苯多羧酸与二氧化碳羧化过程中产物分布与分子特性之间关系的深入研究

IF 1.3 4区 工程技术 Q3 CHEMISTRY, ORGANIC
Rong Wang, Gang Liu, Yu-Qin Sun, Yu-Gao Wang, Jun Shen, Yan-Xia Niu
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引用次数: 0

摘要

摘要 二氧化碳是一种重要的碳资源,可通过羧化反应进行化学利用。本文以 Cs2CO3 为催化剂,进行了苯多羧酸(BPCAs)与 CO2 的羧化反应。通过结合苯并多羧酸与 CO2 羧化反应中分子性质的实验和量子化学计算,探讨了产物分布与苯并多羧酸反应位点 Mulliken 电荷之间的关系。研究发现负 Mulliken 电荷有利于 BPCAs 反应位点的羧化反应。取氢是羧化反应的决定性步骤,计算了 BPCA 分子中不同 C-H 的能垒。结果表明,Mulliken 电荷较负的 C-H 键更容易去质子化,这进一步验证了上述结论。该研究为根据 BPCA 的 Mulliken 电荷预测 BPCA 与 CO2 之间羧化反应的产物分布提供了一种简便的方法。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Insight into Relationship between the Products Distribution and Molecular Properties in Carboxylation between Benzene Polycarboxylic Acids and CO2

Insight into Relationship between the Products Distribution and Molecular Properties in Carboxylation between Benzene Polycarboxylic Acids and CO2

CO2 is an important carbon resource, which could be chemically utilized by carboxylation. In this paper, the carboxylation between benzene polycarboxylic acids (BPCAs) and CO2 was conducted using Cs2CO3 as a catalyst. The relationship between the product distribution and Mulliken charge at the reaction site of BPCAs was explored by combining experiments and quantum chemical calculations of molecular properties in the reaction of carboxylation between BPCAs and CO2. The negative Mulliken charge was found to facilitate carboxylation at the reaction site of BPCAs. Hydrogen abstraction was the rate-determining step for carboxylation, and its energy barrier was calculated for different C–H in the BPCA molecule. The results showed that the C–H bond with the more negative Mulliken charge was more easily deprotonated, which further verified the above conclusion. The study provides a convenient approach to predict a product distribution for carboxylation between BPCAs and CO2 according to the Mulliken charge of BPCAs.

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来源期刊
Petroleum Chemistry
Petroleum Chemistry 工程技术-工程:化工
CiteScore
2.50
自引率
21.40%
发文量
102
审稿时长
6-12 weeks
期刊介绍: Petroleum Chemistry (Neftekhimiya), founded in 1961, offers original papers on and reviews of theoretical and experimental studies concerned with current problems of petroleum chemistry and processing such as chemical composition of crude oils and natural gas liquids; petroleum refining (cracking, hydrocracking, and catalytic reforming); catalysts for petrochemical processes (hydrogenation, isomerization, oxidation, hydroformylation, etc.); activation and catalytic transformation of hydrocarbons and other components of petroleum, natural gas, and other complex organic mixtures; new petrochemicals including lubricants and additives; environmental problems; and information on scientific meetings relevant to these areas. Petroleum Chemistry publishes articles on these topics from members of the scientific community of the former Soviet Union.
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