Reductive Carbocyclization of Homoallylic Alcohols to syn‐Cyclobutanes by a Boron‐Catalyzed Dual Ring‐Closing Pathway

The organoborane‐catalyzed reductive carbocyclization of homoallylic alcohols has been developed by using hydrosilanes as reducing reagents to provide a range of 1,2‐disubstituted arylcyclobutanes. The reaction proceeds in a cis‐selective manner with high efficiency under mild conditions. Mechanistic studies, including deuterium scrambling and Hammett studies, and DFT calculations, suggest a dual ring‐closing pathway.     

Metal complexes of pyrimidine derived ligands – Syntheses,characterization and X-ray crystal structures of Ni(II), Co(III) and Fe(III) complexes of Schiff base ligands derived from S-methyl/S-benzyl dithiocarbazate and 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde

Two new pyrimidine based NNS tridentate Schiff base ligands S-methyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL₁] and S-benzyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL₂] have been synthesised by the 1:1 condensation of 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde and S-methyl/S-benzyl dithiocarbazate. A Ni(II) complex of HL₁ and Co(III) and Fe(III) complexes of HL₂ have been prepared and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and spectroscopic studies. All the bis-chelate complexes have a distorted octahedral arrangement with an N₄S₂ chromophore around the central metal ion. Each ligand molecule binds the metal ion using the pyrimidyl and azomethine nitrogen and thiolato sulfur atoms (except in the nickel complex, one ligand molecule uses the thione sulfur in lieu of thiolato sulfur atom). In the Ni(II) complex, one of the ligand molecules behaves as a neutral tridentate and the other molecule functions as a uninegative tridentate, whereas in the Co(III) and Fe(III) complexes, the ligand molecules behave as monoanionic tridentate. All the complexes were analyzed by single crystal X-ray diffraction and significant differences concerning the distortion from an octahedral geometry of the coordination environment were observed.     

Stereoselective syntheses of unnatural steroidal C(20R) aldehydes by ionic hydrogenation of C-20 tertiary alcohols

Syntheses of three unnatural steroidal C(20R) aldehydes have been realised from 16-dehydropregnenolone acetate. The salient feature of the synthesis is the ionic hydrogenation of C-20 tertiary alcohols leading to the formation of the C(20R) unnatural isomer with complete stereoselectivity. Oxidative hydrolysis of the dithiane moiety furnished the C(20R) aldehydes.     

Organocatalytic oxidative synthesis of C2-functionalized benzoxazoles,naphthoxazoles, benzothiazoles and benzimidazoles

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Multifunctional silk fibroin/PVA bio-nanocomposite films containing TEMPO-oxidized bacterial cellulose nanofibers and silver nanoparticles

Cellulose - Silk fibroin (SF) has been intensively studied as a biobased renewable material for biomedical and other applications. However, its relatively low mechanical properties have limited its...     

Hydrothermal synthesis of dimeric lanthanide compounds: X-ray structure,magnetic study and heterogeneous catalytic epoxidation of olefins

A series of dimeric lanthanide carboxylato complexes [La(5-Br-NIC)₃(H₂O)₂]₂·H₂O (1); [Gd(5-Br-NIC)₃(H₂O)₂]₂ (2), [5-Br-NIC = 5-bromonicotinate] and [Sm(NIC)₃(H₂O)₂]₂ (3) [NIC = nicotinate], have been hydrothermally synthesized and structurally characterized by single crystal X-ray analysis. Complexes 1, 2 and 3 are of similar structure and consist of a basic unit [La(carboxylato)₃(H₂O)₂]₂. In compound 1 lanthanide cation is surrounded by one chelating 5-bromo-nicotinato ligand, two bridging oxygen atoms from 5-bromo-nicotinato and two water molecules, in which each La(III) ion is nine coordinated in a tricapped prismatic geometry. However, in compounds 2 and 3 four carboxylate groups link a pair of lanthanide atoms in the O,O′-bridging mode to generate a paddle-wheel-like centrosymmetric dimer. All the compounds exhibit excellent catalytic performance in olefin epoxidation reaction. The variable temperature magnetic susceptibility measurements showed that the magnetic interaction in [Gd(5-Br-NIC)₃(H₂O)₂]₂ (2), is antiferromagnetic (J = −0.048 cm⁻¹), while compound [Sm(NIC)₃(H₂O)₂]₂ (3), showed a complicated low-temperature magnetic property.     

Vibrational coupling in carboxylic acid dimers

The vibrational level splitting in the ground electronic state of carboxylic acid dimers mediated by the doubly hydrogen-bonded networks are investigated using pure and mixed dimers of benzoic acid with formic acid as molecular prototypes. Within the 0-2000-cm(-1) range, the frequencies for the fundamental and combination vibrations of the two dimers are experimentally measured by using dispersed fluorescence spectroscopy in a supersonic jet expansion. Density-functional-theory calculations predict that most of the dimer vibrations are essentially in-phase and out-of-phase combinations of the monomer modes, and many of such combinations show significantly large splitting in vibrational frequencies. The infrared spectrum of the jet-cooled benzoic acid dimer, reported recently by Bakker et al. [J. Chem. Phys. 119, 11180 (2003)], has been used along with the dispersed fluorescence spectra to analyze the coupled g-u vibrational levels. Assignments of the dispersed fluorescence spectra of the mixed dimer are suggested by comparing the vibronic features with those in the homodimer spectrum and the predictions of density-functional-theory calculation. The fluorescence spectra measured by excitations of the low-lying single vibronic levels of the mixed dimer reveal that the hydrogen-bond vibrations are extensively mixed with the ring modes in the S1 surface.     

Conductance of Some 1:1 Electrolytes in N,N-Dimethylacetamide at 25°C

Precise conductance measurements of solutions of lithium chloride, lithium bromide, lithium iodide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, tetrabutylammonium bromide, and tetrabutylammonium tetraphenylborate in N,N-dimethylacetamide are reported at 25°C in the concentration range 0.005–0.015 mol-dm^–3. The conductance data have been analyzed by the 1978 Fuoss conductance equation in terms of the limiting molar conductance (⁰), the association constant (K _a), and the association diameter (R). The limiting ionic conductances have been estimated from an appropriate division of the limiting molar conductivity of the reference electrolyte Bu₄NBPh₄. Slight ionic association was found for all these salts in this solvent medium. The results further indicate significant solvation of Li⁺ion, while the other ions are found to be unsolvated in N,N-dimethylacetamide.     

A novel tryptamine-appended rhodamine-based chemosensor for selective detection of Hg2+ present in aqueous medium and its biological applications

A novel rhodamine–tryptamine conjugate–based fluorescent and chromogenic chemosensor (RTS) for detection of Hg²⁺ present in water was reported. After gradual addition of Hg²⁺ in aqueous methanol solution of RTS, a strong orange fluorescence and deep-pink coloration were observed. The probe showed high selectivity towards Hg²⁺ compared to other competitive metal ions. The 1:1 binding stoichiometry between RTS and Hg²⁺ was established by Job’s plot analysis and mass spectroscopy. Initial studies showed that the synthesized probe RTS possessed fair non-toxicity and effectively passed through cell walls of model cell systems, viz., human neuroblastoma (SHSY5Y) cells and cervical cells (HeLa) to detect intercellular Hg²⁺ ions, signifying its utility in biological system. The limit of detection (LOD) was found to be 2.1 nM or 0.42 ppb by fluorescence titration. Additionally, the potential relevance of synthesized chemosensor for detecting Hg²⁺ ions in environmental water samples has been demonstrated.

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Conductance of Selected Alkali Metal Salts in Aqueous Binary Mixtures of 2-Methoxyethanol at 25°C

Precise conductance measurements have been performed for lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, sodium perchlorate, and sodium tetraphenylborate in 2-methoxyethanol–water mixtures at four different mole fractions, i.e., 0.056, 0.136, 0.262, and 0.486 of 2-methoxyethanol (69.73 D 26.55) at 25°C in the concentration range 0.0004–0.0642 mol-dm^–3. The limiting molar conductivity °, the association constant K _A, and the association distance R for the solvent mixtures have been evaluated from the conductance concentration data using the 1978 Fuoss conductance equation. The single-ion conductances have been estimated using the reference electrolyte tetrabutylam-monium tetraphynylborate(Bu₄NBPh₄). The analysis of the data indicates that for most salts ion association is appreciable in the solvent mixtures with a mole fraction of the cosolvent of 0.262 or higher. The results have been interpreted in terms of ion-solvent interactions and structural changes in the mixed solvent media.