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相关概念视频

Base-Promoted α-Halogenation of Aldehydes and Ketones00:51

Base-Promoted α-Halogenation of Aldehydes and Ketones

4.3K
α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base.  The reaction begins with the abstraction of  α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction...
4.3K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones01:21

Acid-Catalyzed α-Halogenation of Aldehydes and Ketones

5.0K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
5.0K
Halogenation of Alkenes02:46

Halogenation of Alkenes

20.6K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
20.6K
Nucleophilic Aromatic Substitution: Elimination–Addition01:11

Nucleophilic Aromatic Substitution: Elimination–Addition

5.3K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
5.3K
Acid Halides to Carboxylic Acids: Hydrolysis01:01

Acid Halides to Carboxylic Acids: Hydrolysis

3.7K
Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...
3.7K
E1 Reaction: Kinetics and Mechanism02:46

E1 Reaction: Kinetics and Mechanism

18.2K
Here, in contrast to the E2 reaction mechanism, we delve into the aspects of the E1 reaction mechanism, which has two steps: rate-limiting loss of the leaving group and abstraction of the beta hydrogen by a weak base. Typically, the experimental proof for the E1 mechanism is via kinetic studies or isotope studies. While the former demonstrates the first-order kinetics—the dependence of the reaction solely on substrate concentration—the latter proves the abstraction of hydrogen only...
18.2K

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在脱后进行基质介导的C-C和C-H合

Huihui Kong, Sha Yang, Hongying Gao1,2

  • 1Physikalisches Institut, Westfälische Wilhelms-Universität Münster , Wilhelm-Klemm-Strasse 10, 48149 Münster, Germany.

Journal of the American Chemical Society
|February 11, 2017
PubMed
概括

研究人员在银面上实现了选择性C-H合,使得新型有机分子和聚合物链的合成成为可能. 这一突破使表面化学超越了传统的聚合物制造.

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科学领域:

  • 表面化学
  • 有机合成
  • 纳米技术

背景情况:

  • 通过碳-素 (C-X) 键裂变的分子间碳-碳 (C-C) 合对于合成聚合物纳米结构至关重要.
  • 在终端碳的无控制的C-H合阻碍了共价聚合物的扩展,限制了它们的合成.
  • 脱后的选择性C-H合仍然是表面化学中未经探索的领域.

研究的目的:

  • 研究不同金属表面的选择性C-H合.
  • 通过受控合反应探索合成新有机分子和聚合物链的潜力.
  • 推进表面辅助有机合成的领域.

主要方法:

  • 扫描道显微镜 (STM) 用于高分辨率的表面成像.
  • 用于表面元素和化学状态分析的X射线光电子光谱 (XPS).
  • 密度函数理论 (DFT) 计算以了解反应机制和能量学.

主要成果:

  • 在黄金 (Au) 表面上观察到C-C合.
  • 在银 (Ag) 表面上实现了选择性C-H合,这是一个新发现.
  • 在Ag上选择性C-H合使得聚合物链或新有机分子的独特合成成为可能.

结论:

  • 证明了一种选择性C-H合在Ag111) 表面的新方法.
  • 这种选择性合为复杂有机分子的表面辅助合成开辟了新的途径.
  • 这些发现扩大了表面化学的范围,超越了现场聚合物制造.