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Exploration towards the bromopentafluorosulfanylation reaction of terminal alkynes 末端炔溴五氟磺化反应的探索
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-01 DOI: 10.1016/j.jfluchem.2024.110386
Marie-Rose Ouellet-Du Berger , Jean-Philippe Bouillon , Jean-François Paquin
In this paper, we report our efforts toward the development of a bromopentafluorosulfanylation reaction of terminal alkynes. The use of tetrabromomethane (CBr4) as a bromine atom source allowed the formation of the bromopentafluorosulfanylated product. Practically, however, the desired products could not be separated from the minor chloropentafluorosulfanylated products as well as the dibromoalkene side-products generated under those reaction conditions.
本文报道了末端炔的溴五氟磺化反应的研究进展。使用四溴甲烷(CBr4)作为溴原子源,可以形成溴五氟磺化产品。然而,实际上,所需的产物不能与在这些反应条件下产生的少量氯氟磺酰化产物以及二溴烯烃副产物分离。
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引用次数: 0
New insights into the use of carbon and boron nitride nanotubes as sensors for ClF3: A density functional theory analysis 碳和氮化硼纳米管用作ClF3传感器的新见解:密度泛函理论分析
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-01 DOI: 10.1016/j.jfluchem.2025.110401
Fatemeh Biniaz, Mohammad Reza Zardoost, Mohammad Reza Toosi
The ability of born nitride and carbon nanotubes to adsorb ClF3 was investigated by the density functional theory method. The electronic properties including HOMO and LUMO energies, density of states, chemical potential, electrophilicity index, softness, hardness, and natural bond orbital analysis were studied. Our findings indicate that among the studied tubes the (6,0) CNT is more suitable for adsorbing ClF3 molecule. The adsorption of ClF3 on the nanotubes significantly reduces the energy gap and hardness parameters of the tubes. This factor increases the conductivity of the system. The adsorption energies in the investigated models are negative, which confirm that the adsorption process is thermodynamically favorable and the complexes are stable. Also, among these compounds, (6,0) CNT- ClF3 has the greatest adsorption energy. QTAIM calculations confirm the observed adsorption energies.
采用密度泛函理论研究了氮化碳和碳纳米管对ClF3的吸附能力。研究了其电子性质,包括HOMO和LUMO能、态密度、化学势、亲电性指数、柔软度、硬度和自然键轨道分析。我们的研究结果表明,在所研究的管中,(6,0)碳纳米管更适合吸附ClF3分子。ClF3在纳米管上的吸附显著降低了纳米管的能隙和硬度参数。这一因素增加了体系的导电性。模型的吸附能均为负,说明吸附过程在热力学上是有利的,配合物是稳定的。此外,在这些化合物中,(6,0)CNT- ClF3具有最大的吸附能。QTAIM计算证实了观察到的吸附能。
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引用次数: 0
Investigation of the reaction of hexafluoro-1,4-naphthoquinone with substituted phenols 六氟-1,4-萘醌与取代酚反应的研究
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-01 DOI: 10.1016/j.jfluchem.2025.110402
Ekaterina N. Kudryavtseva, Boris V. Lichitsky, Evgeny V. Tretyakov
Reaction of hexafluoro-1,4-naphthoquinone with various phenols was studied for the first time. It was shown that sodium acetate is a convenient reagent for implementation of the process. The investigated condensation led exclusively to substitution of two fluorine atoms in the quinone core. Based on performed research the method for preparation of substituted 2,3-diaryloxy-5,6,7,8-tetrafluoronaphthalene-1,4-diones was elaborated. Using similar conditions pentafluorobenzo[a]phenoxazine derivatives were obtained from 2-aminophenols. In contrast to phenols cyclic 1,3-diketones in the reaction with perfluoronaphthoquinone act as C-nucleophiles resulting in fluorinated polycondensed furans. Structures of key obtained products were proved using X-ray analysis.
首次研究了六氟-1,4-萘醌与多种酚类化合物的反应。结果表明,醋酸钠是一种简便的试剂。所研究的缩合只导致醌核中两个氟原子的取代。在已有研究的基础上,阐述了取代2,3-二芳氧基-5,6,7,8-四氟萘-1,4-二酮的制备方法。用类似的条件从2-氨基酚中得到五氟苯并[a]苯恶嗪衍生物。与酚类相反,环1,3-二酮在与全氟萘醌的反应中作为c -亲核试剂产生氟化多凝聚呋喃。用x射线分析证实了关键产品的结构。
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引用次数: 0
Regio- and stereochemical behavior of cyclooctane and cyclodecane derivatives containing CF2 moieties 含CF2基团的环辛烷和环癸烷衍生物的区域和立体化学行为
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-01 DOI: 10.1016/j.jfluchem.2025.110397
Matheus P. Freitas
Cyclooctane and cyclodecane are important medium-size rings in organic chemistry, and fluorination can significantly modulate the properties of organic molecules, such as polarity, viscosity, and acidity. In this quantum-chemical study, two CF2 groups replaced the methylene moieties of the most stable conformations of cyclooctane (boat-chair) and cyclodecane (boat-chair-boat) to evaluate the effect of head, corner, and edge substitution on the energetics of the possible structures, including both constitutional and stereochemical-type isomers. It was found that CF2 groups prefer to occupy head (at C5) and corner positions of the cyclooctane ring rather than head (at C1) and edge positions, as these latter positions orient the fluorines endo, causing transannular repulsion. However, the 2,7 isomer, which possesses an edge CF2 group, is remarkably stable due to an unprecedented transannular hydrogen bond between hydrogen at C3 and the CF2 at C7. Similar findings were obtained for the cyclodecane derivatives, indicating that fluorination is preferable in certain positions due to steric and strain relief, while the transannular hydrogen bond also plays a secondary role as a source of stabilization. Given the CF2 groups' ability to order the conformation of these medium-size rings, fluorination may be utilized in systems where this property is required, such as in liquid crystals.
环辛烷和环癸烷是有机化学中重要的中型环,氟化可以显著调节有机分子的极性、粘度和酸度等性质。在这项量子化学研究中,两个CF2基团取代了环辛烷(船椅)和环癸烷(船椅-船)最稳定构象的亚甲基部分,以评估头、角和边取代对可能结构的能量学的影响,包括构式和立体化学型异构体。研究发现,CF2基团更倾向于占据环辛烷环的头部(C5)和角位置,而不是头部(C1)和边缘位置,因为后者的位置使氟的端部定向,引起跨环排斥。然而,2,7同分异构体具有CF2基团,由于C3上的氢和C7上的CF2之间存在前所未有的跨环氢键,因此非常稳定。对于环癸烷衍生物也得到了类似的发现,表明由于空间和应变的缓解,氟化在某些位置更可取,而跨环氢键作为稳定来源也起着次要作用。考虑到CF2基团对这些中等大小环的构象进行排序的能力,氟化可以用于需要这种性质的系统,例如液晶。
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引用次数: 0
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 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 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 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
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 DOI: 10.1016/j.jfluchem.2024.110385
Joseph S. Thrasher
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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 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
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 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
期刊
Journal of Fluorine Chemistry
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