A stereoselective and atom-efficient approach to multifunctionalized five- and six-membered rings via a novel michael-initiated intramolecular Diels-Alder furan reaction

[reaction: see text] A variety of key precursors to the intramolecular Diels-Alder reaction of furan diene (IMDAF) have been prepared via a very facile 1,4-addition of O-, S-, N-, and C-centered nucleophiles possessing unsaturated tether to beta-furyl nitroethylene. Subsequent IMDAF reaction of the 1,4-adducts, carried out under thermal conditions, provided five- and six-membered carbocycles and heterocycles fused to an easily cleavable oxabicycloheptene moiety. The structure and stereochemistry of the cycloadducts were determined by 2D-NMR experiments and further confirmed by X-ray crystallography. The salient features of the strategy include high degree of stereoselectivity (>80:20) in the cycloaddition, atom and step economy, and generation of multiple chiral centers and functionalities. The feasibility of the cleavage of the oxa bridge in the cycloadducts to afford novel multifunctional molecules has also been demonstrated.     

Inhomogeneous minimum of indefinite quadratic forms in five variables of type (3,2) or (2,3): A conjecture of watson

LetQ(x,y,z,t,u) be a real indefinite quadratic form in five variables of type (3,2) or (2,3) and determinantD≠0. The given any real numbersx ₀,y ₀,z ₀,t ₀,u ₀ we can find integersx,y,z,t,u, satisfying $$|Q(x + x_0 ,y + y_0 ,z + z_0 ,t + t_0 ,u + u_0 )| \leqslant (\frac{1}{4}|D|)^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 5}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{$5$}}} .$$ All the cases when the sign of equality holds are also determined.     

New trends in sustainable nanocatalysis: Emerging use of earth abundant metals

Noble metals are well-known to afford highly active, selective and durable catalysts, and have thus been at the core of the development of greener processes. In recent years, however, growing concerns about their scarcity, cost and toxicity has triggered research efforts towards the development of earth-abundant catalysts. In this Current Opinion, recent examples of the use in catalysis of pure earth-abundant metals, earth-abundant metals with minute quantities of noble metals, or earth-abundant metals activated by light are presented. This highlight article showcases the current trends in sustainable organic transformations, catalyzed by nanomaterials.     

A rapid,highly efficient,and general protocol for the synthesis of functionalized triarylmethanes: a straightforward access for the synthesis of (−)-tatarinoid C

A rapid, efficient, and convenient synthesis of functionalized triarylmethane is described by the Friedel–Crafts alkylation of methoxybenzenes with a variety of aldehydes in the presence of BF₃·OEt₂. The generality of the method is demonstrated by screening a variety of di- or tri-substituted arenes as well as substituted aromatic, heteroaromatic, and aliphatic aldehydes. (−)-Tatarinoid C is synthesized in a single step following the same protocol.     

Thermal analysis of hydrogen bonded benzoic acid liquid crystals

Novel homologous series of supramolecular hydrogen bonded liquid crystals have been investigated. Hydrogen bonds are formed between p-n octyloxy benzoic acid and various p-n alkyloxy benzoic acids whose carbon chain length varied from pentyl to dodecyl. These complexes are characterized by Fourier transform infrared spectroscopy, polarizing optical microscopy (POM), and differential scanning calorimetry (DSC). Phase diagram is constructed from POM and DSC data. The order of the phase transitions is determined by Navard and Cox ratio (N _R). Characteristic phases like nematic, smectic C, and smectic F are identified. A new smectic ordering observed in this series is investigated by constructing phase diagram obtained from two binary mixtures of the present homologs. Inter-digitation of lamellar layers is observed to be one of the reasons for the occurrence of new smectic ordering. Optical tilt angle in smectic C phase is fitted to a power law. The magnitude of exponent of the power law is found to concur with the Mean Field theory predicted value.     

Covariate model-based fault tree analysis for risk assessment in chemical process industries: A case study of a chlorine manufacturing facility

Fault tree analysis (FTA) is a promising quantitative technique for risk analysis in chemical process industries (CPIs). In FTA, a certain sequence of basic events (causes) leads to one specific Top event (critical event of interest). However, the conventional fault tree analysis has the limitations of staticity and uncertainty. The staticity in conventional FTA arises due to its inability to accommodate time-dependent characteristics of the process system. Whereas uncertainty primarily lies in the failure probability data of basic events. This paper proposes an innovative methodology that uses a time-dependent covariate model to update the failure probability values of major contributing basic events in FTA. A novel subclass of the family of phase-type distributions is used to model the covariates corresponding to the basic events. The newly developed methodology is applied for a case study in a chlorine manufacturing facility to estimate the chlorine release probability. The blockage in the pipeline was identified as the significant reason for chlorine release from expert opinion and sensitivity analysis. The results of the proposed model of FTA are compared with that of conventional FTA.     

Synthesis,antioxidant activity,and α-glucosidase enzyme inhibition of α-aminophosphonate derivatives bearing piperazine-1,2,3-triazole moiety

A novel series of piperazine-1,2,3-triazole bearing dimethyl(((2-(4-((1H-1,2,3-triazole-4-yl)methyl)piperazin-1-yl)ethylamino)(2-hydroxyaryl)methyl)phosphonate derivatives have been prepared via copper-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC) (Click Reaction) and Schiff base reactions. The synthesized compounds were confirmed by spectral characterization (¹H, ¹³C and ³¹P NMR, and mass). The title compounds were evaluated for in vitro alpha glucosidase enzyme inhibition and in vitro antioxidant activity using DPPH and H₂O₂ methods.     

Synthesis,characterization and antioxidant activity of bis (arylsulfonylmethyl/arylaminosulfonylmethylazolyl) pyridines

A new class of bis(arylsulfonylmethylazolyl)pyridines and bis(arylaminosulfonylmethyl-azolyl)pyridines were synthesized from the synthetic intermediates methyl arylsulfonylacetic acid hydrazide and methyl arylaminosulfonylacetic acid hydrazide adopting a green methodology-ultrasonication. All the synthesized compounds were resulted in higher yield and in shorter reaction times. The spectral parameters such as IR, ¹H NMR, ¹³C NMR, mass and microanalyzes were used to determine the structures of all the synthesized compounds and were assayed for antioxidant activity. The bis(arylaminosulfonylmethylazolyl)pyridines showed higher radical scavenging activity than the bis(arylsulfonylmethylazolyl)pyridines. Besides, unsubstituted, and methyl substituted compounds exhibited greater activity. Among all the tested compounds 8b and 11b were identified as potential antioxidants.