Tetrafluoro(trifluoromethyl)sulfanes Chemical Reactivity and Polar Hyrdophobicity

四氟(三氟甲基)硫烷的化学反应性和极性疏水性

• 批准号: 2154772
• 负责人: John Welch
• 金额: $ 47.24万
• 依托单位: SUNY at Albany
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-15 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154772&HistoricalAwards=false
• 关键词: Tetrafluoro; trifluoromethyl; sulfanes; Chemical; Reactivity

With the support of the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) Program in the Division of Chemistry, Professor John T. Welch of the University at Albany, will investigate a novel thermally and chemically stable functional group that may ultimately replace persistent and toxic compounds used in the preparation of pharmaceuticals and agrochemicals. Unfortunately, the problem of environmental persistence is endangering the use fluorine chemistry in new and currently marketed products for materials science, agrochemical, biochemical and medicinal chemistry is endangered by. For at least 75 years, fluorination and the introduction of fluorinated functional groups has led to significant advances in materials research, in the life sciences and in fundamental chemical investigations. Nearly 20% of pharmaceuticals and 40% of agrochemicals contain fluorine, typically in selectively fluorinated functional groups. It is increasingly apparent that undesirable environmental effects accompany these versatile substituents. Environmental persistence accompanied by bioaccumulation is of particular concern to human health. The chemically and physically robust fluorinated hypervalent sulfur compounds that will be studied are predicted to decompose in an environmentally benign manner preserving the commercial utility of fluorination and fluorinated functionality. These investigations may enable economic competitiveness in the global marketplace that requires environmentally benign replacement groups such as the structures under investigation. Pursuit of this national interest requires the training of research students in the handling of extraordinarily reactive reagents such as bromine trifluoride, chlorine fluoride or fluorine, reagents essential to fluorochemical research. Seventh through twelfth grade students from historically underrepresented groups and economically disadvantaged backgrounds will be engaged in mentored laboratory research, and in collaborative, task-oriented learning to understand the importance of chemical literacy in community activism. The proposed research program will help sustain our ability to train students in this crucial area of chemical technology and research.The electronic interactions and the steric demand of the trifluoromethyl tetrafluorosulfanyl (CF3SF4) group can control reactivity and selectivity CF3SF4-containing reactants. This novel substituent is predicted to have ideal parameters to exhibit the sort of polar hydrophobicity attributes that make it useful for the functionalization of agents designed for protein binding as tools for chemical biology or as candidates for medicinal chemistry. But there are few synthetic, mechanistic and property-related studies surrounding this interesting functional group. The polar and electronic effects of CF3SF4-group substitution on the stereoselectivity of the parent CF3SF4-methyl carbene will be investigated. As rearrangement of carbene insertion products often involve radical intermediates, electrolytic decarboxylation will be used to form CF3SF4-substituted methyl radicals for comparative reaction studies. The influence of the of the CF3SF4 group on reactions will be compared and contrasted with the effect of the trifluoromethyl group. The experimentally derived results will be used to validate the computational predictions of the reactivity of the CF3SF4 -substituted reactants. The CF3SF4-containing products will be tested for susceptibility to benign degradation processes by determining aqueous photostability on irradiation at wavelengths greater than 290 nm. Susceptibility to biodegradation will be determined by establishing the ability of members of the genus Pseudomonas and Streptomyces to grow on CF3SF4-containing products.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学结构、动力学和机理B （CSDM-B）项目的支持下，奥尔巴尼大学的John T. Welch教授将研究一种新的热稳定性和化学稳定性的官能团，这种官能团最终可能取代用于制备药物和农用化学品的持久性和有毒化合物。不幸的是，环境持久性问题正在危及氟化学在材料科学、农化、生化和药物化学的新产品和当前上市产品中的使用。至少75年来，氟化和氟化官能团的引入使材料研究、生命科学和基础化学研究取得了重大进展。近20%的药品和40%的农用化学品含有氟，通常以选择性氟化官能团形式存在。这些多用途取代基对环境的不良影响日益明显。伴随生物积累的环境持久性对人类健康尤为重要。预计将研究的化学和物理上坚固的氟化高价硫化合物将以无害环境的方式分解，保留氟化的商业效用和氟化功能。这些调查可能会提高全球市场的经济竞争力，这需要环境友好的替代群体，如正在调查的结构。为了实现这一国家利益，需要对研究生进行培训，使他们学会处理极具反应性的试剂，如三氟化溴、氟化氯或氟，这些试剂对氟化学研究至关重要。七年级到十二年级的学生，他们来自历史上代表性不足的群体和经济上处于不利地位的背景，将参与指导的实验室研究，并在协作，以任务为导向的学习中了解化学素养在社区行动中的重要性。拟议的研究计划将有助于维持我们在化学技术和研究这一关键领域培养学生的能力。三氟甲基四氟磺酰（CF3SF4）基团的电子相互作用和空间需求可以控制含CF3SF4的反应物的反应活性和选择性。据预测，这种新型取代基具有理想的参数，可以表现出极性疏水性属性，这使得它可以用于化学生物学或药物化学候选药物的蛋白质结合工具的功能化。但是围绕这个有趣的官能团的合成、机械和性质相关的研究很少。研究了cf3sf4基团取代对母体cf3sf4 -甲基甲烷立体选择性的极性和电子效应。由于碳插入产物的重排往往涉及自由基中间体，因此将采用电解脱羧形成cf3sf4取代的甲基自由基进行比较反应研究。将CF3SF4基团对反应的影响与三氟甲基的影响进行比较和对比。实验推导的结果将用于验证CF3SF4取代反应物的反应性的计算预测。含cf3sf4的产品将通过测定波长大于290 nm照射下的水光稳定性来测试对良性降解过程的敏感性。通过建立假单胞菌属和链霉菌属成员在含cf3sf4产品上生长的能力来确定对生物降解的敏感性。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。