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1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview01:26

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

Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
2° Amines to N-Nitrosamines: Reaction with NaNO201:20

2° Amines to N-Nitrosamines: Reaction with NaNO2

Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
Preparation of Amines: Reduction of Oximes and Nitro Compounds01:29

Preparation of Amines: Reduction of Oximes and Nitro Compounds

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,...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism01:37

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

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.
Nitrosation of Enols01:19

Nitrosation of Enols

The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
Diazonium Group Substitution: –OH and –H01:19

Diazonium Group Substitution: –OH and –H

Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.

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Updated: Jun 7, 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

Nitroxide-substituted nitronyl nitroxide and iminonitroxide.

Shuichi Suzuki1, Takanori Furui, Masato Kuratsu

  • 1Department of Chemistry, Graduate School of Science, Osaka City University, Sugimoto Sumiyoshi-ku, Osaka 558-8585, Japan.

Journal of the American Chemical Society
|October 23, 2010
PubMed
Summary

Two novel diradicals, nitronyl nitroxide 1 and iminonitroxide 2, exhibit stable, compact structures with significant positive magnetic exchange interactions, offering potential for advanced magnetic materials.

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Syntheses, Crystallization, and Spectroscopic Characterization of 3,5-Lutidine N-Oxide Dehydrate
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Syntheses, Crystallization, and Spectroscopic Characterization of 3,5-Lutidine N-Oxide Dehydrate

Published on: April 24, 2018

Area of Science:

  • Organic chemistry
  • Materials science
  • Magnetism

Background:

  • Diradicals are molecules with two unpaired electrons, crucial for understanding magnetic phenomena.
  • Nitroxide-substituted nitronyl nitroxides and iminonitroxides represent a class of organic radicals with unique electronic properties.

Purpose of the Study:

  • To synthesize and characterize novel, highly compact diradicals.
  • To investigate the magnetic exchange interactions in these new diradical systems.

Main Methods:

  • Synthesis of nitronyl nitroxide 1 and iminonitroxide 2.
  • Structural and electronic characterization of the diradicals.
  • Magnetic susceptibility measurements to determine exchange interactions.

Main Results:

  • Successfully synthesized highly compact nitroxide-substituted nitronyl nitroxide 1 and iminonitroxide 2.
  • Both diradicals demonstrated stability under ambient, aerated conditions.
  • Large positive magnetic exchange interactions were quantified: J/k(B) = +390 K for 1 and J/k(B) ≈ +550 K for 2.

Conclusions:

  • The synthesized diradicals possess isoelectronic structures analogous to trimethylenemethane.
  • Their stability and significant positive exchange interactions make them promising candidates for molecular magnetism and advanced materials.