59488-00-5Relevant academic research and scientific papers
Nucleophilic and acid catalyst behavior of a protic ionic liquid in a molecular reaction media. Part 1
Adam, Claudia G.,Fortunato, Graciela G.,Mancini, Pedro M.
, p. 460 - 465 (2009)
This work presents a new approach using ionic liquids, namely ethylammonium nitrate. The aim was to analyze how the addition of small amounts of a protic ionic liquid to a pure molecular solvent, modifies the microscopic characteristics of a reaction medium. In order to achieve this, a kinetic study of nucleophilic aromatic substitution reactions between 1-fluoro-2, 4-dinitrobenzene and 1-butylamine or piperidine was developed in this type of binary mixtures. We have detected nucleophiles competition originated by the presence of the ionic solvent at very low concentrations, observing the ethylamine derivative as the main substitution product. Moreover, in the light of previous results we have confirmed that the protic ionic liquid can act as both Broensted acid and/or nucleophile. In this connection, we have selected the nucleophilic addition of amines to carbonyl compounds as reaction model. The protic ionic liquid in the presence of aromatic aldehydes substituted by electron-donating groups makes possible the formation of the corresponding imines with good yields. The results demonstrated that the influence of the protic ionic liquid is very important in the course of both reaction systems. Copyright
Quantitative solid-state reactions of amines with carbonyl compounds and isothiocyanates
Kaupp, Gerd,Schmeyers, Jens,Boy, Juergen
, p. 6899 - 6911 (2007/10/03)
A series of solid-state reactions is reported of gaseous or solid amines with aldehydes to give imines, with solid anhydrides to give diamides (therefrom imides) or amidic carboxylic salts or imides, with solid imides to give diamides, with solid lactones or carbonates to give functionalized carbamic esters, with polycarbonates to give degradative aminolysis, and with solid isothiocyanates to give thioureas. Diamides give imides by solid-state thermolysis or acid catalysis. Various double, two-step, 3-cascade, and sequential reactions are reported in the solid state without melting. The yields are quantitative in 53 reported reaction examples and no workup (except for washings in four cases) is required in the 100% yield reactions. Three initially solid-state reactions but with liquid product were not quantitative. An upscaling to the kg scale shows promise of the technique for large scale applications. Supermicroscopic analyses with AFM elucidate the solid-state mechanism by virtue of far-reaching anisotropic molecular movements in three-step processes. Gas-solid aminolyses of polycarbonates are also studied with AFM. The implications to sustainable chemistry are discussed. (C) 2000 Elsevier Science Ltd.
