Organic Dications: Synthesis, Reactivity and Applications
Organic Dications: Synthesis, Reactivity and Applications
批准号:
EP/H02042X/1
负责人:
John Murphy
金额:
$54.03万
依托单位国家:
英国
项目类别:
Research Grant
财政年份:
2010
资助国家:
英国
项目状态:
已结题
起止时间:
2010 至 --
中文摘要
决定物质反应性的主要因素之一是它们的电荷程度-简单地说,相反的电荷吸引,所以化合物的电荷越多,它的反应性就越强。到目前为止,生产高度亲电(带正电荷)的化合物的方法是使用“超强酸”,即比100%硫酸更强的酸。在超强酸中进行化学反应对于理解由烃衍生的超亲电试剂的反应非常有用。该提案解决了在有机溶剂中含有杂原子(通常是氮)的分子中制备新型和高度亲电物质的问题,并希望研究它们的反应性。它在广泛的化学反应中具有潜在的应用,并且它也可能与英国PLC相关,通过在传统上使用对环境有害的试剂(如铝氢化物)的反应(如Friedel-Crafts反应)的催化剂开发中迈出第一步。超亲电化学也可以解释生物有机反应机制中一些最大的谜题,包括DNA合成(从尿嘧啶形成胸腺嘧啶衍生物)和蛋白质合成(从同型半胱氨酸制备甲硫氨酸-甲硫氨酸是所有基因翻译过程中的起始氨基酸)所需的反应。即使是神秘的,但潜在的非常有用的生产甲烷的二氧化碳是由细菌实现的,可能取决于化学的超亲电体,在这个建议中讨论。这是一个新的冒险化学,我们希望有广泛的应用。
英文摘要
One of the principal factors governing the reactivity of substances is their degree of electric charge - in simple terms, opposite charges attract, so the more charged a compound is, the more reactive it should be. Until now, the way to produce compounds that are highly electrophilic (very positively charged) was to use ''super-acids'', i.e. acids that are stronger than 100% sulfuric acid. Performing chemistry in super-acid has been very useful for understanding the reactions of super-electrophiles derived from hydrocarbons. This proposal addresses the preparation of novel and highly electrophilic species in molecules containing heteratoms (usually nitrogen) in organic solvents, and looks to study their reactivity. It has potential applications across a broad range of chemical reactions, and it could also have relevance to UK plc through taking first steps in the development of catalysts for performing reactions (like Friedel-Crafts reactions) that have traditionally used environmentally harmful reagents such as aluminium trichloride. Super-electrophile chemistry may also explain some of the biggest puzzles in bioorganic reaction mechanisms, involving reactions that are required for DNA synthesis (the formation of thymine derivatives from their uracil counterparts) and protein synthesis (preparation of methionine from homocysteine - methionine is the starting amino acid for all genes during translation). Even the mysterious but potentially very useful production of methane from carbon dioxide that is achieved by bacteria, could depend on the chemistry of the superelectrophiles that are discussed in this proposal.This is a new adventure in chemistry that we expect to have widespread applications.
期刊论文(3)
专著(0)
科研奖励(0)
会议论文
DOI:
10.1002/9783527664160.ch5
发表时间:
2014-08
期刊:
影响因子:
--
作者:
[Callum Scullion;John A. Murphy]
通讯作者:
Callum Scullion;John A. Murphy
Superelectrophilic Amidine Dications: Dealkylation by Triflate Anion
超亲电脒二阳离子:三氟甲磺酸根阴离子脱烷基化
DOI:
10.1002/anie.201202990
发表时间:
2012
期刊:
Angewandte Chemie International Edition
影响因子:
--
作者:
[Kovacevic L]
通讯作者:
Kovacevic L
3Rs of drought: resistance, resilience and recovery - an opportunistic experiment
-
批准号:NE/X016706/1
-
项目类别:Research Grant
-
资助金额:$10.28万
-
财政年份:2023
-
负责人:John Murphy
-
依托单位:
Charged oxide inversion layer (COIL) solar cells
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批准号:EP/V037749/1
-
项目类别:Research Grant
-
资助金额:$58.9万
-
财政年份:2021
-
负责人:John Murphy
-
依托单位:
Computational spectral imaging in the THz band
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批准号:EP/S036261/1
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项目类别:Research Grant
-
资助金额:$29.86万
-
财政年份:2019
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负责人:John Murphy
-
依托单位:
SuperSilicon PV: extending the limits of material performance
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批准号:EP/M024911/1
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项目类别:Research Grant
-
资助金额:$164.8万
-
财政年份:2015
-
负责人:John Murphy
-
依托单位:
Light-Activated Approaches to Highly Challenging Organic Electron Transfer Reactions
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批准号:EP/K033077/1
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项目类别:Research Grant
-
资助金额:$26.99万
-
财政年份:2013
-
负责人:John Murphy
-
依托单位:
Gettering of impurities in silicon: delivering quantitative understanding to improve photovoltaics
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批准号:EP/J01768X/2
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项目类别:Research Grant
-
资助金额:$10.81万
-
财政年份:2013
-
负责人:John Murphy
-
依托单位:
Gettering of impurities in silicon: delivering quantitative understanding to improve photovoltaics
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批准号:EP/J01768X/1
-
项目类别:Research Grant
-
资助金额:$11.41万
-
财政年份:2012
-
负责人:John Murphy
-
依托单位:
Sponsorship for SymPOC 2009
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批准号:EP/G069026/1
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项目类别:Research Grant
-
资助金额:$0.65万
-
财政年份:2009
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负责人:John Murphy
-
依托单位:
Physical Organic Chemistry: Opportunities in Synthesis, Materials and Pharmaceuticals
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批准号:EP/E036244/1
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项目类别:Research Grant
-
资助金额:$338.64万
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财政年份:2007
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负责人:John Murphy
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依托单位:
New Horizons in Organic Electron Transfer
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批准号:EP/E012191/1
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项目类别:Research Grant
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资助金额:$47.71万
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财政年份:2006
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负责人:John Murphy
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依托单位:
U.S.-France Cooperative Research: Toxin-Hormone Hybrid Gene Development
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批准号:8414018
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项目类别:Standard Grant
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资助金额:$0.0万
-
财政年份:1985
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负责人:John Murphy
-
依托单位:
Regulation of the Expression of a Bacteriophage Gene
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批准号:7618924
-
项目类别:Standard Grant
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资助金额:$7.0万
-
财政年份:1976
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负责人:John Murphy
-
依托单位:
Corynebacterium Diptheriae Mediated Control of the Corynephage Beta Tox Gene
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批准号:7421102
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项目类别:Standard Grant
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资助金额:$6.0万
-
财政年份:1974
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负责人:John Murphy
-
依托单位:
海外基金