一种简单,高效和通用的合成方法,用于化物链接的共价有机框架
Zhi-Bei Zhou1, Xiang-Hao Han1, Qiao-Yan Qi1
1Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Journal of the American Chemical Society
|January 17, 2022
概括
研究人员开发了一种新方法来合成稳定的胺共价有机框架 (胺COF). 这种高效的工艺将易于获得的imine COF转化为amide COF,从而提高了材料的可用性.
科学领域:
- 材料科学
- 有机化学
- 纳米技术
背景情况:
- 胺结合的共价有机框架 (胺COF) 为各种应用提供高稳定性和理想的聚胺结构.
- 化物COF的一个重要限制是它们的可访问性受到限制,这阻碍了广泛的实际使用.
- 现有的胺COF合成方法往往复杂或低效.
研究的目的:
- 开发一种简单,高效和可扩展的合成晶体胺COF的方法.
- 通过使用一种新的连接转换策略来克服胺COF的可访问性限制.
- 建立一个探索胺COF实际应用的基础.
主要方法:
- 一种新的结合转换策略,涉及在结合 imine 的 COF 中氧化 imine 结合.
- 在环境条件下使用过氧化 (KHSO5) 作为温和的氧化剂.
- 通过合成七种不同的 imine-linked COF 和克尺度生产,证明了该方法的通用性和可扩展性.
主要成果:
- 通过轻度氧化与伊胺结合的前体成功合成了晶体胺基COF.
- 转化过程是快速的,高效的,在非常温和的反应条件下完成.
- 开发的方法被证明是通用的,可扩展的,并且适用于一系列与 imine 相关的 COF.
结论:
- 已经建立了一种新且高效的方法,用于从易于获得的因胺结合的COF中合成胺基COF.
- 这种方法显著提高了胺COF的可访问性,为其实际实施铺平了道路.
- 开发的合成策略为未来基于聚胺的共价有机框架的探索和利用提供了一个强大的平台.
相关概念视频
01:29Preparation 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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01:28Structures of Carboxylic Acid Derivatives
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Structure of Carboxylic Acid Derivatives
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the...
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the...
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01:19Amines to Amides: Acylation of Amines
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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...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
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01:26Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
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The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...
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01:11Nomenclature of Carboxylic Acid Derivatives: Amides and Nitriles
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Naming Amides
The IUPAC and common names of amides are derived from the parent carboxylic acid, by replacing the suffix “oic acid” and “ic acid,” respectively, with “amide.” In the following example, the IUPAC name ethanamide is derived from ethanoic acid, and the common name, acetamide, is obtained from acetic acid.
The IUPAC and common names of amides are derived from the parent carboxylic acid, by replacing the suffix “oic acid” and “ic acid,” respectively, with “amide.” In the following example, the IUPAC name ethanamide is derived from ethanoic acid, and the common name, acetamide, is obtained from acetic acid.
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01:28Preparation of 1° Amines: Gabriel Synthesis
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Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred method to exclusively make primary amines. The method uses phthalimide, which contains a protected form of nitrogen that participates in alkylation only once to predominantly give primary amines.
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
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