Alcoholate complexes of chromium(III) chloride

Summary A number of alcoholate complexes of chromium chloride with the general formula, CrCl₃ · xROII (R = Me, Et, i-Pr, n-Bu and n-Ilexyl; x = 3 and 4) have been synthesized by the reactions of CrCl₃ · 3 TIIF with an excess of the appropriate alcohols under reflux. Physicochemical studies such as i.r., visible reflectance, electron spin resonance spectra and thermogravimetric measurements, in addition to elemental analyses, throw light on the structure of these complexes.     

The polarography of oximes: II. 1,2-Acenaphthaquinone monoxime

Polarography of 1,2-acenaphthaquinone monoxime has been carried out in buffers (pH 3.5–13.0) of constant ionic strength 0.5 M and 40% alcohol $\text{v}\text{v}$ at 25 ± 0.5 °C. The oxime group underwent diffusion-controlled reduction (4e) over the whole pH range. The number of electrons involved in the reduction was found by coulometric method as well as by incorporating the values of diffusion coefficients, obtained by using a McBain-Dawson cell, into the Ilkovi? equation. Koutecky's method has been used to compute the kinetic parameters (αn_aand ?log K_f.h) for the reduction of the oxime group and a reduction mechanism is proposed.     

New lignan glycosides from Cissus quadrangularis stems

Phytochemical investigation of Cissus quadrangularis stems led to the isolation of one new phenolic glycoside (1) and two new lignan glycosides (7 &; 8) along with twelve known compounds (2–6 &; 9–15). Their chemical structures were determined on the basis of extensive spectroscopic analysis using 1D, 2D NMR, and mass spectrometric analysis. Among the known compounds, 4–6, 9 and 12 were isolated for the first time from the genus Cissus whereas compounds 10, 11 and 13 for the first time from this plant.     

Complexes of divalent oxovanadium,manganese, iron,cobalt, nickel and copper with the ligand derived from the reaction of 2-aminopyridine and acetylacetone

Summary 2-Aminopyridine reacts with acetylacetone in the presence of VO^II, Mn^II, Fe^II, Co^II, Ni^II, and Cu^II metal salts to give complexes of the type [VO(Ap₂ac)₂X]X and [M(Ap₂ac)₂X₂] where (Ap₂ac) is the ligand formedin situ. The complexes are characterised as distorted octahedral by analyses, conductance, molecular weight, magnetic, electronic and i.r. spectral studies. The i.r. studies reveal that two molecules of aminopyridine are joined by a molecule of acetylacetone through a three carbon atom bridge and that the ligand coordinates through the azomethine and imino nitrogen atoms, whereas pyridine does not take part in coordination. The electronic spectra have been interpreted and tentative assignments are made. In the far i.r. spectra, various metal ligand vibrations are observed and discussed. Attempts to carry out electrophilic substitutions in the complexes failed.     

Strained tridecane cage systems

Hexacyclo[6.5.0.0^2,7.0^4,12.0^5,10.0^9.13]tridecane (HCTD) contains two four-membered, two five-membered and two six-membered rings fused into a cage structure which contains about 77.0 kcal/mol of strain energy. Attempts to prepare the thioketal from the diketone of HCTD led to a skeletal rearrangement to produce a cage with one four-membered, four five-membered, and two six-membered rings fused into a cage (RHCTD). The corresponding RHCTD hydrocarbon has a strain energy 13.7 kcal/mol less than that of the starting tridecane (HCTD) which provides the driving force for the rearrangement. The X-ray structures of two HCTD derivatives and one RHCTD derivative are reported. The bond lengths in the three reported structures are normal for cages of this type. The structure of tetracyclo[6.3.0.0^3,7.0^4,11]undecane-5,10-dione mono(ketene 1,3-propanedithioacetal) is discussed also.     

Characterization,luminescence and EPR investigations of Eu2+ activated strontium aluminate phosphor

Strong blue-green light emitting Eu doped SrAl₂O₄ phosphor was synthesized by a low-temperature initiated, self-propagating and gas producing combustion process in a very short time (<5 min). The prepared powder was characterized by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy. The excitation spectrum shows a peak at 397 nm. Upon excitation at 397 nm, the emission spectrum exhibits a well defined broad band with maximum at 493 nm corresponding to 4f⁶5d → 4f⁷ transition. Electron paramagnetic resonance (EPR) measurements at X-band showed low field signals due to Eu²⁺ ions in SrAl₂O₄:Eu.     

Study of assorted interactions of an ionic liquid in significant solvent systems using compensated equation of Fuoss conductance and vibrational mode

Qualitative and quantitative analyses of molecular interaction prevailing in ionic liquid tetrabutylphosphonium methanesulfonate [Bu₄PMS] in dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF) and N,N-dimethyl acetamide (DMA) probed by electrical conductances and Fourier transform infrared (FT-IR) measurements have been reported at 298.15 K. Corresponding conductance data have been analysed using the Fuoss conductance-concentration equation (1978) for ion pair formation. The limiting ionic conductances (λ _o ^± ) have been estimated from the appropriate division of the limiting molar conductivity value of tetrabutylammonium tetraphenylborate [Bu₄NBPh₄] as the ‘reference electrolyte’. The diffusion coefficient (D) has been obtained from Stokes-Einstein relation and the ionic mobility (i) for [Bu₄P]⁺ and MS^? using appropriate equation. The results have been discussed in terms of dipole-dipole interactions, hydrogen bond formation and structural aspect of the solvents and configurational theory. The FT-IR spectra have also been studied to predict the interactions occurring in the system.

La(OTf)3-catalyzed one-pot synthesis of meso-substituted porphyrinic thiazolidinones

Abstract  

An improved synthetic procedure is developed for the regioselective nitration of a phenyl group of meso-tetraphenylporphyrin by using NaNO₂ in a mixture of trichloroacetic acid and AcOH. The meso-(4-nitrophenyl)porphyrins are successfully reduced to corresponding meso-(4-aminophenyl)porphyrins by SnCl₂ under acidic conditions. In addition, an efficient one-pot methodology for synthesizing a series of novel meso-substituted porphyrinic thiazolidinone conjugates is developed by reacting meso-(4-aminophenyl)porphyrins with various aromatic aldehydes and mercaptoacetic acid in refluxing toluene using La(OTf)₃ as a catalyst. The products obtained are characterized on the basis of their spectral data. Preliminary photophysical properties of the newly synthesized compounds are reported.     

Shape factor for bermed wall

This note reports the dependence of shape factor corresponding to the portion of wall behind a berm and above the ground on the angle of berm; the results have been obtained by thermal simulation of heat transfer between the ground and the wall through the berming.