CAJ | 학술논문

为了给有机合成反应路径提供有利的依据,用分光光度法研究了在298.2～313.2 K的碱性介质中二过碘酸合铜(Ⅲ)(DPC)酸根配离子氧化1,3-丙二胺(PDA)的反应动力学及机理.实验结果表明:反应对氧化剂DPC是一级,对还原剂PDA的表观反应级数(nap),1<n_(ap)<2时准一级速率常数k_(obs)随[OH~-]增大而增大,碘酸根离子对反应速率起阻碍作用,且离子强度对反应有弱的负盐效应.据此提出了氧化反应的机理并求出了速控步骤的速率常数及298.2 K时的活化参数.
위료급유궤합성반응로경제공유리적의거,용분광광도법연구료재298.2～313.2 K적감성개질중이과전산합동(Ⅲ)(DPC)산근배리자양화1,3-병이알(PDA)적반응동역학급궤리.실험결과표명:반응대양화제DPC시일급,대환원제PDA적표관반응급수(nap),1<n_(ap)<2시준일급속솔상수k_(obs)수[OH~-]증대이증대,전산근리자대반응속솔기조애작용,차리자강도대반응유약적부염효응.거차제출료양화반응적궤리병구출료속공보취적속솔상수급298.2 K시적활화삼수.
In order to provide a strong basis for the path of organic synthesis, the kinetics of oxidation of 1,3-propanediamine (PDA) by diperiodatocuprater(Ⅲ) (DPC) in alkaline medium have been studied by spectrophotometry in a temperature range of 298.2～313.2 K. The reaction showed pseudo-first order with respect to DPC and 1 <n_(ap)<2 to PDA. It was found that the pseudo-first order rate constant k_(obs) increased with the increase of [OH~-], periodate had a retarding effect on the reaction rate. There is a weak negative salt effect. Based on the experimental results, a probable reaction mechanism of oxidation was proposed. The rate equation derived from the mechanism can explain all the experimental phenomena. The activation parameters along with the rate constants of the rate determined step were calculated and discussed, and thermodynamic quantities were also determined.