Sustainable catalytic systems based on imidazole derivatives
type: CreativeWork
description: This doctoral thesis describes the development of several catalytic systems containing imidazolium salts. It has been divided into four chapters: Chapter 1 describes a novel low transition temperature mixture (LTTM) based on 1-(methoxycarbonylmethyl)-3-methylimidazolium chloride and urea. The LTTM was characterized and then applied to the oxidation of boron compounds (i.e., boronic acids, boronic esters and trifluoroborates) to the corresponding alcohols, obtaining excellent results in short reaction times. The system, which acts as a co-solvent as well as source of oxidizer, achieved three synthetic cycles with a single imidazolium loading, greatly reducing the environmental impact of the protocol. Chapter 2 compiles our findings about the use of a LTTM based on iron(III) and 1-butyl-3-(methoxycarbonylmethyl)imidazolium chloride as a catalyst for the synthesis of quinazolines. The mixture, named IBIS, presents a bifunctional character as both Lewis acid and redox catalyst, affording the desired products in moderate to excellent yields using air as the terminal oxidant in the absence of solvent. In addition, a methodology for the direct synthesis of 2-arylquinazolines from 2-nitrobenzaldehydes is presented and discussed. Chapter 3 details the study of ionic organic solids (IOS) as metal-free heterogeneous catalysts. The IOS 1,3-bis(carboxymethyl)imidazolium chloride effectively catalyzed the C-3 allylation of indoles, providing a single regioisomer in up to quantitative yields and often, pure after simply filtering off the catalyst. The reaction could be performed in gram scale and the catalyst could be reused up to 5 consecutive times without loss of activity. The protocol was then extended to other π-excessive heterocycles, which experienced selective N-allylation. Overall, this methodology proved to be significantly superior in terms of sustainability than those reported in the literature. This chapter also presents the first synthesis of 1,3-bis(sulfomethyl)imid…
abstract: This doctoral thesis describes the development of several catalytic systems containing imidazolium salts. It has been divided into four chapters: Chapter 1 describes a novel low transition temperature mixture (LTTM) based on 1-(methoxycarbonylmethyl)-3-methylimidazolium chloride and urea. The LTTM was characterized and then applied to the oxidation of boron compounds (i.e., boronic acids, boronic esters and trifluoroborates) to the corresponding alcohols, obtaining excellent results in short reaction times. The system, which acts as a co-solvent as well as source of oxidizer, achieved three synthetic cycles with a single imidazolium loading, greatly reducing the environmental impact of the protocol. Chapter 2 compiles our findings about the use of a LTTM based on iron(III) and 1-butyl-3-(methoxycarbonylmethyl)imidazolium chloride as a catalyst for the synthesis of quinazolines. The mixture, named IBIS, presents a bifunctional character as both Lewis acid and redox catalyst, affording the desired products in moderate to excellent yields using air as the terminal oxidant in the absence of solvent. In addition, a methodology for the direct synthesis of 2-arylquinazolines from 2-nitrobenzaldehydes is presented and discussed. Chapter 3 details the study of ionic organic solids (IOS) as metal-free heterogeneous catalysts. The IOS 1,3-bis(carboxymethyl)imidazolium chloride effectively catalyzed the C-3 allylation of indoles, providing a single regioisomer in up to quantitative yields and often, pure after simply filtering off the catalyst. The reaction could be performed in gram scale and the catalyst could be reused up to 5 consecutive times without loss of activity. The protocol was then extended to other π-excessive heterocycles, which experienced selective N-allylation. Overall, this methodology proved to be significantly superior in terms of sustainability than those reported in the literature. This chapter also presents the first synthesis of 1,3-bis(sulfomethyl)imid…
author: Martos, Mario
keywords: Sostenibilidad, Sales de imidazolio, Sólidos iónicos orgánicos, Mezclas de bajo punto de transición, Estructuras metal-orgánicas
date published: 2023
date modified: 2026-07-24T00:52:02Z
provider: University of Alicante
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Alicante