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相关概念视频

Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview01:20

Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview

The Fischer esterification reaction was developed by the German chemist Emil Fischer in 1895. It is a condensation reaction between carboxylic acids and alcohols in an acidic medium to give esters and water.
Limitations of Friedel–Crafts Reactions01:26

Limitations of Friedel–Crafts Reactions

Several restrictions limit the use of Friedel–Crafts reactions. First, the halogen in the alkyl halide must be attached to an sp3-hybridized carbon for the Friedel–Crafts reactions to occur. Vinyl or aryl halides do not react since the carbocations formed are unstable under the reaction conditions. Second, Friedel–Crafts alkylation is susceptible to carbocation rearrangement, and the major products obtained have a rearranged carbon skeleton. In contrast, the acylium ion is stabilized by...
Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism01:13

Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism

Carboxylic acids react with alcohols to yield esters via an acid-catalyzed condensation reaction called Fischer esterification. This is a nucleophilic acyl substitution reaction that proceeds via a tetrahedral intermediate, where a water molecule is eliminated as the leaving group.
Fischer Projections02:18

Fischer Projections

Learning to draw Fischer projections of molecules and understanding their relevance plays a crucial role in the visual depiction of organic molecules. A Fischer projection is a two-dimensional projection on a planar surface to simplify the three-dimensional wedge–dash representation of molecules. This is especially helpful in the case of molecules with multiple chiral centers that can be difficult to draw. Here, all the bonds of interest are represented as horizontal or vertical lines. While...
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene01:13

Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
Amines to Alkenes: Hofmann Elimination01:16

Amines to Alkenes: Hofmann Elimination

Alkenes can be obtained from amines via an E2 elimination. The amine is first converted into a good leaving group, such as a quaternary ammonium salt. This is accomplished by treating the amine with an excess of alkyl halide, which results in a halide salt. Next, the halide salt is transformed into a hydroxide salt that functions as a base to enable elimination.
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...

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A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones
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Published on: January 21, 2020

为什么一些费舍尔的内化失败?

Nihan Çelebi-Ölçüm1, Ben W Boal, Alexander D Huters

  • 1Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.

Journal of the American Chemical Society
|March 30, 2011
PubMed
概括
此摘要是机器生成的。

研究了费舍尔醇合成机制. 电子捐赠组更喜欢N-N键裂变而不是典型的[3,3]-sigmatropic重排路径.

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科学领域:

  • 有机化学 有机化学
  • 计算化学的计算化学

背景情况:

  • 费舍尔醇合成是有机化学中形成醇环的关键反应.
  • 了解相互竞争的反应途径对于优化合成策略至关重要.

研究的目的:

  • 阐明费舍尔醇合成的详细机制.
  • 调查替代剂对反应通路的影响,并确定竞争的裂变机制.

主要方法:

  • 使用了ab initio计算,特别是SCS-MP2/6-31G(d),以建模反应能量.
  • 包含水溶解模型来模拟反应条件.

主要成果:

  • 确定异质N-N键裂变作为一个重要的竞争途径.
  • 证明了电子捐赠替代剂将反应指向N-N键裂变.
  • 表明这些替代剂抑制了酸促进的[3,3]-sigmatropic重组.

结论:

  • 替代效应在决定费舍尔醇合成结果方面发挥着至关重要的作用.
  • 这项研究提供了更深入的机理学理解,有助于合理设计醇合成协议.