从OH-异烯反应中得到的基碳酸的量化
Jun Zhao1, Renyi Zhang, Edward C Fortner
1Department of Atmospheric Sciences, Texas A&M University, College Station, Texas 77843, USA. zhang@ariel.met.tamu.edu
Journal of the American Chemical Society
|March 5, 2004
概括
研究人员使用质子转移反应质谱法 (PTR-MS) 来量化来自异烯反应的碳酸. 这项研究有助于缩小异二烯的碳预算,并改善大气化学模型.
科学领域:
- 大气化学 大气化学
- 有机化学 有机化学
- 频谱学是一种光谱学.
背景情况:
- 异烯是一种主要的生物原挥发性有机化合物,但其大气氧化产物尚未完全理解.
- 碳酸是异烯氧化的重要产物,影响空气质量和气候.
- 准确量化这些产品对于大气模型至关重要.
研究的目的:
- 从OH启动的异烯反应中量化基碳烯.
- 调查反应机制并确定关键中间体.
- 提高对热层臭氧形成和碳化合物化学的理解.
主要方法:
- 使用了与质子转移反应质谱学 (PTR-MS) 合的流动反应器.
- 量化C5-和C4-基碳酸和不和碳酸C5H8O.
- 在受控压力下进行的实验 (约. 100 Torr) 和温度 (298 K) 的情况.
主要成果:
- 确定C5-和C4-基碳酸的产量分别为 (19.3 ± 6.1)%和 (3.3 ± 1.6%).
- 对于不和碳烯C5H8O的产量为 (8.4 ± 2.4)%,证实了对异烯的轻微OH添加.
- 量化碳化合物占以前未量化的碳,使异烯碳封闭成为可能.
结论:
- 该研究成功量化了关键的基碳基,有助于关闭异烯碳预算.
- 揭示了对delta-hydroxyalkoxy基因降解机制的新见解.
- 证明了PTR-MS对碳化合物反应产品量化的实用性,影响了大气化学研究.
相关概念视频
Multiple Halogenation of Methyl Ketones: Haloform Reaction
A method involving the transformation of methyl ketones to carboxylic acids using excess base and halogen is called the haloform reaction. It begins with the deprotonation of α hydrogen to form an enolate ion which reacts with the electrophilic halogen to give an α-halo ketone. The step continues until all the α protons are substituted to form a trihalomethyl ketone. The resulting molecule is unstable, and in the presence of a hydroxide base, it readily undergoes nucleophilic acyl substitution.
Mass Spectrometry: Molecular Fragmentation Overview
The ionization of a molecule into a molecular ion inside the mass spectrometer causes instability in the molecule's structure due to the loss of an electron. This eventually leads to the fragmentation or breaking of some bonds in the molecule. The fragmentation occurs predominantly at specific bonds to yield relatively stable fragments.
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...
Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation
The fragmentation patterns observed for compounds such as carboxylic acids, esters, and amides in the mass spectra include ⍺-cleavage and McLafferty rearrangement. Fragmentation by ⍺-cleavage preferentially occurs at the carbon-carbon bond at the ⍺-position next to the carboxylic group to generate a neutral radical and a cation. Long chain compounds with hydrogen at their γ-carbon undergo McLafferty rearrangement to give a radical cation and a neutral alkene.
For example, the fragmentation of...
For example, the fragmentation of...
Acid-Catalyzed Aldol Addition Reaction
The aldol reaction of a ketone under acidic conditions successfully forms an unsaturated carbonyl as the final product instead of an aldol. The acid-catalyzed aldol reaction is depicted in Figure 1.
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an alkylated β-keto acid.
Reactions of Carboxylic Acids: Introduction
Carboxylic acids possess an acidic –COOH functional group. The acidity can be attributed to the resonance stabilization of their conjugate base, wherein the negative charge is delocalized over both oxygen atoms.


