Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

Lignin as a Partial Polyol Replacement in Polyurethane Flexible Foam

This study was focused on evaluating the suitability of a wide range of lignins, a natural polymer isolated from different plant sources and chemical extractions, in replacing 20 wt.% of petroleum-based polyol in the formulation of PU flexible foams. The main goal was to investigate the effect of unmodified lignin incorporation on the foam’s structural, mechanical, and thermal properties. The hydroxyl contents of the commercial lignins were measured using phosphorus nuclear magnetic resonance (³¹P NMR) spectroscopy, molar mass distributions with gel permeation chromatography (GPC), and thermal properties with differential scanning calorimetry (DSC) techniques. The results showed that incorporating 20 wt.% lignin increased tensile, compression, tear propagation strengths, thermal stability, and the support factor of the developed PU flexible foams. Additionally, statistical analysis of the results showed that foam properties such as density and compression force deflection were positively correlated with lignin’s total hydroxyl content. Studying correlations between lignin properties and the performance of the developed lignin-based PU foams showed that lignins with low hydroxyl content, high flexibility (low T_g), and high solubility in the co-polyol are better candidates for partially substituting petroleum-based polyols in the formulation of flexible PU foams intended for the automotive applications.     

New monodentate and bidentate silylene ligands by DFT

Considering the importance of silylene ligands in transition metal-mediated catalytic reactions, we have scrutinized eight novel monodentate ( 1 – 4 ) and bidentate ( 1 ^′ - 4 ^′ ) derivatives of 2,5-diX-cyclopentasilylene-2,4-dienes (X = NH₂, OH, PH₂, and SH), at M06/6-311++G** level of theory. To probe the complexation ability of our scrutinized silylene ligands with Rh atom ( 1 _Rh - 4 _Rh and 1 ^′ _Rh - 4 ^′ _Rh , respectively), thermodynamic and structural parameters such as complexation energy (ΔE_Com), singlet-triplet energy gap (ΔE_s-t), bond length, along with NBO and atoms in molecules analyses are provided. In going from less electron donating groups (EDGs) to more EDGs (NH₂ > OH > PH₂ > SH), the σ -donor strength and ligand flexibility increase. Structures 1 and 1 ^′ turn out as the most nucleophilic species for showing the highest nucleophilicity (N = 5.47 and 5.40 eV, respectively). Furthermore, they exhibit the highest proton affinity values (PA = 271.46 and 271.23 kcal/mol, respectively). The results indicate that bidentate coordination mode of silylene leads to a stronger Si-Rh complex. The overall orders of σ -donation ability for monodentate and bidentate silylene ligands are 1 > 2 > 3 > 4 and 1 ^′ > 2 ^′ > 3 ^′ > 4 ^′ , respectively.     

Nanomagnetically modified vitamin B3 (Fe3O4@Niacin): An efficient and reusable green biocatalyst for microwave‐assisted rapid synthesis of 2‐amino‐3‐cyanopyridines in aqueous medium

Superparamagnetic nanoparticles of modified vitamin B₃ (Fe₃O₄@Niacin) represent a new, efficient and green biocatalyst for the one‐pot synthesis of 2‐amino‐3‐cyanopyridine derivatives via four‐component condensation reaction between aldehydes, ketones, malononitrile, and ammonium acetate under microwave irradiation in water. This new magnetic organocatalyst was easily isolated from the reaction mixture by magnetic decantation using an external magnet and reused at least six times without significant degradation in the activity. The catalyst was fully characterized by FT‐IR, XRD, SEM, VSM, UV–Vis, DLS and EDS. Excellent yield, very short reaction time (7–10 min), operational simplicity, easy work‐up procedure, avoidance of hazardous or toxic catalysts and organic solvents are the main advantages of this green methodology which makes it more economic than the other conventional methods.     

Convenient synthesis of alkyl thioacetate from alkyl halide using a polymer-supported sodium thioacetate

Alkyl halides are efficiently converted to their corresponding S-alkyl thioacetates under mild and nonaqueous conditions, using polymer-supported sodium thioacetate as a new polymeric reagent at room temperature in high yields and purity. The spent polymeric reagent can be removed quantitatively by filtration and pure products can be obtained by evaporation of the solvent. The spent polymeric reagent can be regenerated and reused several times without its activity changing appreciably.     

Synthesis and characterization of functionalized ordered hexagonal nanoporous carbon nitride with melamine-based dendrimer amines

Mesoporous carbon nitride (MCN-1) and functionalized MCN-1 with melamine-based dendrimer amine (MDA-MCN-1) have been synthesized. These materials are characterized by means of nitrogen adsorption–desorption isotherms, thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, small-angle X-ray scattering (SAXS), wide angle X-ray diffraction (XRD) pattern and Energy dispersive X-ray (EDX). Two bands at 1,434 and 1,550 cm^?1 in FT-IR spectrum of MDA-MCN-1 are clear evidence of an aromatic triazine ring and confirm that the melamine-based dendrimer is formed. The pore diameter is centered at 4.74 nm with a relatively high BET surface area of 102.2 m² g^?1 and a pore volume of 0.12 cm³ g^?1. TGA curves show that samples (MCN-1 and MDA-MCN-1) have high thermal stability compared to the earlier species. The carbon-to-nitrogen ratio calculated from the EDX analysis significantly decreases from 3.87–4.35 to 1.26 in MDA-MCN-1 than MCN-1 material. This indicates that MDA-MCN-1 has high nitrogen content and active adsorption sites in comparison to MCN-1 species.     

Effect of substituents and encapsulation on the catalytic activity of copper(II) complexes of two tridentate Schiff base ligands based on thiophene: benzyl alcohol and phenol oxidation reactions

Encapsulation of Cu(II) complexes of methyl-2-(2-hydroxybenzylideneamino)-4,5,6,7-tetrahydrobenzo[b]-thiophene-3-carboxylate (HL¹) and 2-ethyl-4-methyl 5-(2-hydroxybenzylideneamino)-3-methylthiophene-2,4-dicarboxylate (HL²) in the supercages of zeolite NaY was performed by the flexible ligand method. The neat and encapsulated complexes were characterized by physicochemical and spectroscopic methods and employed as catalysts for oxidation of benzyl alcohol and phenol. The encapsulated complexes were both more reactive and stable as catalysts than the corresponding free complexes. The encapsulated complexes could be reused several times. Complexes of HL² were more reactive than those of HL¹, probably due to the electron-withdrawing effect of the CO₂Et group.     

Synthesis of a new series of pyrazolo[1,5‐a]pyrimidines structurally related to zaleplon

The reaction between 3‐(dimethylamino)/3,3‐bis(methylthio)‐1‐(substituted)prop‐2‐en‐1‐ones and 4‐substituted‐5‐amino‐1H‐pyrazoles afforded new pyrazole[1,5‐a]pyrimidines structurally related to Zaleplon. The chemical modifications introduced at the 3‐, 5‐, and 7‐positions of the bicyclic structure revealed new promising candidates for the treatment of sleep disorders.