• Bulletin of the Korean Chemical Society
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• 제26권4호
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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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• 제43권1호
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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.

• 대한방사성의약품학회지
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• 제3권1호
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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.

• 대한방사성의약품학회지
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• 제1권2호
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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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• 제33권3호
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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. $-CF_3$).

• 공업화학
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• 제27권5호
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• pp.537-542
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• 2016

본 연구에서는 불균일계 불소화 개질 공정을 이용하여 열분해잔사유(PFO)로부터 메조페이스 피치를 제조하였다. 이 공정은 다양한 온도의 직접 불소화 공정과 $390^{\circ}C$의 열처리 공정을 통하여 진행하였다. 제조된 피치는 연화점, 원소분석, 푸리에 변환 적외선 분광 분석, 고분해능 X-ray 회절 분석 그리고 편광 현미경 분석을 실시하였다. 제조된 피치의 탄소 함량은 직접 불소화 공정의 반응 온도 증가에 따라 함께 상승하였으며, 그 산소, 질소 그리고 황 성분은 완전하게 제거되었다. 불소화 온도가 증가함에 따라서, 메조페이스 소구체의 생성, 성장, 합체, 정렬이 관찰되었다. 탄소 육각망면의 층간간격이 감소하였고 결정자 크기가 증가하였다. 또한, 지방족 화합물의 축 중합으로 인한 방향족 화합물의 함량 증가가 관찰되었다. 이러한 결과는 반응 온도의 증가에 따라 증가된 불소 라디칼의 반응성에 기인한다. 불소화 반응은 열분해잔사유가 라디칼 반응에 의한 중합반응의 촉진으로, 방향족 화합물의 생성을 돕는 것으로 판단된다.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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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.

• 폴리머
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• 제27권5호
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• pp.484-492
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• 2003

러빙에 의해 유도된 네마틱 액정의 배향 특성과 그 안정성이 액정-폴리이미드 계면 특성과 어떠한 관계가 있는지를 조사하였다. 합성된 5 종류의 폴리이미드 특성을 분석하고 폴리이미드 배향막에서의 액정 배향의 균일성, 선경사각, 정착 에너지, 그리고 열 안정성을 측정 조사하였다. 러빙된 폴리이미드는 강한 정착의 액정 배향을 유도하고 액정 배향의 특성과 안정성은 배향막 표면에서의 액정과 폴리이미드 간의 분자 차원의 상호작용에 의해 결정된다는 것을 확인하였다. 폴리이미드의 유연성의 증가는 이미드화를 촉진시키며 액정의 선경사각과 배향 안정성을 증대시킨다. 반면에, 폴리이미드의 플루오르화는 액정의 배향성 및 배향 안정성을 감소시키는 것으로 나타났다. 폴리이미드의 방향족과 지방족 고리 이무수물 구조에 따른 액정 배향의 특성과 안정성에는 뚜렷한 차이가 나타나지 않았다.

• 대한화학회지
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• 제13권1호
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• pp.68-74
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• 1969

${\alpha},{\beta$}-dichloro-${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dibromo-${\beta$}-phenyl propionate, Etyyl ${\alpha},{\beta$}-dichloro-${\beta$}-(p-chlorophenyl)propionate, 및 dibromo-styrene 等의 化合物을 各種溶媒(dimethly formamide, diethylene glycol, 및 diethylene glyco monomethyl ether 等) 存在下에서 弗化反應을 시켜 보았으며 放射性弗素-18을 追跡子로 使用하여서 위의 化合物들의 弗化카리에 對한 反應度를 檢査하여 보았다. 一般的으로 弗化反應 生成物은 모노弗化物과 脫할로겐된 二重結合物을 生成하였다. diethylglycol 存在下에서 高溫反應시킨 條件下에서는 二重結合生成物이 많았고 diethylene glyco-monoethyl ether 存在下에서 低溫反應시킨 條件下에서는 弗化物이 多量生成하였다. 모노弗化物의 合成方式 및 確認方法에 關하여 說明하였으며 本反應의 合成上의 用途($F^{18}$ 標識化合物包含)에 言及하였다.