溶剂对二甲基的稳定性和移位的影响:重新检讨制效应
Joshua P Peterson1, Arthur H Winter1
1Department of Chemistry , Iowa State University , 1608 Gilman Hall , Ames , Iowa 50010 , United States.
Journal of the American Chemical Society
|July 30, 2019
概括
与之前的发现相反,极性溶剂增强了基的稳定性. 这项研究证实了关于溶剂对基结稳定和旋转移位的影响的理论预测.
科学领域:
- 有机化学
- 物理化学
- 计算化学
背景情况:
- 捕获效应描述了通过电子捐赠和接受组增强的基稳定.
- 由于电荷分离的共振形式,理论模型预测极性溶剂中的较大定性.
- 之前的实验研究对溶剂对基质稳定性的影响产生了相互矛盾的结果.
研究的目的:
- 实验性地研究溶剂极性的影响,以稳定captodative基.
- 将理论预测与先前的实验观测之间的差异结合起来.
- 提供直接的实验证据,用于溶剂诱导的基稳定.
主要方法:
- 研究了结构相关的甲基.
- 利用激素及其二极体之间的平衡来测量热力学稳定性.
- 在不同极性的溶剂 (托卢和DMF) 中特征自转移.
主要成果:
- 极性溶剂显著稳定了制基,基-二元关联常数变化高达100倍.
- 极性溶剂促使自旋密度向供体替代物转移,并远离基碳.
- 实验结果与理论预测一致, 支持zwitterionic共振结构的作用.
结论:
- 这项研究提供了第一个直接的实验证据,
- 观察到的溶剂效应支持涉及电荷分离共振形式的理论模型.
- 这一发现证实了先前在实验上有争议的,关于代效应的关键理论预测.
相关概念视频
Radical Reactivity: Steric Effects
2.4K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
Along with electronic...
2.4K
Radical Reactivity: Concentration Effects
1.8K
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
1.8K
Chemical Shift: Internal References and Solvent Effects
1.3K
In an NMR sample, precise measurement of the absolute absorption frequencies of nuclei is difficult. A standard internal reference compound is added, and the frequency difference between the reference signal and sample signals is measured.
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
1.3K
Solvents
70.1K
A solvent is a substance, most often a liquid, that can dissolve other substances. Here, the substance being dissolved is called a solute. When a solvent and a solute combine, they form a solution - a homogenous mixture of both the solvent and the solute. Water is a universal biological solvent. Its polar structure allows it to dissolve many other polar compounds. The ability of water to dissolve is governed by a balance between water molecules binding to each other and binding to the solute.
A...
A...
70.1K
IR Absorption Frequency: Delocalization
1.3K
Electron delocalization refers to the distribution of electrons across multiple atoms within a molecule rather than being confined to a single atom or bond. This phenomenon is common in systems with conjugated bonds—structures where alternating single and double bonds allow π-electrons to move freely across the network. The movement of electrons stabilizes the molecule and can affect various chemical properties, including vibrational frequencies observed in IR spectroscopy.
In IR...
In IR...
1.3K
Nomenclature of Aryl and Heterocyclic Amines
3.1K
The simplest aromatic amine is phenylamine, which contains an –NH2 functionality directly attached to an aromatic ring. The name aniline is designated for this skeleton. As shown in Figure 1, the common names of the functionalized anilines involve prefixes ortho-, meta-, and para- to indicate the substitution position. Different functionalized aniline derivatives also have notable trivial names.
3.1K


