基拉替代N-乙烯氨酸胺的无溶剂合成:X射线结构和DFT研究
Guadalupe Hernández Téllez1, José A Reyes-Avendaño2, José M Bravo-Arredondo3,4
1Benemérita Universidad Autónoma de Puebla, Laboratorio de Síntesis de Complejos, Facultad de Ciencias Químicas, Edificio FCQ-6, Ciudad Universitaria, Av. San Claudio y Blvd. 14 Sur, Col. San Manuel, C.P. 72592, Puebla, Pue., México.
ACS omega
|November 10, 2025
概括
这项研究报告了 chiral imines 的无溶剂合成,揭示了替代剂如何控制电子特性和手术活动. 这些发现指导了新型光电子和功能性合材料的设计.
科学领域:
- 有机合成 有机合成
- 材料科学 材料科学 材料科学
- 计算化学的计算化学
背景情况:
- 状物质是功能性材料的有价值的构建块.
- 了解结构属性关系对于设计新材料至关重要.
- 无溶剂合成为环境带来了好处.
研究的目的:
- 通过无溶剂的方法合成新型的基拉替代N-基基尼林.
- 调查替代剂和晶体包装对其性能的影响.
- 通过实验和理论方法探索它们的电子,光学和手术特征.
主要方法:
- 无溶剂合成和物理化学表征.
- 用于分析晶体包装的X射线晶体学.
- 密度函数理论 (DFT) 计算,包括边境分子轨道和TD-DFT分析.
- 电子循环二元化 (ECD) 光谱.电子循环二元化 (ECD) 光谱.
- 自然键轨道 (NBO) 和分子中的原子量子理论 (QTAIM) 分析.
主要成果:
- 五种性伊米因 (I-V) 的高产合成.
- 晶体包装受硬质效应的控制;评估了素结合的染色贡献.
- 在imines III和V中的电子移位导致更小的HOMO-LUMO间隙,增强的电荷转移和更强的棉花效应.
- DFT计算准确地复制了实验结构和光学特性,包括紫外线光谱.
- NBO和QTAIM分析显示了稳定相互作用和弱Cl-Cl接触,影响了超分子组合.
结论:
- 替代剂在调节这些 imines 的电子结构,电荷传输能力和手术活动方面发挥着关键作用.
- 这项研究提供了对基于 imine 的材料结构属性关系的见解.
- 这些发现指导了先进的光电子和功能性合材料的合理设计.
相关概念视频
Structure of Amines
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The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are...
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Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
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Primary amines react with carbonyl compounds—aldehydes and ketones—to generate imines. Imines consist of a C=N double bond and are named Schiff bases after its discoverer—the German chemist Hugo Schiff. On the other hand, secondary amines react with carbonyl compounds to give enamines. In enamines, the presence of a C=C double bond adjacent to the nitrogen atom leads to the delocalization of the lone pair.
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Aldehydes and Ketones with Amines: Imine Formation Mechanism
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Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
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Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
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Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
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Chirality at Nitrogen, Phosphorus, and Sulfur
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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
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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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