溶液中的s-nitrosothiols的催化分解:一个理论和实验研究
Yi-Lei Zhao1, Patrick R McCarren, K N Houk
1Department of Chemistry and Biochemistry, University of California-Los Angeles, Los Angeles, CA 90095-1569, USA.
Journal of the American Chemical Society
|August 4, 2005
概括
这项研究揭示了一种新的链机制,解释了S-nitrosothiol (RSNO) 快速分解. 这种机制解释了氧化剂如何加速RSNO分解,而抗氧化剂如何抑制RSNO分解.
科学领域:
- 化学动力学 化学动力学
- 有机化学 有机化学
- 生物化学 生物化学
背景情况:
- 在氧化条件下,S-尼特罗斯醇 (RSNO) 在溶液中迅速分解.
- S-N 键的同解并不能完全解释观察到的分解速率.
研究的目的:
- 为S-nitrosothiol分解提出一种新的阴阳链机制.
- 为了解释尼特罗斯醇化学中的无法解释的观察结果.
主要方法:
- 关于阴离子链机制的理论建议.
- 动力数据和化学反应性的分析.
主要成果:
- 提出了一种涉及化中间体和酸的阴离子链机制.
- 这种机制解释了氧化剂 (O2,NO) 的加速和抗氧化剂 () 的抑制.
- 该机制解释了硫的替代依赖性和非整体的动态顺序.
结论:
- 拟议的阴阳链机制为S-尼托索醇分解提供了全面的解释.
- 这种机制为生物和化学系统中二醇的反应性提供了新的见解.
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相关概念视频
Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
SN2 Reaction: Mechanism
The kinetic studies of SN2 reactions suggest an essential feature of its mechanism: it is a single-step process without intermediates. Here, both the nucleophile and the substrate participate in the rate-determining step.
The presence of the more electronegative halogen in the substrate creates a polarized carbon-halide bond. The halide pulls the electron cloud generating an electrophilic center at the carbon atom. Thus, the carbon atom carries a partial positive charge while the halide has a...
The presence of the more electronegative halogen in the substrate creates a polarized carbon-halide bond. The halide pulls the electron cloud generating an electrophilic center at the carbon atom. Thus, the carbon atom carries a partial positive charge while the halide has a...
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.
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.
2° Amines to N-Nitrosamines: Reaction with NaNO2
Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
Nitrosation of Enols
The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
