Abstract <p>The synthesis of 2-oxazolines typically relies on homogeneous zinc salts, which offer high activity but suffer from poor recyclability and metal contamination. Here, we demonstrate that commercially available zinc oxide (ZnO) functions as an efficient and reusable heterogeneous catalyst for the cyclodehydration of amino alcohols with nitriles under solvent-free conditions. Time-resolved <sup>1</sup>H NMR kinetics were recorded for the formation of five products (MeOx, EtOx, iPrOx, BuOx, PhOx), revealing a characteristic sigmoidal conversion profile. Classical kinetic models, including first-order, power-law and Langmuir-type expressions, failed to describe the data, while a logistic kinetic model provided excellent fits for all the product formation, capturing the induction phase, rapid cooperative acceleration and late-stage saturation. This behavior is rationalized by progressive surface activation, evolving adsorption equilibria, and partial ZnO site blocking during the course of the reaction. Scanning electron microscopy and powder X-ray diffraction analyses confirm that the catalyst retains its wurtzite structure and morphology and can be reused without loss of integrity. This work highlights logistic kinetics as a useful descriptor for heterogeneous Lewis-acid catalysis and establishes ZnO as a low-cost, recyclable platform for oxazoline synthesis.</p> Graphical abstract <p>Graphical abstract illustrates the solvent-free cyclodehydration of nitriles and amino alcohols to synthesize 2-oxazolines using a reusable heterogeneous zinc oxide catalyst. Time-resolved <sup>1</sup>H NMR kinetics demonstrate a distinct sigmoidal conversion profile accurately described by a logistic kinetic model rather than classical rate expressions.</p>

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Zinc oxide as reusable heterogeneous catalyst for oxazoline synthesis: A kinetic and reusability study

  • Anusree Suresh,
  • Gorachand Badaraita,
  • Akhila Mekha,
  • Santhana Gopal Ramkumar

摘要

Abstract

The synthesis of 2-oxazolines typically relies on homogeneous zinc salts, which offer high activity but suffer from poor recyclability and metal contamination. Here, we demonstrate that commercially available zinc oxide (ZnO) functions as an efficient and reusable heterogeneous catalyst for the cyclodehydration of amino alcohols with nitriles under solvent-free conditions. Time-resolved 1H NMR kinetics were recorded for the formation of five products (MeOx, EtOx, iPrOx, BuOx, PhOx), revealing a characteristic sigmoidal conversion profile. Classical kinetic models, including first-order, power-law and Langmuir-type expressions, failed to describe the data, while a logistic kinetic model provided excellent fits for all the product formation, capturing the induction phase, rapid cooperative acceleration and late-stage saturation. This behavior is rationalized by progressive surface activation, evolving adsorption equilibria, and partial ZnO site blocking during the course of the reaction. Scanning electron microscopy and powder X-ray diffraction analyses confirm that the catalyst retains its wurtzite structure and morphology and can be reused without loss of integrity. This work highlights logistic kinetics as a useful descriptor for heterogeneous Lewis-acid catalysis and establishes ZnO as a low-cost, recyclable platform for oxazoline synthesis.

Graphical abstract

Graphical abstract illustrates the solvent-free cyclodehydration of nitriles and amino alcohols to synthesize 2-oxazolines using a reusable heterogeneous zinc oxide catalyst. Time-resolved 1H NMR kinetics demonstrate a distinct sigmoidal conversion profile accurately described by a logistic kinetic model rather than classical rate expressions.