直接从碳酸和酸中合成胺基
Nivedita Bhardwaj1, Nancy Tripathi1, Sanjay Kumar1
1Department of Pharmaceutical Engineering & Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi-221005, India. sjain.phe@iitbhu.ac.in.
Organic & biomolecular chemistry
|September 6, 2023
概括
这项研究引入了一种新型的胺合成方法,使用碳酸和化 (ZnCl2) 催化剂的酸和化. 这种高效的工艺只产生氨气作为副产品,简化了和天然产品衍生物合成.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 胺基键的形成对于合成和自然产品至关重要.
- 现有的方法通常需要恶劣的条件或特殊的试剂.
- 从碳酸和氨基酸直接合成是非常理想的.
研究的目的:
- 开发一种新的,直接的胺合成方法.
- 探索用氨酸作为胺组分在胺合成中的使用.
- 建立一个催化系统,以有效地形成胺基键.
主要方法:
- 使用碳酸和酸作为起始材料.
- 使用大量的催化化 (ZnCl).
- 氨气 (NH3气体) 是唯一的副产品.
主要成果:
- 直接从碳酸和酸中成功合成胺.
- 一个简单而高效的催化方法的演示.
- 确定氨 (NH3) 是唯一的副产品.
结论:
- 这项工作介绍了使用碳酸盐和酸盐直接合成胺的第一份报告.
- 开发的方法为合成和天然产品衍生物提供了一个简单且潜在的可扩展的途径.
- 使用ZnCl2为这种转化提供了一个有效的催化系统.
相关概念视频
Preparation of Amides
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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...
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Amides can undergo either acid-catalyzed hydrolysis or base-promoted hydrolysis through a typical nucleophilic acyl substitution. Each hydrolysis requires severe conditions.
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
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Nitriles (R–CN) can be converted into carboxylic acids (R–COOH) upon treatment with aqueous acids, i.e., upon hydrolysis of nitriles. Under base-catalyzed conditions, carboxylate anions (R–COO−) are formed.
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Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
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Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
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