使用硫化的环胺的范围和局限性
Roland Appel1, Nicolai Hartmann, Herbert Mayr
1Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13, 81377 München, Germany.
Journal of the American Chemical Society
|December 1, 2010
概括
这项研究使用紫外线对光谱学量化硫化的反应性. 确定了硫化核性参数,为与酸离子和迈克尔受体等电的反应建立了统一的反应性尺度.
科学领域:
- 有机化学 有机化学
- 反应动力学反应动力学
背景情况:
- 硫化物是有机合成中的多功能试剂.
- 量化它们的反应性对于预测反应结果至关重要.
- 目前评估硫化核友性的现有方法是有限的.
研究的目的:
- 为了确定硫化物与各种电友的反应速率.
- 为了确定硫化核友性和电友电友性之间的定量相关性.
- 开发一个统一的硫化物反应度表.
主要方法:
- 使用紫外线光谱法测量DMSO在20°C的反应速率.
- 确定了与基离子和迈克尔受体反应的二次速率常数 (log k(2)).
- 线性自由能量关系被用来将速率常数与电友性参数相关联.
主要成果:
- 在二次速率常数和电友的电友性参数 (E) 之间发现了线性相关性.
- 计算了硫化的核友特异性参数 (N和s).
- 循环化反应的速率常量显示出与一个阶段性机制的一致性,核友攻击作为速率决定的步骤.
结论:
- 该研究提供了第一个对硫化物反应性的定量方法,克服了pK(aH) 相对关系的局限性.
- 为硫化物建立了一个统一的反应度表,适用于与碳酸盐和迈克尔受体的反应.
- 这些发现支持硫化循环化反应的阶段性机制.
相关概念视频
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
Cycloaddition Reactions: MO Requirements for Thermal Activation
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
Stability of Substituted Cyclohexanes
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
Preparation and Reactions of Thiols
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
Limitations of Friedel–Crafts Reactions
Several restrictions limit the use of Friedel–Crafts reactions. First, the halogen in the alkyl halide must be attached to an sp3-hybridized carbon for the Friedel–Crafts reactions to occur. Vinyl or aryl halides do not react since the carbocations formed are unstable under the reaction conditions. Second, Friedel–Crafts alkylation is susceptible to carbocation rearrangement, and the major products obtained have a rearranged carbon skeleton. In contrast, the acylium ion is stabilized by...

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