冠醚介质中长链卤代烷烃与~(125)I、~(82)Br的交换反应

    AN EXCHANGE REACTION BETWEEN 1-BROMO-HEXADECANE AND 125I OR 82Br IN THE CROWN ETHER MEDIUM

    • 摘要: 本文研究了在冠醚介质中~(125)I、~(82)Br与1-Br-十六烷的交换反应,以及不同冠醚、不同阳离子对反应速度和产率的影响。研究了在苯并12-冠-4介质中、~(125)I、~(82)Br与1-Br-十六烷的反应动力学,首次测定了该反应的动力学参数,为短寿命同位素标记化合物的制备提供了快速、有效的新方法。

       

      Abstract: A rapid method is described for the labelling of 1-bromohexadecane with 125I and 82Br in the presence of crown ether which is used as a solvent. Benzo-12-crown-4, 15-crown-5, 18-crown-6 and 24-crown-8 are chosen as crown ethers because of its low melting point, In an isotopic exchange between 1-bromohexadecane and 125I and 82Br, the substrate and radioactive alkali halides are dissolved in the crown ether solvent. The unsolvated and "naked radioactive anions" have more reactive ability than those in the conventional condition. Our results show that there is a great crown ether effect in the halogen atom exchange or isotopic exchange. The time dependence of 1-bromohexadecane with 125I and 82Br and kinetics of isotopic exchange reactions in the benzo-12-crpwn-4 medium are studied, and the velocity constants of reaction from half-life of exchange reaction at various temperatures obtained. The activation energy of these isotopic exchange reactions is calculated from a plot where the velocity of reaction against the reciprocal temperature is a straight line. The effects of cations (Li+, Na+, K+) complexed with benzo-12-crown-4 and 15-crown-5 in exchange reaction are also examined.

       

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