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.
{"title":"Exploration of 2-(pentafluoro-λ6-sulfanyl)ethane-1-sulfonyl chloride as a novel pentafluorosulfanylation reagent","authors":"Laurianne Verret , Kelly Burchell-Reyes , Jean-François Morin , Jean-François Paquin","doi":"10.1016/j.jfluchem.2024.110387","DOIUrl":"10.1016/j.jfluchem.2024.110387","url":null,"abstract":"<div><div>In this paper, we report our initial results on the development of 2-(pentafluoro-λ<sup>6</sup>-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 SF<sub>5</sub>Cl, 2-(pentafluoro-λ<sup>6</sup>-sulfanyl)ethane-1-sulfonyl chloride is a liquid under ambient conditions. Its reaction with substituted-phenylvinyl acetates under photoredox catalysis provided the corresponding α-SF<sub>5</sub>-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.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"282 ","pages":"Article 110387"},"PeriodicalIF":1.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143152577","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}
Pub Date : 2025-01-01DOI: 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.
{"title":"Solid-state chemistry of inorganic fluorides: From tungsten-bronze types to functionalized nanofluorides: A review","authors":"Alain Tressaud","doi":"10.1016/j.jfluchem.2024.110374","DOIUrl":"10.1016/j.jfluchem.2024.110374","url":null,"abstract":"<div><div>Solid-state chemistry of inorganic fluorides has gained great importance in the second half of 20<sup>th</sup> 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 A<sub>x</sub>MF<sub>3</sub> 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 ReO<sub>3</sub>, 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, F<sub>2</sub>.</div><div>The aim of this article is to review the solid-state chemistry of fluorides having the formula A<sub>x</sub>MF<sub>3</sub> 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 ReO<sub>3</sub>, perovskite, defect-pyrochlore, hexagonal- and tetragonal- tungsten bronze types.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"281 ","pages":"Article 110374"},"PeriodicalIF":1.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171963","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}
Pub Date : 2025-01-01DOI: 10.1016/j.jfluchem.2024.110385
Joseph S. Thrasher
{"title":"Obituary “Professor Dr. Andreas Josef Kornath – May 6, 1965 — March 5, 2024”.","authors":"Joseph S. Thrasher","doi":"10.1016/j.jfluchem.2024.110385","DOIUrl":"10.1016/j.jfluchem.2024.110385","url":null,"abstract":"","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"281 ","pages":"Article 110385"},"PeriodicalIF":1.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100104","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 : 2025-01-01DOI: 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
{"title":"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]","authors":"Jiayao Li , Vyacheslav I. Krasnov , Elena V. Karpova , Rodion V. Andreev , Inna K. Shundrina , IrinaYu Bagryanskaya , Galina A. Selivanova","doi":"10.1016/j.jfluchem.2024.110388","DOIUrl":"10.1016/j.jfluchem.2024.110388","url":null,"abstract":"","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"281 ","pages":"Article 110388"},"PeriodicalIF":1.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143092394","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}
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.
{"title":"Corrosion of iron in liquid uranium hexafluoride at 80 °C. Part II: Corrosion mechanism","authors":"Mickaël Achour , Laure Martinelli , Sylvie Chatain , Fréderic Miserque , Laurent Jouffret , Marc Dubois , Pierre Bonnet , Ania Selmi , Bertrand Morel , Sylvie Delpech","doi":"10.1016/j.jfluchem.2024.110373","DOIUrl":"10.1016/j.jfluchem.2024.110373","url":null,"abstract":"<div><div>Thanks to species identification and growth interface localization experiments, a mechanism of iron corrosion in liquid UF<sub>6</sub> at 80 °C was suggested. After an UF<sub>6</sub> dissociation step, resulting fluorine (HF, F<sup>-</sup> or F•) was adsorbed at the FeF<sub>2</sub> external interface and diffused into the iron fluoride layer via fluorine vacancy. FeF<sub>2</sub> grew thus at the FeF<sub>2</sub>/Fe interface. Two FeF<sub>2</sub> growth kinetics were observed depending on the presence or absence of NO<sub>x</sub>F impurities. Both corrosion rates were controlled by the cathodic reaction and presence of NO<sub>x</sub>F catalysed it.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"281 ","pages":"Article 110373"},"PeriodicalIF":1.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171964","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 : 2025-01-01DOI: 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).
{"title":"Lipophilicity effects of monofluorination at the tertiary aliphatic carbon as a function of α-substituent","authors":"Kostiantyn P. Melnykov , Oleksandr S. Liashuk , Oleh Smyrnov , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Viktor Yakubovskyi , Oleksandr O. Grygorenko","doi":"10.1016/j.jfluchem.2024.110384","DOIUrl":"10.1016/j.jfluchem.2024.110384","url":null,"abstract":"<div><div>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 ΔLog<em>P</em> values strongly depend on the nature of α-substituent present at the C-4 position. In particular, ΔLog<em>P</em> 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).</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"281 ","pages":"Article 110384"},"PeriodicalIF":1.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100105","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 : 2024-11-01DOI: 10.1016/j.jfluchem.2024.110368
Ivan A. Kochnev, Lyudmila S. Zavyalova, Azaliia I. Avkhadieva, Nikolay A. Tverdokhlebov, Alexey Y. Barkov
In this work, we present a synthetic protocol for the synthesis of non-symmetrical fluoroalkylated triketones. The synthesis is based on the reaction of benzoyl acetones with esters in the presence of excess lithium hydride. The tautomeric equilibrium of triketones in CDCl3 and DMSO‑d6 solutions was studied. The synthetic application of 1,3,5-triketones has been demonstrated. A method has been developed for the efficient synthesis of 2-aryl-6-(polyfluoroalkyl)-4H-pyran-4-ones by dehydrative cyclization.
{"title":"6-Polyfluoroalkyl-1-arylhexane-1,3,5-triones: Syntheses, ring-chain tautomerism and dehydrative cyclization to 6-polyfluoroalkyl-1-arylpyran-4H-ones","authors":"Ivan A. Kochnev, Lyudmila S. Zavyalova, Azaliia I. Avkhadieva, Nikolay A. Tverdokhlebov, Alexey Y. Barkov","doi":"10.1016/j.jfluchem.2024.110368","DOIUrl":"10.1016/j.jfluchem.2024.110368","url":null,"abstract":"<div><div>In this work, we present a synthetic protocol for the synthesis of non-symmetrical fluoroalkylated triketones. The synthesis is based on the reaction of benzoyl acetones with esters in the presence of excess lithium hydride. The tautomeric equilibrium of triketones in CDCl<sub>3</sub> and DMSO‑<em>d</em><sub>6</sub> solutions was studied. The synthetic application of 1,3,5-triketones has been demonstrated. A method has been developed for the efficient synthesis of 2-aryl-6-(polyfluoroalkyl)-4<em>H</em>-pyran-4-ones by dehydrative cyclization.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"280 ","pages":"Article 110368"},"PeriodicalIF":1.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142660305","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 : 2024-11-01DOI: 10.1016/j.jfluchem.2024.110366
Aya Takano, Fuji Saito, Hiroyuki Murata, Tsuyuka Sugiishi, Hideki Amii
Nucleophilic aromatic substitution (SNAr) contributes to creating a variety of useful materials. It is well-known that selective SNAr reactions of perfluorinated aromatics such as hexafluorobenzene with nucleophiles are difficult to achieve using conventional macro batch systems due to the contamination of the di-substituted products. To take advantage of flow microreactor system, we succeeded in the controlled SNAr reactions of hexafluorobenzene with organolithiums employing continuous flow reactors.
{"title":"Controlled nucleophilic aromatic substitution of hexafluorobenzene using a flow microreactor","authors":"Aya Takano, Fuji Saito, Hiroyuki Murata, Tsuyuka Sugiishi, Hideki Amii","doi":"10.1016/j.jfluchem.2024.110366","DOIUrl":"10.1016/j.jfluchem.2024.110366","url":null,"abstract":"<div><div>Nucleophilic aromatic substitution (S<sub>N</sub>Ar) contributes to creating a variety of useful materials. It is well-known that selective S<sub>N</sub>Ar reactions of perfluorinated aromatics such as hexafluorobenzene with nucleophiles are difficult to achieve using conventional macro batch systems due to the contamination of the di-substituted products. To take advantage of flow microreactor system, we succeeded in the controlled S<sub>N</sub>Ar reactions of hexafluorobenzene with organolithiums employing continuous flow reactors.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"280 ","pages":"Article 110366"},"PeriodicalIF":1.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554884","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}
Pub Date : 2024-11-01DOI: 10.1016/j.jfluchem.2024.110372
Guojie Yin , Jingjing Huang , Pengfei Hu , Weijun Fu
The direct difluoromethylation/cyclization of biarylvinyl azides with easily accessible [bis(difluoroacetoxy)iodo]benzene is achieved by visible-light-mediated radical difluoromethylation/iminyl cyclization process under mild conditions. The reaction initiates the decarboxylation of difluoromethyl carboxylic acids through light-induced the homolytic cleavage of [bis(difluoroacetoxy)iodo]benzene and affords a series of difluoromethyl functionalized phenanthridines in moderate to good yields. This strategy has the advantages of simple and readily available materials and transition metal-free conditions, thus boding well for the widespread applications of this method in medical and synthetic chemistry.
{"title":"Visible-light-induced radical difluoromethylation/cyclization of biarylvinyl azides: Facile access to CF2H-labelled phenanthridines","authors":"Guojie Yin , Jingjing Huang , Pengfei Hu , Weijun Fu","doi":"10.1016/j.jfluchem.2024.110372","DOIUrl":"10.1016/j.jfluchem.2024.110372","url":null,"abstract":"<div><div>The direct difluoromethylation/cyclization of biarylvinyl azides with easily accessible [bis(difluoroacetoxy)iodo]benzene is achieved by visible-light-mediated radical difluoromethylation/iminyl cyclization process under mild conditions. The reaction initiates the decarboxylation of difluoromethyl carboxylic acids through light-induced the homolytic cleavage of [bis(difluoroacetoxy)iodo]benzene and affords a series of difluoromethyl functionalized phenanthridines in moderate to good yields. This strategy has the advantages of simple and readily available materials and transition metal-free conditions, thus boding well for the widespread applications of this method in medical and synthetic chemistry.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"280 ","pages":"Article 110372"},"PeriodicalIF":1.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142746228","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}
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