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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 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。
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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 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。
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引用次数: 0
Highly diversified fluorinated chromane-thiadiazol-saturated cyclic amine hybrids: Design, synthesis, single crystal XRD and MCF-7 Cell-line Study 高度多样化的氟化铬-噻二唑饱和环胺杂化物:设计、合成、单晶XRD和MCF-7细胞系研究
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-06-12 DOI: 10.1016/j.jfluchem.2025.110448
Bhavika Mohite , Bhadreshkumar K. Chabhadiya , Nishith Teraiya , Khushal Kapadiya , Ramavatar Meena , Aniruddhasinh Rana , Smita Jauhari
The current study focuses on the synthesis and characterization of novel fluorinated chromane derivatives, aiming to explore their structural and biological potential. The molecular framework integrates fluorine for enhanced physicochemical properties, employing nucleophilic substitution and cyclization strategies. The synthesized derivatives (4a–4j) were characterized using advanced spectroscopic methods (1H NMR, 19F NMR, 13C NMR, and mass spectrometry) and crystallographic analysis, confirming their structural core. Biological evaluations against MCF-7 breast cancer cells revealed significant cytotoxicity, with compounds 4 g and 4f demonstrating superior activity (IC50: 2.73 µM and 3.81 µM, respectively) compared to the standard sunitinib (IC50: 5.00 µM). SAR analysis highlights the role of specific cycloaliphatic and polar substituents in enhancing activity. Additionally, docking studies targeting VEGFR2 elucidated key binding interactions, corroborating the compounds' potential as anticancer agents. This work showed the incorporation of fluorine and the rational design of fluorinated scaffolds for drug development.
本课题主要研究新型氟化铬衍生物的合成和表征,探索其结构和生物学潜力。分子框架集成氟增强物理化学性质,采用亲核取代和环化策略。合成的衍生物(4a-4j)采用先进的光谱方法(1H NMR, 19F NMR, 13C NMR和质谱)和晶体学分析进行了表征,确定了它们的结构核心。对MCF-7乳腺癌细胞的生物学评价显示出显著的细胞毒性,化合物4 g和4f与标准舒尼替尼(IC50: 5.00µM)相比,显示出更强的活性(IC50分别为2.73µM和3.81µM)。SAR分析强调了特定环脂肪族取代基和极性取代基在增强活性中的作用。此外,针对VEGFR2的对接研究阐明了关键的结合相互作用,证实了这些化合物作为抗癌药物的潜力。这项工作表明氟的结合和氟化支架的合理设计用于药物开发。
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引用次数: 0
Synthesis and properties of energetic N-fluorodinitromethyl heterocyclic salts 含能n -氟二硝基甲基杂环盐的合成与性能研究
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-05-27 DOI: 10.1016/j.jfluchem.2025.110436
Andrei A. Gakh , Victor V. Semenov
The synthesis of a new class of energetic salts, N-fluorodinitromethyl heterocyclic salts, was accomplished by electrophilic fluorination of corresponding heterocyclic N-dinitromethyl ylides with diluted fluorine. These salts represent rare examples of compounds containing a fluorodinitromethyl moiety directly attached to a positively charged nitrogen atom. Further improvements can be achieved in combination with explosophoric anions, such as the cyanodinitromethanide anion. Despite their unusual structural features, N-fluorodinitromethyl heterocyclic salts have good thermal and chemical stability under ambient conditions.
用稀释氟将相应的n -二硝基甲基杂环化合物亲电氟化,合成了一类新的能盐n -氟二硝基甲基杂环盐。这些盐是含有氟二硝基甲基部分直接与带正电的氮原子相连的化合物的罕见例子。进一步的改进可以与爆炸阴离子结合,如氰二硝基甲烷阴离子。尽管n -氟二硝基甲基杂环盐具有不同寻常的结构特征,但在环境条件下具有良好的热稳定性和化学稳定性。
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引用次数: 0
Synthesis of 1,1,2,2,3,3,4,4-octafluoro-4-[(1,2,2-trifluoroethenyl)oxy]butanesulfonyl fluoride 1,1,2,2,3,3,4,4-辛氟-4-[(1,2,2-三氟乙烯基)氧]丁烷磺酰氟的合成
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-05-24 DOI: 10.1016/j.jfluchem.2025.110432
Nobuyuki Uematsu , Hideo Saito , Masa-aki Sasayama , Sayuri Aoki , Mikihiko Nakamura , Nobuto Hoshi , Masanori Ikeda
We investigated two synthetic routes (Route A: first synthesis of the CF2CFO group and then the SO2F group, Route B: first synthesis of the SO2F group and then the CF2CFO group) to synthesize CF2CFO(CF2)4SO2F (SSC monomer), the raw material for the short-side-chain perfluorinated polymer electrolyte membrane, from I(CF2)4I using the same commercially available reagents but in different order of use. In Route A, by-products [CF2CFO(CF2)4I and the compound presumed to have the structure of CF2SO2F] were formed in the second half of the synthesis of SSC monomer, but they were difficult to remove from SSC monomer. On the other hand, in Route B, by-product I(CF2)4I formed in the first half of the synthesis of SSC monomer was easily removed by the conversion with oleum. In addition, the reaction of I(CF2)4I with Na2S2O4 produced I(CF2)4SO2Na and NaO2S(CF2)4SO2Na, which were separated by the extraction operation with ethyl acetate, and NaO2S(CF2)4SO2Na was converted to I(CF2)4I by chlorine gas in the presence of NaI. We chose Route B and obtained high-purity SSC monomer.
采用相同的市售试剂,但使用顺序不同的方法,从I(CF2)4I合成短侧链全氟聚合物电解质膜原料CF2CFO(CF2)4SO2F (SSC单体),研究了两种合成路线(A:先合成CF2CFO基团,再合成SO2F基团,B:先合成SO2F基团,再合成CF2CFO基团,B:先合成SO2F基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团,B:先合成cf2f基团。在路线A中,在SSC单体合成的后半程生成了副产物[CF2CFO(CF2)4I]和推测具有CF2SO2F结构的化合物,但它们很难从SSC单体中去除。另一方面,在B路线中,合成SSC单体前半部分形成的副产物I(CF2)4I很容易通过与发油的转化去除。此外,I(CF2)4I与Na2S2O4反应生成I(CF2)4SO2Na和NaO2S(CF2)4SO2Na,通过乙酸乙酯萃取操作分离,NaO2S(CF2)4SO2Na在NaI存在下经氯气转化为I(CF2)4I。我们选择路线B,得到了高纯度的SSC单体。
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引用次数: 0
Efficient synthesis, structure and anti-influenza virus activity of fluorinated pyrido[4,3-b][1,4]thiazine 1,1-dioxide derivatives 氟化吡啶[4,3-b][1,4]噻嗪1,1-二衍生物的高效合成、结构及抗流感病毒活性
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-01 DOI: 10.1016/j.jfluchem.2025.110430
Larisa Politanskaya , Bulat Khasanov , Irina Bagryanskaya , Maria Niukalova , Sergey Aksakov , Irina Balashova , Vladimir Zarubaev
A series of fluorinated bicyclic fused compounds, containing fragments of pyridine and 3,4-dihydro-2H-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.
在多氟前驱体中,通过n -亲核试剂卤素原子的一锅取代,合成了一系列含吡啶和3,4-二氢- 2h -1,4-噻嗪1,1-二氧化基片段的氟化双环融合化合物。杂环部分的形成分为两个阶段,从侧链上的Br取代开始,然后是分子内的氨基脱氟。用x射线衍射分析证实了部分杂环的结构。此外,在MDCK细胞培养中测定了它们对甲型流感/波多黎各/8/34 (H1N1)病毒的抑制活性,并发现了化合物先导物。
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引用次数: 0
Synthesis and characterization of 5-(trifluoromethyl)tetrazol-based energetic salts 5-(三氟甲基)四唑基含能盐的合成与表征
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-01 DOI: 10.1016/j.jfluchem.2025.110427
Jiawen Deng , Lukang Lin , Yahan Zhang , Xu Yao , Jun Zhang , Jin-Hong Lin , Wenbin Yi , Xing Zheng , Ji-Chang Xiao
Two types of 5-trifluoromethyl tetrazole-based energetic salts were successfully synthesized from trifluoroacetamide and sodium azide. The synthetic approach is characterized by its simplicity and safety. The X-ray diffraction analysis reveals the presence of both intermolecular and intramolecular hydrogen bonding within the crystal lattice of energetic salts. The synthesized compound 4 demonstrated notable physical properties, including high densities (1.64 g cm-3), great thermal stability (with decomposition temperatures of 167 °C), and excellent insensitivity (impact sensitivity exceeding 40 J). These attributes suggest that the compound 4 possess promising energetic performance and is potential candidates for use as insensitive high-energy materials.
以三氟乙酰胺和叠氮化钠为原料,成功合成了两种5-三氟甲基四唑类含能盐。该方法具有简单、安全的特点。x射线衍射分析揭示了能盐晶格中存在分子间和分子内氢键。合成的化合物4具有显著的物理性能,包括高密度(1.64 g cm-3)、热稳定性(分解温度为167℃)和优异的不敏感性(冲击灵敏度超过40 J)。这些特性表明该化合物4具有良好的能量性能,是用作不敏感高能材料的潜在候选者。
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引用次数: 0
Fluorination of sulfonyl hydrazides with fluorine gas for the synthesis of sulfonyl fluorides 磺酰肼用氟气氟化合成磺酰氟
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-01 DOI: 10.1016/j.jfluchem.2025.110425
Zhou Yu , Sheng Wang , Wenbo Chen , Lele Wen , Long Lu
An efficient method for synthesizing sulfonyl fluorides by fluorinating sulfonyl hydrazides with 10 % F2/N2 was developed. This transformation demonstrated a broad substrate scope, yielding a series of sulfonyl fluorides in moderate to good yields. Additionally, a 10 g scale experiment was conducted, demonstrating the practicality of this method.
研究了以10% F2/N2氟化磺酰肼合成磺酰氟的有效方法。这一转变显示出广泛的底物范围,以中等到良好的产量生产一系列磺酰氟。并进行了10 g尺度的实验,验证了该方法的实用性。
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引用次数: 0
One electron into the multilayer cyclic hexamer of hydrogen fluoride 一个电子进入多层环六聚体氟化氢
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-01 DOI: 10.1016/j.jfluchem.2025.110429
Hai-Han Liu, Zhong-Min Su, Hong-Liang Xu
Due to its toxicity and hazard, the experimental observation of the structure and characteristics of hydrogen fluoride (HF) clusters poses significant challenges. In this work, by integrating theoretical analysis with prior experimental findings, we determined that the stable chair-like hexamer structure (HF)6 can be transformed into a planar cyclic anion (HF)6@e upon the addition of a single electron. Excitingly, there is a larger interaction (Eint = -9.92 kcal/mol) between the two (HF)6 layers in [(HF)6]2@e: an innovative one electron sigma bond (σ1e) emerges. Further, the geometry of σ1e can be adjusted by varying the strength of the additional electric field. This study offers new insights into the HF clusters and demands further explorations in this field.
由于氟化氢(HF)团簇的毒性和危害性,对其结构和特性的实验观察具有很大的挑战性。在这项工作中,通过将理论分析与先前的实验结果相结合,我们确定了稳定的椅子状六聚体结构(HF)6在添加单个电子后可以转化为平面环状阴离子(HF)6@e。令人兴奋的是,在[(HF)6]2@e中,两个(HF)6层之间存在更大的相互作用(Eint = -9.92 kcal/mol):出现了一个创新的单电子sigma键(σ1e)。此外,可以通过改变外加电场的强度来调整σ1e的几何形状。该研究为HF簇的研究提供了新的见解,需要在该领域进行进一步的探索。
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引用次数: 0
Difluoroamination of diaryl gem-dichlorides with difluorosulfamate tetramethylammonium salts 二芳基宝石二氯化物与二氟磺胺四甲基铵盐的二氟胺化
IF 1.7 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-01 DOI: 10.1016/j.jfluchem.2025.110428
Sheng Wang , Zhou Yu , Wenbo Chen , Yaming Wu , Chun-Hui Xing , Long Lu
An efficient and mild approach was developed for the difluoroamination of diaryl gem‑dichlorides. This transformation was achieved using the ferric chloride as a Lewis acid and difluorosulfamate tetramethylammonium salt as the difluoroamination reagent. The method exhibited moderate functional group tolerance, highlighting its versatility for introducing difluoroamino groups. And the retention of the CCl bond in the product offers the potential possibilities for subsequent modifications.
开发了一种高效、温和的二氯二芳基宝石二氟胺化方法。这种转化是用三氯化铁作为刘易斯酸和二氟磺胺四甲基铵盐作为二氟胺化试剂实现的。该方法表现出适度的官能团耐受性,突出了其引入二氟氨基的通用性。CCl键在产品中的保留为后续改性提供了潜在的可能性。
{"title":"Difluoroamination of diaryl gem-dichlorides with difluorosulfamate tetramethylammonium salts","authors":"Sheng Wang ,&nbsp;Zhou Yu ,&nbsp;Wenbo Chen ,&nbsp;Yaming Wu ,&nbsp;Chun-Hui Xing ,&nbsp;Long Lu","doi":"10.1016/j.jfluchem.2025.110428","DOIUrl":"10.1016/j.jfluchem.2025.110428","url":null,"abstract":"<div><div>An efficient and mild approach was developed for the difluoroamination of diaryl gem‑dichlorides. This transformation was achieved using the ferric chloride as a Lewis acid and difluorosulfamate tetramethylammonium salt as the difluoroamination reagent. The method exhibited moderate functional group tolerance, highlighting its versatility for introducing difluoroamino groups. And the retention of the C<img>Cl bond in the product offers the potential possibilities for subsequent modifications.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110428"},"PeriodicalIF":1.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143912819","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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