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Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
From azides to nitro compounds in a few seconds using HOF.CH3CN
1School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 69978, Israel. rozens@post.tau.ac.il
Journal of the American Chemical Society
|July 3, 2003
Summary
Hydroxylammonium formate acetonitrile (HOF.CH3CN) efficiently converts azides to nitro compounds. Nitroso derivatives are key intermediates in this rapid oxygen-transfer reaction.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
- Reaction Mechanisms
Background:
- Oxygen-transfer reactions are crucial in organic synthesis.
- Azides are versatile precursors for nitrogen-containing compounds.
- Efficient methods for synthesizing nitro compounds are highly sought after.
Purpose of the Study:
- To investigate the efficacy of hydroxylammonium formate acetonitrile (HOF.CH3CN) as an oxygen-transfer agent.
- To explore the reaction of HOF.CH3CN with various azides for nitro compound synthesis.
- To elucidate the reaction mechanism, including intermediate identification.
Main Methods:
- Reaction of HOF.CH3CN with a range of azide compounds.
- Characterization of the resulting nitro compounds.
- Investigation of reaction intermediates, specifically nitroso derivatives.
- Comparative study using meta-chloroperoxybenzoic acid (MCPBA) and dimethyldioxirane (DMDO) as control reagents.
Main Results:
- HOF.CH3CN demonstrated high efficiency in converting azides to nitro compounds.
- Excellent yields and very short reaction times were achieved.
- Nitroso derivatives were identified as key reaction intermediates.
- No reaction was observed when using MCPBA or DMDO, with starting materials fully recovered.
Conclusions:
- HOF.CH3CN is a highly effective reagent for the synthesis of nitro compounds from azides.
- The reaction proceeds via nitroso intermediate formation.
- HOF.CH3CN offers a significant advantage over MCPBA and DMDO for this specific transformation.
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