中的反应性

基本信息

  • 批准号:
    1152379
  • 负责人:
  • 金额:
    $ 55万
  • 依托单位:
  • 依托单位国家:
    美国
  • 项目类别:
    Continuing Grant
  • 财政年份:
    2012
  • 资助国家:
    美国
  • 起止时间:
    2012-07-01 至 2015-06-30
  • 项目状态:
    已结题

项目摘要

Experimental reactivity studies on organic bi- and polyradicals are hindered by the difficulty of generating them cleanly in solution, in addition to their high reactivity and short lifetime. Information on the factors that control the chemical properties of carbon-centered sigma-type biradicals, such as the benzynes and their analogs, is highly desirable since it may allow one to "tune" their reactivity by varying structural details, and hence design bi- and polyradicals with tailored properties. This research program uses the "distonic ion approach" to study the reactivity of gaseous, carbon-centered, sigma-type mono-, bi- and triradicals via their charged analogs by using Fourier-transform ion cyclotron resonance mass spectrometers, a flowing afterglow quadrupole-octapole-quadrupole apparatus, and most recently, a linear quadrupole ion trap. These studies have demonstrated that the electron affinity and singlet-triplet gap of biradicals, as well as dehydrocarbon atom separation for meta-benzyne analogs, are among the reactivity controlling factors that can be used to "tune" the reactivity of some of these species. However, only few different ortho- and meta-benzyne analogs, and most remarkably, no para-benzyne analogs, have been studied thus far. Hence, this research will now be extended to several different and differently substituted ortho- and meta-benzyne analogs. With the means to generate para-benzyne analogs in the gas phase, an examination of their reactions is planned. Finally, the factors that control the reactivity of related tri- and tetraradicals will also be explored.The ability to predict, control and rationalize the outcomes of chemical reactions frequently requires knowledge of key reaction intermediates. Aromatic compounds that carry one (monoradicals) or more unpaired electrons (polyradicals) play an important role, for example, in organic synthesis and the biological activity of organic compounds. This research focuses on improving fundamental understanding of the chemical properties of these reactive intermediates. Ultimately, this research will lead to improved methods to synthesize new organic compounds, including drugs and new materials, as well as more rational design of new drugs. The new experimental methodologies developed here for the characterization of reaction intermediates will have an impact on experimental physical and physical organic chemistry. The broader societal impacts and enhancement of infrastructure include a large number of ethnically diverse, highly qualified science Ph.D. candidates, improved methodology for chemical analysis of organic compounds (including petroleum), and a more solid knowledge base for the design and synthesis of new organic materials and drugs.
除了其高反应性和短寿命之外,有机双自由基和多自由基的实验反应性研究还因在溶液中清洁地生成它们的困难而受到阻碍。关于控制以碳为中心的西格玛型双自由基(例如苯炔及其类似物)的化学性质的因素的信息是非常需要的,因为它可以允许人们通过改变结构细节来“调整”它们的反应性,从而设计双自由基。以及具有定制特性的多自由基。该研究计划使用“双张离子方法”,通过使用傅里叶变换离子回旋共振质谱仪(流动余辉四极杆)来研究气态、碳中心、西格玛型单基、双基和三基通过其带电类似物的反应性-八极-四极杆装置,以及最近的线性四极杆离子阱。这些研究表明,双自由基的电子亲和力和单线态-三线态间隙,以及间苯炔类似物的脱烃原子分离,都是反应性控制因素,可用于“调整”其中一些物质的反应性。然而,迄今为止,仅研究了几种不同的邻位和间位苯类似物,并且最值得注意的是,没有对位苯类似物进行了研究。因此,这项研究现在将扩展到几种不同的和不同取代的邻位和间位苯类似物。通过在气相中生成对苯炔类似物的方法,计划对其反应进行检查。最后,还将探讨控制相关三自由基和四自由基反应性的因素。预测、控制和合理化化学反应结果的能力通常需要了解关键反应中间体。携带一个(单自由基)或多个不成对电子(多自由基)的芳香族化合物在有机合成和有机化合物的生物活性等方面发挥着重要作用。这项研究的重点是提高对这些反应中间体化学性质的基本了解。最终,这项研究将改进合成新有机化合物(包括药物和新材料)的方法,以及更合理的新药设计。这里开发的用于表征反应中间体的新实验方法将对实验物理和物理有机化学产生影响。更广泛的社会影响和基础设施的增强包括大量种族多样化、高素质的科学博士。候选人,有机化合物(包括石油)化学分析的改进方法,以及新有机材料和药物的设计和合成的更坚实的知识基础。

项目成果

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Hilkka Kenttamaa其他文献

Hilkka Kenttamaa的其他文献

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{{ truncateString('Hilkka Kenttamaa', 18)}}的其他基金

Aryloxenium Cations
芳基氧阳离子
  • 批准号:
    2154079
  • 财政年份:
    2022
  • 资助金额:
    $ 55万
  • 项目类别:
    Continuing Grant
Gas-phase and Solution Reactivity Studies on para-Benzyne Analogs and Related Bi, Tri- and Tetraradicals
对苯炔类似物及相关双基、三基和四基的气相和溶液反应性研究
  • 批准号:
    1464712
  • 财政年份:
    2015
  • 资助金额:
    $ 55万
  • 项目类别:
    Continuing Grant
Gas-Phase Studies of Organic Sigma-type Polyradicals
有机西格玛型多自由基的气相研究
  • 批准号:
    0910466
  • 财政年份:
    2009
  • 资助金额:
    $ 55万
  • 项目类别:
    Continuing Grant
Gas-Phase Studies of Organic Bi-, Tri- and Tetraradicals
有机双自由基、三自由基和四自由基的气相研究
  • 批准号:
    0616798
  • 财政年份:
    2006
  • 资助金额:
    $ 55万
  • 项目类别:
    Continuing Grant
Gas-Phase Studies of Organic Biradicals
有机双自由基的气相研究
  • 批准号:
    0315480
  • 财政年份:
    2003
  • 资助金额:
    $ 55万
  • 项目类别:
    Standard Grant
GOALI: Gas-Phase Reactions of Neutral Organic Molecules Desorbed by Laser-Induced Acoustic Waves
目标:激光诱导声波解吸中性有机分子的气相反应
  • 批准号:
    0092119
  • 财政年份:
    2001
  • 资助金额:
    $ 55万
  • 项目类别:
    Standard Grant
Gas-Phase Studies of Charged Aromatic Radicals and Biradicals
带电芳香自由基和双自由基的气相研究
  • 批准号:
    0078924
  • 财政年份:
    2000
  • 资助金额:
    $ 55万
  • 项目类别:
    Standard Grant
Flowing Afterglow-Guided Ion Beam Studies of Reactive Organic Intermediates
反应性有机中间体的流动余辉引导离子束研究
  • 批准号:
    9732696
  • 财政年份:
    1998
  • 资助金额:
    $ 55万
  • 项目类别:
    Continuing Grant
Gas-Phase Studies of Substituted Aromatic Radicals, Biradicals and Polyradicals
取代芳族自由基、双自由基和多自由基的气相研究
  • 批准号:
    9710456
  • 财政年份:
    1997
  • 资助金额:
    $ 55万
  • 项目类别:
    Standard Grant
Oxidative Damage and Repair of Biological Macromolecules
生物大分子的氧化损伤与修复
  • 批准号:
    9631701
  • 财政年份:
    1996
  • 资助金额:
    $ 55万
  • 项目类别:
    Standard Grant

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超双疏表面静电驱动化学反应及其可控性研究
  • 批准号:
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  • 批准年份:
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