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Synthesis, purification and characterisation of novel PFAS following nontarget analysis 基于非靶标分析的新型PFAS的合成、纯化和表征
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-01 Epub Date: 2025-01-25 DOI: 10.1016/j.jfluchem.2025.110398
Ana R.L. Araujo , Anton Pavlov , Jon Eigil Johansen , Sicco Brandsma , Huiling Liu
PFAS, or per- and polyfluorinated alkyl substances, are among the most prevalent environmental contaminants. Because of their toxicity and widespread use, these substances must be regulated in order to reduce the associated hazards. Effective regulation requires accurate measurement of PFAS concentrations, but the lack of commercially available reference standards hinders the identification and quantification of novel PFAS discovered through nontarget analysis techniques. In this work, we aimed to fill this gap by synthetising new PFAS reference standards, based on findings reported in the literature through nontarget assays.
We performed the synthesis of 17 novel PFAS reference standards, including three fluorotelomer thioether amido sulfonic acid (FTSASs), three fluorotelomer sulfonyl amido sulfonic acid (FtSO2AoS), 6:2 Fluorotelomer sulfinyl amido sulfonic acid (6:2 FtSOAo), three perfluoroalkane sulfonamide diacetic acids (FASEE diacids), three perfluroalkyl amidoalkyl amine (PFAAAm), perfluoro (4-methyl-3,6-dioxaoct-7-ene) sodium sulfonate (PS acid sodium salt), perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonic acid (PS acid), perfluoro-3-{ [1-(ethenyloxy)propan-2-yl]oxy}propanoic acid (EVE acid), and 6- (2,2,3,3,4,4,4-Heptafluorobutoxy)hexan-1-ol. Various chemical reactions were carried out to synthesise the chemicals, and the Dry Column Vacuum Chromatography (DCVC) was selected as the best purification technique. The linear isomer product was obtained by recrystallisation when branched isomers were present. The identity and purity of the synthesised reference standards were confirmed using a combination of NMR spectroscopy (¹H, ¹⁹F, ¹³C) and mass spectrometry (m/z, LC-MS, or GC–MS).
全氟和多氟烷基物质是最普遍的环境污染物之一。由于这些物质的毒性和广泛使用,必须对其进行管制,以减少相关的危害。有效的监管需要准确测量PFAS浓度,但缺乏商业参考标准阻碍了通过非目标分析技术发现的新型PFAS的鉴定和定量。在这项工作中,我们的目标是根据文献中报道的非靶向分析结果,通过合成新的PFAS参考标准来填补这一空白。我们合成了17个新的PFAS标准品,包括3个氟端粒硫醚氨基磺酸(FTSASs)、3个氟端粒磺酰氨基磺酸(FtSO2AoS)、6:2氟端粒磺酰氨基磺酸(6:2 FtSOAo)、3个全氟烷磺酰胺二乙酸(FASEE二酸)、3个全氟烷基酰胺烷基胺(PFAAAm)、3个全氟(4-甲基-3,6-二草辛烷-7-烯)磺酸钠(PS酸钠盐)、全氟(4-甲基-3,6-二氧辛-7-烯)磺酸(PS酸)、全氟-3-{[1-(乙基氧基)丙烷-2-基]氧}丙烷酸(EVE酸)和6-(2,2,3,3,4,4,4-七氟丁氧基)己烷-1-醇。通过多种化学反应合成该化合物,并选择干柱真空色谱法(DCVC)作为最佳纯化技术。当分支异构体存在时,通过再结晶得到线性异构体产物。采用核磁共振波谱(¹H,¹⁹F,¹³C)和质谱(m/z, LC-MS或GC-MS)相结合的方法确认合成标准品的鉴定和纯度。
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引用次数: 0
Introducing CF3 group at alkenyl C=C bond. Recent developments 在烯基C=C键上引入CF3基团。最近的进展
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-01 Epub Date: 2025-02-10 DOI: 10.1016/j.jfluchem.2025.110403
Karolina Paszek, Henryk Koroniak, Katarzyna Koroniak–Szejn
Recently, significant interest has been developed in pharmaceuticals containing fluorine The biological effects depend on the number and type of fluorine groups in the drug molecule. Much attention has been also paid to improve biological activity, in vivo stability, or bioavailability by studying the chemical modification of peptide structure. The most frequently studied fluorine-containing functional group is the trifluoromethyl group, which also occurs as a C(sp2)–CF3 bond. The trifluoromethyl alkyl group structure helps the peptide maintain its original β-turn structure, effectively mimicking the natural peptide bond, which allows it to function as its isostere. Therefore, the development of methods for synthesizing the trifluoromethylalkene group is becoming increasingly popular due to the potential of the products as building blocks of bioactive molecules. This review describes various methods for the preparation of the compounds with a trifluoromethylalkene group using trifluorinating reagents via the transition metal-mediated and the transition metal-free trifluoromethylation reactions.
近年来,含氟药物引起了人们极大的兴趣。药物分子中氟基团的数量和类型决定了药物的生物学效应。通过研究肽结构的化学修饰来提高生物活性、体内稳定性或生物利用度也受到了很大的关注。最常被研究的含氟官能团是三氟甲基,它也以C(sp2) -CF3键的形式出现。三氟甲基烷基结构有助于肽保持其原始的β-转结构,有效地模仿天然肽键,使其具有同位体的功能。因此,开发合成三氟甲基烯烃的方法越来越受欢迎,因为这些产品有可能成为生物活性分子的组成部分。综述了利用三氟化试剂通过过渡金属介导和无过渡金属的三氟甲基化反应制备含三氟甲基烯烃化合物的各种方法。
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引用次数: 0
Exploration of 2-(pentafluoro-λ6-sulfanyl)ethane-1-sulfonyl chloride as a novel pentafluorosulfanylation reagent 2-(五氟-λ6-磺酰)乙烷-1-磺酰氯作为新型五氟磺酰化试剂的探索
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-01 Epub Date: 2024-12-27 DOI: 10.1016/j.jfluchem.2024.110387
Laurianne Verret , Kelly Burchell-Reyes , Jean-François Morin , Jean-François Paquin
In this paper, we report our initial results on the development of 2-(pentafluoro-λ6-sulfanyl)ethane-1-sulfonyl chloride as a novel pentafluorosulfanylation reagent. The targeted reagent was synthesized in five steps from vinyl acetate. As opposed to gaseous SF5Cl, 2-(pentafluoro-λ6-sulfanyl)ethane-1-sulfonyl chloride is a liquid under ambient conditions. Its reaction with substituted-phenylvinyl acetates under photoredox catalysis provided the corresponding α-SF5-ketones in low to moderate yields due in part to an incomplete desulfonylation step. Nonetheless, these results serve as a promising starting point for the further development of pentafluorosulfanylation reagent.
本文报道了2-(五氟-λ6-磺酰)乙烷-1-磺酰氯作为新型五氟磺酰化试剂的初步研究结果。以醋酸乙烯为原料,分五步合成了目标试剂。与气态的SF5Cl相反,2-(五氟-λ6-磺酰)乙烷-1-磺酰氯在环境条件下是液体。在光氧化还原催化下,它与取代的苯基醋酸乙烯酯反应产生了相应的α- sf5酮,产率低至中等,部分原因是不完全的脱硫步骤。尽管如此,这些结果为进一步开发五氟磺化试剂提供了一个有希望的起点。
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引用次数: 0
Solid-state chemistry of inorganic fluorides: From tungsten-bronze types to functionalized nanofluorides: A review 无机氟化物的固态化学:从钨青铜型到功能化纳米氟化物:综述
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-01-01 Epub Date: 2024-12-06 DOI: 10.1016/j.jfluchem.2024.110374
Alain Tressaud
Solid-state chemistry of inorganic fluorides has gained great importance in the second half of 20th century. It aims at identifying the relationships between the structural networks and the physical properties resulting from interactions within these networks. One of the most significant results was the discovery in the 1960s of series of AxMF3 fluorides with structures similar to those of tungsten oxide bronzes. The investigation of other compounds mainly based on Al, Ga and transition metals with structures derived from ReO3, hexagonal tungsten bronze (HTB), tetragonal tungsten bronzes (TTB), defect pyrochlore and perovskite was soon launched in relation, in a first step, to their magnetic properties. Such interest was further extended to various properties such as positive electrodes in Li-ion batteries, UV absorbers, multiferroic components. Today, solid-state inorganic fluorides are present at the nano-sized level as components in many advanced technologies, including Li batteries or all solid-state fluorine batteries, micro- or nano-photonics, up- or down-conversion fluorescent probes, solid-state lasers, nonlinear optics, nuclear cycle, superhydrophobic coatings, etc. It has been pointed out that most of these outstanding properties can be correlated to the exceptional electronic properties of elemental fluorine, F2.
The aim of this article is to review the solid-state chemistry of fluorides having the formula AxMF3 over several decades, from their discovery in the 1960s to the interesting physical-chemical properties more recently investigated on these phases that derive from the ReO3, perovskite, defect-pyrochlore, hexagonal- and tetragonal- tungsten bronze types.
无机氟化物的固态化学在20世纪下半叶得到了极大的重视。它旨在确定结构网络与这些网络内相互作用产生的物理性质之间的关系。最重要的成果之一是在20世纪60年代发现了一系列与氧化钨青铜结构相似的AxMF3氟化物。其他主要基于Al、Ga和过渡金属的化合物,其结构来源于ReO3、六方钨青铜(HTB)、四方钨青铜(TTB)、缺陷焦绿石和钙钛矿,这是研究其磁性能的第一步。这种兴趣进一步扩展到各种性质,如锂离子电池的正极,紫外线吸收剂,多铁性元件。今天,固态无机氟化物作为纳米级的成分存在于许多先进技术中,包括锂电池或所有固态氟电池、微或纳米光子学、向上或向下转换荧光探针、固态激光器、非线性光学、核循环、超疏水涂层等。指出这些突出的性质大多与氟元素F2的特殊电子性质有关。本文的目的是回顾几十年来分子式为AxMF3的氟化物的固态化学性质,从它们在20世纪60年代被发现到最近在这些由ReO3、钙钛矿、缺陷焦绿石、六方和四方钨青铜类型衍生的相上研究的有趣的物理化学性质。
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引用次数: 0
Obituary “Professor Dr. Andreas Josef Kornath – May 6, 1965 — March 5, 2024”. 讣告“Andreas Josef Kornath教授博士- 1965年5月6日- 2024年3月5日”。
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-01-01 Epub Date: 2024-12-24 DOI: 10.1016/j.jfluchem.2024.110385
Joseph S. Thrasher
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引用次数: 0
Corrigendum to “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” [Journal of Fluorine Chemistry, 2024, 277, 110313] “含或不含苯并咪唑2-羧酸的氟化1,2-苯二胺在多磷酸介质中的转化:氟化2,2 ' -双苯并咪唑和苯并咪唑-2,3-二胺的合成”的勘误[氟化学杂志,2024,277,110313]
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-01-01 Epub Date: 2024-12-29 DOI: 10.1016/j.jfluchem.2024.110388
Jiayao Li , Vyacheslav I. Krasnov , Elena V. Karpova , Rodion V. Andreev , Inna K. Shundrina , IrinaYu Bagryanskaya , Galina A. Selivanova
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引用次数: 0
Corrosion of iron in liquid uranium hexafluoride at 80 °C. Part II: Corrosion mechanism 铁在液态六氟化铀中80°C的腐蚀。第二部分:腐蚀机理
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-01-01 Epub Date: 2024-12-10 DOI: 10.1016/j.jfluchem.2024.110373
Mickaël Achour , Laure Martinelli , Sylvie Chatain , Fréderic Miserque , Laurent Jouffret , Marc Dubois , Pierre Bonnet , Ania Selmi , Bertrand Morel , Sylvie Delpech
Thanks to species identification and growth interface localization experiments, a mechanism of iron corrosion in liquid UF6 at 80 °C was suggested. After an UF6 dissociation step, resulting fluorine (HF, F- or F•) was adsorbed at the FeF2 external interface and diffused into the iron fluoride layer via fluorine vacancy. FeF2 grew thus at the FeF2/Fe interface. Two FeF2 growth kinetics were observed depending on the presence or absence of NOxF impurities. Both corrosion rates were controlled by the cathodic reaction and presence of NOxF catalysed it.
通过物种鉴定和生长界面定位实验,提出了铁在80℃液态UF6中的腐蚀机理。经过一个UF6解离步骤后,生成的氟(HF、F-或F•)被吸附在FeF2外界面上,并通过氟空位扩散到氟化铁层中。FeF2在FeF2/Fe界面生长。观察到两种FeF2生长动力学取决于noxx杂质的存在或不存在。两种腐蚀速率均受阴极反应和nox催化反应的控制。
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引用次数: 0
Lipophilicity effects of monofluorination at the tertiary aliphatic carbon as a function of α-substituent 叔脂肪碳单氟化对α-取代基亲脂性的影响
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-01-01 Epub Date: 2024-12-19 DOI: 10.1016/j.jfluchem.2024.110384
Kostiantyn P. Melnykov , Oleksandr S. Liashuk , Oleh Smyrnov , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Viktor Yakubovskyi , Oleksandr O. Grygorenko
Effects of monofluorination at the tertiary aliphatic carbon on the compound's lipophilicity were measured for a series of model 4-substituted piperidine-derived benzamides. It was found that the observed ΔLogP values strongly depend on the nature of α-substituent present at the C-4 position. In particular, ΔLogP increased with increasing the substituent's electronegativity (as described by field effect). Using qualitative molecular electrostatic potential surface (MEPS) analysis, we suggested that the fluorine effect on the compound's lipophilicity in the studied systems is defined by electronic distribution modulation at the neighboring atoms (especially Hydrogens).
对一系列模型4取代哌啶衍生苯酰胺进行了单氟化对化合物亲脂性的影响。研究发现ΔLogP值与C-4位置α-取代基的性质密切相关。特别是,ΔLogP随着取代基电负性的增加而增加(用场效应来描述)。通过定性分子静电电位表面(MEPS)分析,我们认为氟对化合物亲脂性的影响是通过邻近原子(尤其是氢原子)的电子分布调制来定义的。
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引用次数: 0
Obituary “Friedhelm (Felix) Aubke” “讣告:弗里德赫尔姆(菲利克斯)奥布克”。
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-01-01 Epub Date: 2024-12-20 DOI: 10.1016/j.jfluchem.2024.110383
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引用次数: 0
The synthesis of N-Trifluoromethyl hydroxylamine from (trifluoromethyl)trimethylsilane 从(三氟甲基)三甲基硅烷合成 N-三氟甲基羟胺
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-01 Epub Date: 2024-10-16 DOI: 10.1016/j.jfluchem.2024.110356
Haixia Song, Qin Wang, Xingjie Ruan, Weilong Hu, Le Liu, Xin-Hua Duan, Mingyou Hu
We have presented a straightforward approach for the synthesis of N-CF3 hydroxylamines, utilizing TMSCF3 for the N-trifluoromethylation of nitrosoarenes with the assistance of CsF. This method demonstrates excellent tolerance towards various functional groups and can be applied to a wide range of substrates, highlighting its versatility and utility in synthetic applications. The nucleophilic N-trifluoromethylation pathway for N-CF3 hydroxylamines provides a practical protocol for the synthesis of promising molecular architectures in the field of medicinal chemistry.
我们提出了一种直接合成 N-CF3 羟基胺的方法,利用 TMSCF3 在 CsF 的辅助下对亚硝基烯烃进行 N-三氟甲基化反应。该方法对各种官能团具有极佳的耐受性,可用于多种底物,突出了其在合成应用中的多功能性和实用性。N-CF3 羟基胺的亲核 N-三氟甲基化途径为药物化学领域合成前景广阔的分子结构提供了一个实用的方案。
{"title":"The synthesis of N-Trifluoromethyl hydroxylamine from (trifluoromethyl)trimethylsilane","authors":"Haixia Song,&nbsp;Qin Wang,&nbsp;Xingjie Ruan,&nbsp;Weilong Hu,&nbsp;Le Liu,&nbsp;Xin-Hua Duan,&nbsp;Mingyou Hu","doi":"10.1016/j.jfluchem.2024.110356","DOIUrl":"10.1016/j.jfluchem.2024.110356","url":null,"abstract":"<div><div>We have presented a straightforward approach for the synthesis of <em>N</em>-CF<sub>3</sub> hydroxylamines, utilizing TMSCF<sub>3</sub> for the <em>N</em>-trifluoromethylation of nitrosoarenes with the assistance of CsF. This method demonstrates excellent tolerance towards various functional groups and can be applied to a wide range of substrates, highlighting its versatility and utility in synthetic applications. The nucleophilic <em>N</em>-trifluoromethylation pathway for <em>N</em>-CF<sub>3</sub> hydroxylamines provides a practical protocol for the synthesis of promising molecular architectures in the field of medicinal chemistry.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"280 ","pages":"Article 110356"},"PeriodicalIF":1.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142527123","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
期刊
Journal of Fluorine Chemistry
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