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Related Concept Videos

Enolate Mechanism Conventions01:15

Enolate Mechanism Conventions

When a carbonyl compound is treated with a strong base, the α position gets deprotonated to give a resonance-stabilized intermediate called an enolate. Enolates are ambident nucleophiles because they possess two nucleophilic sites that can attack an electrophile owing to the delocalization of the negative charge between the α carbon and oxygen atoms. When the oxygen atom attacks an electrophile, it is called O-attack, whereas electrophilic attack via the α carbon is known as C-attack.
C-attack...
Nitriles to Ketones: Grignard Reaction00:57

Nitriles to Ketones: Grignard Reaction

Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles react with a Grignard reagent, followed by an aqueous acid, to yield ketones. The reaction introduces a new carbon–carbon bond. The alkyl–magnesium bond in the Grignard reagent is highly polar, so the alkyl carbon develops a carbanionic character and acts as a nucleophile.
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Preparation of Nitriles01:12

Preparation of Nitriles

One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...
Reactivity of Enolate Ions01:23

Reactivity of Enolate Ions

Enolate ions are formed by the acid–base reaction of a carbonyl compound with a base. This leads to deprotonation of the α hydrogen atom, leading to a resonance-stabilized enolate ion where one of the contributing structures is an oxyanion, which imparts additional stability. Therefore, the proton on the α carbon is more acidic in nature than that of other sp3-hybridized C–H bonds but less acidic than those in O–H bonds where the negative charge in the conjugate base is localized on the oxygen...
Electrophilic Aromatic Substitution: Nitration of Benzene01:20

Electrophilic Aromatic Substitution: Nitration of Benzene

The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.
α-Alkylation of Ketones via Enolate Ions01:10

α-Alkylation of Ketones via Enolate Ions

Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the strong interaction...

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Related Experiment Video

Updated: Jun 12, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
08:12

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

Published on: August 16, 2018

Metalated nitrile and enolate chlorinations.

Bhaskar Reddy Pitta1, Fraser F Fleming

  • 1Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA.

Organic Letters
|May 21, 2010
PubMed
Summary
This summary is machine-generated.

This study introduces a new method for anionic chlorination of alkylnitriles using metalated nitriles and enolates. The process efficiently synthesizes alpha-chloronitriles under mild conditions, tolerating various functional groups.

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Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
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Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

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Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
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Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

Published on: February 24, 2015

Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry

Background:

  • Alpha-chloronitriles are valuable synthetic intermediates.
  • Synthesizing alpha-chloronitriles under mild conditions remains a challenge.

Purpose of the Study:

  • To develop a general and efficient method for anionic chlorination of alkylnitriles.
  • To synthesize diverse alpha-chloronitriles and chloroesters under mild conditions.

Main Methods:

  • Utilizing metalated nitriles and enolates as nucleophiles.
  • Employing 2-chloro-2-fluoro-2-phenylacetonitrile as the chlorine source.

Main Results:

  • Achieved rapid and efficient chlorine abstraction from the substrate.
  • Generated a diverse range of chloronitriles and chloroesters.
  • Demonstrated the first general anionic chlorination of alkylnitriles.
  • Showcased tolerance to numerous functional groups.

Conclusions:

  • The developed method offers a mild and versatile route to alpha-chloronitriles.
  • This approach overcomes previous limitations in synthesizing these important compounds.