Journal of Fluorine Chemistry最新文献_第4页

Regioselective difunctionalization of alkenes with CF2FG Moieties 烯烃与 CF2FG 分子的区域选择性双官能化

IF 1.7 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-07-01 DOI: 10.1016/j.jfluchem.2024.110296

Thomas Castanheiro, Tatiana Besset

引用次数: 0

Alkali-fluoride-salt-accelerated oxidation behavior of graphite under air atmosphere 石墨在空气环境下的碱-氟化物-盐加速氧化行为

IF 1.7 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-07-01 DOI: 10.1016/j.jfluchem.2024.110310

Meicheng Xu , Xiangmin Xie , Xian Tang , Cheng Yang , Zhean Su

{"title":"Alkali-fluoride-salt-accelerated oxidation behavior of graphite under air atmosphere","authors":"Meicheng Xu , Xiangmin Xie , Xian Tang , Cheng Yang , Zhean Su","doi":"10.1016/j.jfluchem.2024.110310","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2024.110310","url":null,"abstract":"<div>Air ingress accident scenarios may result in the oxidation of graphite matrix materials and cause serious safety problems in molten salt reactor. However, the oxidation behavior of the molten-salt-infiltrated graphite remains elusive. In this study, the effect of alkali fluoride salts (LiF, NaF, KF and ternary salt FLiNaK) on the oxidation behavior of graphite powder under air atmosphere was investigated. Thermogravimetric analysis and oxidation tests manifest that the initial oxidation temperature of the graphite is reduced from 720 °C to 510–610 °C, because of the presence of the alkali fluoride salts. The catalytic oxidation effect follows the order of KF > NaF > LiF. Careful characterizations reveal that the pristine graphite is mainly oxidized at the graphite edges, while salt-infiltrated graphite is mainly damaged at the graphitic basal planes. Density functional theory calculations suggest that the doping of alkali metal atoms does not change the physical adsorption feature of the oxygen molecule on the graphite plane surface, but increases its adsorption energy to facilitate the graphite oxidation reactions.</div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"277 ","pages":"Article 110310"},"PeriodicalIF":1.7,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141543103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of proton-conductive Perfluoro(Benzylphosphonic Acid)s via polymer side chain phosphorylation 通过聚合物侧链磷酸化合成质子导电全氟(苄基膦酸)

IF 1.7 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-07-01 DOI: 10.1016/j.jfluchem.2024.110312

Elizabeth Salako, Matthew Thompson, Rong Jiang, Yong Gao

{"title":"Synthesis of proton-conductive Perfluoro(Benzylphosphonic Acid)s via polymer side chain phosphorylation","authors":"Elizabeth Salako, Matthew Thompson, Rong Jiang, Yong Gao","doi":"10.1016/j.jfluchem.2024.110312","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2024.110312","url":null,"abstract":"<div>Nafion™ utilizes -SO3H groups for proton conduction. Using an alternative proton-exchange functionality like -PO3H2, -COOH, etc., to replace -SO3H in ion conductive fluoropolymers has attracted significant attention. For example, composite membranes comprising Nafion™ and perfluoro(carboxylic acid) bearing a -COOH group on its side chains have been used in color-alkali cells to reduce unwanted electrolyte crossovers. In the present paper, we reported a new synthetic strategy for constructing novel -PO3H2-bearing fluoropolymers (FBP). Our method employs a ZnI2-promoted phosphorylation reaction of triethyl phosphite that converts benzyl alcohol on a side chain of a fluoropolymer into a benzylphosphodiester group, followed by trimethylsilyl chloride (TMSCl) hydrolysis to yield FBP. This strategy has enabled us to graft a fluoropolymer side chain directly with phosphonic acid. Although the in-plane proton conductivities of FBP fluoropolymers are lower than those of Nafion™ 115, most FBPs, especially Homo-FBP that has no fluoroalkyl ether group on its side chains, are significantly more stable against hydroxyl radical degradations in Fenton tests. This paper presents a new method for the synthesis of -PO3H2-containing fluoropolymers and our work also confirms a novel strategy for enhancing the long-term stability of a proton-conductive fluoropolymer in electrical devices—eliminating or reducing fluoroalkyl ether groups on the side chains of the polymer.</div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"277 ","pages":"Article 110312"},"PeriodicalIF":1.7,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141582743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Transformation of fluorinated 1,2-phenylenediamines in polyphosphoric acid medium with or without the benzimidazole 2-carboxylic acid: synthesis of fluorinated 2,2′-bibenzimidazoles and phenazine-2,3-diamines 氟化 1,2-苯二胺在含有或不含苯并咪唑 2-羧酸的多磷酸介质中的转化：氟化 2,2′-联苯并咪唑和吩嗪-2,3-二胺的合成

IF 1.7 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-07-01 DOI: 10.1016/j.jfluchem.2024.110313

Jiayao Li , Vyacheslav I. Krasnov , Elena V. Karpova , Rodion V. Andreev , Inna K. Shundrina , Irina Yu. Bagryanskaya , Galina A. Selivanova

{"title":"Transformation of fluorinated 1,2-phenylenediamines in polyphosphoric acid medium with or without the benzimidazole 2-carboxylic acid: synthesis of fluorinated 2,2′-bibenzimidazoles and phenazine-2,3-diamines","authors":"Jiayao Li , Vyacheslav I. Krasnov , Elena V. Karpova , Rodion V. Andreev , Inna K. Shundrina , Irina Yu. Bagryanskaya , Galina A. Selivanova","doi":"10.1016/j.jfluchem.2024.110313","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2024.110313","url":null,"abstract":"<div>A series of asymmetrically fluorinated 2,2′-bibenzimidazoles were obtained by reaction of benzimidazole-2-carboxylic acid with fluorinated 1,2-phenylenediamines in polyphosphoric acid at elevated temperature. The tautomers of fluorinated 2,2′-bibenzimidazoles with a predominance of isomers containing F atoms in distant position relative to the NH group of the benzimidazole fragment are detected in DMSO‑d6 using NMR spectroscopy. The ratio of tautomers depends on the number and arrangement of F atoms in the initial fluorinated 1,2-phenylenediamines. Under similar conditions fluorinated 1,2-phenylenediamines in the presence of benzimidazole-2-carboxylic acid, but without its participation as well as without it, give fluorinated phenazine-2,3-diamines. The direction of transformation of fluorinated 1,2-phenylenediamines depends on the number and position of F atoms. Under similar conditions phenazine-2,3-diamine is not formed from non-fluorinated 1,2-phenylenediamine, but it is obtained with the presence of fluorinated 1,2-phenylenediamines. When fluorinated 1,2-phenylenediamines contain F atoms simultaneously at the positions 4 and 5, the hydrodefluorination of initial fluorinated 1,2-phenylenediamines occurs, resulting in less fluorinated 2,2′-bibenzimidazoles and phenazine-2,3-diamines. Hydrodefluorination of fluorinated 1,2-phenylenediamines in a polyphosphoric acid at elevated temperatures is the first example of the hydrodefluorination of fluorinated aromatic compounds containing strong donor substituents, such as amino groups. Polyphosphoric acid is shown to be a suitable medium for redox processes.</div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"277 ","pages":"Article 110313"},"PeriodicalIF":1.7,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141582662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Study on the oxidative decomposition mechanism of R1234ye(E): A DFT study R1234ye(E) 的氧化分解机理研究：DFT 研究

IF 1.9 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-06-08 DOI: 10.1016/j.jfluchem.2024.110309

Biao Feng , Bingrui Wang , Jiachang Wang , Wuwen Chen , Linrui Jian , Zhao Zhang , Dan Wang , Guanjia Zhao , Suxia Ma

{"title":"Study on the oxidative decomposition mechanism of R1234ye(E): A DFT study","authors":"Biao Feng , Bingrui Wang , Jiachang Wang , Wuwen Chen , Linrui Jian , Zhao Zhang , Dan Wang , Guanjia Zhao , Suxia Ma","doi":"10.1016/j.jfluchem.2024.110309","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2024.110309","url":null,"abstract":"<div>R1234ye(E) is an environmentally friendly working fluid that can be applied in refrigeration, heat pumps, and organic Rankine cycle systems, but it has issues with oxidative decomposition and flammability. Therefore, based on density functional theory, the oxidative decomposition mechanism of R1234ye(E) has been studied. The results indicate that the oxidative decomposition of R1234ye(E) is a typical chain reaction. The first stage is a chain-initiation reaction, where R1234ye(E) generates a large number of free radicals through initial self thermal decomposition reactions and collision reactions with oxygen. The most likely to occur is path 1–2, which is a homolytic reaction with an energy barrier of only 347.91 kJ/mol. The second stage is the chain-propagation reaction, including the reactions between R1234ye(E) and different free radical and subsequent reactions. The most likely to occur is path 5–1, which is a hydrogen abstraction reaction with an energy barrier of only 21.83 kJ/mol. The last stage is the chain-termination reaction, where the intermediates or products of the above reactions continue to react with the active free radicals until they are consumed. When all the reactants and free radicals are consumed and stable products are generated, the oxidative decomposition reaction ends. The research results provide a reference for the safe application of R1234ye(E) and other HFOs working fluids.</div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"277 ","pages":"Article 110309"},"PeriodicalIF":1.9,"publicationDate":"2024-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141322382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis and physicochemical evaluation of tetrafluorinated GABA analogue 四氟 GABA 类似物的合成与理化评价

IF 1.9 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-06-07 DOI: 10.1016/j.jfluchem.2024.110307

Danylo Marych , Vitaliy Bilenko , Yaryna V. Ilchuk , Serhii Kinakh , Vadym Soloviov , Andriy Yatsymyrskiy , Oleksandr Liashuk , Svitlana Shishkina , Igor V. Komarov , Oleksandr O. Grygorenko

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Base-mediated formal [4+1] annulation of ortho-hydroxyphenyl substituted para-quinone methides and CF3-imidoyl sulfoxonium ylides to access trifluoroacetimidoyl-substituted 2,3-dihydrobenzofurans 碱介导的正羟基苯基取代对苯醌甲酯与 CF3-亚氨酰基磺酰的正规 [4+1] 环化反应，以获得三氟乙酰亚氨酰基取代的 2,3-二氢苯并呋喃

IF 1.9 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-06-06 DOI: 10.1016/j.jfluchem.2024.110308

Chen Li, Mingshuo Zhou, Zhengkai Chen

引用次数: 0

Predicting the increase in electron affinity of phenoxy upon fluorination 预测氟化时苯氧基电子亲和力的增加

IF 1.9 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-06-04 DOI: 10.1016/j.jfluchem.2024.110306

Connor J. Clarke , Jemma A. Gibbard , William D.G. Brittain , Jan R.R. Verlet

{"title":"Predicting the increase in electron affinity of phenoxy upon fluorination","authors":"Connor J. Clarke , Jemma A. Gibbard , William D.G. Brittain , Jan R.R. Verlet","doi":"10.1016/j.jfluchem.2024.110306","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2024.110306","url":null,"abstract":"<div>The site-specific fluorination of organic compounds can alter their electron affinity, EA, which in turn can be used to control their reactivity, physical properties, or binding affinities. Using anion photoelectron spectroscopy, we show that for the multiply fluorinated phenoxy radical, the change in EA is predominantly additive per fluorination and can be predicted by the simple formula: ΔEA = <math><msub><mo>∑</mo><mi>i</mi></msub></math>ΔEAi − ΔEAC, where the numeric index i indicates the positions of fluorination. A small cooperative effect, ΔEAC, destabilizes the anion, but this only accounts for 11 % of the total ΔEA, in the extreme case of pentafluorophenolate. Our experimental results are consistent with those calculated using density functional theory, demonstrating the suitability of electronic structure calculations in the prediction of fluorination effects, for practical use in the synthetic design of organofluorines.</div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"277 ","pages":"Article 110306"},"PeriodicalIF":1.9,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022113924000666/pdfft?md5=f172a7bc78139c8a25db0881ccb09f5b&pid=1-s2.0-S0022113924000666-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141250083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chemically assisted degradation of 1,3-dioxo-2-difluoromethylene-4-trifluoromethoxy-5-difluoroammonium acetate dioxole 化学辅助降解 1,3-二氧代-2-二氟亚基-4-三氟甲氧基-5-二氟乙酸铵二恶英

IF 1.9 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-05-01 DOI: 10.1016/j.jfluchem.2024.110295

I. Wlassics, E. Lo Presti, R. Biancardi, C. Monzani, S. Barbieri

{"title":"Chemically assisted degradation of 1,3-dioxo-2-difluoromethylene-4-trifluoromethoxy-5-difluoroammonium acetate dioxole","authors":"I. Wlassics, E. Lo Presti, R. Biancardi, C. Monzani, S. Barbieri","doi":"10.1016/j.jfluchem.2024.110295","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2024.110295","url":null,"abstract":"<div>Recently, there has been a great strive to find new and efficient methods for the degradation of perfluorinated alkylated substances.In this research work, we present recent advancements and results in the degradation of the surfactant “cC6O4-NH4+” (I) (1,3-dioxo-2-difluoromethylene-4-trifluoromethoxy-5-difluoroammonium acetate dioxole) which demonstrates that it can be efficiently degraded in mild conditions, even at 20 °C.The results of several different and innovative chemical strategies, such as DMSO induced decomposition at mild temperatures, thermal decomposition, acid/base chemistry induced decomposition, all of which decomposed cC6O4 to CO2 + HF/F− in many cases ≥ 99.9%mol will be presented. All results will be supported by the respective kinetics, rates of reaction, thermodynamic reaction parameters, mechanisms of reaction, decomposition products, qualitative and quantitative spectroscopic analyses.</div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"276 ","pages":"Article 110295"},"PeriodicalIF":1.9,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140947215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bayesian optimization assisted screening conditions for visible light-induced hydroxy-perfluoroalkylation 贝叶斯优化法辅助筛选可见光诱导的羟基-全氟烷基化条件

IF 1.9 4区化学

Journal of Fluorine Chemistry Pub Date : 2024-05-01 DOI: 10.1016/j.jfluchem.2024.110294

Koto Tagami , Masaru Kondo , Shinobu Takizawa , Nobuyuki Mase , Tomoko Yajima

引用次数: 0