关于使用尼特罗尼尔氧化物区分氧化物和氧化的区别
Uri Samuni1, Yuval Samuni, Sara Goldstein
1Department of Chemistry and Biochemistry, Queens College, City University of New York, Flushing, New York 11367, USA.
Journal of the American Chemical Society
|May 28, 2010
概括
使用基氧化物检测氧化 (NO) 复杂化,氧化 (HNO) 反应形成氧胺. 尼烯氧化物只能在低度下区分NO和HNO.
科学领域:
- 生物化学 生物化学
- 化学生物学 化学生物学
- 生理学 生理学 生理学
背景情况:
- 精确检测氧化 (NO) 和化 (HNO) 对于理解它们的生物作用至关重要.
- 尼烯氧化物,如C-PTIO,通常用于检测NO通过其反应形成imino氧化物.
研究的目的:
- 为了研究HNO和尼烯氧化物之间的反应机制.
- 确定HNO与C-PTIO反应的速率常数.
- 评估基氧化物在NO和HNO之间区分的潜力.
主要方法:
- 使用安吉利盐 (AS) 作为HNO供体.
- 采用甲基球蛋白作为一个竞争剂来量化反应速率.
- 用光谱分析识别反应产物.
主要成果:
- HNO很容易与基氧化物 (例如,C-PTIO,PTIO) 反应,形成伊米诺氧化物和氧胺.
- 通过HNO减少C-PTIO的速率常数被确定为 (1.4 ± 0.2) x 10^5 M^-1 s^-1 在pH7.0时.
- 完全转化为伊米诺氧胺发生在较高的AS与基氧化物比率.
结论:
- 尼нил氧化物被HNO降解为氧胺,然后转化为伊米诺氧化物和伊米诺氧胺.
- 反应途径只允许在氧化和氧化的度明显低于氧化生产时区分NO和HNO.
相关概念视频
01:261° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
01:19Nitrosation 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.
01:202° 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.
01:371° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
02:52Resonance
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N-O and N=O bonds.
01:28Structures of Carboxylic Acid Derivatives
Structure of Carboxylic Acid Derivatives
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...