关于在分子-根反应中预反应复合物的重要性:通过OH从化物中提取
J R Alvarez-Idaboy1, N Mora-Diez, R J Boyd
1Laboratorio de Química Computacional y Teórica, Facultad de Química, Universidad de La Habana, Havana 10400, Cuba.
Journal of the American Chemical Society
|July 18, 2001
概括
这项研究描述了基与甲和甲的反应,发现提取是有利的. 计算的反应速率与实验数据一致,突出显示了前反应复合物的重要性.
科学领域:
- 大气化学 大气化学
- 化学动力学 化学动力学
- 计算化学计算化学
背景情况:
- 基 (OH) 反应在大气化学中至关重要.
- 了解OH与甲和乙等小合物的反应对于大气建模至关重要.
研究的目的:
- 通过计算来研究OH + 甲和OH + 乙的反应机制和动力学.
- 确定这些反应的首选反应路径和激活能量.
主要方法:
- 使用了精确的初始量子化学方法,使用了大基数集.
- 采用了经典的过渡状态理论,包括预反应复合体形成.
- 计算的反应速率常数.
主要成果:
- 抽取是主要的反应途径;OH添加是不利的.
- 获得了接近零的 (甲) 和负的 (乙) 激活能量,与实验值相匹配.
- 计算的速率常数准确地重现了实验数据.
结论:
- 理论模型,包括预反应复合体,成功地解释了实验动力学.
- 精确计算能量障碍和道化因素对于理解这些大气反应至关重要.
相关概念视频
Synthesis and Decomposition Reactions
Synthesis and decomposition are two types of redox reactions. Synthesis means to make something, whereas decomposition means to break something. The reactions are accompanied by chemical and energy changes.
Nucleophilic Substitution Reactions
Historical perspective
In 1896, the German chemist Paul Walden discovered that he could interconvert pure enantiomeric (+) and (-) malic acids through a series of reactions. This conversion suggested the involvement of optical inversion during the substitution reaction. Further, in 1930, Sir Christopher Ingold described for the first time two different forms of nucleophilic substitution reactions, which are known as SN1 (nucleophilic substitution unimolecular) and SN2 (nucleophilic substitution...
In 1896, the German chemist Paul Walden discovered that he could interconvert pure enantiomeric (+) and (-) malic acids through a series of reactions. This conversion suggested the involvement of optical inversion during the substitution reaction. Further, in 1930, Sir Christopher Ingold described for the first time two different forms of nucleophilic substitution reactions, which are known as SN1 (nucleophilic substitution unimolecular) and SN2 (nucleophilic substitution...
Preparation of Alcohols via Substitution Reactions
Overview
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
Preparation of Diols and Pinacol Rearrangement
Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
C–C Bond Formation: Aldol Condensation Overview
Aldol condensation is an important route in synthetic organic chemistry used to generate a new carbon–carbon bond under basic or acidic conditions. The aldol condensation reaction presented in Figure 1 constitutes an aldol addition reaction followed by the dehydration process.
C–C Bond Cleavage: Retro-Aldol Reaction
The reverse of the aldol addition reaction is called the retro-aldol reaction. Here, the carbon–carbon bond in the aldol product is cleaved under acidic or basic conditions to form two molecules of carbonyl compounds. The mechanism of the reaction consists of three steps.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.


