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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 7, Number 3
JKCSEZ 7(3)
June 20, 1963 

 
Title
Reaction of Potassium Fluoride with Organic Halogen Compounds. (Part 1) Reactions of Potassium Fluoride with Organic Halides, Acids, and Esters in presence of Dimethyl Formamide and their Pyrolytic Decaboxylation in presence of Potassium Fluoride

유기 할로겐 화합물과 불화가리의 반응 (제1보) 유기 할라이드, 산 및 에스테르와 불화가리의 디메칠 호름아마이드 용매계 반응 및 고온-탈탄산-열분해 반응
Author
You Sun Kim

김유선
Keywords
Abstract
『디메칠호롬아마이드』용매계에서 유기함할로겐화합물을 불화가리와 반응시켜 본 결과 CF3COOH, C3F7COOH, C2F3COOH와 같은 함불소유기산에서는 탈탄산반응이 일어나며, 함염소함기산, CH2ClCOOH, CH3CHClCOOH, CHCl2COOH 및 o-Cl-C5H4COOH은 일부 불화반응이 일어나고 쌍합(dimerization)반응이 수반된다는 것을 구명하였다. 방향족할라이드류에서는 반응도를 나타내지 않았으나 방향환에 유전자치환기가 두개있는 시약에서는 주로 쌍합반응을 일으켰다. 알콜 및 에스테르류는 통상적인 불화반응을 잘 일으켰다. 같은 반은을 사용치 않고 고온에서 진행시켜 본 결과 쌍합반응물의 수률을 증가시켰고 o-CLC3H4COOH에서는 환화물(fluorenone)을 소양생성하였다. 반응단계중의 각 시약의 소모및 생성에 대한 화학양적관계를 비교검사한 결과 산의 반응에서는 보통 탈탄소반응보다 불화반응이 우선 진행됨을 구명하였다. 불화가리의 반응격발작용및 반응기구에 관하여서는 논의하였다.

Reactions between potassium fluoride with organic halogen-containing carboxylic acids in dimethyl formamide solvent gave a decarboxylation reaction for the case of fluoro carboxylic acids of the type of CF3COOH, C3F7COOH, and C2F5COOH, whereas an additional partial fluorination together with dimerization reaction occurred for the chlorine containing acids of the type of CH2ClCOOH, CH3CHClCOOH, CHCl2COOH and o-Cl-C6H4-COOH. The phenyl halides showed no reactivity, but the halides with two electron attracting substituents on the benzene ring gave mainly dimerization reaction. The esters and alcohols gave an usual fluorination reaction. The same reactions in absence of the solvent at the elevated temperature increase the yield of the dimerized product and gave the cyclized product, fluorenone, in case of ο-chlorobenzoic acid. It was found that the fluorination usually precede the decarboxylation reaction by checking the stiochemical sequence of reaction. Catalytic influence of potassium fluoride were discussed and the mechanism of the reaction was considered.

Page
189 - 196
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