相关实验视频
Updated: Jul 9, 2026

06:53
Fabrication and Optimization of Type II Silicon Clathrate Films
Published on: October 14, 2025
在酸中的β效应
Valentina Dichiarante1, Andrea Salvaneschi, Stefano Protti
1Department of Organic Chemistry, University of Pavia, viale Taramelli 10, 27100 Pavia, Italy.
Journal of the American Chemical Society
|December 7, 2007
概括
三甲基基 (TMS) 基稳定了在化的光异质解过程中形成的正氧基基. 这种β效应将化学物质引导到单片酸,并允许轻松,单光移动的化.
科学领域:
- 摄影化学的使用.
- 有机化学 有机化学
- 有机合成 有机合成
背景情况:
- 化的光异质解产生化.
- 替代剂对反应中间体的影响尚未完全理解.
- 整形替代的化是光化学中的关键基质.
研究的目的:
- 为了研究对正三甲基基的β作用.
- 为了比较化和非化酸盐的反应性.
- 探索作为光化学反应中的指导和可移动组的潜力.
主要方法:
- 在酒精溶剂中光化学辐射正三甲基替代的化,和N,N-二甲基.
- 反应结果与无类似物进行比较.
- 在UB3LYP/6-311+G(2d,p) 层面使用密度函数理论 (DFT) 的计算分析.
主要成果:
- 三甲基 (TMS) 基对-键光裂变的影响很小,但可显著稳定三重 (4 kcal/mol) 和单重 (9 kcal/mol) 酸.
- 在化和中,有利于系统间交叉到更稳定的单基离子,从而产生高效的乙烯形成.
- 通过在酒精中通过光诱导的 protiodesilylation 消除 TMS 组,作为可光移动的指导组.
结论:
- 的β效应稳定了酸,使其能够控制光化学反应途径.
- 可以使用TMS组作为指导组来获取单片基离子化学.
- 这项研究展示了光化学化和随后的轻松去除的单程序.
相关概念视频
Types of Semiconductors
Intrinsic semiconductors are highly pure materials with no impurities. At absolute zero, these semiconductors behave as perfect insulators because all the valence electrons are bound, and the conduction band is empty, disallowing electrical conduction. The Fermi level is a concept used to describe the probability of occupancy of energy levels by electrons at thermal equilibrium. In intrinsic semiconductors, the Fermi level is positioned at the midpoint of the energy gap at absolute zero. When...
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.
Carbocations
Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Radical Reactivity: Steric Effects
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 factors, steric factors also account...
Along with electronic factors, steric factors also account...

