Dispersion Stability of Fluorinated Multi-Walled Carbon Nanotubes in FC-27 Refrigerant

In order to achieve the dispersion stability of multi-walled carbon nanotubes (MWCNT) in a fluorinated refrigerant (FC-72) used in various cooling purposes, fluorinated MWCNT (MWCNT-F) was prepared by a combined process of oxidation and fluorination. As a fluorine source, (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane was used to react with hydroxyl groups on MWCNT (MWCNT-OH) generated by chemical oxidation. Pristine MWCNT, MWCNT-OH, and MWCNT-F were dispersed in FC-72 and MWCNT-F was also dispersed in polar and nonpolar solvents. The MWCNT-F has excellent colloidal stability in FC-72 because of the chemical affinity between FC-72 and functional groups (-CF_n) on the side walls of MWCNT. Through surface modifications, we could obtain the enhanced dispersion stability of MWCNT in a refrigerant. This homogenous MWCNT solution in FC-72 may be used to increase the heat transfer in FC-72 based nanofluids.     

Decarboxylative Fluorination of Arylcarboxylic Acids Promoted by ortho‐Hydroxy and Amino Groups

A novel decarboxylative fluorination process has been developed for the synthesis of ortho‐hydroxy/amino arylfluorides from salicylic acid analogs, in which the ortho‐hydroxy/amino group plays an important role in the transformation. In addition, various arylfluorides are obtained in good to excellent yields under mild conditions.     

Bis‐tert‐Alcohol‐Functionalized Crown‐6‐Calix[4]arene: An Organic Promoter for Nucleophilic Fluorination

A bis‐tert‐alcohol‐functionalized crown‐6‐calix[4]arene (BACCA) was designed and prepared as a multifunctional organic promoter for nucleophilic fluorinations with CsF. By formation of a CsF/BACCA complex, BACCA could release a significantly active and selective fluoride source for S_N2 fluorination reactions. The origin of the promoting effects of BACCA was studied by quantum chemical methods. The role of BACCA was revealed to be separation of the metal fluoride to a large distance (>8 Å), thereby producing an essentially “free” F^?. The synergistic actions of the crown‐6‐calix[4]arene subunit (whose O atoms coordinate the counter‐cation Cs⁺) and the terminal tert‐alcohol OH groups (forming controlled hydrogen bonds with F^?) of BACCA led to tremendous efficiency in S_N2 fluorination of base‐sensitive substrates.     

Products formed at intermediate stages of electrochemical perfluorination of propionyl and n-butyryl chlorides. Further evidence in support of NiF3 mediated free radical pathway

The partially fluorinated HF soluble intermediates formed during the electrochemical perfluorination of propionyl chloride (PC) and n-butyryl chloride (n-BC) were analyzed after passing 0%, 25%, 50%, 75% and 100% of theoretical charge required for the fluorination of PC and n-BC. The acid fluorides formed were converted to their corresponding sodium salt by alkali treatment and were separated by methanol extraction. The methanol was subsequently removed from the extract by vacuum distillation and the residue containing partially fluorinated sodium carboxylates was analyzed using ¹⁹F and ¹H NMR spectra. Initial perfluorination on activated electrode surface indicates the operation of ‘zipper-mechanism’. Formation of partially fluorinated product mixture, initial selectivity towards primary and secondary carbon, carbon chain isomerization and formation of cleaved and coupled products support the general operation of free radical pathway in the overall electrochemical process.     

Research of Fluorination Process of Rutile Concentrate

The brief review of industrial technologies of titanium-containing concentrates processing has been carried out. Drawbacks of the existing titanium manufacture schemes are shown and the necessity of the essentially new fluoride technologies development has been proved. The reactions proceeding during the fluorination of rutile concentrate with element fluoride are described in the given work. The thermodynamic research of the process has been carried using ASTRA software. Dependence of mass concentration change of titanium tetrafluoride has been investigated in products of reaction on the temperature of the process, and the choice of optimum excess of fluoride has been proved.     

Transannular additions of selectfluor and xenon difluoride: regioselectivity and mechanism

The addition of 1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo[2.2.2]octane bis‐tetrafluoroborate (F‐TEDA) to unsaturated systems was modelled computationally at the ab initio levels and studied experimentally. The reaction of olefins with F‐TEDA is driven exclusively by charge transfer and displays the antibonding orbital picture in the transition structure for F‐transfer, similarly to that for the reactions of olefins with F‐radical. In contrast, the electrophilic and concerted fluorinations, respectively with H₂O???F⁺ complex and with F₂, show strong bonding interactions between the fluorine and olefin moieties in the transition structures. The reaction with F‐TEDA involves an initial formation of highly delocalized charge‐transfer complexes in the first step with further low‐barrier (ca 4 kcal) migration of fluorine and is best described as an inner‐sphere electron transfer. This nonelectrophilic mechanism is operative for the transannular addition of F‐TEDA to 3‐methylene‐7‐ethylidenebicyclo[3.3.1]nonane studied experimentally. The addition mode is determined by the formation of a more stable complex via the ethylidene fragment and demonstrates selectivities that differ from conventional electrophilic additions. This mechanistic scenario may be extended to the fluorination with xenon difluoride where similar products are formed in high yields. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron‐Rich Substrates

Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene‐types and tolerance of electron‐rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene‐types that is tolerant of electron‐rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex‐cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales.     

Enantioselective Palladium(II)‐Catalyzed Oxidative Aminofluorination of Unactivated Alkenes with Et4NF⋅3 HF as a Fluoride Source

The first asymmetric Pd^II‐catalyzed aminofluorination of unactivated alkenes using chiral quinoline‐oxazolines (Quox) as ligands has been developed. This reaction provides easy access to a wide array of enantiomerically enriched β‐fluoropiperidines in good yields and with excellent enantioselectivity. Notably, Et₄NF?3 HF as a readily accessible nucleophilic fluoride source was found to play an essential role in the enantioselective control, and CsOCF₃ also acts a key additive to improve the excellent ee value of products.     

Spatially Resolved Bottom‐Side Fluorination of Graphene by Two‐Dimensional Substrate Patterning

Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene‐based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM‐EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen‐containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom‐side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene‐based devices.