• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.599-602
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• 2005

The aromatic fluorination method involving the acid-catalyzed decomposition of a triazene in an ionic liquid is a very convenient and efficient way to prepare a variety of aromatic fluorides in a lab-scale. It should be particularly useful for the preparation aryl fluorides substituted with electron withdrawing substituents. Fluorination of triazene 1 (1.0 mmol) and p-toluenesulfonic acid (1.2 mmol) in an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][$BF_4$], 2.5 mL) proceeds very smoothly at 80 ${^{\circ}C}$ with or without an external source of fluoride, providing 73% yield in 30 min. Unlike diazonium salts, triazene precursors are stable enough to be stored for a long period of time without a noticeable decomposition.

• Nuclear Medicine and Molecular Imaging
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• v.43 no.1
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• pp.1-9
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• 2009

As many new drug substances contained various aromatic rings and fluorine attached to an electron rich aromatic ring or on the meta-position, a strategy towards improvement in aromatic fluorination of these compounds is highly desirable. The introduction of fluorine-18 onto aromatic rings showed in the limited condition containing electron withdrawing group (EWG) on the para- or ortho-position to get reasonable radiochemical yield so far. No-carrier added (NCA) [$^{18}F$]fluoroarene syntheses by iodonium salts recently reported that has the potential to greatly increase the yield in systems or positions that normally not reactive enough to give sufficient yields in simple model reaction. This review describes the methodological approach towards effective aromatic fluorination by diaryliodonium salts and future prospects in an application of novel PET radiotracer.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.3 no.1
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• pp.3-14
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• 2017

Nucleophilic aromatic fluorination has been one of the most explored methods in fluorin-18 based radiochemistry. Unlike electrophilic $[^{18}F]$fluorination methods, no-carrier-added nucleophilic radiofluorination with cyclotron-produced $[^{18}F]$fluoride ion offers better specific radioactivity which is essential aspect to obtain good quality images from positron emission tomography. Contrary to amenable aliphatic radiofluorination, the development of reliable aromatic $[^{18}F]$fluorination methods has been pursued by many research groups; however, no viable method has yet been established. Recently, hypervalent iodine compound draws increasing attention as versatile radiolabeling precursor for various $[^{18}F]$fluoroarenes, since it bears the capacity to introduce fluorine-18 either on electron-deficient or electron-rich aryl ring with enhanced regiospecificity. Other classes of hypervalent iodine congeners often utilized in radiochemistry are iodylarenes, iodonium ylides, and spirocyclic iodonium ylides. Recently developed spirocyclic iodonium ylides have already been avidly employed to provide various $[^{18}F]$aryl fluorides with high labeling efficiency. This metal-free protocol would afford efficient routes, replacing the traditional approaches to $[^{18}F]$fluoroarenes, from prosthetic labeling synthons to complex PET radiotracers.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.1 no.2
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• pp.80-87
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• 2015

Carbon-fluorine (C-F) bonds have been found ubiquitously in pharmaceuticals, radiopharmaceuticals, agrochemicals, and material science due to their unique properties such as thermal and oxidative stability and lipophilicity to improve bioavailability. For the past five years, there have been significant advances in F-18 fluorination of aromatic complex molecules combined with the development of late-stage fluorination reactions. More recently, direct incorporation of F-18 to fluorinated aromatic molecules via borylation of C-F bonds has been developed by Niwa and Hosoya. In this minireview, we will discuss the progress of C-F bondborylation of fluorinated arenes utilizing transition metal catalysts and the impact on the development of F-18 radiotracers for positron emission tomography (PET).

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.881-884
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• 2012

We report a quantum chemical study of an extremely efficient nucleophilic aromatic fluorination in molten salts. We describe that the mechanism involves solvent anion interacting with the ion pair nucleophile $M^+F^-$(M = Na, K, Rb, Cs) to accelerate the reaction. We show that our proposed mechanism may well explain the excellent efficiency of molten salts for SNAr reactions, the relative efficacy of the metal cations, and also the observed large difference in rate constants in two molten salts $(n-C_4H_9)_4N^+\;CX_3SO_3^-$, (X=H, F) with slightly different sidechain ($-CH_3$ vs. $-CF_3$).

• Applied Chemistry for Engineering
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• v.27 no.5
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• pp.537-542
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• 2016

In this study, we have prepared mesophase pitch from pyrolysis fuel oil (PFO) by heterogeneous reforming process. This process was conducted by direct fluorination at various temperature and followed by the heat treatment at $390^{\circ}C$. The reformed pitch was then investigated by softening point analysis, elemental analysis, fourier-transform infrared spectroscopy, high resolution X-ray diffraction and polarization microscope analysis. Carbon contents of reformed pitch increased according to increasing the reaction temperature of fluorination, while oxygen, nitrogen and sulfur contents were completely eliminated. As the fluorination temperature increased, the creation, growth, coalescence and alignment process of mesophase spheres were observed. Also the interlayer spacing of carbon hexagonal planar structure decreased, while its crystalline size increased. In addition, aromatic ring compound contents increased by the condensation polymerization of aliphatic compound. These results can be attributed to the radical reactivity of the fluorine increased as the reaction temperature increased. It was considered that the fluorination reaction could help PFO to generate aromatic compounds, via promoting polymerization by radical reaction.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2571-2574
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• 2010

We investigate the mechanism of $S_NAr$ fluorination reactions under the influence of protic solvents and ions. We find that counterion or protic solvent alone retards the $S_NAr$ reactions, but together they may promote the reaction. In this mechanism, the protic solvent acts on the counterion as a Lewis base, and the nucleophile reacts as an ion pair. We also show that an anion (mesylate) may exhibit catalytic effects, suggesting the role of ionic liquids for accelerating the $S_NAr$ reactions.

• Polymer(Korea)
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• v.27 no.5
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• pp.484-492
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• 2003

How the characteristics and stability of the rubbing-induced alignment of nematic liquid crystals (LCs) relate to the interfacial characteristics of LC-polyimide has been studied. The characteristics of the LC alignment (such as the LC texture, the pretilt angle, and the anchoring energy) and their thermal stability have been investigated for 5 polyimides synthesized for this work. The work showed that the rubbed polyimide alignment layer induces the strong LC anchoring and that the characteristics and stability of LC alignment are determined by the short-ranged interactions between LC and polyimide molecules at the alignment layer surface. The increased flexibility of the polyimide accelerates thermal imidization, increases the pretilt angle, and improves the alignment stability. It also turned out that fluorination of the polyimide tends to deteriorate the alignment uniformity and stability. No distinct differences in the alignment characteristics were shown for the aromatic- and alicyclic-dianhydride polyimides.

• Journal of the Korean Chemical Society
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• v.13 no.1
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• pp.68-74
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• 1969

Flourination of Ethyl, ${\alpha},{\beta$}-dichloro-${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dibromo ${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dichloro ${\beta$}-(p-chloro-phenyl) propionate, and dibromostyrene by potassium fluoride were investigated in presence of dimethyl formamide, diethylene glycol, and diethylene glycol monomethyl-ether. The reactivity of these organic halogen esters and hydrocarbons towards potassium fluoride was checked further by means of radioactive fluorine-18. tracer. Generally, the reaction gave monofluoride together with dehalogenated olefin. The formation of olefine was increased when the reaction was done at high reaction temperature in presence of diethylene glycol, whereas the lower reaction temperature in presence of diethyleneglycol monomethyl ether favored the formation of mono fluoride in a good yield. The procedures and methods of the identification of monofluorides were described and the feasibility of this reaction of fluorine containing ester including the F-18 labelled compounds was discussed.