可回收的无合物催化剂用于乙酸盐的氧碳化
Wenyu Wang1, Zhusong Cao1, Yuya Hu1,2
1Leibniz Institute for Catalysis e.V. (LIKAT Rostock), Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
ChemSusChem
|June 27, 2025
概括
一种新的无联体催化剂有效地将乙酸盐转化为基酸盐. 这种廉价和可回收的系统实现了高产量和选择性,提供了可持续的工业解决方案.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 绿色化学 绿色化学
背景情况:
- 对于工业应用来说,直接碳化C ((sp3) -Cl键是具有挑战性的.
- 目前的方法往往依赖于昂贵的贵金属和不可回收的配体.
- 由于催化剂成本和恢复问题,可扩展性有限.
研究的目的:
- 开发一种成本效益高,可回收的催化剂,用于氧碳化.
- 为了使从乙酸盐中合成dialkyl malonates.
- 为工业化工合成提供可持续的替代品.
主要方法:
- 开发一种使用CoCO3.3的无联体基催化剂.
- 对乙酸盐的氧碳化反应反应条件的优化.
- 在多个循环中研究催化剂的可回收性和活性.
- 使用福里埃变换红外光谱学识别活性物种.
主要成果:
- 达到高达99%的产品产量,几乎100%的化学选择性.
- 证明高催化剂活性和选择性,即使经过8次回收 (>95%的产量).
- 消除了对溶剂和相移转剂的需求.
- 确定了活跃的催化物种为[Co(CO) ]-.
结论:
- 无联体的催化剂是高效的,有选择性的,可回收用于dialkyl malonate合成.
- 该系统为工业氧碳化提供了一种具有成本效益和环保性的替代方案.
- 催化剂的可回收性和低负载性为大规模工业实施提供了显著的潜力.
相关概念视频
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
19.0K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
19.0K
Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives
2.8K
Aldehydes are more reactive than carboxylic acids and hence, can get over-reduced to alcohol in the presence of strong reducing agents. Therefore, carboxylic acids are inefficient in preparing aldehydes using LAH.
Carboxylic acid derivatives like acid chlorides and esters are more easily reducible than the corresponding acids. The derivatives reduce in the presence of mild reducing agents to give aldehydes. Aldehydes can also be prepared by Rosenmund reduction, that is, the reduction of...
Carboxylic acid derivatives like acid chlorides and esters are more easily reducible than the corresponding acids. The derivatives reduce in the presence of mild reducing agents to give aldehydes. Aldehydes can also be prepared by Rosenmund reduction, that is, the reduction of...
2.8K
Oxidations of Aldehydes and Ketones to Carboxylic Acids
4.2K
Oxidation of aldehydes and ketones results in the formation of carboxylic acids. Aldehydes, bearing hydrogen next to the carbonyl group, are easily oxidized compared to ketones. This is because an aldehydic proton can easily be abstracted during oxidation.
Aldehydes readily undergo oxidation in strong oxidizing agents such as potassium permanganate and chromic acid. The oxidation can also be carried out using mild oxidizing agents such as silver oxide. In fact, aldehydes can be easily oxidized...
Aldehydes readily undergo oxidation in strong oxidizing agents such as potassium permanganate and chromic acid. The oxidation can also be carried out using mild oxidizing agents such as silver oxide. In fact, aldehydes can be easily oxidized...
4.2K
Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation
4.4K
Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
The carbonyl center is...
The carbonyl center is...
4.4K
Alkynes to Carboxylic Acids: Oxidative Cleavage
5.7K
Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions...
5.7K
Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids
3.7K
Although it is possible to reduce a carboxylic acid to an aldehyde, strong reducing agents, like lithium aluminum hydride (LAH), prohibit a controlled reduction, instead causing the generated aldehyde to instantly over-reduce to a primary alcohol.
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H]...
Reducing carboxylic acid derivatives like acyl chlorides (RCOCl), esters (RCO2R′), and nitriles (RCN) using milder aluminum hydride agents like lithium tri-tert-butoxyaluminum hydride [LiAlH(O-t-Bu)3] and diisobutylaluminum hydride [DIBAL-H]...
3.7K


