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Related Concept Videos

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism01:26

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism

4.0K
The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...
4.0K
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview01:07

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview

3.6K
In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.
3.6K
Multiple Halogenation of Methyl Ketones: Haloform Reaction01:28

Multiple Halogenation of Methyl Ketones: Haloform Reaction

2.9K
A method involving the transformation of methyl ketones to carboxylic acids using excess base and halogen is called the haloform reaction. It begins with the deprotonation of α hydrogen to form an enolate ion which reacts with the electrophilic halogen to give an α-halo ketone. The step continues until all the α protons are substituted to form a trihalomethyl ketone. The resulting molecule is unstable, and in the presence of a hydroxide base, it readily undergoes nucleophilic...
2.9K
Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction01:26

Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction

4.1K
α-Substituted ketones or aldehydes can be synthesized from enamines by the Stork enamine reaction, named after its pioneer Gilbert Stork. Enamines are useful synthetic intermediates where the lone pair on nitrogen is in conjugation with the C=C bond. They resemble enolate ions, as the resonance forms of both species have a nucleophilic α carbon.
4.1K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview01:32

Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview

3.8K
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
3.8K
Amines to Alkenes: Hofmann Elimination01:16

Amines to Alkenes: Hofmann Elimination

3.2K
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...
3.2K

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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Hectogram-Scale Synthesis of Carbamates Using Electrochemical Hofmann Rearrangement in Flow.

Darryl F Nater1, Rong Zhao2, Johannes Rocker3

  • 1Max-Planck-Institute for Chemical Energy Conversion, Department of Electrosynthesis, Stiftstraße 34-36, Mülheim an der Ruhr 45470, Germany.

Organic Process Research & Development
|September 25, 2025
PubMed
Summary
This summary is machine-generated.

Electrochemical Hofmann rearrangement of carboxamides is now feasible on a large scale using sodium bromide in methanol. This method efficiently generates reagents in situ, offering a sustainable synthetic route.

Keywords:
Hofmann degradationbromide mediationelectrosynthesisglassy carbonsandwich cellscale-up

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Area of Science:

  • Organic Chemistry
  • Electrochemistry
  • Green Chemistry

Background:

  • The Hofmann rearrangement is a key organic reaction for converting amides to amines.
  • Traditional Hofmann rearrangement methods often involve hazardous reagents and stoichiometric waste.
  • Developing scalable and environmentally friendly alternatives is crucial for industrial applications.

Purpose of the Study:

  • To establish a scalable electrochemical method for the Hofmann rearrangement of alkyl and aryl carboxamides.
  • To investigate the role of supporting electrolyte and solvent in the electrochemical process.
  • To optimize reaction conditions for high productivity using simple electrochemical cells.

Main Methods:

  • Electrolysis of sodium bromide in methanol to generate halogen species and base equivalents.
  • Utilizing a simple glassy carbon anode in commercially available plate-frame cells.
  • Conducting the reaction on a hectogram scale.

Main Results:

  • Successful electrochemical Hofmann rearrangement of alkyl and aryl carboxamides.
  • Demonstrated in situ generation of necessary reagents via electrolysis.
  • Achieved a productivity of 104 mmol per hour with 162 cm² of anode surface.
  • Identified the dual role of supporting electrolyte and solvent as mediators and reaction partners.

Conclusions:

  • Electrochemical Hofmann rearrangement offers a scalable, efficient, and potentially greener alternative to traditional methods.
  • The described method utilizes readily available materials and simple equipment.
  • This approach facilitates large-scale synthesis of amines from carboxamides via electrochemistry.