Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds  

作　　者：Yang Zhou Qiang Zeng Hongyan He Kejia Wu Fuqiao Liu Xuehui Li 

机构地区：[1]School of Chemistry and Chemical Engineering,The Guangdong Provincial Key Laboratory of Green Chemical Product Technology,State Key Laboratory of Pulp and Paper Engineering,South China University of Technology,Guangzhou,Guangdong,510640,China [2]CAS Key Laboratory of Green Process and Engineering,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,China

出　　处：《Green Energy & Environment》2024年第1期114-125,共12页绿色能源与环境（英文版）

基　　金：The authors gratefully acknowledge the financial support of the Natural Science Foundation of China,China(Grant No.21975082 and 21736003);the Guangdong Basic and Applied Basic Research Foundation(Grant Number:2019A1515011472 and 2022A1515011341);the Science and Technology Program of Guangzhou(Grant Number:202102080479).

摘　　要：In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

关 键 词：Lignin model compounds β-O-4 dimers Electrochemical oxidation Oxidation mechanisms Substituent effect 

分 类 号：O646[理学—物理化学]