Toward Biomass-Based Organic Electronics: Continuous Flow Synthesis and Electropolymerization of N-Substituted Pyrroles

Abstract

Pyrroles are foundational building blocks in a wide array of disciplines, including chemistry, pharmaceuticals, and materials science. Currently sourced from nonrenewable fossil sources, there is a strive to explore alternative and sustainable synthetic pathways to pyrroles utilizing renewable feedstocks. The utilization of biomass resources presents a compelling solution, particularly given that several key bulk and fine chemicals already originate from biomass. For instance, 2,5-dimethoxytetrahydrofuran and aniline are promising candidates for biomass-based chemical production. In this study, we present an innovative approach for synthesizing N-substituted pyrroles by modifying the Clauson-Kaas protocol, starting from 2,5-dimethoxytetrahydrofuran as the precursor. The developed methodology offers the advantage of producing pyrroles under mild reaction conditions with the potential for catalyst-free reactions depending upon the structural features of the substrate. We devised protocols suitable for both continuous flow and batch reactions, enabling the conversion of a wide range of anilines and sulfonamides into their respective N-substituted pyrroles with good to excellent yields. Moreover, we demonstrate the feasibility of depositing thin films of the corresponding polymers onto electrodes through in situ electropolymerization. This innovative application showcases the potential for sustainable, biomass-based organic electronics, thus, paving the way for environmentally friendly advancements in this field.