二胺的反应:液相和固体-液相转移催化剂由N,N",N",N" - 甲基二乙胺
Yun Ma1, Ryan A Woltornist1, Russell F Algera1
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States.
Journal of the American Chemical Society
|August 10, 2021
概括
含有N,N,N′,N′′-五甲基二甲基胺 (PMDTA) 的DMEA和碳化合物的二甲基胺 (NaDA) 与各种有机化合物进行有效反应. 在PMDTA
科学领域:
- 有机化学
- 催化剂
- 反应机制
背景情况:
- 二胺 (NaDA) 是有机合成中使用的强基.
- 氨基添加剂可以影响基媒反应的反应性和选择性.
- 了解PMDTA等添加剂的作用对于优化反应条件至关重要.
研究的目的:
- 调查DMEA与PMDTA混合中的NaDA的反应性.
- 将PMDTA与TMEDA的催化效能进行比较.
- 阐明PMDTA在NaDA中介反应中的三功能性和可溶性的机制作用.
主要方法:
- 使用各种基质 (化物,环氧化物等) 的反应动力学研究. ) 的情况.
- 计算研究以了解协调和反应性.
- 与PMDTA和没有PMDTA的催化活性以及与TMEDA的催化活性进行比较.
- 探索固体液体相转移催化 (SLPTC) 条件.
主要成果:
- 在DMEA/碳化合物混合物中的NaDA与PMDTA会与广泛的有机基质发生反应.
- 由于其三功能性和可溶性,PMDTA具有显著的催化加速 (> 30倍).
- 反应通过完全基于单体的途径进行.
- 超过10次,PMDTA没有抑制,这表明其具有很高的催化稳定性.
结论:
- PMDTA是一种高效的纳达介导反应催化剂,其性能优于TMEDA.
- PMDTA的三功能性和可溶性是其催化活性的关键.
- 在异质条件下优化这些反应提供了一个有希望的途径.
更多相关视频
相关概念视频
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
2.5K
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.
2.5K
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
2.0K
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
2.0K
Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia
9.8K
Alkynes can be reduced to trans-alkenes using sodium or lithium in liquid ammonia. The reaction, known as dissolving metal reduction, proceeds with an anti addition of hydrogen across the carbon–carbon triple bond to form the trans product. Since ammonia exists as a gas (bp = −33°C) at room temperature, the reaction is carried out at low temperatures using a mixture of dry ice (sublimes at −78°C) and acetone.
When dissolved in liquid ammonia, an alkali metal,...
When dissolved in liquid ammonia, an alkali metal,...
9.8K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
4.2K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
4.2K
Diazonium Group Substitution: –OH and –H
3.0K
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
3.0K
Preparation of Amides
3.4K
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
3.4K


