Journal of Fluorine Chemistry最新文献

{"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":"2025-02-24","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":"Clean photochemical conversion of perfluoroalkylated phenanthrene-9,10-o-quinones to perfluoroalkylated diphenic anhydrides","authors":"Shankar Gairhe,&nbsp;Mason Ferrie,&nbsp;Haoran Sun","doi":"10.1016/j.jfluchem.2025.110406","DOIUrl":"10.1016/j.jfluchem.2025.110406","url":null,"abstract":"<div><div>Under light irradiation, carbonyl compounds interact with molecular oxygen, a common excited state quencher, resulting in the formation of either triplet state-oxygen adducts or singlet oxygen via energy transfer. With phenanthrene-9,10-o-quinones, molecular oxygen usually adds on molecular structures forming triplet state-oxygen adducts which then convert to different final products, often complex mixtures. Here, we report that perfluoroalkylated phenanthrene-9,10-o-quinones exclusively undergo light mediated transformation into diphenic anhydride derivatives.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"283 ","pages":"Article 110406"},"PeriodicalIF":1.7,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521298","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":"Fluorine-containing isosteres enable a structure-activity relationship study of gingerol derivatives","authors":"Shelby E. Cooper,&nbsp;Diarta Kabashi,&nbsp;Marlin E. Yacoub,&nbsp;Jessica A. Molen,&nbsp;Osman Farhan,&nbsp;Christina Farley,&nbsp;Samantha Yencha,&nbsp;Michelle M. Figueiredo,&nbsp;Nidheesh Phadnis,&nbsp;Wynter Henry,&nbsp;Julian A. Harris,&nbsp;Frank Wilkinson,&nbsp;John A. Milligan","doi":"10.1016/j.jfluchem.2025.110400","DOIUrl":"10.1016/j.jfluchem.2025.110400","url":null,"abstract":"<div><div>A series of fluorinated and non-fluorinated [6]-gingerol, [6]-paradol, [6]-shogaol and ferulate derivatives were synthesized. Testing these analogs in anti-proliferation assays with MCF-7, A549, HCT-116 and HEK-293 cell lines provided insight into the structural features that contribute to the anti-proliferative activity of naturally occurring ginger constituents. In particular, the use of both vinyl and alkyl trifluoromethyl isosteres allowed us to evaluate the structure-activity impact of the enone motif found in shogaols. Our results indicate that enone-containing derivatives have a higher potency, suggesting the conjugated enone motif characteristic of shogaols may be primarily responsible for the anti-cancer activity of the broader natural product family.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110400"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"2-Trifluoromethoxyacetic acid – Synthesis and characterization","authors":"Thorsten Meier ,&nbsp;Sabine Lorenzen ,&nbsp;Tanja Knuplez ,&nbsp;Tobias Preitschopf ,&nbsp;Karsten Koppe ,&nbsp;Peter Barthen ,&nbsp;Rüdiger Bertermann ,&nbsp;Michael Schulte ,&nbsp;Nikolai Ignat‘ev ,&nbsp;Maik Finze","doi":"10.1016/j.jfluchem.2025.110396","DOIUrl":"10.1016/j.jfluchem.2025.110396","url":null,"abstract":"<div><div>A straightforward and high-yield synthesis of 2-trifluoromethoxyacetic acid CF₃OCH₂C(O)OH starting from trifluoromethyl triflate CF₃SO₂OCF₃ is described. The trifluoromethoxide anion was generated from trifluoromethyl triflate and a fluoride source followed by a nucleophilic substitution reaction with the {OCF₃}^– ion to yield CF₃OCH₂C(O)OC₂H₅. The ester was converted into M{CF₃OCH₂CO₂} (M = Na, K) and the acid CF₃OCH₂C(O)OH was obtained from the sodium salt and HCl. In addition, the silver(I) salt of the {CF₃OCH₂CO₂}^– anion was synthesized from CF₃OCH₂C(O)OH and silver(I) oxide. The study includes a new synthesis for the starting compound CF₃SO₂OCF₃ and a detailed description for the preparation of [N(CH₃)₄]{OCF₃}. Furthermore, the crystal structures of CF₃OCH₂C(O)OH, CF₃OCH₂C(O)OC₂H₅, M{CF₃OCH₂CO₂} (M = K, Ag), and [N(CH₃)₄]{OCF₃} are reported.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110396"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143152572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel synthetic method of 1,1,2,2-tetrafluoro-2-[(1,2,2-trifluoroethenyl)oxy]ethanesulfonyl fluoride","authors":"Nobuyuki Uematsu ,&nbsp;Yasuhiro Nagato ,&nbsp;Ken-ichi Yakigaya ,&nbsp;Kaishi Hori ,&nbsp;Hideki Date ,&nbsp;Akitake Nakamura ,&nbsp;Kazuki Maeda","doi":"10.1016/j.jfluchem.2025.110399","DOIUrl":"10.1016/j.jfluchem.2025.110399","url":null,"abstract":"<div><div>A novel synthetic method of 1,1,2,2-tetrafluoro-2-[(1,2,2-trifluoroethenyl)oxy]ethanesulfonyl fluoride, the raw material for perfluorinated polymer electrolyte membranes, was developed from the starting material CF₃CF(COF)O(CF₂)₂SO₂F via the ring-opening reaction of cyclic compound and the cleavage reaction of vinyl sulfonic anhydride using commercially available reagents.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110399"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143152573","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 poly [2,3,5,6-tetrafluoro-4-(trifluoromethyl) phenylaminophosphazene]/LiNbO3 nanocomposites and characterization of their morphological, mechanical, and piezoelectric behavior for energy harvesting applications","authors":"Nand Kumar ,&nbsp;Nagmani Manikpuri ,&nbsp;Atanu Giri ,&nbsp;Om Prakash Gautam","doi":"10.1016/j.jfluchem.2025.110404","DOIUrl":"10.1016/j.jfluchem.2025.110404","url":null,"abstract":"<div><div>The use of polymer nanocomposites for piezoelectric energy harvesting applications has created exciting opportunities in flexible electronics. In this research, we synthesized poly [2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenylaminophosphazene (PTPP)]/LiNbO₃ nanocomposites by incorporating trigonal crystalline lithium niobate nanoparticles (average particle size ∼ 45 nm) into PTPP via solution casting method. Further, we investigated the effects of different concentrations of lithium niobate (LiNbO₃) nanoparticles on the thermal, mechanical, and piezoelectric performance of the PTPP nanocomposites. The synthesized nanocomposites exhibited strong interfacial interactions between the organic and inorganic phases, resulting in a uniform morphology across all compositions, except for the 8 % loading, which showed some agglomeration. Additionally, both PTPP and its nanocomposites demonstrated high thermal stability, with the highest char yield of 64.1 % observed at 8 % LiNbO₃ loading. Mechanical testing revealed a significant improvement in tensile strength (224 %) and a reduction in elongation at break (34.4 %) with 8 % LiNbO₃ loading. These enhancements in thermal and mechanical properties were attributed to the presence of strong C-F bonds and LiNbO₃ content in the nanocomposites. Besides this, dynamic mechanical analysis indicated that 8 % LiNbO₃-loaded PTPP nanocomposite also exhibited the lowest tan δ value of 0.68 and the highest energy storage capacity with minimal loss over a high-temperature range due to the restricted mobility of polymer chain with the addition of nanoparticles. PTPP also exhibited a piezoelectric effect with a coefficient of 26.4 pC/N, which was further enhanced by the incorporation of LiNbO₃, reaching a maximum increase of 6.4 %. These novel nanocomposites show great potential for energy-harvesting applications in electronic devices.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110404"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421260","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":"Exploration towards the bromopentafluorosulfanylation reaction of terminal alkynes","authors":"Marie-Rose Ouellet-Du Berger ,&nbsp;Jean-Philippe Bouillon ,&nbsp;Jean-François Paquin","doi":"10.1016/j.jfluchem.2024.110386","DOIUrl":"10.1016/j.jfluchem.2024.110386","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110386"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143152574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New insights into the use of carbon and boron nitride nanotubes as sensors for ClF3: A density functional theory analysis","authors":"Fatemeh Biniaz,&nbsp;Mohammad Reza Zardoost,&nbsp;Mohammad Reza Toosi","doi":"10.1016/j.jfluchem.2025.110401","DOIUrl":"10.1016/j.jfluchem.2025.110401","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110401"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143354279","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":"Regio- and stereochemical behavior of cyclooctane and cyclodecane derivatives containing CF2 moieties","authors":"Matheus P. Freitas","doi":"10.1016/j.jfluchem.2025.110397","DOIUrl":"10.1016/j.jfluchem.2025.110397","url":null,"abstract":"<div><div>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 <em>endo</em>, causing transannular repulsion. However, the <strong>2,7</strong> 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.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110397"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143152575","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, purification and characterisation of novel PFAS following nontarget analysis","authors":"Ana R.L. Araujo ,&nbsp;Anton Pavlov ,&nbsp;Jon Eigil Johansen ,&nbsp;Sicco Brandsma ,&nbsp;Huiling Liu","doi":"10.1016/j.jfluchem.2025.110398","DOIUrl":"10.1016/j.jfluchem.2025.110398","url":null,"abstract":"<div><div>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.</div><div>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<em>/z</em>, LC-MS, or GC–MS).</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110398"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143152576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}