Xianda Wu , Minghong Chen , Shuiyun Zheng , Fu-Sheng He , Jie Wu
{"title":"Iron-catalyzed sulfur alkylation of sulfenamides with in situ-generated 2,2,2-trifluorodiazoethane","authors":"Xianda Wu , Minghong Chen , Shuiyun Zheng , Fu-Sheng He , Jie Wu","doi":"10.1016/j.jfluchem.2023.110219","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110219","url":null,"abstract":"<div><p>Herein, we report an iron-catalyzed sulfur alkylation between sulfenamides and in situ-generated 2,2,2-trifluorodiazoethane to access sulfilimines. This protocol involves the use of inexpensive PcFe as the catalyst. The reaction features operational simplicity, mild conditions and open air, providing a facile approach to trifloromethylated sulfilimines in moderate to good yields.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"273 ","pages":"Article 110219"},"PeriodicalIF":1.9,"publicationDate":"2023-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022113923001343/pdfft?md5=553798a2f2fba0a48fde5f6c2dadcf38&pid=1-s2.0-S0022113923001343-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138356247","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}
Ita Hajdin , Romana Pajkert , Haibo Mei , Jianlin Han , Gerd-Volker Röschenthaler
{"title":"Regioselective synthesis of 3H-Pyrazoles bearing difluoromethyl phosphonate group","authors":"Ita Hajdin , Romana Pajkert , Haibo Mei , Jianlin Han , Gerd-Volker Röschenthaler","doi":"10.1016/j.jfluchem.2023.110218","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110218","url":null,"abstract":"<div><p>A catalyst- and solvent-free 1,3-dipolar cycloaddition of a bench-stable diazo reagent, 2-diazo-1,1,3,3,3-pentafluoropropyl phosphonate with selected alkynes is reported. As a result, a series of novel 3<em>H</em>-pyrazoles bearing difluoromethyl phosphonate unit is obtained in moderate-to-excellent yields. This approach provides an efficient and easy route to this valuable class of compounds.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"273 ","pages":"Article 110218"},"PeriodicalIF":1.9,"publicationDate":"2023-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022113923001331/pdfft?md5=2523facc66ddde6ec6d026abbd80531a&pid=1-s2.0-S0022113923001331-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138413313","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}
Bohdan Moroz , Kostiantyn P. Melnykov , Serhii Holovach , Andrey A. Filatov , Oleksii Raievskyi , Maksym Platonov , Oleksandr Liashuk , Dmytro M. Volochnyuk , Oleksandr O. Grygorenko
{"title":"6,6-Difluorobicyclo[3.1.0]hexane as a Rigidified 4,4-Difluorocyclohexane Mimetic: Multigram Synthesis, Physicochemical Characterization, and Incorporation into Maraviroc Analogs","authors":"Bohdan Moroz , Kostiantyn P. Melnykov , Serhii Holovach , Andrey A. Filatov , Oleksii Raievskyi , Maksym Platonov , Oleksandr Liashuk , Dmytro M. Volochnyuk , Oleksandr O. Grygorenko","doi":"10.1016/j.jfluchem.2023.110215","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110215","url":null,"abstract":"<div><p>Multigram synthesis of diastereomerically pure <em>cis</em>- and <em>trans</em>-6,6-difluorobicyclo[3.1.0]hexane building blocks starting from commercially available compounds is described. The diastereomeric mixture obtained by reaction of TMSCF<sub>3</sub> – NaI system with non-activated cyclopentene fragment using the slow addition protocol was effectively separated by flash column chromatography. Further simple chemical transformations produced diastereopure amines and carboxylic acids – promising building blocks for drug discovery. Physicochemical properties (i.e., p<em>K</em><sub>a</sub> and Log<em>P</em>) were measured for the title scaffold derivatives and compared with those with monocyclic and non-fluorinated counterparts. Two rigidified analogues of marketed anti-HIV drug Maraviroc were synthesized and evaluated by docking and molecular dynamics studies.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110215"},"PeriodicalIF":1.9,"publicationDate":"2023-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022113923001306/pdfft?md5=6b209a7e966e9b87dc7824b606cbc60e&pid=1-s2.0-S0022113923001306-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92023261","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}
Tao Shen , Chenjun Jiang , Yifeng Lai , Linlin Wu , Liangquan Zhang , Chao Qian
{"title":"Continuous flow fluorination facilitated by KF assisted by water: From batch to continuous flow","authors":"Tao Shen , Chenjun Jiang , Yifeng Lai , Linlin Wu , Liangquan Zhang , Chao Qian","doi":"10.1016/j.jfluchem.2023.110210","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110210","url":null,"abstract":"<div><p>Continuous fluorination presents a promising technology due to its potential for simple operation, process safety, and scale-up capabilities. However, when the metal fluoride was used as a fluorine source, the continuous fluorination process was hampered by solubility problem. In this work, we developed a water-assisted continuous flow operation for nucleophilic fluorination facilitated by KF. The effects of water on solubilization and activation step were revealed by the density functional theory (DFT) study. The continuous fluorination was successfully carried out in the tubular reactor, and the desired yield was obtained. The mass transfer performance in the tubular reactor was revealed by computational fluid dynamics (CFD) simulations. Besides, the kinetic study of the reaction in flow was also presented. Furthermore, the comparison with other two reported methods revealed the superiority of the continuous fluorination.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110210"},"PeriodicalIF":1.9,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92131142","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":"Study of carbon-flax hybrid composites modified by fibre fluorination","authors":"Jean-Charles Agopian , Olivier Téraube , Samar Hajjar-Garreau , Karine Charlet , Marc Dubois","doi":"10.1016/j.jfluchem.2023.110213","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110213","url":null,"abstract":"<div><p>Knowing that fibre reinforced polymers are sensitive to moisture through their interphases, carbon and flax fibres sized with Bisphenol A diglycidyl ether were fluorinated under a N<sub>2</sub>/F<sub>2</sub> atmosphere. Because of differences in reactivity of gaseous F<sub>2</sub> between fibres and sizing, only the latter has been fluorinated, resulting in a covalent grafting of fluorine atoms onto the fibres, that has been evidenced by Infrared spectroscopy, and X-Ray Photoelectron Spectroscopy. Fluorinated fibres exhibit enhanced mechanical properties, as highlighted by tensile tests. Hybrid and non-hybrid composite materials were then fabricated with vacuum infusion process, using non-fluorinated and fluorinated carbon and flax fibres. Their hydrothermal behaviour and mechanical properties were investigated, in order to study the impact of both hybridisation and fibre fluorination on the composite properties. A better water resistance was observed for polymer materials reinforced with fluorinated fibres, whereas their mechanical properties were slightly lower than polymers reinforced with non-fluorinated fibres.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110213"},"PeriodicalIF":1.9,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92023259","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}
Jia-Lu Hu , Mu-Xian Fu , Ji-Chang Xiao , Jin-Hong Lin
{"title":"Thiocarbonyl fluoride generated in situ from difluorocarbene for cyclization of vicinal X-H substituted amines (X = N, O or S)","authors":"Jia-Lu Hu , Mu-Xian Fu , Ji-Chang Xiao , Jin-Hong Lin","doi":"10.1016/j.jfluchem.2023.110212","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110212","url":null,"abstract":"<div><p>Difluorocarbene has served as a versatile intermediate in organic synthesis. The transformation of difluorocarbene into thiocarbonyl fluoride, which was discovered by us previously, can be developed as a synthetic tool for the cyclization of vicinal X-H substituted amines to provide various five-membered heterocycles. However, aryl amines are required to be used and difluoromethylation of the N<img>H bond or a newly generated S-H bond cannot be suppressed. Herein we describe the use of thiocarbonyl fluoride generated <em>in situ</em> as a thiocarbonyl source for the cyclization of vicinal X-H substituted alkyl amines (<em>X</em> = N<em>,</em> O, S) to provide imidazolidine-2-thiones, oxazolidine-2-thiones and thiazolidine-2-thiones. The use of alkyl amines constructs different heterocycles with those obtained from aryl amines. The free N<img>H bond remains intact without being difluoromethylated.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110212"},"PeriodicalIF":1.9,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92023263","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}
Qingshan Wu , Tianyi Zhao , Mingjie Liu , Guanglong Zhang , Jinwei Zhang , Cunguo Lin , Yichi Chen
{"title":"Influence of fluorine incorporation into waterborne acrylic coatings on resulting hydrophobic, thermal stability and drag- reduction properties","authors":"Qingshan Wu , Tianyi Zhao , Mingjie Liu , Guanglong Zhang , Jinwei Zhang , Cunguo Lin , Yichi Chen","doi":"10.1016/j.jfluchem.2023.110217","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110217","url":null,"abstract":"<div><p>Fluorinated polyacrylate copolymers containing various amounts of 1H,1H,2H,2H-perfluorooctyl methacrylate (FA) were synthesized via a miniemulsion polymerization process. The characteristics of latex particles and films were investigated using transmission electron microscopy, dynamic light scattering, attenuated total reflectance Fourier transform infrared spectroscopy, <sup>1</sup>H and <sup>19</sup>F nuclear magnetic resonance spectroscopy, atomic force microscopy, energy dispersive spectroscopy, water contact angle measurements, and thermogravimetric analysis. The results showed that particle size increased almost linearly with FA content, and the surface hydrophobicity of the films increased with FA content up to 14.6 wt% and then plateaued. As the FA content increased, the surface roughness of the films initially increased and then decreased. The thermal stability of fluorinated polyacrylate was significantly enhanced when a high amount of FA was incorporated into the polymer chains. The fluorinated acrylic copolymer coating also exhibited a significant drag reduction effect, with the maximum drag reduction ratio reaching 12% at a water flow velocity of 0.8 m/s.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110217"},"PeriodicalIF":1.9,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92023258","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":"Growth and luminescence characteristics of LiYF4: Yb,Er nanoparticles","authors":"Shuang Wu, Yanhui Dong, Hao Cui, Daguang Li, Weiping Qin","doi":"10.1016/j.jfluchem.2023.110209","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110209","url":null,"abstract":"<div><p>The morphology and size of LiYF<sub>4</sub>:Yb,Er nanoparticles were controlled using an automatic nanomaterial synthesizer by changing the reaction time at high temperature. It was found that the nanoparticles underwent a growth and change process from small to large and then to small, and then remained at a basically stable size, reflecting the different growth stages of the nanoparticles, such as nucleation, growth, phase transition, and internal Ostwald ripening, etc. XRD analyses showed that LiF nanocrystals were first formed during the reaction process, and then all the products were converted into LiYF<sub>4</sub> nanocrystals. Under the excitation of a 980 nm laser, the LiYF<sub>4</sub>:Yb,Er nanoparticles showed regular downconversion and upconversion luminescence properties, which was basically consistent with the regularity of nanocrystal growth. The experimental results showed that the upconversion luminescence and downconversion luminescence intensities of nanocrystals increasd rapidly when the synthesis time was between 0 and 50 min, and they increased slowly after the synthesis time exceeded 50 min.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110209"},"PeriodicalIF":1.9,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92096297","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":"Chemistry of new polyfluorinated oxiranyl anions and epoxy silanes","authors":"Viacheslav Petrov","doi":"10.1016/j.jfluchem.2023.110208","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110208","url":null,"abstract":"<div><p>The reaction of partially fluorinated epoxides with strong, hindered bases in the presence of electrophiles resulted in functionalization of the epoxy ring. For example, the reaction of hexafluoroisobutene epoxide with LDA and trimethyl- or triethychlorosilanes at low temperature led to the formation of the corresponding epoxy silanes. In the case of the E- and Z-epoxides of 1,1,1,3,3,3-hexafluorobutene-2, the deprotonation step can be successfully carried out using i-PrMgCl<sup>.</sup>LiCl (Turbo Grignard reagent), and the reaction with chlorosilanes can be carried out at ambient temperature, which significantly simplifies the synthetic protocol. The process was found to be stereospecific, proceeding with complete retention of configuration of the epoxide ring and giving access to pure <em>E-</em> or <em>Z-</em>isomers of the corresponding epoxy silanes. Using this protocol, the corresponding epoxy silanes were also prepared from the epoxides of <em>E-</em>3,3,3,1-tetrafluoropropene-1 and 3,3,3-trifluoropropene-1.</p><p>The new silanes were demonstrated to be convenient reagents for the transfer of a fluorinated epoxy moiety to carbonyl compounds under fluoride anion catalysis. This process was shown to proceed with complete retention of the geometry of the epoxy ring.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110208"},"PeriodicalIF":1.9,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92023257","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}
Nathaniel G. Garrison , Stefan Andrew Harry , Maxime A. Siegler , Guilherme Cariello , Rodrigo A. Cormanich , Thomas Lectka
{"title":"The CF⋅⋅⋅HCF2 interaction: A combination of hydrogen bonding and n → σ* stabilization","authors":"Nathaniel G. Garrison , Stefan Andrew Harry , Maxime A. Siegler , Guilherme Cariello , Rodrigo A. Cormanich , Thomas Lectka","doi":"10.1016/j.jfluchem.2023.110191","DOIUrl":"https://doi.org/10.1016/j.jfluchem.2023.110191","url":null,"abstract":"<div><p>In this communication, we explore a unique molecule that exhibits a substantial interaction between a CF<sub>2</sub>H group and a C<img>F group. In medicinal chemistry, CF<sub>2</sub>H groups are known as weak hydrogen bond donors, and C<img>F groups as weak H-bond acceptors. Seldom are they paired up together in an array such that their unique properties can be examined. In this case, we establish that along with an attractive hydrogen bonding interaction, an <em>n</em> → <em>σ</em>* component anchors the interactions. A unique combination of steric and hyperconjugative effects ‘switches’ the interaction away from previously reported dominant tetrel-type bonding in the case of a CH<sub>2</sub>F and CF interation towards an unusualy complex hybrid interaction. Crystallographic, computational, and spectroscopic studies illuminate the problem.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"272 ","pages":"Article 110191"},"PeriodicalIF":1.9,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"92096295","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}