Ruthenium-Induced Decomposition of Hexamethylenetetramine as a Tool for the Acid-Free Sommelet Reaction in Aqueous Medium.

Abstract

Hexamethylenetetramine (HMTA) is one of the most versatile and most utilized nitrogen-containing heterocyclic compounds in academia and industry. Most of the reactions involving HMTA employ stoichiometric or excess amounts of acid, which hamper the sustainability of the reactions. Herein, we report the first example of the ruthenium-mediated decomposition of HMTA at room temperature, supported by a detailed mechanistic study using thermogravimetric analysis/differential thermal analysis, variable-temperature NMR, UV-vis spectroscopy, and density functional theory techniques. The mechanism study also involves a comparison of the decomposition of HMTA, protonated HMTA, [RuCl3(HMTA)], and [FeCl3(HMTA)], which revealed that [RuCl3(HMTA)] decomposes at the lowest temperature and has the lowest HOMO-LUMO band gap of 2.66 eV. The ruthenium-induced decomposition of HMTA is successfully used as a tool to increase the sustainability of the Sommelet reaction as it employs simple RuCl3·nH2O as a catalyst in as low as 0.5 mol % concentration in aqueous medium. The developed methodology is found to be very selective and efficient even for the very challenging substrates, namely, aliphatic aldehydes and substrates with electron-withdrawing substituents. The findings of this work are the first of its kind in which ruthenium is employed in the Sommelet reaction and also provide a possible platform to improve the sustainability of all reactions involving HMTA as a reactant/reagent.