寡合体-寡合体与寡合体-合体C(2) -C(2) 合反应在多 Pyrrole 增长过程中
J C Lacroix1, F Maurel, P C Lacaze
1Institut de Topologie et de Dynamique des Systèmes, Université de Paris 7-Denis Diderot, associé au CNRS (UPRES-A 7086), 1 rue Guy de la Brosse, 75005 Paris, France.
Journal of the American Chemical Society
|July 18, 2001
概括
模拟了寡聚烯的电化学氧化过程. 对较长的寡聚烯来说,观察到较短的合距离和更快的水中二元化,影响了聚合物形成机制.
科学领域:
- 电化学 电化学 电化学
- 计算化学计算化学
- 聚合物科学 聚合物科学
背景情况:
- 寡聚烯醇是重要的导电聚合物.
- 了解它们的激素离子合是控制聚合的关键.
研究的目的:
- 为了建模C(2) -C(2) '合反应的小聚烯基根基-.
- 研究寡合体长度和溶剂对合机制的影响.
主要方法:
- 使用过渡状态计算.
- 电化学氧化产生了基子 - - 离子.
- 溶剂效应被纳入模型中.
主要成果:
- 过渡状态中的合距离随着寡合体长度的增加而减少.
- 在气相中,二元化速率下降,但在水中,随着寡合体的长度而增加.
- 对于四氧化和六氧化的形成,寡合体-单体合比寡合体-寡合体合更快.
结论:
- 溶剂的极性显著影响了寡聚烯基基的基离子二元化速率.
- 长时间的奥利戈皮罗尔形成的机制可能涉及dcation-neutral单元合.
- 这些发现为控制烯衍生物的电聚合提供了洞察力.
相关概念视频
Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
Five-Membered Heterocyclic Aromatic Compounds: Overview
Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom, respectively.
Pericyclic Reactions: Introduction
Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...


