ABSTRACT
A new model, based on the presence of the excited state iminium ion (Ar = NH2+), is proposed to interpret the solvatochromic behavior of symmetric 1,5- and 1,8-diaminonaphtahelenes (DANs) in aprotic to protic media. The importance of using explicit solvent models during DFT calculations in protic solvents to find the proper excited structure for symmetric molecules is also highlighted.
ABSTRACT
Aromatic isocyanides have gained a lot of attention lately as promising antifungal and anticancer drugs, as well as high-performance fluorescent analytical probes for the detection of toxic metals, such as mercury, even in vivo. Since this topic is relatively new and aromatic isocyanides possess unique photophysical properties, the understanding of structure-behavior relationships and the preparation of novel potentially biologically active derivatives are of paramount importance. Here, we report the photophysical characterization of 1,5-diisocyanonaphthalene (DIN) backed by quantum chemical calculations. It was discovered that DIN undergoes hydrolysis in certain solvents in the presence of oxonium ions. By the careful control of the reaction conditions for the first time, the nonsymmetric product 1-formamido-5-isocyanonaphthalene (ICNF) could be prepared. Contrary to expectations, the monoformamido derivative showed a significant solvatochromic behavior with a ~50 nm range from hexane to water. This behavior was explained by the enhanced H-bond-forming ability of the formamide group. The significance of the hydrolysis reaction is that the isocyano group is converted to formamide in living organisms. Therefore, ICNF could be a potential drug (for example, antifungal) and the reaction can be used as a model for the preparation of other nonsymmetric formamido-isocyanoarenes. In contrast to its relative 1-amino-5-iscyanonaphthalene (ICAN), ICNF is highly fluorescent in water, enabling the development of a fluorescent turnoff probe.
Subject(s)
Antifungal Agents , Fluorescent Dyes , Antifungal Agents/pharmacology , Hydrolysis , Fluorescent Dyes/chemistry , Water , CyanidesABSTRACT
Aniline (AN) is one of the most important compounds in the chemical industry and is prepared by the catalytic hydrogenation of nitrobenzene (NB). The development of novel, multifunctional catalysts which are easily recoverable from the reaction mixture is, therefore, of paramount importance. Compared to conventional filtration, magnetic separation is favored because it is cheaper and more facile. For satisfying these requirements, we developed manganese ferrite (MnFe2O4)-supported, magnetically separable palladium catalysts with high catalytic activity in the hydrogenation of nitrobenzene to aniline. In addition to high NB conversion and AN yield, remarkable aniline selectivity (above 96 n/n%) was achieved. Surprisingly, the magnetic support alone also shows moderate catalytic activity even without noble metals, and thus, up to 94 n/n% nitrobenzene conversion, along with 47 n/n% aniline yield, are attainable. After adding palladium nanoparticles to the support, the combined catalytic activity of the two nanomaterials yielded a fast, efficient, and highly selective catalyst. During the test of the Pd/MnFe2O4 catalyst in NB hydrogenation, no by-products were detected, and consequently, above 96 n/n% aniline yield and 96 n/n% selectivity were achieved. The activity of the Pd/MnFe2O4 catalyst was not particularly sensitive to the hydrogenation temperature, and reuse tests indicate its applicability in at least four cycles without regeneration. The remarkable catalytic activity and other favorable properties can make our catalyst potentially applicable to both NB hydrogenation and other similar or slightly different reactions.
