Journal of Fluorine Chemistry最新文献

英文中文

Study on fluorination of didymium oxide [(NdPr)2O3] using ammonium bifluoride (NH4HF2) route 用双氟化铵（NH4HF2）路线氟化氧化二钕[(NdPr)2O3]的研究

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-07-01 DOI: 10.1016/j.jfluchem.2025.110460

Prafulla S. Sarode, D.N. Ambare, D.K. Sahoo

In the present study, the production of anhydrous didymium fluoride [(NdPr)F₃] by fluorination of didymium oxide [(NdPr)₂O₃] using ammonium bifluoride (NH₄HF₂) was investigated. The experimental setup used and the synthesis method as well as the analysis of the product were discussed in detail in the manuscript. Thermogravimetry-differential scanning calorimetry (TG-DSC) technique was employed to identify the mechanism and determine the necessary temperature range for the fluorination reaction. The phase composition of the obtained products (intermediate and final product) were analysed using X-ray diffraction (XRD) analysis. The effects of process parameters such as temperature, composition and reaction time on the fluorination reaction have been studied in detail. Pure anhydrous (NdPr)F₃, suitable for the production of NdPr metal, was produced under the optimal operating conditions established in this study.

研究了以双氟化铵（NH4HF2）为原料，氟化氧化二钕[(NdPr)2O3]生产无水氟化二钕[(NdPr)F3]的工艺。文中对所采用的实验装置、合成方法以及产物的分析进行了详细的讨论。采用热重-差示扫描量热（TG-DSC）技术对氟化反应机理进行了分析，确定了氟化反应所需的温度范围。用x射线衍射（XRD）分析了所得产物（中间产物和最终产物）的相组成。详细研究了温度、组成、反应时间等工艺参数对氟化反应的影响。在本研究确定的最佳操作条件下，制备出了适合生产NdPr金属的纯无水（NdPr）F3。

引用次数: 0

Recent advances in direct 1,2-bis-trifluoro-methylation, -methoxylation, -methylthiolation, and –methylselenylation of unsaturated hydrocarbons 不饱和烃1,2-二-三氟直接甲基化、-甲氧基化、-甲基硫代化和-甲基硒化的最新进展

IF 1.9 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-07-01 DOI: 10.1016/j.jfluchem.2025.110454

Ahmed Kareem Obaid Aldulaimi , Huseyn Imanov , Shakir Mahmood Saeed , Wadhah Hasan Alkhazali , Waam Mohammed Taher , Mariem Alwan , Mahmood Jasem Jawad , Hiba Mushtaq , Esmail Vessally

Owing to its high efficiency, substrate versatility, operational simplicity, and product structure diversity, difunctionalization is a topic of current interest. In this context, some attention has been recently paid to the direct 1,2-bis-trifluorometh(ox)yl(thiol/selenyl)ation of abundant and easily accessible unsaturated hydrocarbons for the single-step construction of biologically important 1,2-bis(trifluoro-methyl/methoxyl/thiol/selenyl)ated compounds. In this Mini-Review, we summarize the recent progress and advances in this attractive field with emphasis on the mechanistic aspect of these reactions.

由于它的高效率、基板的多功能性、操作的简单性和产品结构的多样性，双功能化是当前人们感兴趣的一个话题。在此背景下，最近人们开始关注大量易获得的不饱和烃的1,2-二（甲氧基）-三氟醚（ox）基（硫醇/硒基）直接化，以一步构建具有重要生物学意义的1,2-二（三氟甲基/甲氧基/硫醇/硒基）化化合物。在这篇综述中，我们总结了这一有吸引力的领域的最新进展和进展，重点介绍了这些反应的机理方面。

引用次数: 0

Base-mediated [3 + 2] cyclization/rearrangement of N-2,2,2-trifluoroethylisatin ketimines with diethyl azodicarboxylate for construction of spirooxindoles containing trifluoromethyl-1,2,4-triazoles n -2,2,2-三氟乙基化atin酮胺与二乙基偶氮二羧酸酯的碱介导[3 + 2]环化/重排以构建含三氟甲基-1,2,4-三唑的螺菌吲哚

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-07-01 DOI: 10.1016/j.jfluchem.2025.110452

Yabo Zhang , Liangjun Chen , Wenhe Shi , Panpan Guo , Yan Fu , Ran Guo

This study descripts a DABCO-mediated tandem [3 + 2] cyclization/rearrangement reaction between N-2,2,2-trifluoroethylisatin ketimines with diethyl azodicarboxylate to successfully synthesize a series of spirooxindoles containing trifluoromethyl-1,2,4-triazoles. This method demonstrates good substrate applicability and achieved up to 92 % yield under mild reaction conditions, which provided an efficient synthetic strategy for the construction of novel spirooxindole-embedded trifluoromethyl triazoles.

本研究描述了dabco介导的n -2,2,2-三氟乙基化atin酮胺与二乙基偶氮二羧酸酯的串联[3 + 2]环化/重排反应，成功合成了一系列含三氟甲基-1,2,4-三唑的螺菌吲哚。该方法具有良好的底物适应性，在温和的反应条件下，产率高达92%，为构建新型螺旋体吲哚包埋的三氟甲基三唑提供了一种有效的合成策略。

引用次数: 0

PFAS analytical methods – A practical guide PFAS分析方法。实用指南

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-07-01 DOI: 10.1016/j.jfluchem.2025.110444

Graham K. Ansell, Hassan Javed

The state of the science surrounding per- and polyfluoroalkyl substances (PFAS) has advanced rapidly in recent years, with significant progress made in understanding their physicochemical properties, environmental occurrence, chemistry, and fate and transport. These advancements have been driven by breakthroughs in PFAS analytical capabilities, including the development of robust analytical methods and the availability of higher-resolution instruments. Today, a wide array of PFAS analytical methods exist, with several developed by U.S. federal agencies, including the United States Environmental Protection Agency (USEPA). Additionally, numerous PFAS screening methods have also been developed, primarily for research purposes. This article provides an overview of these methods from a practitioner’s perspective, highlighting their strengths, limitations, and critical caveats to consider when employing them. The aim is to offer a concise guide to PFAS analytical methods, benefiting not only the scientific community but also individuals new to PFAS who are navigating the rapidly evolving regulatory and litigation landscape.

近年来，全氟烷基和多氟烷基物质（PFAS）的科学研究进展迅速，在了解其理化性质、环境发生、化学性质、命运和运输等方面取得了重大进展。这些进步是由PFAS分析能力的突破所推动的，包括强大的分析方法的发展和更高分辨率仪器的可用性。今天，存在大量的PFAS分析方法，其中一些是由美国联邦机构开发的，包括美国环境保护署（USEPA）。此外，还开发了许多PFAS筛选方法，主要用于研究目的。本文从实践者的角度概述了这些方法，强调了它们的优点、局限性，以及在使用它们时需要考虑的关键注意事项。其目的是提供PFAS分析方法的简明指南，不仅有利于科学界，也有利于那些正在快速发展的监管和诉讼环境中导航的PFAS新手。

引用次数: 0

Microwave-assisted sodium borohydride/lanthanide rare earth chlorides system for reduction of terminal carboxyl groups in liquid fluoroelastomer 微波辅助硼氢化钠/镧系稀土氯化物体系还原液态氟弹性体末端羧基

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-07-01 DOI: 10.1016/j.jfluchem.2025.110457

Qi Wang, Ranran Qi, Xiaojie Zhang, Mingyi Liao

Liquid terminal carboxyl fluororubber (LTCFs) derived from poly(vinylidene fluoride-co-hexafluoropropylene) was efficiently converted to liquid terminal hydroxyl fluororubber (LTHFs) through a microwave-assisted reduction process employing NaBH₄/lanthanide chloride (MCl₃; M = La, Ce, Sm, Gd) catalytic systems. Comprehensive structural characterization via FTIR, UV–Vis, ¹H NMR, GPC, and titration analyses confirmed the transformation of terminal carboxyl groups (-COOH) to hydroxyl groups (-OH) while simultaneously reducing backbone carbon-carbon double bonds (-C = C-) to single bonds (-C-C-). Systematic evaluation revealed NaBH₄/CeCl₃, NaBH₄/SmCl₃, and NaBH₄/GdCl₃ systems achieved exceptional reduction efficiencies exceeding 80 %. Process optimization using the NaBH₄/SmCl₃ system established optimal parameters: 4 min microwave irradiation at 320 W power, SmCl₃/-COOH molar ratio of 2:1, and substrate/solvent ratio of 1:10 (g/mL), yielding 84.60 % conversion efficiency. The microwave methodology demonstrated remarkable temporal efficiency, achieving >80 % conversion within 4 min compared to conventional thermal methods requiring hours. This accelerated process significantly enhanced reaction kinetics while maintaining structural fidelity, as evidenced by comprehensive spectroscopic and chromatographic analyses. The work establishes a robust microwave-assisted platform for precise fluororubber functional group modification with potential applications in advanced fluoropolymer synthesis.

以聚偏氟乙烯-共六氟丙烯为原料，采用NaBH4/氯化镧(MCl3；M = La, Ce, Sm, Gd)催化体系。通过FTIR， UV-Vis, 1H NMR， GPC和滴定分析等综合结构表征证实了末端羧基（- cooh）转化为羟基（- oh），同时主碳-碳双键（-C = C-）还原为单键（-C-C-）。系统评价表明，NaBH4/CeCl3、NaBH4/SmCl3和NaBH4/GdCl3体系的还原效率超过80%。采用NaBH4/SmCl3体系进行工艺优化，确定了最佳工艺参数：微波辐照功率为320 W， SmCl3/-COOH摩尔比为2:1，底物/溶剂比为1:10 (g/mL)，转化率为84.60%。微波方法显示出显著的时间效率，与需要数小时的传统热方法相比，在4分钟内实现80%的转换。这一加速过程显著增强了反应动力学，同时保持结构保真度，如全面的光谱和色谱分析所证明的那样。这项工作为精确的氟橡胶官能团修饰建立了一个强大的微波辅助平台，在先进的含氟聚合物合成中具有潜在的应用前景。

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引用次数: 0

Electrophilic aromatic fluorination of N-Arylacetamides: A computational and efficacy study n -芳基乙酰胺的亲电芳氟化：计算和功效研究

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-07-01 DOI: 10.1016/j.jfluchem.2025.110455

Meghan Betourney, Hannah Ashton, Gabrielle Costello, Jordan Hunter, Sang H. Park, Benjamin Shepler, Joseph C. Sloop, Matthew Stancea, Karla Wilmott

Using selected N⁺-F and N-F fluorinating agents, a series of fluorinated N-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 N-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 N-arylacetamides are discussed. A preference for fluorination ortho to the acetamido and trifluoroacetamido groups was observed for most N-arylacetamides investigated. An exception to this trend was found in the case of N-(4-methoxyphenyl)acetamide, where fluorination ortho to the methoxy group predominated. Computationally determined partial charge distribution results for the N-arylacetamides featured in this study were found to support the experimentally observed fluorination regiochemistry.

选用N+-F和N-F氟化剂，通过亲电芳代取代法制备了一系列N-芳基酰乙酰胺。改变反应物比例和反应条件，以确定对单氟化的选择性，并提供最佳的产品转化率，范围为0 - 94%。此外，对选定的n -芳基乙酰胺进行了水溶液和离子液体介质、超声和微波辐照的氟化，并与在乙腈中进行的常规氟化条件进行了比较。讨论了温度、反应时间和溶剂对氟化反应的影响，以及氟化剂反应活性、氟化选择性和产物分布的变化趋势。对大多数被研究的n -芳基乙酰酰胺，观察到对乙酰氨基和三氟乙酰氨基基团的氟化邻位的偏好。在N-（4-甲氧基苯基）乙酰胺的情况下发现了这一趋势的例外，其中甲氧基的氟化邻位占主导地位。计算确定的本研究中n -芳基乙酰胺的部分电荷分布结果支持实验观察到的氟化区域化学。

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引用次数: 0

Physicochemical characterization of fluoride solid electrolyte PbSnF4 synthesized via sonochemical reaction 声化学合成氟固体电解质PbSnF4的理化性质

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-06-27 DOI: 10.1016/j.jfluchem.2025.110450

Meena M , Benson K Money , Amrtha Bhide

Demand for batteries with enhanced energy density and improved thermal safety is a key focus for researchers striving to build a sustainable environment. As fluoride ion batteries (FIB) are expected to exhibit high energy density and exceptional thermal stability, research activities are focused on identifying fluoride ion-conducting electrolytes. Among the various fluoride ion conductors, PbSnF₄, renowned for its superior ionic conductivity, is typically synthesized via mechanochemical reaction. In the present work, PbSnF₄ was synthesized via an acoustic cavitation-driven sonochemical reaction. This novel synthesis route has reduced the duration of the synthesis process to a few minutes compared with several hours for the mechanochemical reaction. The structural, morphological, and ionic transport properties are investigated. The ionic conductivity of the resulting orthorhombic PbSnF₄ is evaluated to be 4.5 × 10⁻⁴ S/cm at RT. The contribution of fluoride ions to the total ionic conductivity is estimated via the DC polarization technique as 0.92. The electrochemical stability window (ESW) is measured through cyclic voltammetry (CV) as 0.7 V with PbF₂/PbSnF₄/SS cell configuration.

对具有更高能量密度和更好热安全性的电池的需求是研究人员努力建立可持续环境的关键焦点。由于氟离子电池预计将表现出高能量密度和特殊的热稳定性，研究活动的重点是确定氟离子导电电解质。在各种氟化物离子导体中，PbSnF4以其优异的离子电导率而闻名，通常是通过机械化学反应合成的。本研究采用声空化驱动的声化学反应合成了PbSnF4。这种新的合成路线将合成过程的持续时间从机械化学反应的几个小时缩短到几分钟。研究了其结构、形态和离子输运性质。得到的正交PbSnF4的离子电导率在室温下估计为4.5 × 10⁻4 S/cm。通过直流极化技术估计氟离子对总离子电导率的贡献为0.92。在PbF2/PbSnF4/SS电池结构下，通过循环伏安法（CV）测量电化学稳定窗口（ESW）为0.7 V。

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引用次数: 0

Pentafluorinated thevinol scaffold for opioid ligands 阿片配体的五氟化醇支架

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-06-20 DOI: 10.1016/j.jfluchem.2025.110451

Sergey N. Gorlov , Irina V. Sandulenko , Alexander F. Smol'yakov , Аndrey А. Tyutyunov , Maria I. Godovikova , Sergey K. Moiseev

An addition reaction of Me₃SiCF₂CF₃ to the carbonyl group of thevinal (10), a morphinan derivative, followed by an oxidation of the resulting mixture of the C(20)-epimeric secondary alcohols (20R)-11a and (20S)-11b (15:1) resulted in the first preparation of the pentafluorinated ketone 12. The latter is expected to serve as a starting compound for the preparation of thevinols and orvinols, putative opioid receptor ligands pentafluorinated within their C(20)-centered pharmacophore. It was shown that MeLi and MeMgI, indeed, add to the carbonyl group of ketone 12 to afford the mixture of C(20)-epimeric tertiary alcohols, pentafluoroethylthevinols, with the 20R-isomer predominating. The reduction of ketone 12 with LiAlH₄ also results in the formation of a mixture of the C(20)-epimeric pentafluorothevinols (20R)-11a and (20S)-11b However, the ratio of the epimers (1:8) is opposite to that one obtained from the reaction of aldehyde 10 with Me₃SiCF₂CF₃.

Me3SiCF2CF3与morphinan衍生物vinal（10）的羰基加成反应，然后氧化生成的C(20)-外聚二次醇(20R)-11a和(20S)-11b（15:1）的混合物，首次制备了五氟化酮12。后者有望作为一种起始化合物，用于制备醇醇和鸟苷醇，这两种假定的阿片受体配体在其C（20）中心药效团内五氟化。结果表明，MeLi和MeMgI确实加入到酮12的羰基上，形成以20r -异构体为主的C(20)-外聚叔醇和五氟乙基醇的混合物。酮12与LiAlH4的还原也会生成C(20)-外聚体五氟醇(20R)-11a和(20S)-11b的混合物，但外聚体的比例（1:8）与醛10与Me3SiCF2CF3反应的比例相反。

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引用次数: 0

Purification of uranium tetrafluoride using ammonium bifluoride 用二氟化铵提纯四氟化铀

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-06-19 DOI: 10.1016/j.jfluchem.2025.110449

Kyle R. Foster , Juliano Schorne-Pinto , Ronald E. Booth , Annabelle Husek , Mina Aziziha , Hunter B. Tisdale , Bernie W.N. Fitzpatrick , Hans-Conrad zur Loye , Markus H.A. Piro , Theodore M. Besmann

A method of purification for UF₄ utilizing NH₄HF₂ was investigated to remove oxygen and hydrate impurities from the salt. The original salt exhibited a melting point at 915–920 °C, which corresponds to the eutectic temperature of the UF₄-UO₂ system, showing clear signs of oxygen contamination. To purify the salt, an air-tight reaction vessel inside an argon glovebox was used to react UF₄/NH₄HF₂ mixtures at elevated temperatures under a continuous flow of inert gas. The process yielded a significantly purer UF₄ salt as confirmed via inert gas fusion, X-ray diffraction, differential scanning calorimetry and inductively coupled plasma-optical emission spectrometry.

研究了一种利用NH4HF2提纯UF4的方法，以去除盐中的氧和水合杂质。原始盐的熔点为915-920℃，与UF4-UO2体系的共晶温度相对应，显示出明显的氧污染迹象。为了提纯盐，在氩气手套箱内的气密反应容器在连续流动的惰性气体下，在高温下对UF4/NH4HF2混合物进行反应。通过惰性气体熔合、x射线衍射、差示扫描量热法和电感耦合等离子体光学发射光谱法证实，该工艺产生了明显纯净的UF4盐。

引用次数: 0

Cobalt-catalyzed C-H perfluoroalkylation of anilines 钴催化苯胺的C-H全氟烷基化

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Fluorine Chemistry

Pub Date : 2025-06-16 DOI: 10.1016/j.jfluchem.2025.110437

Shota Mizuno , Yoichi Obitsu , Munenori Inoue

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.

研究了在温和条件下钴催化苯胺的全氟烷基化反应。Co(acac)2/dppe/Zn的组合有效地催化了苯胺衍生物与全氟烷基碘化物的全氟烷基化反应，得到了产率良好至中等的相应目标产物。提出了详细的反应机理，发现产率与底物有关，因为反应是通过类似自由基加成的反应进行的。

引用次数: 0

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