Fluorine Source Research Articles

Study on dissociation mechanism and process of regenerated cryolite

Solid waste produced in the process of aluminum electrolysis is a substantial secondary source of fluorine, the fluoride electrolyte in aluminum electrolysis carbon slag accounts for about 75%. Regenerative cryolite, extracted from anode carbon residue through flotation or calcination, possesses a significant potential for fluorine recovery. The fluoride in regenerated cryolite is mainly insoluble, making its efficient dissociation crucial for utilizing the solid waste from aluminum electrolysis. This study uses regenerative cryolite and sodium carbonate to examine how roasting temperature, time, and the reagent-to-cryolite ratio (R/C) affect cryolite dissociation. Dissociation efficiency is measured using indices like baking loss, leaching loss, fluoride ion concentration in the leachate, and fluoride ion conversion rate. Optimal dissociation is achieved at 780-820°, 2.0-2.5 hours roasting time, and an R/C ratio of 1.0-1.2. Orthogonal experimental results highlight the predominant influence of R/C, with roasting temperature being the secondary factor and roasting time having the least impact. Notably, at 780°, 2.0 hours, and an R/C ratio of 1.2:1, the fluoride ion conversion rate reaches a peak of 94.23%. This allows for recycling and production of high-value fluoride products, benefiting both the environment and the economy.

Photocatalyzed Aryl C‐H Fluorocarbonylation with CF2Br2

AbstractThe use of abundant and inexpensive fluorine feedstocks to synthesize fluorinated compounds is a promising strategy that has not been extensively investigated. Dibromodifluoromethane (CF2Br2) is an inexpensive fluorine source that has rarely been used for C−H fluoroalkylation. This study reveals an iridium‐catalyzed, tunable strategy for synthesizing acyl fluorides and difluorobromomethylated products using CF2Br2. To achieve the desired products, this process only requires the change of solvent (from DMSO to 1,4‐dioxane) under blue LED illumination. A variety of arenes and heteroarenes with electron‐donating substituents were successfully used, yielding the corresponding products in moderate to good yields. Mechanistic experiments revealed that DMSO served a dual role, functioning as both solvent and nucleophilic reagent in C−H fluorocarbonylation.

Photoredox-Catalyzed Three-Component Construction of Aryl Sulfonyl Fluoride Using KHF2: Late-Stage Drug Fluorosulfonylation.

Aryl sulfonyl fluorides are prominently featured in organic synthesis and medicinal chemistry. Herein, a metal-free photoredox-catalyzed three-component assembly of aryl sulfonyl fluoride via aryl sulfonyl ammonium salt intermediate has been reported. A variety of structurally diverse aryl sulfonyl fluorides were synthesized rapidly from dibenzothiophenium (DBT) salts under mild conditions by using KHF2 as the fluorine source. Notably, this methodology can be employed as an efficient and sustainable approach for late-stage drug fluorosulfonylation. Good yields and broad functionality tolerance were the features of this methodology. Moreover, the derivatization of aryl sulfonyl fluoride molecules was also demonstrated to showcase its synthetic utility.

Electrochemical Construction of C−F Bonds: Recent Advances and Future Perspectives

AbstractIdeal pathways to synthesize fluorinated compounds were pursued for over 100 years, due to wide application of organofluorides in materials, agrochemicals and pharmaceuticals. In this regard, electro‐organic synthesis, evolved as a sustainable and scalable approach in various synthetic protocols, stands out as a promising strategy. As a result, many novel and attracting applications of introduction of fluorine items into organic compounds by direct and redox‐mediated electrochemical methods has been reported, especially in recent five years. In this review, we are aim to highlight the reaction scopes, reaction mechanism, the fundamental aspects and the fluorine source variation in electrochemcial fluoriation transformation.

Fluorine-Tuned Carbon-Based Nickel Single-Atom Catalysts for Scalable and Highly Efficient CO2 Electrocatalytic Reduction.

Electrocatalytic CO2 reduction is garnering significant interest due to its potential applications in mitigating CO2 and producing fuel. However, the scaling up of related catalysis is still hindered by several challenges, including the cost of the catalytic materials, low selectivity, small current densities to maintain desirable selectivity. In this study, Fluorine (F) atoms were introduced into an N-doped carbon-supported single nickel (Ni) atom catalyst via facile polymer-assisted pyrolysis. This method not only maintains the high atom utilization efficiency of Ni in a cost-effective and sustainable manner but also effectively manipulates the electronic structure of the active Ni-N4 site through F doping. The catalyst has also been further optimized by controlling the F states, including convalent and semi-ionic states, by adjusting the fluorine sources involved. Consequently, this catalyst with unique structure exhibited comparable electrocatalytic performance for CO2-to-CO conversion, achieving a Faradaic efficiency (FE) of over 99% across a wide potential range and an exceptional CO evolution rate of 9.5 × 104 h-1 at -1.16 V vs reversible hydrogen electrode (RHE). It also delivered a practical current of 400 mA cm-2 while maintaining more than 95% CO FE. Experimental analysis combined with density functional theory (DFT) calculations have also shown that F-doping modifies the electron configuration at the central Ni-N4 sites. This modification lowers the energy barrier for CO2 activation, thereby facilitating the production of the crucial *COOH intermediate.

A red-emitting phosphor Na3AlF6:Mn4+: Green synthesis, optical characteristics, thermal stability and application in high-performance warm WLED

Mn4+-doped fluoride red phosphors have been widely used in warm WLEDs, but the preparation of such phosphor requires the use of a large amount of HF as a fluorine source and an acidic environment. How to reduce the excessive use of highly toxic HF in the preparation process and achieve green synthesis has become a hot research topic. Therefore, a simple green synthesis strategy is proposed in this work to synthesize a series of red-emitting phosphors Na3AlF6:Mn4+. The highly toxic HF solution is replaced by using a low toxicity reaction system (HCl/HNO3 + NH4F), which reduces the direct use of HF. X-ray powder diffraction, energy-dispersive X-ray spectrometer and scanning electron microscope are employed to determine the crystal structure, composition and morphology of all samples. Optical properties are characterized using excitation spectra, emission spectra and fluorescence lifetime curves. The calculation results indicate that the red-light has low correlated color temperature and the excellent color purity, and Na3AlF6 host can provide a strong crystal field environment for Mn4+. In addition, different aluminum sources and Mn4+ doping concentrations are used to explore the optimal preparation condition. The mechanisms of concentration quenching and thermal quenching have also been systematically explored. The stabilities of red-light emission intensity and color are investigated under the high temperature. The integral PL intensity at 423 K is 47 % of the initial value at 298 K. The activation energy, the chromaticity shift and the chromaticity coordinate variation are also systematically calculated. More importantly, a high-performance warm WLED with low correlated color temperature (CCT = 3296 K) and high color rendering index (Ra = 94.7) is achieved by using Na3AlF6:Mn4+ as a red-emitting material. Not only that, the warm WLED exhibits strong output stability under high driving current. The discovery of this work provides a comprehensive understanding for the rational design of high-performance Mn4+-activated fluoride red phosphors via a simple green synthesis strategy.

Photocatalyzed Aryl C-H Fluorocarbonylation with CF2Br2.

The use of abundant and inexpensive fluorine feedstocks to synthesize fluorinated compounds is a promising strategy that has not been extensively investigated. Dibromodifluoromethane (CF2Br2) is an inexpensive fluorine source that has rarely been used for C-H fluoroalkylation. This study reveals an iridium-catalyzed, tunable strategy for synthesizing acyl fluorides and difluorobromomethylated products using CF2Br2. To achieve the desired products, this process only requires the change of solvent (from DMSO to 1,4-dioxane) under blue LED illumination. A variety of arenes and heteroarenes with electron-donating substituents were successfully used, yielding the corresponding products in moderate to good yields. Mechanistic experiments revealed that DMSO served a dual role, functioning as both solvent and nucleophilic reagent in C-H fluorocarbonylation.

Selectfluor-triggered C–H halogenations of enaminones with copper(I) halide (CuX) for the synthesis of 3-halochromones

Abstract A practical and efficient synthetic route to construct a variety of 3-halochromones has been realized using Selectfluor reagent as a fluorine source, or Selectfluor-copper(I) halide combination as halogen source under mild conditions. This reaction proceeds via a sequence of electrophilic cation addition, and cyclization leading to a broad range of 3-halochromones in good to excellent yields in a short period of time. Additionally, the utilization of commercially available and cost-effective Selectfluor and copper(I) halide renders this system highly practical.

A unified flow strategy for the preparation and use of trifluoromethyl-heteroatom anions.

The trifluoromethyl group (CF3) is a key functionality in pharmaceutical and agrochemical development, greatly enhancing the efficacy and properties of resulting compounds. However, attaching the CF3 group to heteroatoms such as sulfur, oxygen, and nitrogen poses challenges because of the lack of general synthetic methods and reliance on bespoke reagents. Here, we present a modular flow platform that streamlines the synthesis of heteroatom-CF3 motifs. Our method uses readily available organic precursors in combination with cesium fluoride as the primary fluorine source, facilitating the rapid generation of N-trifluoromethyl(R) [NCF3(R)], SCF3 (trifluoromethylthio), and OCF3 (trifluoromethoxy) anions on demand without reliance on perfluoroalkyl precursor reagents. This strategy offers a more environmentally friendly synthesis of trifluoromethyl(heteroatom)-containing molecules, with the potential for scalability in manufacturing processes facilitated by flow technology.

Occurrence, Main Source and Health Risks of Fluorine in Mine Water

Occurrence, Main Source and Health Risks of Fluorine in Mine Water

Preparation and application of boron and fluorine co-doped rGO electrochemical sensor

N, NF, and NS-doped reduced graphene oxide(rGO) are used for the detection of dopamine (DA), however, the sensitivity and linear detection range still need to be improved. In this paper, BF-doped reduced graphene oxide (BFrGO) synthesized by hydrothermal method using fluoroboric acid as boron and fluorine sources used for the efficient detection of DA. The electrochemical detection results under the optimal buffer solution pH = 3.4 showed that the sensitivity of its detection of DA is as high as 0.804 μA/μM, the linear detection range is in the range of 5–100 μM, and the detection limit is 0.98 μM. XPS showed the formation of BC3, BC2O, BCO2, C–F half-ionic and C–F ionic bonds. DFT calculations show that B doping of rGO provides active sites and enhances its electrical conductivity. and F doping of rGO introduces new electrically active sites and improves the charge transfer ability. The synergistic effect of BF provides more active sites and enhances the charge transfer ability and adsorption energy. The BFrGO as an electrochemical sensor will provide new research directions.

Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles.

This study elucidates the mechanisms and principles governing chemoselectivity in synthesizing two distinct N-heterocycles, benzimidazole thiazine and benzothiazole imidazole, through BF3•OEt2-catalyzed cyclization reactions of propargyl alcohols with benzimidazole thiols. Employing density functional theory calculations, we highlight the crucial role of fluorine source in influencing chemoselectivity. In DCM, BF3, as the catalytic center, coordinates with propargyl alcohol's hydroxyl group to form a precursor. Conversely, in DMF, [BF2•DMF]+, formed from DMF and BF3•OEt2, acts as the catalytic center, activating the propargyl alcohol's hydroxyl group. The mechanisms in both solvents involve sequential steps: B-O bond formation, C-O bond cleavage, S-C bond formation, hydrogen atom transfer (HAT), cyclization, and deprotonation. A notable difference is the HAT process: in DCM, it follows a 1,5-HAT process, while in DMF, BF4- formation from DMF and BF3•OEt2 provides a fluorine source and introduces steric hindrance, favoring a 1,6-HAT process and leading to unique chemoselectivity. This pioneering research showcases the impact of DMF on cyclization reactions, offering valuable insights for comprehending and designing reactions driven by fluorine sources. Crucially, our results propose an innovative reaction mechanism featuring lower potential energy surfaces, enhancing our understanding of the intricate interplay among reactants, catalysts, and solvents.

Reaction pathways for the formation of complex fluorides revealed by in situ synchrotron X-ray diffraction

This study investigated the reaction between LiF, Mo metal, and CuF2 as a solid-state fluorine source to form a complex fluoride, tetragonal trirutile (TR)-type Li2MoF6, in an Ni metal tube by in situ synchrotron X-ray diffraction (SXRD) experiments. As a result, two formation pathways of TR-type Li2MoF6 were identified: one involving a reaction among intermediate phases, i.e., MoF3, and an unknown Mo-containing fluoride, and the starting materials, i.e., LiF, Mo, and CuF2, the other involving a direct reaction between LiF, Mo, and CuF2. The combination of in situ SXRD with differential scanning calorimetry (DSC) revealed that the direct reaction was facilitated by the presence of the liquid phase of LiF-CuF2. Further, the first-order phase transition of Li2MoF6 with a great volume change of 21% was found to occur in the vicinity of 520 °C–550 °C reversibly. Finally, this study demonstrated that an in situ SXRD experiment supported by DSC measurement is a powerful tool for revealing the reaction routes and identifying new phases occurring in sample-loaded metal tubes.

Improving LiFe0.4Mn0.6PO4 Nanoplate Performance by a Dual Modification Strategy toward the Practical Application of Li-Ion Batteries

A novel composite consisting of fluorine-doped carbon and graphene double-coated LiMn0.6Fe0.4PO4 (LMFP) nanorods was synthesized via a facile low-temperature solvothermal method that employs a hybrid glucose and polyvinylidene fluoride as carbon and fluorine sources. As revealed by physicochemical characterization, F-doped carbon coating and graphene form a ‘point-to-surface’ conductive network, facilitating rapid electron transport and mitigating electrochemical polarization. Furthermore, the uniform thickness of the F-doped carbon coating alters the growth of nanoparticles and prevents direct contact between the material and the electrolyte, thereby enhancing structural stability. The strongly electronegative F− can inhibit the structural changes in LMFP during charge/discharge, thus reducing the Jahn–Teller effect of Mn3+. The distinctive architecture of the LMFP/C-F/G cathode material exhibits excellent electrochemical properties, exhibiting an initial discharge capacity of 163.1 mAh g−1 at 0.1 C and a constant Coulombic efficiency of 99.7% over 100 cycles. Notably, the LMFP/C-F/G cathode material achieves an impressive energy density of 607.6 Wh kg−1, surpassing that of commercial counterparts. Moreover, it delivers a reversible capacity of 90.3 mAh g−1 at a high current rate of 5 C. The high-capacity capability and energy density of the prepared materials give them great potential for use in next-generation lithium-ion batteries.

Iron photocatalysis via Brønsted acid-unlocked ligand-to-metal charge transfer

Reforming sustainable 3d-metal-based visible light catalytic platforms for inert bulk chemical activation is highly desirable. Herein, we demonstrate the use of a Brønsted acid to unlock robust and practical iron ligand-to-metal charge transfer (LMCT) photocatalysis for the activation of multifarious inert haloalkylcarboxylates (CnXmCOO−, X = F or Cl) to produce CnXm radicals. This process enables the fluoro-polyhaloalkylation of non-activated alkenes by combining easily available Selectfluor as a fluorine source. Valuable alkyl fluorides including potential drug molecules can be easily obtained through this protocol. Mechanistic studies indicate that the real light-harvesting species may derive from the in situ-assembly of Fe3+, CnXmCOO−, H+, and acetonitrile solvent, in which the Brønsted acid indeed increases the efficiency of LMCT between the iron center and CnXmCOO− via hydrogen-bond interactions. We anticipate that this Brønsted acid-unlocked iron LMCT platform would be an intriguing sustainable option to execute the activation of inert compounds.

Green and Efficient Protocols for the Synthesis of Sulfonyl Fluorides Using Potassium Fluoride as the Sole Fluorine Source

Green and Efficient Protocols for the Synthesis of Sulfonyl Fluorides Using Potassium Fluoride as the Sole Fluorine Source

Benzylic C(sp3)-H fluorination.

The selective fluorination of C(sp3)-H bonds is an attractive target, particularly for pharmaceutical and agrochemical applications. Consequently, over recent years much attention has been focused on C(sp3)-H fluorination, and several methods that are selective for benzylic C-H bonds have been reported. These protocols operate via several distinct mechanistic pathways and involve a variety of fluorine sources with distinct reactivity profiles. This review aims to give context to these transformations and strategies, highlighting the different tactics to achieve fluorination of benzylic C-H bonds.

Tetrafluoroisopropylation of alkenes and alkynes enabled by photocatalytic consecutive difluoromethylation with CF2HSO2Na

Direct assembly of complex fluorinated motifs from simple fluorine sources is an attractive frontier of synthetic chemistry. Reported herein is an unconventional protocol for achieving tetrafluoroisopropylation by using commercially available CF2HSO2Na as a convenient source of the tetrafluoroisopropyl [(CF2H)2CH] group, which finds widespread applications in life science and material science. Visible-light-induced hydrotetrafluoroisopropylation of alkenes and carbotetrafluoroisopropylation of alkynes have been thus developed. Various structurally diverse α-tetrafluoroisopropyl carbonyls and cyclopentanones are selectively constructed under mild conditions. A photocatalytic triple difluoromethylation cascade, driven by consecutive reductive radical/polar crossover processes, leads to the direct assembly of a tetrafluoroisopropyl moiety from CF2HSO2Na. This C1-to-C3 fluoroalkylation protocol provides a practical strategy for the rapid construction of polyfluorinated compounds that are otherwise difficult to access, thus significantly enhancing the boundary of fluoroalkylation chemistry.

Electrochemically Direct Fluorination Functionalization of Styrenes with Different Fluorine Source: Access to Fluoroalkyl Derivatives.

A mild protocol for electrochemically oxidative fluorodifunctionalization of styrenes has been demonstrated. The reaction proceeds under metal, external oxidant, and catalyst free conditions, allowing tunable access to a wide variety of synthetically useful fluoroalkyl derivatives, such as β-fluorosulfone/fluoromethyl, fluorothiocyanation, and vinylsulfonyl derivatives. Moreover, CsF was shown to be the proper fluorine source for this electrochemical fluorodifunctionalization transformation.

Selectfluor and alcohol-mediated synthesis of bicyclic oxyfluorination compounds by Wagner-Meerwein rearrangement.

Herein, we report the first environmentally friendly systematic fluoroalkoxylation reactions in bicyclic systems. New oxyfluorination products were obtained with excellent yields (up to 98%) via Wagner-Meerwein rearrangement using benzonorbornadiene and the chiral natural compound (+)-camphene as bicyclic alkenes, selectfluor as an electrophilic fluorine source, and water and various alcohols as nucleophile sources. The structure of bicyclic oxy- and alkoxyfluorine compounds was determined by NMR and QTOF-MS analyses.