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Preparation of Nitriles01:12

Preparation of Nitriles

2.3K
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...
2.3K
Electrophilic Aromatic Substitution: Nitration of Benzene01:20

Electrophilic Aromatic Substitution: Nitration of Benzene

7.3K
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.
7.3K
Nitriles to Ketones: Grignard Reaction00:57

Nitriles to Ketones: Grignard Reaction

5.2K
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...
5.2K
Preparation of Amines: Reduction of Oximes and Nitro Compounds01:29

Preparation of Amines: Reduction of Oximes and Nitro Compounds

4.2K
Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
4.2K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

6.8K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
6.8K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism01:37

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism

4.2K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
4.2K

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Updated: Nov 1, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
10:51

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Published on: April 10, 2015

12.4K

Nitrile Oxidation at a Ruthenium Complex leading to Intermolecular Imido Group Transfer.

James E Bird1, Cole A Hammond1, Kjersti G Oberle1

  • 1Hope College Department of Chemistry, Holland, MI 49423, United States.

Organometallics
|June 24, 2021
PubMed
Summary
This summary is machine-generated.

Ruthenium-catalyzed nitrile oxidation occurs without ligand dissociation, forming an N-acyl-dimethylsulfoximine via intermolecular imido group transfer. This pathway offers a new route to reactive metal-imido intermediates for amination reactions.

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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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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Organic Synthesis

Background:

  • Ruthenium complexes are versatile catalysts in organic synthesis.
  • Nitrile oxidation is a challenging transformation with limited synthetic routes.
  • Understanding reaction mechanisms is crucial for developing new catalytic processes.

Purpose of the Study:

  • To investigate the mechanism of acetonitrile ligand oxidation by an iodosoarene.
  • To identify the key intermediates and products in the ruthenium-catalyzed nitrile oxidation.
  • To explore the potential of nitrile oxidation as a pathway to metal-imido intermediates.

Main Methods:

  • 1H NMR spectroscopy in deuterated dimethylsulfoxide.
  • Kinetic studies to determine reaction rates and orders.
  • Independent synthesis and characterization of the reaction product.

Main Results:

  • Nitrile oxidation occurs directly on the coordinated acetonitrile ligand without prior dissociation.
  • The reaction yields N-acyl-dimethylsulfoximine, indicating intermolecular imido group transfer.
  • A reactive ruthenium(IV)imido intermediate is proposed to facilitate the imido transfer.

Conclusions:

  • Nitrile oxidation provides a novel pathway to access reactive metal-imido intermediates.
  • This methodology enables intermolecular imido group transfer to substrates.
  • The findings suggest potential applications in amination and aziridination reactions.