以CO<sub>2</sub>为羧基源温和高效制水杨酸类化合物

郑修畅; 李国玲; 赵云; 倪中海; 陆诗建; 陆超

doi:10.12434/j.issn.2097-2547.20240194

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以CO₂为羧基源温和高效制水杨酸类化合物

低碳分子转化合成 | 更新时间：2025-02-27

- 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
- 低碳化学与化工 2025, 50(2): 53-60.
- 作者机构：
  
  1.中国矿业大学化工学院，江苏徐州 221116
  2.中国矿业大学碳中和研究院，江苏徐州 221116
  3.中电华创电力技术研究有限公司，上海 200086
- 作者简介：
  
  郑修畅（2000—），硕士研究生，研究方向为CO2转化利用，E-mail：919969359@qq.com。
  倪中海（1976—），博士，教授，研究方向为功能有机材料，E-mail：nizhonghai@cumt.edu.cn。
- 基金信息：
  
  江苏省碳达峰碳中和科技创新专项(BE2023852);中国矿业大学安全学科群自主创新项目(2022ZZX03)
- DOI：10.12434/j.issn.2097-2547.20240194
  中图分类号： TQ245.4
- 收稿日期：2024-04-30，
  
  修回日期：2024-05-29，
  
  纸质出版日期：2025-02-25
- 稿件说明：
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郑修畅,李国玲,赵云等.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(02):53-60.

ZHENG Xiuchang,LI Guoling,ZHAO Yun,et al.Mild and efficient preparation of salicylic acid compounds with CO₂ as carboxyl source[J].Low-carbon Chemistry and Chemical Engineering,2025,50(02):53-60.
郑修畅,李国玲,赵云等.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(02):53-60. DOI： 10.12434/j.issn.2097-2547.20240194.

ZHENG Xiuchang,LI Guoling,ZHAO Yun,et al.Mild and efficient preparation of salicylic acid compounds with CO₂ as carboxyl source[J].Low-carbon Chemistry and Chemical Engineering,2025,50(02):53-60. DOI： 10.12434/j.issn.2097-2547.20240194.

摘要

水杨酸类化合物是一种广泛用于医药、香料、染料、农药和橡胶助剂等精细化学品的重要原料。然而基于Kolbe-Schmitt反应，由CO

作为羧基源制备水杨酸类化合物时存在温度高、压力高、反应时间长和收率低等问题。提出了一种通过CO

羧化苯酚或4-取代基苯酚合成水杨酸类化合物的新方法。以KOH为脱质子碱，二甲苯为溶剂，Cs

、K

和2

6-三甲基苯酚钾盐（TMPK）为共催化剂，高效羧化苯酚和4-取代基苯酚制备水杨酸类化合物，并表征了各羧化产物的理化性质。系统考察了催化剂用量、CO

压力、温度、助催化剂用量、反应时间和反应底物等对苯酚和4-取代基苯酚羧化反应的影响，提出了碳酸盐与TMPK共催化合成水杨酸和5-取代基水杨酸可能的反应机理。结果显示，Cs

+ TMPK的催化剂组合有效优化了反应条件，实现了温和条件（温度为120 ℃、 CO

压力为0.5 MPa、

(Cs

(TMPK):

(原料)为1:1:1和反应时间为4 h）下CO

高效羧化苯酚（单程收率为60%）和4-取代基苯酚（单程收率为60%~90%）制备水杨酸类化合物。以该法合成的羧化产物邻位选择性高达100%。

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 CO

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 CO

carboxylation phenol and 4-substituted phenol was presented

which uses KOH as deprotonation base

xylene as solvent

and 2

6-trimethylphenol potassium salt (TMPK) as cocatalysts to achieve CO

efficient carboxylation phenol and 4-substituted phenol. The physicochemical properties of each carboxylation product were characterized. The effects of catalyst dosage

pressure

temperature

cocatalyst dosage

reaction time and reaction substrate on the carboxylation reaction of phenol and 4-substituted phenol were systematically investigated. The po

ssible 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 Cs

+ TMPK effectively optimizes the reaction conditions. Under mild conditions

the preparation of salicylic acid compounds by efficient CO

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

Keywords

references

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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

DOI：10.12434/j.issn.2097-2547.20240194

摘要

Abstract

关键词

Keywords

references

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