One-pot synthesis of novel 3,10-dihydro-2H-1,3-oxazepino[7,6-b]indoles via 1,4-dipolar cycloaddition reaction

3,10-Dihydro-2H-1,3-oxazepino[7,6-b]indoles are synthesized via a convenient one-pot three-component 1,4-dipolar cycloaddition reaction, involving 3-alkyl(aryl)imidazo[1,5-a]pyridines, dimethyl acetylenedicarboxylate (DMAD) and N-alkylisatins. Structures of the newly synthesized heterocycles are evidenced from spectral data and further confirmed by single crystal X-ray diffraction. A plausible reaction mechanism is advanced, whereby the intermediate 1,4-dipole, generated in situ from imidazo[1,5-a]pyridine and DMAD, initially adds to the keto group of N-alkylisatins to form the corresponding 1,3-oxazin-spiro-oxindole cycloadduct. The latter undergoes subsequent unprecedented skeletal rearrangement through a cascade of bond breaking and bond making processes, eventually leading to ring enlargement, furnishing the tricyclic oxazepino[7,6-b]indole ring system as the end product.     

A Robust 3D Cage‐like Ultramicroporous Network Structure with High Gas‐Uptake Capacity

A three‐dimensional (3D) cage‐like organic network (3D‐CON) structure synthesized by the straightforward condensation of building blocks designed with gas adsorption properties is presented. The 3D‐CON can be prepared using an easy but powerful route, which is essential for commercial scale‐up. The resulting fused aromatic 3D‐CON exhibited a high Brunauer–Emmett–Teller (BET) specific surface area of up to 2247 m² g^?1. More importantly, the 3D‐CON displayed outstanding low pressure hydrogen (H₂, 2.64 wt %, 1.0 bar and 77 K), methane (CH₄, 2.4 wt %, 1.0 bar and 273 K), and carbon dioxide (CO₂, 26.7 wt %, 1.0 bar and 273 K) uptake with a high isosteric heat of adsorption (H₂, 8.10 kJ mol^?1; CH₄, 18.72 kJ mol^?1; CO₂, 31.87 kJ mol^?1). These values are among the best reported for organic networks with high thermal stability (ca. 600 °C).     

Herbicidal activity of pure compound isolated from rhizosphere inhabiting Aspergillus flavus

In the quest for bioactive natural products of fungal origin, Aspergillus flavus was isolated from rhizosphere of Mentha piperita using Potato Dextrose Agar (PDA) and Czapec Yeast Broth (CYB) nutrient media for metabolites production. In total, three different metabolites were purified using HPLC/LCMS and the structures were established using 500 Varian NMR experiments. Further the isolated metabolites in different concentrations (10, 100, 1000 μg/mL) were tested for herbicidal activity using Completely Randomized design (CRD) against the seeds of Silybum marianum and Avena fatua which are major threats to wheat crop in Pakistan. Among the isolated metabolites, one compound was found active against the test weed species whose activity is reported in the present work. The chemical name of the compound is 2-(1, 4-dihydroxybutan-2-yl)-1, 3-dihydroxy-6, 8-dimethoxyanthracene-9, 10(4aH, 9aH)-dione with mass of 388. Results showed that all seeds germinated in control treatment; however, with the metabolite treated, the growth was retarded to different levels in all parts of the weeds. At a dose of 1000 μg/mL of the pure compound, 100% seeds of S. marianum and 60% seeds of A. fatua were inhibited. Interestingly, the pure compound exhibited less inhibition of 10% towards the seeds of common wheat (Triticum aestivum).     

Recent progress of poly (N-isopropylacrylamide) hybrid hydrogels: synthesis,fundamentals and applications – review

Hydrogels, having nanomaterials (e.g. nanoparticles and nanorods) incorporated inside their polymeric meshes, are generally called hybrid gels/hydrogels. These assemblies combine the properties of both hydrogels and nanomaterials in one system. These responsive hybrid hydrogels, particularly polymerized N-isopropylacrylamide (PoNip) polymeric gels, have been extensively exploited for various multi-disciplinary applications in the literature over the past two decades because of their unique and exquisite particulars. Next generation assemblies have been prepared by using the smart nature of these gels toward the general incentives (e.g. temperature, ionic strength, and pH) in the fields of nanocatalysis, water purification, drug delivery, photonics, and optics. This review presents an overview of the PoNip hybrid assemblies engineered over the past 7 years i.e. 2010–2016 and extensively discusses the interaction of the incorporated nanomaterial with the polymeric chains of the hydrogels as it is the most significant factor which makes these assemblies attractive for all the associated applications. Moreover, this article also describes the preparative routes, properties, classification, and applications of these hybrid hydrogels in the fields of medicine, environment, catalysis, and nanotechnology.     

Kinetics and electrochemical studies on superoxide

Rate constants for the reaction of superoxide O^- ₂ with various substrates were obtained through stationary electrode polarography theory and technique. In solvent acetonitrile, the substrate and the rate constants of the reaction O^- ₂ + AH^{- k2}Product, are, AH = isopropanol (k₂ < 0.01 M^-1 s^-1); ethanol (k₂ = 1.42 × 10² M^-1 s^-1); methanol (k₂ = 1.1 × 10⁷ M^-1 s^-1), H₂O (k₂ = 1.0 × 10⁵ M^-1 s^-1). In MeCN, O^-2 was found to be rather unreactive towards glucose and acetone but it reacts with fructose and sucrose catalytically. However, in DMF2, O^- ₂reacts with glucose and fructose with k2 order of 105 M-1 s-1. The mechanism of the reaction of O^- ₂ with the substrates (AH) is proposed as O^- ₃ + AH k₂O, AH^k2 _k-1 k [O₂H + AH]^-, _k-2O₂H + A^- with k₁ = 10⁹ M^-1 s^-1 and k^-1 = 10⁸ -10⁹ s^-1. With these values of k_-1 and k₁, k k₂(obs). The reversible E_1/2 for O₂ + e O^- ₂ in various solvents: MeCN, acetone, isopropanol, methanol, H₂O were obtained either directly from the reversible voltammogram or from experimental voltammograms and the rate constants obtained (as above) using stationary electrode polargraphy theory; E_1/2 being -0.82 (MeCN),-0.85 (acetone),-0.72 (isopropanol);-0.66 (MeOH),-0.56 (H2O) vs SCE.     

Five new peltogynoids from underground parts of Iris bungei: a Mongolian medicinal plant

Five new peltogynoids, irisoids A-E (1-5), have been isolated from the underground parts of Iris bungei. The structures of the new compounds were established on the basis of spectroscopic methods and were found to be 1,8,10-trihydroxy-9-methoxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (1), 1,8-dihydroxy-9,10-dimethoxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (2), 1,10-dihydroxy-8,9-dimethoxy-[1]benzopyrano-13,2-c][2]-benzopyran-7(5H)-one (3), 1,8-dihydroxy-9,10-methylenedioxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (4), and 1,8,11-trihydroxy-9,10-methylenedioxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (5). The structure of irisoid B (2) was established unambiguously by X-ray diffraction study.     

Two New Spirostanol Glycosides from Cestrum parqui

Two new steroidal glycosides, parquisoside A ( 1 ) and B ( 2 ) were isolated from the aerial parts of Cestrum parqui (family Solanaceae). Their common aglycone is a new steroid of the spirostane series, which we name parquigenin. It has the structure (3β,24S,25S)‐spirost‐5‐ene‐3,24‐diol, i.e. a (24S,25S)‐24‐hydroxydiosgenin. The structures of parquisosides A and B were elucidated as (3β,24S,25S)‐spirost‐5‐ene‐3,24‐diol 3‐O‐{[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)}‐β‐D ‐glucopyranoside ( 1 ) and (3β,24S,25S)‐spirost‐5‐ene‐3,24‐diol 3‐O‐{[α‐L ‐rhamnopyranosyl)‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)}‐β‐D ‐glucopyranoside ( 2 ), respectively, on the basis of detailed spectroscopic studies and chemical analysis. The crude extract of Cestrum parqui showed inhibition of carrageenin‐induced edema.     

Cohirsine - a novel isoquinolone alkaloid from

A novel alkaloid, cohirsine (1) was isolated from . Its structure has been investigated by extensive NMR studies including 2D NMR experiments. Its stereochemistry has been determined by 2D NOESY and NOE difference measurements.     

The structure of the diazonium coupling products of phenacyl thiocyanate and phenacyl selenocyanate with diazotized 3-phenyl-5-aminopyrazole

The reaction of diazotized 3-phenyl-5-aminopyrazole with phenacyl thiocyanate 1a and phenacyl selenocyanate 1b afforded directly 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-thiadiazole monohydrate 9a and 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-selenadiazole monohydrate 9b , respectively. The products 9a and 9b were also obtained from the reaction of C-benzoyl-N-(3-phenyl-5-pyrazolyl)formohydrazidoyl bromide 10 with potassium thiocyanate and potassium selenocyanate, respectively. Acetylation, benzoylation, and nitrosation of 9 afforded the corresponding diacetyl, dibenzoyl, and nitroso derivatives 11-13 , respectively. Cyclization of C-benzoyl-N-(3-phenyl-5-pyrazolyl)-nitrilimine 6 was shown to give the pyrazolo [5,1-d]triazole 8 and not the pyrazolo[5,1-c]-as-triazine derivative 7 , as previously reported.     

Uncharged encapsulated iron(II) complexes: transfer chemical potentials and solvation in water-methanol and water-t-butanol mixtures

Summary Transfer chemical potentials have been determined from measured solubilities for four uncharged encapsulated iron(II) complexes containing three diimine ligating moieties and O₃BOBu-n and O₃BF capping groups, in H₂O–MeOH andt-BuOH–H₂O solvent mixtures, The trends in transfer chemical potentials are discussed in terms of the natures of the encapsulating ligands, and are compared with those for a selection of other iron(II)-diimine complexes.