从环氧化物和二氧化碳中形成循环碳酸盐的催化剂的氨基-MeOH二元系统:一个DFT机理性调查
Young Kee Kang1, Hae Sook Park2
1Department of Chemistry, Chungbuk National University, Cheongju, Chungbuk 28644, Republic of Korea.
The Journal of organic chemistry
|April 8, 2025
概括
氨基/MeOH二元系统有效地催化了从氧化物 (PO) 和CO2中形成碳酸盐 (PC). 这些系统显著降低了激活能量,罗利丁/MeOH显示出增强的同质催化活性.
科学领域:
- 计算化学计算化学
- 催化剂是一种催化剂.
- 绿色化学 绿色化学
背景情况:
- 碳酸 (PC) 是一种有价值的化学中间体.
- 从氧化物 (PO) 和二氧化碳中有效合成PC对于可持续的化学生产至关重要.
- 氨基和酒精联合催化剂系统提供了增强反应速度的潜力.
研究的目的:
- 阐明从PO和CO2中形成PC的详细DFT催化机制.
- 调查氨/MeOH二元系统作为催化剂的作用.
- 为了比较不同氨基的催化效率 (MeNH2,Me2NH,Me3N,pyrrolidine) 与MeOH.
主要方法:
- 用密度函数理论 (DFT) 的计算来建模反应路径.
- 对环开启和环关闭步骤的过渡状态 (ts1和ts2) 的研究.
- 对催化和未催化通路的激活能量障碍的分析.
主要成果:
- 在所有研究的系统中,环闭阶段被确定为速度决定的阶段.
- 与未催化途径相比,氨基/MeOH二元系统显著减少了约20kcalmol-1的激活障碍.
- Me2NH/MeOH和pyrrolidine/MeOH系统在测试的阿里法胺中表现出更高的催化效率.
结论:
- 氨基/MeOH二进制系统为PC合成提供了有效的催化路径.
- 作为一种与MeOH的液态同质催化剂,由于与PO的混合性更好,Pyrrolidine提供了更好的性能.
- DFT研究为优化PC形成催化剂提供了有价值的机理见解.
相关概念视频
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
2.1K
Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.
2.1K
Base-Catalyzed Ring-Opening of Epoxides
8.1K
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
8.1K
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
3.3K
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
3.3K
Acid-Catalyzed Ring-Opening of Epoxides
7.0K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
7.0K
Aldol Condensation with β-Diesters: Knoevenagel Condensation
2.9K
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.
2.9K
Ethers from Alkenes: Alcohol Addition and Alkoxymercuration-Demercuration
7.7K
Overview
Ethers can also be prepared from alkenes through acid-catalyzed addition of alcohols and alkoxymercuration–demercuration.
Preparation of Ethers by Acid-Catalyzed Addition of Alcohol to Alkenes
The acid-catalyzed addition of alcohol to an alkene involves treating the alkene with an excess of alcohol in the presence of an acid catalyst to form an ether under suitable conditions. The hydrogen will add to the less substituted carbon so that the nucleophile can attack the more...
Ethers can also be prepared from alkenes through acid-catalyzed addition of alcohols and alkoxymercuration–demercuration.
Preparation of Ethers by Acid-Catalyzed Addition of Alcohol to Alkenes
The acid-catalyzed addition of alcohol to an alkene involves treating the alkene with an excess of alcohol in the presence of an acid catalyst to form an ether under suitable conditions. The hydrogen will add to the less substituted carbon so that the nucleophile can attack the more...
7.7K


