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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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Video Experimental Relacionado

Updated: Jun 3, 2026

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones
07:30

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

Published on: January 21, 2020

¿Por qué fallan algunas indolizaciones de Fischer?

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
Resumen
Este resumen es generado por máquina.

Se estudiaron los mecanismos de síntesis de indol de Fischer. Los grupos donantes de electrones favorecen la escisión de enlaces N-N en lugar de la ruta típica de reordenamiento sigmatrópico [3,3]-sigmatrópico.

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Área de la Ciencia:

  • Química orgánica es la química orgánica.
  • Química computacional es la química computacional.

Sus antecedentes:

  • La síntesis de indol de Fischer es una reacción crucial en la química orgánica para la formación de anillos de indol.
  • Comprender las vías de reacción competitivas es esencial para optimizar las estrategias sintéticas.

Objetivo del estudio:

  • Para aclarar los mecanismos detallados de la síntesis de indol de Fischer.
  • Investigar la influencia de los sustituyentes en las vías de reacción e identificar mecanismos de escisión competidores.

Principales métodos:

  • Utilizó cálculos ab initio, específicamente SCS-MP2/6-31G(d), para modelar las energías de reacción.
  • Incorpora modelos de disolución acuosa para simular las condiciones de reacción.

Principales resultados:

  • Identificó la escisión de enlaces N-N heterolíticos como una vía de competencia significativa.
  • Demostró que los sustituyentes donantes de electrones dirigen la reacción hacia la escisión del enlace N-N.
  • Se demostró que estos sustituyentes inhiben el reordenamiento [3,3]-sigmatrópico promovido por el ácido.

Conclusiones:

  • Los efectos de sustitución juegan un papel crítico en la determinación del resultado de la síntesis de indol de Fischer.
  • El estudio proporciona una comprensión mecánica más profunda, ayudando en el diseño racional de los protocolos de síntesis de indoles.