Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Halogen Containing Heterocyclic Compounds (Part Ⅱ) Halogenation of Furfuryl Derivatives-Maleic Anhydride Adduct

含할로겐 異元素環化合物에 關한 硏究 (第2報) 풀퍼릴誘導體-마레인酸無水物 附加物의 할로겐化反應

  • Kim, You-Sun (Division of Chemistry, Atomic Energy Research Institute) ;
  • Kim, Chung-Hee (Division of Chemistry, Atomic Energy Research Institute)
  • Published : 19650600
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Abstract

The exo adduct between furfuryl derivatives (furan, furfuryl acetate and furfuryl alcohol) and maleic anhydride were prepared in the presence of ethyl ether. The bromination of the exo adduct of each derivatives gave a monobromolactone and dibromoacid when the reaction was done in the presence of water. The formation of the bromolactone was proved to be dependent to the carboxylic participation to the incipient rearranged carbonium ion of a classical type, and the participation was sterically hindered by the steric structure of the substituents. The bromination of the furan-maleic anhydride adduct in the presence of organic solvent $(CCl_4,\;CH_2Cl_2)$ gave the dibromide, whereas the photochlorination of the same adduct in the presence of carbon tetrachloride gave the tetrachloride. The procedure of the preparation and the reaction path of the halogenation were described.

퓨란, 醋酸풀퍼릴, 풀퍼릴알코올과 마레인酸無水物을 에틸 에테르 存在下에서 附加反應시켜 exo附加物을 만들고 이 化合物들에 對한 臭素化反應을 물 存在下에서 行한 바 各各 모노부롬化락톤 및 디브롬酸을 生成하였으며 락톤의 生成收率은 轉位된 carbonium ion에 對한 carboxylic acid의 反應기여(participation)에 依하여 決定되면 化合物 自體의 立體條件(steric requirement)이 그 기여에 영향을 준다는 것을 究明하였다. 퓨란附加物을 有機溶媒(四鹽化炭素, 메틸렌크로라이드)存在下에서 臭素化反應하면 二臭化物이 生成하고 光線 存在下에서 鹽素化反應하면 四鹽化反應物이 生成됨을 究明하였다. 各 化合物의 合成方式 및 反應過程에 關하여 論及하였다.

Keywords

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