Tritium-Labeled Compounds IX. Determination of Isotope Effects in Reactions Yielding Water-t from Nonvolatile Reactants. Oxidation of Aldoses-1-t With Iodine.

Horace S Isbell, Lorna T Sniegoski
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Abstract

A convenient method is presented for estimating isotope effects in reactions which yield water-t. The water-t is separated by freeze-drying, and k*/k is calculated from the extent of the reaction and the ratio of the radioactivity of the water-t to that of the initial reactant. Application of the method to the oxidation of aldoses-1-t at 25 °C with iodine in alkaline solution gives values for k*/k ranging from 0.12 to 0.17, with an average of 0.14. There are no significant differences in the values of k*/k obtained for aldoses differing in configuration, or for pentoses and hexoses. The isotope effect corresponds to a ratio of one to seven for the respective rates of reaction of the labeled and unlabeled molecules.

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氚标记化合物 IX.测定非挥发性反应物在生成水-t 反应中的同位素效应。碘氧化醛-1-t。
本文提出了一种简便的方法,用于估算产生水-t 的反应中的同位素效应。通过冷冻干燥分离出水-t,然后根据反应程度和水-t 的放射性与初始反应物的放射性之比计算出 k*/k。将该方法应用于在 25 °C 下用碘在碱性溶液中氧化醛糖-1-t,得出的 k*/k 值在 0.12 到 0.17 之间,平均值为 0.14。不同构型的醛糖、戊糖和己糖的 k*/k 值没有明显差异。同位素效应相当于已标记和未标记分子各自反应速率的一比七。
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