2, 6-Diamination of substituted pyridines via heterogeneous Chichibabin reaction. Issue 3 (20th January 2016)

• Record Type: Journal Article
• Authors: Mastalir, Matthias; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl
• Is Part Of: Tetrahedron letters. Volume 57:Issue 3(2016)
• Page Start: 333
• Page End: 336
• Publication Date: 2016-01-20
• Subjects: Amination -- 2, 6-Diaminopyridines -- Heterocycles -- Chichibabin reaction; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2015.12.013
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: A series of methyl, tert -butyl, phenyl, pyridinyl, and hydroxyl substituted 2, 6-diaminopyridines are prepared via the heterogeneous Chichibabin amination in neat mineral oil at temperatures up to 215 °C with an overall reaction time of 3–5 h. Abstract: A series of ring substituted pyridines were selected for the sodium amide initiated heterogeneous Chichibabin amination to obtain 2, 6-diaminopyridine derivatives which are important synthons for the preparation of PNP pincer ligands. The substrates were treated with an excess of sodium amide in neat mineral oil as solvent under an argon atmosphere. The reaction required temperatures of up to 215 °C under vigorous stirring with an overall reaction time of 3–5 h. In the case of methyl, tert -butyl, phenyl, pyridinyl, and hydroxyl substituted pyridines the desired products were obtained in good to excellent yields (63–96%). Thus, the Chichibabin reaction provides an inexpensive and economic alternative to methodologies starting from halopyridines or pyridine N -oxides provided that the substituents are inert under the harsh reaction conditions.