低碳化学与化工2025，Vol.50Issue(2)：53-60,8.DOI:10.12434/j.issn.2097-2547.20240194
以CO2为羧基源温和高效制水杨酸类化合物
Mild and efficient preparation of salicylic acid compounds with CO2 as carboxyl source
摘要
Abstract
Salicylic acid compounds are an important raw material widely used in fine chemicals such as medicine,spices,dyes,pesticides and rubber additives,etc.However,based on the Kolbe-Schmitt reaction,the preparation of salicylic acid compounds with CO2 as a carboxyl source has some problems,such as high temperature,high pressure,long reaction time and low yield.A new method for the synthesis of salicylic acid compounds by CO2 carboxylation phenol and 4-substituted phenol was presented,which uses KOH as deprotonation base,xylene as solvent,Cs2CO3,K2CO3 and 2,4,6-trimethylphenol potassium salt(TMPK)as cocatalysts to achieve CO2 efficient carboxylation phenol and 4-substituted phenol.The physicochemical properties of each carboxylation product were characterized.The effects of catalyst dosage,CO2 pressure,temperature,cocatalyst dosage,reaction time and reaction substrate on the carboxylation reaction of phenol and 4-substituted phenol were systematically investigated.The possible reaction mechanism of the synthesis of salicylic acid and 5-substituted salicylic acid cocatalyzed by carbonate and TMPK was proposed.The results show that the catalyst combination of Cs2CO3+TMPK effectively optimizes the reaction conditions.Under mild conditions,the preparation of salicylic acid compounds by efficient CO2 carboxylation phenol(one-way yield of 60%)and 4-substituted phenol(one-way yield of 60%～90%)was realized.The ortho-selectivity of carboxylation products synthesized by this method is as high as 100%.关键词
Kolbe-Schmitt反应/CO2/Cs2CO3/2,4,6-三甲基苯酚/5-取代基水杨酸/羧化Key words
Kolbe-Schmitt reaction/CO2/Cs2CO3/2,4,6-trimethylphenol/5-substituted salicylic acid/carboxylation分类
化学化工引用本文复制引用
郑修畅,李国玲,赵云,倪中海,陆诗建,陆超..以CO2为羧基源温和高效制水杨酸类化合物[J].低碳化学与化工,2025,50(2):53-60,8.基金项目
江苏省碳达峰碳中和科技创新专项(BE2023852) （BE2023852）
中国矿业大学安全学科群自主创新项目(2022ZZX03). （2022ZZX03）
