Modular Synthesis of Azines Bearing a Guanidine Core from N-Heterocyclic Carbene (NHC)-Derived Selenoureas and Diazo Reagents.

N-Heterocyclic carbene (NHC)-derived selenoureas comprise a fundamentally important class of NHC derivatives, with key applications in coordination chemistry and the determination of NHC electronic properties. Considering the broad reactivity of chalcogen-containing compounds, it is surprising to note that the use of NHC-derived selenoureas as organic synthons remains essentially unexplored. The present contribution introduces a novel, straightforward transformation leading to azines bearing a guanidine moiety, through the reaction of a wide range of NHC-derived selenoureas with commercially available diazo compounds, in the presence of triphenylphosphine. This transformation offers a new approach to such products, having biological, materials chemistry, and organic synthesis applications. The guanidine-bearing azines are obtained in excellent yields, with all manipulations taking place in air. A reaction mechanism is proposed, based on both experimental mechanistic findings and density functional theory (DFT) calculations. A one-pot, multicomponent transesterification reaction between selenoureas, α-diazoesters, alcohols, and triphenylphosphine was also developed, providing highly functionalized azines.

Microwave-Assisted, Copper-Catalyzed Domino O-H/C-H Arylation Reaction toward the Synthesis of Oxygen-Doped Polyaromatic Molecules.

Benzoxanthenes and their analogues are a very important class of compounds mainly due to their wide range of biological and technological applications. The development of a new methodology for their synthesis, involving an Ullmann-type coupling followed by an intramolecular C-H arylation, catalyzed by copper in a domino fashion, is reported. A variety of para-substituted phenols are amenable to this methodology, affording the desired products in moderate to good yields. Our protocol is expedient and practical and is carried out under microwave irradiation in only 3 min under air. A plausible catalytic cycle is proposed based on experimental mechanistic investigations and density functional theory (DFT) calculations.

Kevlar®, Nomex®, and VAR Modification by Small Organic Molecules Anchoring: Transfusing Antibacterial Properties and Improving Water Repellency.

The surface modification of fabrics composed of Kevlar®, Nomex®, or VAR was extensively investigated. Kevlar® and Nomex® are widely-utilized aramid materials, whereas VAR is a technical fabric comprising 64% viscose, 24% para-aramid (Kevlar®), 10% polyamide, and 2% antistatic fibers. Both aramid materials and cellulose/viscose exhibit exceptional mechanical properties that render them valuable in a wide range of applications. For the herein studied modification of Kevlar®, Nomex®, and VAR, we used small organic molecules 3-allyl-5,5-dimethylhydantoin (ADMH) and 3-(acrylamidopropyl)trimethylammonium chloride (APTAC), which were anchored onto the materials under study via graft polymerization. By doing so, excellent antibacterial properties were induced in the three studied fabrics. Their water repellency was improved in most cases as well. Extensive characterization studies were conducted to probe the properties of the modified materials, employing Raman and FTIR spectroscopies, Scanning Electron Microscopy (SEM), and thermogravimetric analysis (TGA).

VAR Fabric Modification: Inducing Antibacterial Properties, Altering Wettability/Water Repellence, and Understanding Reactivity at the Molecular Level.

The present work focuses on the surface coating of VAR technical fibers, consisting of 64% viscose (cellulose), 24% Kevlar, 10% other types of polyamides, and 2% antistatic polymers. Kevlar is an aramid material exhibiting excellent mechanical properties, while cellulose is a natural linear polymer composed of repeating ß-d-glucose units, having several applications in the materials industry. Herein, we synthesized novel, tailor-designed organic molecules possessing functional groups able to anchor on VAR fabrics and cellulose materials, thus altering their properties on demand. To this end, we utilized methyl-α-d-glucopyranose as a model compound, both to optimize the reaction conditions, before applying them to the material and to understand the chemical behavior of the material at the molecular level. The efficient coating of the VAR fabric with the tailor-made compounds was then implemented. Thorough characterization studies using Raman and IR spectroscopies as well as SEM imaging and thermogravimetric analysis were also carried out. The wettability and water repellency and antibacterial properties of the modified VAR fabrics were also investigated in detail. To the best of our knowledge, such an approach has not been previously explored, among other factors regarding the understanding of the anchoring mechanism at the molecular level. The proposed modification protocol holds the potential to improve the properties of various cellulose-based materials beyond VAR fabrics.