Synthesis of novel tricyclic and tetracyclic sultone scaffolds via intramolecular 1,3-dipolar cycloaddition reactions

The initially prepared 2-formylphenyl-(E)-2-phenylethenesulfonates from the condensation of (E)-2-phenylethenesulfonyl chloride with 2-hydroxybenzaldehyde derivatives underwent intramolecular [3+2] cycloaddition with methyl or phenylhydroxylamine, sarcosine, and l-proline, affording the corresponding novel isoxazolidine, pyrrolidine and pyrrolizidine-annulated γ,δ-benzo-δ-sultones, respectively, in good yields. Unambiguous assignment of the molecular structures was carried out by single-crystal X-ray diffraction.     

Nanoparticles tungstophosphoric acid supported on polyamic acid: catalytic synthesis of 1,8-dioxo-decahydroacridines and bulky bis(1,8-dioxo-decahydroacridine)s

Tungstophosphoric acid nanoparticles supported on polyamic acid (TPA NPs/PAA) was prepared and employed as a catalyst for the facile selective synthesis of 1,8-dioxo-decahydroacridines and some bulky bis(1,8-dioxo-decahydroacridine)s via one-pot condensation of 5,5-dimethyl-1,3-cyclohexanedione and various aldehydes with aniline or ammonium acetate in ethanol–water solution. This catalyst was characterized by FT-IR, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermogravimetric analysis (TG), energy-dispersive X-ray analysis (EDAX), and inductively coupled plasma optical emission spectrometry (ICP-OES). The catalyst showed high thermal stability and good reusability. The products were isolated in high purity and the catalyst was easily separated in a simple workup and recycled several times without noticeable loss of activity under the described reaction conditions. The reaction is characterized by short reaction time, high efficiency, and mild reaction conditions.     

An efficient FeCl3/SiO2 NPs as a reusable heterogeneous catalyzed five-component reactions of tetrahydropyridines under mild conditions

A convenient, simple, and multicomponent coupling strategy has been developed for the synthesis of highly functionalized tetrahydropyridines using FeCl₃/SiO₂ NPs as catalyst. This method demonstrated five-component coupling reactions of 1,3-dicarbonyl compounds, aromatic aldehydes and amines without an inert atmosphere. Atom economy, good yields, environmentally benign, and mild reaction conditions are some of the important features of this protocol. Notably, this catalyst could be recycled and reused for several times without noticeably decreasing the catalytic activity.     

Palladium‐anchored multidentate SBA‐15/di‐urea nanoreactor: A highly active catalyst for Suzuki coupling reaction

Modification of mesoporous silica was carried out by reaction of SBA‐15 with di‐urea‐based ligand. Next, with the help of this ligand, palladium ions were anchored within the multidentate SBA‐15/di‐urea pore channels with high dispersion. The SBA‐15/di‐urea/Pd catalyst was characterized using various techniques. Theoretical calculations indicated that each palladium ion was strongly interacted with one nitrogen and two oxygen atoms from the multidentate di‐urea ligand located in SBA‐15 channels and these interactions remained during the catalytic cycle. These results are in good agreement with those of hot filtration test: the palladium ions have very high stability against leaching from the SBA‐15/di‐urea support. The catalytic performance of SBA‐15/di‐urea/Pd nanostructure was examined for the Suzuki coupling reaction of phenylboronic acid and electronically diverse aryl halides under mild conditions with a minimal amount of Pd (0.26 mol%). Compared to previous reports, this protocol afforded some advantages such as short reaction times, high yields of products, catalyst stability without leaching, easy catalyst recovery and preservation of catalytic activity for at least six successive runs.     

Polyelectrolyte Nanocomposite Membranes Using Surface Modified Nanosilica for Fuel Cell Applications

The preparation and characterization of a new type of nanocomposite polyelectrolyte membrane (PEM), based on Nafion® (E. I. du Pont de Nemours and Co., Ltd., for its copolymer of tetrafluoroethylene and perfluorinated vinyl ether) and sulfonic acid (-SO₃H) or phosphotungstic acid (PWA) modified nanosilica (Si-SO₃H or Si-PWA, respectively), for direct methanol fuel cell (DMFC) applications are described. Physical characteristics of these manufactured nanocomposite membranes were investigated by scanning electron microscopy (SEM), water uptake, methanol permeability and ion exchange capacity, as well as proton conductivity. The Nafion®/Si-PWA and Nafion®/Si-SO₃H membranes showed higher proton conductivity, lower methanol permeability and, as a consequence, a higher selectivity parameter, in comparison to the neat Nafion® or Nafion®/pristine nanosilica membranes. The obtained results indicated that both the Nafion®/Si-PWA and Nafion®/Si-SO₃H membranes could be utilized as promising polyelectrolyte membranes for direct methanol fuel cell applications.     

Fabricating and improving properties of copper matrix nanocomposites by electroless copper-coated MWCNTs

In this study, copper (Cu) nanocomposites reinforced by coated multiwall carbon nanotubes (MWCNTs) have been fabricated with different weight fractions of MWCNT. In the first step, the as-received MWCNTs were coated with Cu using electroless deposition process. In the next step, combination of sonication and ball milling (with two milling time of 1.5 and 3 h) was used for preparing MWCNT/Cu composite powders. Finally, the disk-shaped specimens were sintered by hot-press sintering machine. Characterization of sintered nanocomposites revealed that increasing milling time led to improved mechanical properties, but higher defect density on the MWCNT sidewalls is obtained which is especially undesirable for electrical properties of nanocomposite. Our results indicated that simultaneous improvements of interface reactions and distribution uniformity of MWCNTs and Cu are key factors for obtaining enhanced mechanical properties. Accordingly, enhancement of up to ~150 and ~86 % in microhardness compared to pure Cu and 1 wt% as-received MWCNT/Cu was achieved by addition of 1 wt% Cu-coated MWCNT. On the contrary, existence of oxygen atoms in the Cu and coated MWCNT interface (from functional groups and deposited copper oxide) obstructs considerable improvement of electrical resistivity compared to as-received MWCNT/Cu nanocomposites.     

Efficient access to novel hexahydro-chromene and tetrahydro-pyrano[2,3-d]pyrimidine-annulated benzo-δ-sultones via a domino Knöevenagel-hetero-Diels-Alder reaction in water

An efficient catalyst-free, diastereosective synthesis of novel hexahydro-chromene and tetrahydro-pyrano[2,3-d]pyrimidine-annulated benzo-δ-sultones is described. A number of 2-formyl-4-phenyl (E)-2-phenylethenesulfonates were synthesized and underwent a one-pot domino Knöevenagel-hetero-Diels-Alder reaction, respectively, with dimedone and N,N-dimethylbarbituric acid in water, affording the desired products in moderate to excellent yields.     

Kinetic Study and NBO Analysis of the Dehydrogenation Mechanism of Five‐membered Ring Heterocyclic 2,5‐Dihydro‐[furan,thiophene, selenophene

The theoretical study of the dehydrogenation of 2,5‐dihydro‐[furan ( 1 ), thiophene ( 2 ), and selenophene ( 3 )] was carried out using ab initio molecular orbital (MO) and density functional theory (DFT) methods at the B3LYP/6‐311G**//B3LYP/6‐311G** and MP2/6‐311G**//B3LYP/6‐311G** levels of theory. Among the used methods in this study, the obtained results show that B3LYP/6‐311G** method is in good agreement with the available experimental values. Based on the optimized ground state geometries using B3LYP/6‐311G** method, the natural bond orbital (NBO) analysis of donor‐acceptor (bond‐antibond) interactions revealed that the stabilization energies associated with the electronic delocalization from non‐bonding lone‐pair orbitals [LP(e)_X3] to δ*_{C(1)  H(2)} antibonding orbital, decrease from compounds 1 to 3 . The LP(e)_X3→δ*_{C(1)  H(2)} resonance energies for compounds 1 – 3 are 23.37, 16.05 and 12.46 kJ/mol, respectively. Also, the LP(e)_X3→δ*_{C(1)  H(2)} delocalizations could fairly explain the decrease of occupancies of LP(e)_X3 non‐bonding orbitals in ring of compounds 1 – 3 ( 3 > 2 > 1 ). The electronic delocalization from LP(e)_X3 non‐bonding orbitals to δ*_{C(1)  H(2)} antibonding orbital increases the ground state structure stability, Therefore, the decrease of LP(e)_X3→δ*_{C(1)  H(2)} delocalizations could fairly explain the kinetic of the dehydrogenation reactions of compounds 1 – 3 (k ₁ >k ₂ >k ₃ ). Also, the donor‐acceptor interactions, as obtained from NBO analysis, revealed that the (_C(4)C(7)→δ*_{C(1)  H(2)} resonance energies decrease from compounds 1 to 3 . Further, the results showed that the energy gaps between (_C(4)C(7) bonding and δ*_{C(1)  H(2)} antibonding orbitals decrease from compounds 1 to 3 . The results suggest also that in compounds 1 – 3 , the hydrogen eliminations are controlled by LP(e)→δ* resonance energies. Analysis of bond order, natural bond orbital charges, bond indexes, synchronicity parameters, and IRC calculations indicate that these reactions are occurring through a concerted and synchronous six‐membered cyclic transition state type of mechanism.