Wednesday, April 22, 2020

DIAZOTISATION REACTION

Diazotisation





The nitrosation of primary aromatic amines with nitrous acid (generated in situ from sodium nitrite and a strong acid, such as hydrochloric acid, sulfuric acid, or HBF4) leads to diazonium salts, which can be isolated if the counterion is non-nucleophilic.


Diazonium salts are important intermediates for the preparation of halides (Sandmeyer ReactionSchiemann Reaction), and azo compounds. Diazonium salts can react as pseudohalide-type electrophiles, and can therefore be used in specific protocols for the Heck Reaction or Suzuki Coupling.


The intermediates resulting from the diazotization of primary, aliphatic amines are unstable; they are rapidly converted into carbocations after loss of nitrogen, and yield products derived from substitution, elimination or rearrangement processes.



Mechanism of Diazotisation









Recent Literature




A convenient and general one-step preparation of aromatic and some heterocyclic iodides in good yields includes a sequential diazotization-iodination of aromatic amines with KI, NaNO2, and p-TsOH in acetonitrile at room temperature.




Sulfonic Acid Based Cation-Exchange Resin: A Novel Proton Source for One-Pot Diazotization-Iodination of Aromatic Amines in Water




Unusually Stable, Versatile, and Pure Arenediazonium Tosylates: Their Preparation, Structures, and Synthetic Applicability




A Simple and Effective Synthesis of Aryl Azides via Arenediazonium Tosylates




Methanol-Promoted Borylation of Arylamines: A Simple and Green Synthetic Method to Arylboronic Acids and Arylboronates




Efficient Synthesis of 2-Amino Acid by Homologation of β2-Amino Acids Involving the Reformatsky Reaction and Mannich-Type Imminium Electrophile




Synthesis and properties of bis(hetaryl)azo dyes

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