Pub Date : 2025-10-01Epub Date: 2025-09-18DOI: 10.1016/j.jfluchem.2025.110479
Olga A. Zhupikova, Vyacheslav I. Krasnov, Olga I. Yarovaya, Andrey A. Nefedov, Vadim V. Bardin, Yuri V. Gatilov, Artem D. Rogachev, Nariman F. Salakhutdinov, Mikhail V. Khvostov
In this work, the Selectfluor-mediated transformation of cedrol and cedrene under the Ritter reaction conditions is presented for the first time. The possibility of the formation of acetamides, including fluorine-containing compounds, is shown. In the absence of Selectfluor, no amides are formed from cedrol under the conditions of the classical Ritter reaction and the only reaction product is cedrene.
{"title":"Selectfluor-mediated transformation of cedrol and cedrene under the Ritter reaction conditions","authors":"Olga A. Zhupikova, Vyacheslav I. Krasnov, Olga I. Yarovaya, Andrey A. Nefedov, Vadim V. Bardin, Yuri V. Gatilov, Artem D. Rogachev, Nariman F. Salakhutdinov, Mikhail V. Khvostov","doi":"10.1016/j.jfluchem.2025.110479","DOIUrl":"10.1016/j.jfluchem.2025.110479","url":null,"abstract":"<div><div>In this work, the Selectfluor-mediated transformation of cedrol and cedrene under the Ritter reaction conditions is presented for the first time. The possibility of the formation of acetamides, including fluorine-containing compounds, is shown. In the absence of Selectfluor, no amides are formed from cedrol under the conditions of the classical Ritter reaction and the only reaction product is cedrene.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110479"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105714","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}
Pub Date : 2025-10-01Epub Date: 2025-09-22DOI: 10.1016/j.jfluchem.2025.110480
Mohammad Rizehbandi, Behzad Khalili, Khatereh Ghauri
This study used density functional theory (DFT) calculations to investigate the properties of four novel dianionic ionic liquids (DAILs) named as [PMIM]2[TFTP], [PMTA1]2[TFTP], [PMTA2]2[TFTP] and [PMTTA]2[TFTP]. These DAILs consist of a tetrafluoro terephthalate ([TFTP]2-) dianion and various functionalized imidazolium, triazolium and tetrazolium-based cations allowing for an analysis of how cation structure (specifically nitrogen atom number and position) and fluorination affect the DAILs' stability, electronic properties, and electrochemical behavior. The research evaluated energetic, electronic, and thermodynamic parameters, as well as electrostatic potential maps and topological properties, to understand the relationship between DAIL structure and its characteristics. The fluorinated dianion showed a planar preference for interaction with the cation's five-membered rings. Importantly, hydrogen bonding, in conjunction with electrostatic interactions, significantly contributes to the stability of these DAILs and will likely influence their physicochemical properties and suitability for specific applications. The interaction energies for the most stable configurations of the examined DAILs vary between -235.82 and -269.36 kcal mol-1 at M06–2X-GD3/AUG-cc-pVDZ theory level and following a decreasing trend in the order of: [PMIM]2[TFTP] < [PMTA1]2[TFTP] < [PMTA2]2[TFTP] < [PMTTA]2[TFTP]. Additionally, the HOMO–LUMO energy gaps, spanning from 6.49 to 7.38 eV, highlighted notable stability trends in the series. Charge transfer values obtained through NBO analysis were observed between 0.2318 and 0.7307 a.u., reaffirming the contributions of hydrogen bonding.
{"title":"A density functional theory approach for design of fluorine-containing dianionic ionic liquids and investigation of some of their physical and chemical properties","authors":"Mohammad Rizehbandi, Behzad Khalili, Khatereh Ghauri","doi":"10.1016/j.jfluchem.2025.110480","DOIUrl":"10.1016/j.jfluchem.2025.110480","url":null,"abstract":"<div><div>This study used density functional theory (DFT) calculations to investigate the properties of four novel dianionic ionic liquids (DAILs) named as [PMIM]<sub>2</sub>[TFTP], [PMTA1]<sub>2</sub>[TFTP], [PMTA2]<sub>2</sub>[TFTP] and [PMTTA]<sub>2</sub>[TFTP]. These DAILs consist of a tetrafluoro terephthalate ([TFTP]<sup>2-</sup>) dianion and various functionalized imidazolium, triazolium and tetrazolium-based cations allowing for an analysis of how cation structure (specifically nitrogen atom number and position) and fluorination affect the DAILs' stability, electronic properties, and electrochemical behavior. The research evaluated energetic, electronic, and thermodynamic parameters, as well as electrostatic potential maps and topological properties, to understand the relationship between DAIL structure and its characteristics. The fluorinated dianion showed a planar preference for interaction with the cation's five-membered rings. Importantly, hydrogen bonding, in conjunction with electrostatic interactions, significantly contributes to the stability of these DAILs and will likely influence their physicochemical properties and suitability for specific applications. The interaction energies for the most stable configurations of the examined DAILs vary between -235.82 and -269.36 kcal mol<sup>-1</sup> at M06–2X-GD3/AUG-cc-pVDZ theory level and following a decreasing trend in the order of: [PMIM]<sub>2</sub>[TFTP] < [PMTA1]<sub>2</sub>[TFTP] < [PMTA2]<sub>2</sub>[TFTP] < [PMTTA]<sub>2</sub>[TFTP]. Additionally, the HOMO–LUMO energy gaps, spanning from 6.49 to 7.38 eV, highlighted notable stability trends in the series. Charge transfer values obtained through NBO analysis were observed between 0.2318 and 0.7307 a.u., reaffirming the contributions of hydrogen bonding.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110480"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216482","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}
Pub Date : 2025-10-01Epub Date: 2025-09-10DOI: 10.1016/j.jfluchem.2025.110478
J.H. Kim, C.H. Cho, I.J. Kang, J.K. Yang, H. Choi
Nitrogen trifluoride (NF3), with a global warming potential (GWP) of 16,100, is increasingly being used in the manufacturing of flat-panel displays, photovoltaics, light-emitting diodes (LEDs), and other microelectronics and semiconductors, and efficient processes for its removal using less energy to increase productivity are being developed. In this study, an optimal process was developed by comparing the processes of injecting oxygen and steam as the oxidising agents to increase the decomposition rate of NF3 using a microwave plasma torch. Using a microwave plasma torch, 1000 J/L of energy was saved compared to the previous method of applying the gas treatment flow rate of a commercially available scrubber (nitrogen: 250 L/min, NF3:5000 ppm). In the optimal process, steam (6 and 10 g/min) was used as the oxidising agent, 1000 J/L of energy was consumed, and at least 5 kW of plasma power was used. Under these conditions, destruction and removal efficiencies (DREs) of > 99 % were achieved. For theoretical verification, chemical reaction rates of NF3 with oxygen and steam were calculated and compared with the experimental results. The comparison showed that the chemical reaction rate of steam was higher than that of oxygen, and the experiment confirmed that when steam was used as an oxidising agent, NF3 could be decomposed using less energy than that of oxygen.
{"title":"Experimental and theoretical studies for optimization of NF3 removal from semiconductor processes using microwave plasma torch","authors":"J.H. Kim, C.H. Cho, I.J. Kang, J.K. Yang, H. Choi","doi":"10.1016/j.jfluchem.2025.110478","DOIUrl":"10.1016/j.jfluchem.2025.110478","url":null,"abstract":"<div><div>Nitrogen trifluoride (NF<sub>3</sub>), with a global warming potential (GWP) of 16,100, is increasingly being used in the manufacturing of flat-panel displays, photovoltaics, light-emitting diodes (LEDs), and other microelectronics and semiconductors, and efficient processes for its removal using less energy to increase productivity are being developed. In this study, an optimal process was developed by comparing the processes of injecting oxygen and steam as the oxidising agents to increase the decomposition rate of NF<sub>3</sub> using a microwave plasma torch. Using a microwave plasma torch, 1000 J/L of energy was saved compared to the previous method of applying the gas treatment flow rate of a commercially available scrubber (nitrogen: 250 L/min, NF<sub>3</sub>:5000 ppm). In the optimal process, steam (6 and 10 g/min) was used as the oxidising agent, 1000 J/L of energy was consumed, and at least 5 kW of plasma power was used. Under these conditions, destruction and removal efficiencies (DREs) of > 99 % were achieved. For theoretical verification, chemical reaction rates of NF<sub>3</sub> with oxygen and steam were calculated and compared with the experimental results. The comparison showed that the chemical reaction rate of steam was higher than that of oxygen, and the experiment confirmed that when steam was used as an oxidising agent, NF<sub>3</sub> could be decomposed using less energy than that of oxygen.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110478"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057336","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}
Pub Date : 2025-10-01Epub Date: 2025-10-13DOI: 10.1016/j.jfluchem.2025.110487
Craig Sommer, Dakota L. Leenstra, Ryan Fjordbotten, Douglas Turnbull, Stacey D. Wetmore, Michael Gerken
Lewis acid-base adducts of MOF4 (M = Mo or W) with 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) were synthesized from their parent CH3CN adducts and the bases as insoluble off-white or yellow (MoOF4(bipy)) powders. Additionally, the adduct between WOF4 and 4,4′-di‑tert‑butyl‑2,2′-bipyridine (dtbipy) was synthesized in the same manner. The adducts were characterized by Raman and infrared spectroscopy and the vibrational assignment was aided by DFT calculations. DFT geometry optimizations of the adducts predict pentagonal bipyramidal structures with the bidentate bases coordinating in the equatorial plane. NBO analyses of the adducts were done to better understand the bonding as well as the stability of the heptacoordinated adducts.
{"title":"Syntheses, characterization, and computational study of heptacoordinate adducts of WOF4 and MoOF4","authors":"Craig Sommer, Dakota L. Leenstra, Ryan Fjordbotten, Douglas Turnbull, Stacey D. Wetmore, Michael Gerken","doi":"10.1016/j.jfluchem.2025.110487","DOIUrl":"10.1016/j.jfluchem.2025.110487","url":null,"abstract":"<div><div>Lewis acid-base adducts of MOF<sub>4</sub> (M = Mo or W) with 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) were synthesized from their parent CH<sub>3</sub>CN adducts and the bases as insoluble off-white or yellow (MoOF<sub>4</sub>(bipy)) powders. Additionally, the adduct between WOF<sub>4</sub> and 4,4′-di‑tert‑butyl‑2,2′-bipyridine (dtbipy) was synthesized in the same manner. The adducts were characterized by Raman and infrared spectroscopy and the vibrational assignment was aided by DFT calculations. DFT geometry optimizations of the adducts predict pentagonal bipyramidal structures with the bidentate bases coordinating in the equatorial plane. NBO analyses of the adducts were done to better understand the bonding as well as the stability of the heptacoordinated adducts.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110487"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145332617","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}
Pub Date : 2025-07-01Epub Date: 2025-05-27DOI: 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.
{"title":"Synthesis and properties of energetic N-fluorodinitromethyl heterocyclic salts","authors":"Andrei A. Gakh , Victor V. Semenov","doi":"10.1016/j.jfluchem.2025.110436","DOIUrl":"10.1016/j.jfluchem.2025.110436","url":null,"abstract":"<div><div>The synthesis of a new class of energetic salts, <em>N</em>-fluorodinitromethyl heterocyclic salts, was accomplished by electrophilic fluorination of corresponding heterocyclic <em>N-</em>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, <em>N</em>-fluorodinitromethyl heterocyclic salts have good thermal and chemical stability under ambient conditions.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"285 ","pages":"Article 110436"},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144212474","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}
Pub Date : 2025-07-01Epub Date: 2025-06-19DOI: 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.
{"title":"Purification of uranium tetrafluoride using ammonium bifluoride","authors":"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","doi":"10.1016/j.jfluchem.2025.110449","DOIUrl":"10.1016/j.jfluchem.2025.110449","url":null,"abstract":"<div><div>A method of purification for UF<sub>4</sub> utilizing NH<sub>4</sub>HF<sub>2</sub> 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 UF<sub>4</sub>-UO<sub>2</sub> system, showing clear signs of oxygen contamination. To purify the salt, an air-tight reaction vessel inside an argon glovebox was used to react UF<sub>4</sub>/NH<sub>4</sub>HF<sub>2</sub> mixtures at elevated temperatures under a continuous flow of inert gas. The process yielded a significantly purer UF<sub>4</sub> salt as confirmed via inert gas fusion, X-ray diffraction, differential scanning calorimetry and inductively coupled plasma-optical emission spectrometry.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"285 ","pages":"Article 110449"},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144502612","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}
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.
{"title":"Synthesis of 1,1,2,2,3,3,4,4-octafluoro-4-[(1,2,2-trifluoroethenyl)oxy]butanesulfonyl fluoride","authors":"Nobuyuki Uematsu , Hideo Saito , Masa-aki Sasayama , Sayuri Aoki , Mikihiko Nakamura , Nobuto Hoshi , Masanori Ikeda","doi":"10.1016/j.jfluchem.2025.110432","DOIUrl":"10.1016/j.jfluchem.2025.110432","url":null,"abstract":"<div><div>We investigated two synthetic routes (Route A: first synthesis of the CF<sub>2</sub><img>CFO group and then the SO<sub>2</sub>F group, Route B: first synthesis of the SO<sub>2</sub>F group and then the CF<sub>2</sub><img>CFO group) to synthesize CF<sub>2</sub><img>CFO(CF<sub>2</sub>)<sub>4</sub>SO<sub>2</sub>F (SSC monomer), the raw material for the short-side-chain perfluorinated polymer electrolyte membrane, from I(CF<sub>2</sub>)<sub>4</sub>I using the same commercially available reagents but in different order of use. In Route A, by-products [CF<sub>2</sub><img>CFO(CF<sub>2</sub>)<sub>4</sub>I and the compound presumed to have the structure of CF<sub>2</sub>SO<sub>2</sub>F] 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(CF<sub>2</sub>)<sub>4</sub>I 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(CF<sub>2</sub>)<sub>4</sub>I with Na<sub>2</sub>S<sub>2</sub>O<sub>4</sub> produced I(CF<sub>2</sub>)<sub>4</sub>SO<sub>2</sub>Na and NaO<sub>2</sub>S(CF<sub>2</sub>)<sub>4</sub>SO<sub>2</sub>Na, which were separated by the extraction operation with ethyl acetate, and NaO<sub>2</sub>S(CF<sub>2</sub>)<sub>4</sub>SO<sub>2</sub>Na was converted to I(CF<sub>2</sub>)<sub>4</sub>I by chlorine gas in the presence of NaI. We chose Route B and obtained high-purity SSC monomer.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"285 ","pages":"Article 110432"},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144205051","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}
Pub Date : 2025-07-01Epub Date: 2025-08-06DOI: 10.1016/j.jfluchem.2025.110458
Weihao Li , Qiaoya Wang , Yanchen Zhou , Zuci Ke , Yuhui Niu , Weiwei Hou , Sheng Wang , Mingyou Hu
Fluorinated carboxylic acids play a crucial role in pharmaceuticals and agrochemicals. However, the common synthetic routes involving the hydrolysis of carboxylic acid esters often face challenges such as defluorination and decarboxylation. These obstacles are overcome by utilizing an acid hydrolysis approach, leading to the selective and effective synthesis of fluorinated carboxylic acids. This method is distinguished by its high efficiency (up to 92% yield), versatility across various substrates including α- and β-fluorinated phenylacetates and α-heteroaryl esters, complete retention of fluorine substituents (non-defluorinative) in fluorinated carboxylic acid esters. Moreover, this protocol ensures complete stereoretention for chiral α-trifluoromethyl carboxylic esters and non-fluorinated carboxylic esters, further highlighting its synthetic utility in asymmetric transformations.
{"title":"Non-defluorinative Hydrolysis of α- and β-Fluorinated Carboxylic Acid Esters","authors":"Weihao Li , Qiaoya Wang , Yanchen Zhou , Zuci Ke , Yuhui Niu , Weiwei Hou , Sheng Wang , Mingyou Hu","doi":"10.1016/j.jfluchem.2025.110458","DOIUrl":"10.1016/j.jfluchem.2025.110458","url":null,"abstract":"<div><div>Fluorinated carboxylic acids play a crucial role in pharmaceuticals and agrochemicals. However, the common synthetic routes involving the hydrolysis of carboxylic acid esters often face challenges such as defluorination and decarboxylation. These obstacles are overcome by utilizing an acid hydrolysis approach, leading to the selective and effective synthesis of fluorinated carboxylic acids. This method is distinguished by its high efficiency (up to 92% yield), versatility across various substrates including <em>α</em>- and <em>β</em>-fluorinated phenylacetates and <em>α</em>-heteroaryl esters, complete retention of fluorine substituents (non-defluorinative) in fluorinated carboxylic acid esters. Moreover, this protocol ensures complete stereoretention for chiral <em>α</em>-trifluoromethyl carboxylic esters and non-fluorinated carboxylic esters, further highlighting its synthetic utility in asymmetric transformations.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"285 ","pages":"Article 110458"},"PeriodicalIF":1.9,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144781157","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}
Pub Date : 2025-07-01Epub Date: 2025-08-27DOI: 10.1016/j.jfluchem.2025.110462
Versha Joshi , Durgesh Nandini , Roli Purwar
Per- and Polyfluoroalkylated Substances (PFASs) have plethora of usage due to their distinctive structure and unconventional performance. Global occurrence of legacy PFASs possesses serious concern due to their high persistence, toxicity, bioaccumulative behaviour and pervasive distribution in the environment, biota and humans. As conventional PFASs are being regulated, short chain perfluoroalkyl carboxylates or sulfonates with C4 and C6 hydrophobic chain length are increasingly being utilized as a substitute. Although the short chain alternatives lie in the eagle’s eye of the environmental fraternity, their unrivalled performance in fire-fighting gives them an edge over the other available contemporaries. This review prospects the synthetic methodologies of relevant zwitterionic fluorosurfactants specifically in accordance to newer and safer designs highlighting the comparison of surface properties with traditional long chain fluorinated surfactants. Additionally, it includes the application of the newly tailored fluorinated zwitterionic surfactant in the field of firefighting foam, its potential benefits and irreplaceable performance in comparison to the legacy PFAS including assessment of its environmental impact on ecology and human life.
{"title":"Environmental implications of alternatives to Per- and Polyfluoroalkylated Substances (PFAS): Synthesis and role in Aqueous Film Forming Foam (AFFF)","authors":"Versha Joshi , Durgesh Nandini , Roli Purwar","doi":"10.1016/j.jfluchem.2025.110462","DOIUrl":"10.1016/j.jfluchem.2025.110462","url":null,"abstract":"<div><div>Per- and Polyfluoroalkylated Substances (PFASs) have plethora of usage due to their distinctive structure and unconventional performance. Global occurrence of legacy PFASs possesses serious concern due to their high persistence, toxicity, bioaccumulative behaviour and pervasive distribution in the environment, biota and humans. As conventional PFASs are being regulated, short chain perfluoroalkyl carboxylates or sulfonates with C<sub>4</sub> and C<sub>6</sub> hydrophobic chain length are increasingly being utilized as a substitute. Although the short chain alternatives lie in the eagle’s eye of the environmental fraternity, their unrivalled performance in fire-fighting gives them an edge over the other available contemporaries. This review prospects the synthetic methodologies of relevant zwitterionic fluorosurfactants specifically in accordance to newer and safer designs highlighting the comparison of surface properties with traditional long chain fluorinated surfactants. Additionally, it includes the application of the newly tailored fluorinated zwitterionic surfactant in the field of firefighting foam, its potential benefits and irreplaceable performance in comparison to the legacy PFAS including assessment of its environmental impact on ecology and human life.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"285 ","pages":"Article 110462"},"PeriodicalIF":1.9,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144908541","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}
Pub Date : 2025-07-01Epub Date: 2025-07-10DOI: 10.1016/j.jfluchem.2025.110456
Yu Zhang , Bao Feng Du , Jinpeng Miao , Xian Jin Yang
A transition-metal-free radical addition/cyclization reaction has been developed for the synthesis of Isoquinoline-1,3(2H,4H)‑dione derivatives by the decarboxylation of 3,3,3-trifluoro-2,2-dimethylpropanoic acid and N-methylacrylamide. This mild and convenient method provides a new synthetic route for introducing C(CF3)Me2 group into the Isoquinoline-1,3(2H,4H)‑dione scaffold, which exhibits a wide functional group tolerance and features substrate scope.
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