Ｔ‐ｆｏｒ‐Ｈ交換反応における脂環式アルコール及びカルボン酸の速度論的反応解析

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  • Kinetic Analysis of the Reactivity of Aliphatic Cyclic Alcohols and Carboxylic Acids in the T-for-H Exchange Reaction
  • T for H コウカン ハンノウ ニ オケル シカンシキ アルコール オヨビ カルボンサン ノ ソクドロンテキ ハンノウ カイセキ

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In order to quantitatively evaluate the influence of tritium (3H or T) on various functional groups in environment, the hydrogen isotope exchange reaction (T for-H exchange reaction) between tritium-labeled poly (vinyl alcohol) and each aliphatic cyclic alcohol (or carboxylic acid) has been dynamically observed in the range of 50 to 90°C. Consequently, the activities of the aliphatic cyclic alcohol and carboxylic acid increased with increasing reaction time. Applying the A″-McKay plot method to the observed data, the rate constants (k) for these materials were obtained. Using the k, the relation between the number of carbon atoms in the ring in each alcohol and the reactivity of the alcohol was quantitatively compared. Then, to clarify the effect of relative atomic charge of O atom (connected with the H atom in the hydroxy (or carboxy) group in the material) on the reactivity of the material, the MOPAC method was used.<BR>From both the above-mentioned and the obtained previously, the following nine items were found as to aliphatic cyclic alcohols (and carboxylic acids) in the T-for-H exchange reaction. (1) The reactivity of aliphatic cyclic alcohols (and carboxylic acids) depends on the temperature. (2) The reactivity of the cyclic materials decreases with increasing number of carbon atoms in the ring. (3) The reactivity of the aliphatic cyclic carboxylic acid seems to be smaller than that of aliphatic cyclic alcohol, and be larger than that of aliphatic cyclic amine. (4) For aliphatic cyclic alcohols, correlation exists between k and relative atomic charges of O atom obtained by the MOPAC method, but the tendency for aliphatic cyclic carboxylic acid is not clear. (5) As to having the same number of carbon atoms in each ring, the reactivity of the aliphatic cyclic carboxylic acid including the side chain is smaller than of the aliphatic cyclic carboxylic acid including no side chain. (6) The reactivity of aliphatic cyclic carboxylic acid is larger than that of aliphatic normal carboxylic acid. (7) The reactivity of these materials dissolved in 1, 4-dioxane is smaller than that in p-xylene. (8) Using both the MOPAC and the A″-McKay plot methods, the actual analysis of aliphatic cyclic alcohols can be more possible. (9) The method used in this work is useful for evaluating influence of T on environment.

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