Efficient N-arylation of 4-chloroquinazolines en route to novel 4-anilinoquinazolines as potential anticancer agents

Microwave-mediated N-arylation of 4-chloroquinazolines in THF/H2O rapidly and efficiently afforded a library of novel 6-halo-2-phenyl-substituted 4-anilinoquinazolines. The methodology was compatible with numerous ortho-, meta-, and para-substituted N-methylanilines as well as substituted anilines and furnished the corresponding 4-anilinoquinazolines in good yields. Preliminary screening of the synthesized compounds against tumor cells (HCT-116 and T98G) showed promising antiproliferative properties.

Roboustness of Hydrogen Bonding in the Construction of Supramolecular Architechures in Protonated Perchlorate Salts

Five new multicomponent salts of perchloric acid with a series of substituted anilines and N-heterocyclic amines namely Diphenylaminium perchlorate (DPAPC) (1), 2, 5-dichloroanilinium perchlorate (25DAP) hydrate (2), 4-Methylanilinium perchlorate (4MAPC) (3), 4-diamino-6-methyl-1, 3, 5-triazin-1-ium hydrogen perchlorate (24DAMTHP) (4) and 8-hydroxyquinolinium hydrogen perchlorate (8HQP) (5) were prepared and structurally characterized. The entire complexes were subjected to FTIR and elemental analysis. A vast family of intermolecular contacts N-H…O, O-H…O, N-H…N and C-H…O were observed, which are key ingredient in the generation of privileged supramolecular self-assemblies appeared as one-dimensional chain, two-dimensional ladder and helix. Cambridge structural Database (CSD) analysis of 52 hits revealed the perchloric acid display higher propensity of ladder architectures. Molecular stability of the complexes were studied by quantum chemical calculations using DFT/B3LYP method with 6-31G(d,p) basis set. Further their relative charge distributions were identified using molecular electrostatic potential map. The use of Hirshfeld surfaces in combination with fingerprint plots was visualized in order to study the closer contacts within the molecule. The relative contribution of whole percentage of interactions associated is highlighted.

Hydroxylamine-mediated C–C amination via an aza-hock rearrangement

Despite the widespread use of anilines, synthetic challenges to these targets still exist. Selectivity is often an issue, when using the traditional nitration-reduction sequence or more modern approaches, including arene C–H aminations catalyzed by transition metals, photosensitizers, or electrodes. Accordingly, there is still a need for general methods to rapidly, directly access specific isomers of substituted anilines. Here, we report a simple route towards the synthesis of such motifs starting from benzyl alcohols, which are converted to anilines by the use of arylsulfonyl hydroxylamines, via an aza-Hock rearrangement. Good to excellent yields are observed. The method is applicable to various benzyl alcohol surrogates (such as ethers, esters, and halides) as well as simple alkylarenes. Functionalizations of pharmaceutically relevant structures are feasible under the reaction conditions. Over ten amination reagents can be used, which facilitates the rapid assembly of a vast set of compounds.

1,3-Bis(trifluoromethyl)prop-2-ene 1-Iminium Salts ‒ Reactions with Alkoxybenzenes and Anilines

1,3-Bis(trifluoromethyl)prop-2-ene 1-iminium triflate salts were prepared for the first time and some synthetic applications as 1,3-biselectrophilic building blocks were established. They were found to react with dimethoxybenzenes or methylene-1,2-dioxybenzenes to furnish vinylogous trifluoroacetylaton products (4-aryl-1,1,1,5,5,5-hexafluoropent-3-en-2-ones) and 1-dialkylamino-1,3-bis(trifluoromethyl)-1H-indenes. With aniline and ring-substituted anilines, 2,4-bis(trifluoromethyl)quinolines were formed. An unusual 4H-pyran, formally a condensation product of the N,N-dimethyl-1,3-bis(trifluoromethyl)prop-2-en-1-iminium ion and its enaminone precursor, is also reported.

Combined Spectroscopic and Computational Study of Nitrobenzene Activation on Non-Noble Metals-Based Mono- and Bimetallic Catalysts

In this paper, substituted anilines are industrially obtained by direct hydrogenation of nitroaromatic compounds with molecular H2 using metals as catalysts. Previous theoretical studies proposed that the mechanism of the reaction depends on the nature of the metal used as a catalyst, and that rationally designed bimetallic materials might show improved catalytic performance. Herein, we present IR spectroscopic studies of nitrobenzene interactions with monometallic Ni/SiO2, Cu/SiO2 and Pd/SiO2, and with bimetallic CuNi/SiO2 and CuPd/SiO2 catalysts, both in the absence and presence of H2, combined with density functional theory (DFT) calculations on selected bimetallic NiCu(111) and PdCu(111) models. The results obtained experimentally confirm that the reaction mechanism on non-noble metals such as Ni proceeds through N-O bond dissociation, generating nitrosobenzene intermediates, while, on noble metals, such as Pd, H-attack is necessary to activate the NO bond. Moreover, a bimetallic CuPd/SiO2 catalyst with a Pd enriched surface is prepared that exhibits an enhanced H2 dissociation ability and a particular reactivity at the boundary between the two metals.

In situ decoration of Au NPs over polydopamine encapsulated GO/Fe3O4 nanoparticles as a recyclable nanocatalyst for the reduction of nitroarenes

A new and efficient catalyst has been designed and prepared via in situ immobilization of Au NPs fabricated polydopamine (PDA)-shelled Fe3O4 nanoparticle anchored over graphene oxide (GO) (GO/Fe3O4@PDA/Au). This novel, architecturally interesting magnetic nanocomposite was fully characterized using different analytical techniques such as Field Emission Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, elemental mapping, Transmission Electron Microscopy, Fourier Transformed Infrared Spectroscopy, X-ray Diffraction and Inductively Coupled Plasma-Atomic Electron Spectroscopy. Catalytic activity of this material was successfully explored in the reduction of nitroarenes to their corresponding substituted anilines, using NaBH4 as reducing agent at ambient conditions. The most significant merits for this protocol were smooth and clean catalysis at room temperature with excellent productivity, sustainable conditions, ease of separation of catalyst from the reaction mixture by using a magnetic bar and most importantly reusability of the catalyst at least 8 times without any pre-activation, minimum loss of activity and considerable leaching.