Angeli–Rimini reaction

Chemical test

The reaction is used in a chemical test for the detection of aldehydes in combination with ferric chloride. In this test a few drops of aldehyde containing specimen is dissolved in ethanol, the sulfonamide is added together with some sodium hydroxide solution and then the solution is acidified to Congo red. An added drop of ferric chloride will turn the solution an intense red when aldehyde is present. The sulfonamide can be prepared by reaction of hydroxylamine and benzenesulfonyl chloride in ethanol with potassium metal.

Reaction mechanism

The reaction mechanism for this reaction is not clear and several potential pathways exist. The N-hydroxybenzenesulfonamide 1 or its deprotonated form 2 is a nucleophile in reaction with the aldehyde 3 to intermediate 4. After intramolecular proton exchange to 5 a sulfinic acid anion is split off and hydroxamic acid 8 results through nitroso compound 6 and intermediate 7. Alternatively aziridine intermediate 9 directly forms the end=product. The formation of the nitrene intermediate 10 is ruled out given the lack of reactivity of the chemical mixture towards simple alkenes.

Scope

The Angeli–Rimini reaction has recently been applied in solid-phase synthesis with the sulfonamide covalently linked to a polystyrene solid support.

References

References

1. [[Angelo Angeli]] [[Gazz. Chim. Ital.]] '''1896''', 26, 17.
2. Rimini, E. [[Gazz. Chim. Ital.]] '''1901''', 31, 84.
3. Gattermann, Ludwig, ''The Practical Methods of Organic Chemistry'', '''1937''' [https://www.sciencemadness.org/library/books/gatterman_1937.pdf#search=%22Angeli-Rimini%20reaction%22 Link] (4.5 MB)
4. ''Reaction of aldehydes with N-hydroxybenzenesulfonamide. Acetal formation catalyzed by nucleophiles''Alfred Hassner, E. Wiederkehr, and A. J. Kascheres [[J. Org. Chem.]]; '''1970'''; 35(6) pp 1962 - 1964; ({{doi. 10.1021/jo00831a052)
5. ''Angeli-Rimini's Reaction on Solid Support: A New Approach to Hydroxamic Acids'' Andrea Porcheddu and Giampaolo Giacomelli [[J. Org. Chem.]]; '''2006'''; 71(18) pp 7057 - 7059; (Note) ({{doi. 10.1021/jo061018g)