二次同位素对碳素酸和的酸度的影响
Charles L Perrin1, Yanmei Dong
1Department of Chemistry 0358, University of California-San Diego, La Jolla, California 92093-0358, USA. cperrin@ucsd.edu
Journal of the American Chemical Society
|March 16, 2007
概括
乳同位素对酸度的影响 (IEs) 测量了碳素酸和. 化降低了酸度,不管的位置如何,IEs在芳香酸中具有惊人的稳定性.
科学领域:
- 物理化学 物理化学
- 有机化学 有机化学
- 同位素效应的影响
背景情况:
- 二次同位素效应 (IEs) 提供了对分子结构和结合的洞察.
- 了解酸度和质子转移机制在化学中至关重要.
研究的目的:
- 准确测量二次同位素对碳酸和的酸度的影响.
- 调查位置对这些同位素效应的影响.
- 用计算方法阐明二次同位素效应的起源.
主要方法:
- 测量同位素效应的NMR定位方法,用于测量同位素异构物混合物的同位素效应.
- 初学者计算化学用于理论支持.
主要成果:
- 化始终降低了酸度 (高达0.031在DeltaPK每D).
- 在亚酸酸中,IEs随着离酸性质子的距离而减少.
- 一个令人惊的发现:和酸中的IE保持不变,无论的位置如何 (ortho,meta,para).
- Ab initio计算高估了实验IEs,其中的差异没有归因于solvation.
结论:
- 二次同位素效应主要是由同位素敏感振动在去质子化时零点能量的变化所决定的.
- 对于芳香酸,振动分析和电子密度解释了观察到的IE,与简单的移位或感应效应相矛盾.
- 该研究提供了证据证明这些同位素效应的诱导起源.
相关概念视频
Substituent Effects on Acidity of Carboxylic Acids
The acidity of carboxylic acids is influenced by the nature of the substituents bounded to the functional group. The acid strength is determined by the stability of the carboxylate anion—the conjugate base formed by dissociating the corresponding carboxylic acid.
Acidity of Carboxylic Acids
Carboxylic acids are the strongest organic acids. However, their acidic strength is much less than mineral acids like HCl. Carboxylic acids ionize in water and readily lose the hydroxyl proton to form a resonance-stabilized carboxylate ion.
Acidity and Basicity of Carboxylic Acid Derivatives
Carboxylic acids are the strongest among organic acids, as they readily lose the hydroxyl proton to form a resonance-stabilized carboxylate ion. In comparison, the acid derivatives lack acidic hydrogens directly attached to a functional group. In these compounds, the acidic nature arises from their ability to lose α hydrogens, making them weakly acidic.
The relative acidic strength of the derivatives can be explained based on the extent of resonance stabilization of the conjugate base. The...
The relative acidic strength of the derivatives can be explained based on the extent of resonance stabilization of the conjugate base. The...
Acidity and Basicity of Alcohols and Phenols
Like water, alcohols are weak acids and bases. This is attributed to the polarization of the O–H bond making the hydrogen partially positive. Moreover, the electron pairs on the oxygen atom of alcohol make it both basic and nucleophilic. Protonation of an alcohol converts hydroxide, a poor leaving group, into water—a good one. The two acid–base equilibria corresponding to ethanol are depicted below.
NMR and Mass Spectroscopy of Carboxylic Acids
In ¹H NMR spectroscopy, acidic protons (–COOH) of carboxylic acids are highly deshielded and absorb far downfield, at around 9–12 ppm. The chemical shift value depends on the concentration and solvent used.
While α protons of carboxylic acids absorb at 2–2.5 ppm, β protons absorb further upfield.
Carboxylic acids are easily identified by dissolving them in deuterium oxide, which results in a rapid exchange of the acidic protons with deuterium. This leads to the disappearance of the acidic...
While α protons of carboxylic acids absorb at 2–2.5 ppm, β protons absorb further upfield.
Carboxylic acids are easily identified by dissolving them in deuterium oxide, which results in a rapid exchange of the acidic protons with deuterium. This leads to the disappearance of the acidic...
Acid Strength and Molecular Structure
Binary Acids and Bases
In the absence of any leveling effect, the acid strength of binary compounds of hydrogen with nonmetals (A) increases as the H-A bond strength decreases down a group in the periodic table. For group 17, the order of increasing acidity is HF < HCl < HBr < HI. Likewise, for group 16, the order of increasing acid strength is H2O < H2S < H2Se < H2Te. Across a row in the periodic table, the acid strength of binary hydrogen compounds increases with increasing...
In the absence of any leveling effect, the acid strength of binary compounds of hydrogen with nonmetals (A) increases as the H-A bond strength decreases down a group in the periodic table. For group 17, the order of increasing acidity is HF < HCl < HBr < HI. Likewise, for group 16, the order of increasing acid strength is H2O < H2S < H2Se < H2Te. Across a row in the periodic table, the acid strength of binary hydrogen compounds increases with increasing...


