Rh(II) acetate catalyzed cyclopropanation of styrenes with enaldiazo esters: diastereoselective synthesis of enal-cyclopropanes

An efficient Rh(II) acetate catalyzed highly diastereoselective cyclopropanation of styrenes with enaldiazo esters has been developed (up to >95:5 dr and 62–82% yield). The reaction is proposed to involve diacceptor electrophilic rhodium enalcarbenoids and constitutes the first direct synthesis of enal-cyclopropanes with an all carbon γ-quaternary stereocenter.     

O-Tolyldithiocarbonate Complexes of Iron(II) and Iron(III)

Abstract

Reactions of O-tolyldithiocarbonate ligands, (o-, m-, and p-CH₃C₆H₄O)CS₂Na, with anhydrous FeCl₂ (1:2 molar ratio) and with FeCl₃ (1:1 and 1:3 molar ratio) yielded the complexes [{(CreO)CS₂}₂Fe] and [{(CreO)CS₂}_nFeCl_3–n] (Cre = o-, m-, and p-CH₃C₆H₄; n = 1 and 3), respectively. These complexes were reacted with nitrogen and phosphorus donor ligands in dichloromethane, which afforded the adducts corresponded to [{(CreO)CS₂}₂Fe.xL] and [(CreO)CS₂FeCl₂.xL] {x = 1, L = N₂C₁₂H₈; x = 2, L = NC₅H₅, P(C₆H₅)₃}. Elemental analyses and IR, UV-visible, and mass spectroscopic and magnetic studies indicated bidentate mode of bonding by dithiocarbonate ligands leading to sixcoordination around the iron atom as a consequence of Fe…Fe interaction in the complexes [{(CreO)CS₂}₂Fe] and [(CreO)CS₂FeCl₂]. The complexes exhibited antifungal activity. The fungicidal activity of the complexes has been tested by poisoned food technique using fungi Fusarium sp.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Antifungal Activity.     

Minimizing algebraic connectivity over graphs made with some given blocks

This article describes the structure of the graph minimizing the algebraic connectivity among all connected graphs made with some given blocks with fixed number of pendant blocks, the blocks that have exactly one point of articulation. As an application, we conclude that over all graphs made with given blocks, the algebraic connectivity is minimum for a graph whose block structure is a path.     

Novel Sensing Assembly Comprising Engineered Gold Dendrites and MWCNT‐AuNPs Nanohybrid for Acetaminophen Detection in Human Urine

A layered nanohybrid comprising of multi walled carbon nanotubes(MWCNT)‐gold nanoparticles (AuNPs) has been designed as a matrix for the development of Au dendritic nanostructures (AuDN) with enhanced catalytic activity. The developed sensor matrix was thoroughly characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and energy dispersive X‐ray spectroscopy (EDX). The developed sensor probe MWCNT‐AuNPs/AuDN over glassy carbon electrode (GCE) was used for the label free detection of acetaminophen (AP), a commonly used drug associated with hepatotoxicity when overdosed, as a model molecule. The final sensor probe was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV). The sensor shows excellent analytical performances with a linear dynamic range (LDR) of 100 to 7500 nM, and a low limit of detection (LOD) of 2.12 (±0.03) nM, which is better than recently reported AP sensors. The practical application / clinical possibilities of the final sensor were evaluated by real sample analysis in human urine by spike and recovery method, where the AP recoveries were found in between 92 % to 96 %. The sensor probe shows negligible response towards co‐existing interfering molecules like glucose, urea, uric acid and various amino acids, which are commonly found in real samples (p<0.001, n=3). The shelf life of the sensor probe was evaluated and found to be stable for 8 weeks. The fabricated sensor probe using MWCNT‐AuNPs/AuDN is easy to fabricate, simple, robust, and able to detect AP in urine with high recoveries shows its possibilities to be used in clinical settings.     

[Hydroxy(tosyloxy)iodo]benzene in Organic Synthesis: A Facile Synthesis of Furo[3,2-c]coumarins Using α-Tosyloxyketones

Facile synthesis of furo[3,2-c]coumarins (2a–g) via cyclocondensation of 4-hydroxycoumarin and α-tosyloxyketones (1a–g) is described. A plausible mechanism involving C-C bond formation followed by 5-exo-tet cyclization is suggested.     

Synthesis of Arylglyoxylic Acids and Their Collision-Induced Dissociation

Abstract

A variety of substituted arylglyoxylic acids (2a?g) were synthesized via oxidation of the corresponding aryl-methylketones (1a–e) using selenium dioxide or Friedel–Crafts acylation of phenol (3) with ethyl chlorooxoacetate and further transformations. It was found that the arylglyoxylic acids (2) undergo facile unimolecular dissociation with loss of carbon monoxide to give the corresponding arylcarboxylic acids (7) under collisionally induced mass spectrometric conditions.     

Effect of transition metal salt additive on the structural packing and thermal stability of the non-aqueous lyotropic mesophases

The present study demonstrates the interfacial interplay between transition metal salt (TMS) additive and range of non-aqueous lyotropic mesophases. Structural aspect reveals the substantial influence of the additive addition on the self-assembly and packing of micelles as intense growth of hexagonal planes was seen in the vicinity of the pre-existed lamellar mesophase (as the surfactant concentration loomed to the higher value in the parent binary mixture). Such structural modulations certainly resulted from reduction in optimal surface area of head group and packing parameter under the influence of interfacial interactions amid charged counter ions and metal salt additive. The origin and thermal stability of hexagonal ordering have been addressed and discussed.     

Structural and dielectric behaviour of non-aqueous lyotropic mixtures: influence of amphiphile chain lengths and counter ions

This study highlights the effects of amphiphile chain length and counter ions on the self-assembly and dielectric behaviour of non-aqueous lyotropic liquid crystals. Two-dimensional hexagonal mesophase is seen for short-chain length sodium dodecyl sulphate, while lamellar and multiwall lamellar mesophases are noticed for long-chain length cetyltrimethylammonium bromide and polyoxyethylene (20) sorbitan monolaurate amphiphiles in the non-aqueous domains of ethylene glycol. A strong influence of amphiphile counter ions is seen on static dielectric constant, loss factor, relaxation frequency and relaxation time of these lyotropic mixtures. Refractive indices of these lyotropic phases are also highlighted.     

Effect of solvent polarity on the self-assembly and dielectric dynamics of non-aqueous lyotropic liquid crystalline phases

Binary mixtures comprising cetylpyridinium chloride and non-aqueous solvents of varying polarity [ethylene glycol (ε ~ 37.2) and formamide (ε ~ 109)] were studied via X-ray diffraction, polarisation optical microscopy, differential scanning calorimetry and dielectric spectroscopy. Layered lamellar mesophase was observed in both mixtures. Formamide-based mesophase was found more ordered and stable up to higher temperature (140°C). Ordering and stability of the mesophase was explained considering the higher polarity and dipolar–dipolar interactions of formamide. Dielectric spectroscopy demonstrates the large magnitudes of capacitance and permittivity (Cp ≈ 9 µF and ε ≈ 2428) for mesophase derived from formamide. Dynamical relaxation parameters of both mixtures were discussed and correlated with their structural aspects.