Journal of Fluorine Chemistry最新文献

{"title":"Electrophilic aromatic fluorination of N-Arylacetamides: A computational and efficacy study","authors":"Meghan Betourney,&nbsp;Hannah Ashton,&nbsp;Gabrielle Costello,&nbsp;Jordan Hunter,&nbsp;Sang H. Park,&nbsp;Benjamin Shepler,&nbsp;Joseph C. Sloop,&nbsp;Matthew Stancea,&nbsp;Karla Wilmott","doi":"10.1016/j.jfluchem.2025.110455","DOIUrl":"10.1016/j.jfluchem.2025.110455","url":null,"abstract":"<div><div>Using selected <em>N</em>⁺-F and N-F fluorinating agents, a series of fluorinated <em>N</em>-arylacetamides have been prepared via electrophilic aromatic substitution. Reactant ratios and reaction conditions were varied to ascertain selectivity toward mono-fluorination and to provide optimum conversion to products, which ranged from 0–94 %. In addition, fluorinations of selected <em>N</em>-arylacetamides were undertaken using aqueous and ionic liquid media, sonication and microwave irradiative methods, and were compared with conventional fluorination conditions conducted in acetonitrile. Temperature, reaction time and solvent effects on fluorination as well as trends observed in fluorinating agent reactivity, fluorination selectivity and product distribution for these <em>N</em>-arylacetamides are discussed. A preference for fluorination <em>ortho</em> to the acetamido and trifluoroacetamido groups was observed for most <em>N</em>-arylacetamides investigated. An exception to this trend was found in the case of <em>N</em>-(4-methoxyphenyl)acetamide, where fluorination <em>ortho</em> to the methoxy group predominated. Computationally determined partial charge distribution results for the <em>N</em>-arylacetamides featured in this study were found to support the experimentally observed fluorination regiochemistry.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"285 ","pages":"Article 110455"},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144605468","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}

{"title":"Cobalt-catalyzed C-H perfluoroalkylation of anilines","authors":"Shota Mizuno ,&nbsp;Yoichi Obitsu ,&nbsp;Munenori Inoue","doi":"10.1016/j.jfluchem.2025.110437","DOIUrl":"10.1016/j.jfluchem.2025.110437","url":null,"abstract":"<div><div>Cobalt-catalyzed perfluoroalkylation of anilines under mild conditions was developed. The combination of Co(acac)₂/dppe/Zn efficiently catalyzed perfluoroalkylation of aniline derivatives with perfluoroalkyl iodides to give the corresponding target products in good to moderate yields. A detailed reaction mechanism was proposed, and it was found that the yields are substrate-dependent because the reaction proceeds by a radical addition-like reaction.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"285 ","pages":"Article 110437"},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144291111","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}

{"title":"Efficient synthesis, structure and anti-influenza virus activity of fluorinated pyrido[4,3-b][1,4]thiazine 1,1-dioxide derivatives","authors":"Larisa Politanskaya ,&nbsp;Bulat Khasanov ,&nbsp;Irina Bagryanskaya ,&nbsp;Maria Niukalova ,&nbsp;Sergey Aksakov ,&nbsp;Irina Balashova ,&nbsp;Vladimir Zarubaev","doi":"10.1016/j.jfluchem.2025.110430","DOIUrl":"10.1016/j.jfluchem.2025.110430","url":null,"abstract":"<div><div>A series of fluorinated bicyclic fused compounds, containing fragments of pyridine and 3,4-dihydro-2<em>H</em>-1,4-thiazine 1,1-dioxide were synthesized via one-pot substitution of halogen atoms by N-nucleophiles in polyfluorinated precursor. Formation of the heterocyclic moiety was proceed as a two-stage process starting from Br replacement at the side chain followed by intramolecular aminodefluorination. The structures of some of the obtained heterocycles were confirmed using X-ray diffraction analysis. In addition, their inhibitory activity against influenza A/Puerto Rico/8/34 (H1N1) virus in MDCK cell culture was evaluated and compound-leader was found.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110430"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143916887","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}

{"title":"Retro-favorskii reaction employing fluoride sources and its use as immobilization strategy","authors":"Andrea Giovanelli ,&nbsp;Marco Carlotti","doi":"10.1016/j.jfluchem.2025.110405","DOIUrl":"10.1016/j.jfluchem.2025.110405","url":null,"abstract":"<div><div>In this study, we developed a novel and simple approach to perform retro-Favorskii type reactions comprising the use of a readily available fluoride source. Compared to the methods usually employed – which rely on the use of strong basic systems, such as KOH in toluene, at high temperatures and a reaction time of several hours – the one we propose employs milder conditions, shorter reaction times, is compatible with more solvents, and produces no appreciable amount of byproducts, thus allowing simple workup procedures. The reaction we describe is enabled by the strong basic character of the fluoride ion in absence of water. However, we observed that the reaction is remarkably tolerant to humidity and no anhydrous conditions are needed, making the reaction extremely straightforward to perform. The possibility of performing such reactions in a fast and reliable manner, without the appreciable formation of byproducts, can offer new interesting opportunities to efficiently employ propargyl alcohols derivatives as a masking group for carbonyls. The latter approach can be particularly interesting for the synthesis and derivatization of carbonyl-rich compounds – such as large, conjugated, electron-deficient systems or quinoid-based pigments – for which the limited solubility often precludes the synthesis of certain derivatives or their application in functional devices.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110405"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143473934","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}

{"title":"Addition reaction of 1,6-diiodoperfluorohexane with ethylene: Process optimization and kinetic study","authors":"Zihan Ai,&nbsp;Baohe Wang,&nbsp;Zhaobang Zhang,&nbsp;Bangxing Yin,&nbsp;Jing Zhu,&nbsp;Jing Ma","doi":"10.1016/j.jfluchem.2025.110419","DOIUrl":"10.1016/j.jfluchem.2025.110419","url":null,"abstract":"<div><div>The fluorine-containing compound with symmetrical structure (I-C₂H₄-(CF₂)_n-C₂H₄-I) is a widely used the intermediate of fluorine-containing copolymer having various applications in the organic fluorine chemical industry. Herein, the addition reaction of 1,6-diiodoperfluorohexane (I-C₆F₁₂-I) with ethylene was studied at different temperatures (130 to 170 °C), reaction time (4 to 12 h), solvents (acetonitrile, DMF, Py, n-hexane) and initiators (AIBN, DTBP, CuI, CuCl). The yield of the product (I-C₂H_4<img>C₆F_12<img>C₂H₄-I) was up to 73 % under optimal reaction conditions (150 °C, 10 h, CuI, acetonitrile). The kinetic equation of the reaction was derived through further studies on the reaction kinetics. The addition reaction is a consecutive reaction, the reaction order and the activation energy of the first step (I-C₆F₁₂-I to I-C₆F_12<img>C₂H₄-I) are 1.131 and 56.53 kJ mol^-1, and the reaction order and the activation energy of the second step (I-C₆F_12<img>C₂H₄-I to I-C₂H_4<img>C₆F_12<img>C₂H₄-I) are 0.479 and 49.81 kJ mol^-1. These are important results that allows for further process intensification and designing of reactor.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110419"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641787","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}

{"title":"Synthesis of fluorinated 4H-chromen-4-ones from 2-hydroxyacetophenones and in vitro evaluation of their anticancer and antiviral activity","authors":"Larisa Politanskaya ,&nbsp;Jiaying Wang ,&nbsp;Yulia Meshkova ,&nbsp;Mariya Marenina ,&nbsp;Tatyana Tolstikova ,&nbsp;Maria Niukalova ,&nbsp;Iana Esaulkova ,&nbsp;Alexandrina Volobueva ,&nbsp;Vladimir Zarubaev","doi":"10.1016/j.jfluchem.2025.110421","DOIUrl":"10.1016/j.jfluchem.2025.110421","url":null,"abstract":"<div><div>Simple and useful approaches to the synthesis of a large series of 2-X-substituted 4<em>H</em>-chromen-4-one derivatives (X = Me, CF₃, SH, COOMe, COOEt), fluorinated on benzene ring, are reported. Firstly a series of 2-hydroxyacetophenones – the versatile building blocks – was synthesized <em>via</em> Fries rearrangement of acylphenols or by the Sonogashira reaction of polyfluorinated <em>o</em>-iodophenols with TIPS-acetylene, followed by the hydration of the triple bond. Then the transformations of the obtained fluorinated 2-hydroxyacetophenones with ethyl acetate, diethyl oxalate, carbon disulfide and anhydrides of carboxylic acids in the presence of base were investigated. The synthesis of 8-aryl substituted 4<em>H</em>-chromen-4-ones was achieved through the electrophilic iodination of phenolic compounds, followed by the Suzuki coupling of the resulting iodine-containing substrates (2-hydroxyacetophenones or chromene derivatives) with arylboric acids. In this way less reactive biologically important fluorinated 2-hydroxyacetophenones were successfully used extending the scope of the 4<em>H</em>-chromen-4-one family having potential biological activity. Some of the obtained fluorinated chromones were evaluated for cytotoxicity in MCF-7, HepG2, HeLa human cancer cells and in normal human foreskin fibroblast cells (hT'ER B'j1). It has been established that compound <strong>33</strong> has the most pronounced anticancer activity. Screening of all synthesized compounds (35 examples) for their inhibitory activity against influenza A virus A/Puerto Rico/8/34 (H1N1) in the MDCK cell culture revealed that a number of heterocycles (<strong>32, 41, 31, 11, 3, 35</strong>) differing both in the degree of fluorination and the nature of the substituents exhibit a significant antiviral effect (SI = 12 – 24). Among the studied compounds 2-methyl-4<em>H</em>-chromen-4-ones <strong>31, 35</strong> and <strong>3</strong> showed pronounced antiviral inhibitory activity (IC₅₀ = 2 – 5 μM). The most promising compound <strong>32</strong>, containing 6,7,8-trifluorosubstituted scaffold demonstrated low toxicity (CC₅₀ = 823 μM) and high virus inhibition activity (IC₅₀ = 35 μM) caused SI = 24, which allows it to be considered as potential drug-candidate in further in-depth studies.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110421"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641788","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}

{"title":"Fluorinated vs. non-fluorinated 1,3-dimethoxypropane: A comparative analysis for lithium metal battery applications","authors":"Alexander A. Hizbullin,&nbsp;Irina V. Kutovaya,&nbsp;Olga I. Shmatova","doi":"10.1016/j.jfluchem.2025.110418","DOIUrl":"10.1016/j.jfluchem.2025.110418","url":null,"abstract":"","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110418"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552016","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}

{"title":"Electrochemical reduction behavior of Si(IV) ions in LiF-SiO2 and KF-SiO2 melts at 1173 K","authors":"Yuta Suzuki ,&nbsp;Takuya Goto","doi":"10.1016/j.jfluchem.2025.110420","DOIUrl":"10.1016/j.jfluchem.2025.110420","url":null,"abstract":"<div><div>Metal electrodeposition from metal oxides is beneficial not only in the terrestrial metal smelting process but also in the process of recovering metals from minerals on the Moon and Mars. In the electrochemical process, a binary melt of metal oxide and metal fluoride can be a promising reaction media for constructing a practical electrolytic system that allows metal recovery directly from metal oxide at lower temperatures. In this study, the electrochemical reduction behavior of Si(IV) ions in LiF-SiO₂ and KF-SiO₂ melts at 1173 K, which included 10 mol% SiO₂, was studied toward controlling the electrodeposition process of crystalline Si in high-temperature melts with higher SiO₂ composition ratios. The dissolution behavior of SiO₂ was investigated by high-temperature Raman spectroscopy and density functional theory calculation, revealing that Si(IV) complex ions such as Si₃F₇–2 K are formed in the KF-SiO₂ system, whereas Si(IV) ion was not easily bonded to constituent ions of the LiF-SiO₂ melt. It was demonstrated that polycrystalline Si could be obtained by potentiostatic electrolysis in both melts, and the reduction rate of Si(IV) ions was faster in the LiF-SiO₂ system. The Raman spectroscopy and XRD analysis revealed that the electrodeposits were the polycrystalline Si and the alloys such as Li-Si and K-Si. The reported data on the interaction between fluoride ions and Si(IV) ions in the binary melt of metal fluoride and SiO₂ will contribute to realizing an in-situ resource utilization process that enables one-step Si recovery from SiO₂.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110420"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552015","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}

{"title":"Theoretical study on the compatibility of C4F7N decomposition products with metal oxides: First-principles","authors":"Gang Peng ,&nbsp;Xiajin Rao ,&nbsp;Dajian Li ,&nbsp;Benli Liu ,&nbsp;Yingyu Wu","doi":"10.1016/j.jfluchem.2025.110417","DOIUrl":"10.1016/j.jfluchem.2025.110417","url":null,"abstract":"<div><div>The compatibility between the gas and solid materials within the gas chamber is key to ensuring the safe operation of electrical equipment. Current research primarily focuses on the compatibility between the C₄F₇N (Heptafluoroisobutyronitrile) and the solid materials used in equipment. However, C₄F₇N decomposes under electrical and thermal fault conditions, while metal materials are also prone to oxidation during the manufacturing and operation processes. In this paper, the interaction systems between the main decomposition products of C₄F₇N (CO, CF₄ and C₃F₆(perfluoropropene)) and typical metal surface oxides (Al₂O₃, CuO) are established. Based on first-principles, the interaction energy, charge transfer, electronic density of states, differential charge density, and weak interaction forces are evaluated as five microscopic parameters. The interaction mechanisms between the decomposition products of C₄F₇N and the surface oxides of typical metal materials are analyzed at the microscopic level, further assessing their compatibility. The results show that both CO and CF₄ exhibit weak interactions with the Al₂O₃(0 0 0 1) interface, demonstrating good compatibility. However, the interaction energy between C₃F₆ and the Al₂O₃(0 0 0 1) interface reaches -3.13 eV with a charge transfer of 0.336e, showing significant charge accumulation, as well as stronger interactions, and the apparent overlap between the 2p orbitals of F atoms and the 3p orbitals of Al atoms between 0eV-6eV. This suggests the potential formation of chemical bonds, leading to poor compatibility. The interactions between CO, CF₄ and C₃F₆ with the CuO(1 1 1) interface are all weak, indicating good compatibility. In conclusion, to ensure the safe operation of C₄F₇N/CO₂ environmentally friendly gas-insulated equipment, it is recommended to maximize the use of copper materials in metal equipment and avoid prolonged exposure of the equipment to environments prone to oxidation, thereby further enhancing the stability and reliability of the equipment.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110417"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552017","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}

{"title":"Radical 1,2-fluoroalkylation/stannylation of terminal alkynes","authors":"Vyacheslav I. Supranovich,&nbsp;Alexander D. Dilman","doi":"10.1016/j.jfluchem.2025.110422","DOIUrl":"10.1016/j.jfluchem.2025.110422","url":null,"abstract":"<div><div>A method for the radical 1,2-fluoroalkylation/stannylation of terminal alkynes using fluorinated bromides and a tin(II) salt is described. The reaction is performed under photocatalytic conditions and involves radical addition at the triple bond followed by interaction of the vinyl radical with tin(II). Treatment of the reaction mixture with butylzinc bromide leads to vinyl tributylstannanes, which can be involved in the Stille cross-coupling or subjected to iododestannylation.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110422"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143684634","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}