Reaction of Organic Halogen Compounds with Metals (Part II) A Formation of Organic Chlorine Zinc Complex in Various Solvents

有機할로겐 化合物과 金屬과의 反應 (第 2 報) 有機亞鉛 클로린콤푸렉쓰 生成에 關한 各種 용매효과

  • Kim, You-Sun (Chemistry Division, Atomic Energy Research Institute)
  • 김유선 (原子力硏究所 化學硏究室)
  • Published : 19650300

Abstract

Reaction of monochloroacetic acid with zinc in presence of toluene, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and dioxane solvents showed the solvent effect in order of dimethylformamide, dioxane, dimethyl sulfoxide, toluene, acetonitrile, and tetrahydrofuran. The increasing reactivity of the reagents was observed in order of the polarity and hydrophilicity of the solvent. The same reaction of ethyl monochloroacetate in the same series of solvents showed also the solvent effect, but the difference was not large as compared to that of the acid. The reaction of the acid, ester, zinc, and carbonyl precursors such as benzaldehyde and 4-heptanone gave the Reformatsky reaction product in the case of the aldehyde, but the reactivity with 4-heptanone was slight. The yield of the product was varied by the method of addition of reagents. The best yield observed in case of the acid reaction was 38.5% of the hydroxy acid and 0.8g of the salt in presence of acetonitrile and in case of the ester reaction 19.3% of ethyl cinnamate and 21.6% of polymer. The variation of the reactivity of reagents due to the reaction temperature was observed in case of carbonyl reaction. The result was discussed in terms of the solvent effect and the procedures were described.

토루엔, 디메틸폴움아마이드, 디메틸슬포옥사이드, 테트라하이드로퓨란, 아세토나이트라일 및 디옥센 等 溶媒存在下에서 모노클로로醋酸과 亞鉛을 反應시켜 본 結果, 溶媒효果를 나타내었다. 反應試藥의 反應度가 溶媒의 極性 및 親水性에 따라 增加하였다. 같은 溶媒系를 使用하여 에틸모노클로로醋酸을 反應시켜 본 結果, 溶媒효果를 나타냈으나 酸의 境遇보다 그 差가 크지 못하였다. 酸, 에스타, 亞鉛 및 카보닐化合物(벤즈알데히드 및 4-헤프타논)의 反應에 있어서는 알데하이드의 境遇에 있어서는 Reformatsky 反應生成物을 주었으나, 4-헤프타논과의 反應度는 없었다. 反應生成物의 收率은 試藥添加方法에 따라 變化되었다. 最高收率은 酸의 하이드로옥시酸(38.5%), 0.8g의 salt(아세트나이트라일溶媒)이며, 에스타의 境遇에는 에틸신나메이트(19.3%), 폴리머(21.6%)이였다. 카보닐化合物의 境遇에 있어서는 反應溫度에 따라 試藥의 反應度의 變化가 있었다. 硏究結果를 溶媒效果에 關聯시켜 論議하였으며, 硏究方法에 關하여 記述하였다.

Keywords

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