Cadmium(II) complexes of (arylazo)imidazoles: synthesis, structure, photochromism, and density functional theory calculation

Reaction between CdX2 and 1-alkyl-2-(phenylazo)imidazole (RaaiR') has isolated complexes of composition Cd(RaaiR')2X2 in MeOH or MeCN. Crystallization of Cd(RaaiR')2I2 from N,N-dimethylformamide (DMF) has separated [Cd(RaaiR')I2.DMF], while Cd(RaaiR')2X2 (X = Cl and Br) remains unchanged in its composition upon crystallization under identical conditions. The structure has been established by spectral (UV-vis and 1H NMR) data and confirmation in the latter case by a single-crystal X-ray diffraction study of [Cd(TaiMe)I2.DMF] [where TaiMe = 1-methyl-2-(p-tolylazo)imidazole]. UV-light irradiation in a MeCN solution of Cd(RaaiR')2I2 and [Cd(RaaiR')I2.DMF] shows trans-to-cis isomerization of coordinated azoimidazole. The reverse transformation, cis-to-trans, is very slow with visible light irradiation. Quantum yields (phit-->c) of trans-to-cis isomerization are calculated, and the free ligand shows higher phi values than their cadmium(II) iodo complexes. The cis-to-trans isomerization is a thermally induced process. The activation energy (Ea) of cis-to-trans isomerization is calculated by a controlled-temperature experiment. The effects of the anions (Cl-, Br-, I-, and ClO4-) and the number of coordinated azoimidazoles (RaaiR') [Cd(RaaiR') or Cd(RaaiR')2] on the rate and quantum yields of photochromism are established in this work. A slow rate of photoisomerization of [Cd(RaaiR')4](ClO4)2 compared to Cd(RaaiR')I2 or Cd(RaaiR')2X2 may be associated with the increased mass and rotor volume of the complexes. The rate of isomerization is also dependent on the nature of X and follows the sequence Cd(RaaiR')2Cl2 < Cd(RaaiR')2Br2 < Cd(RaaiR')2I2. It may be related to the size and electronegativity of halide, which reduces the effective molar association in the order of I < Br < Cl and hence the rate. Gaussian 03 calculations of representative complexes and free ligands are used to explain the difference in the rates and quantum yields of photoisomerization.     

RP-HPTLC densitometric determination and validation of vanillin and related phenolic compounds in accelerated solvent extract of Vanilla planifolia*

A simple, fast and sensitive RP-HPTLC method is developed for simultaneous quantitative determination of vanillin and related phenolic compounds in ethanolic extracts of Vanilla planifolia pods. In addition to this, the applicability of accelerated solvent extraction (ASE) as an alternative to microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE) and Soxhlet extraction was also explored for the rapid extraction of phenolic compounds in vanilla pods. Good separation was achieved on aluminium plates precoated with silica gel RP-18 F(254S) in the mobile phase of methanol/water/isopropanol/acetic acid (30:65:2:3, by volume). The method showed good linearity, high precision and good recovery of compounds of interest. ASE showed good extraction efficiency in less time as compared to other techniques for all the phenolic compounds. The present method would be useful for analytical research and for routine analysis of vanilla extracts for their quality control.     

Stress studies on acyclovir

Acyclovir is an antiviral drug of choice in the treatment of many types of herpes virus infections, including genital herpes simplex infections, herpetic conjunctivitis, herpes simplex encephalitis, etc. The present study describes the degradation behavior of acyclovir under different International Conference on Harmonization recommended stress conditions (hydrolysis, oxidation, photolysis, and thermal decomposition) in order to establish a validated stability-indicating high-performance liquid chromatography method. Acyclovir is found to degrade extensively in acidic conditions and oxidative stress. Mild degradation of the drug occurs in alkaline and neutral conditions. The drug is stable to dry heat. The drug is found to be sufficiently stable after light exposure in a solid state; however, photolytic degradation is observed when the drug is exposed as a solution in water. The major degradation product in acidic hydrolysis and photolysis is identified as guanine through comparison with the standard. Separation of drug and the degradation products under various conditions is successfully achieved on a C-18 column utilizing water-methanol in the ratio of 90:10. The flow rate is 1 mL/min, and the detection wavelength is 252 nm. The method is validated with respect to linearity, precision, accuracy, selectivity, specificity, and robustness. The mean values of slope and correlation coefficient are 39.307 and 0.9998 with relative standard deviation values less than 2%. The recovery of the drug is found to be in the range of 97.34% to 102.35%. From the previous study it is concluded that the stability-indicating method developed for acyclovir can be used for analysis of the drug in various stability samples.     

The OH-stretching and OOH-bending overtone spectrum of HOONO

We have simulated the HOONO vibrational overtone spectrum with use of a local mode Hamiltonian that includes the OH-stretching, OOH-bending, and NOOH-torsional modes and coupling between all three modes. The local mode parameters and the dipole moment function are calculated with coupled-cluster ab initio theory and an augmented Dunning-type triple-zeta basis set. We investigate the accuracy of the local mode parameters obtained from two different potential-energy fitting routines, as well as the sensitivity of these parameters to the basis set employed. We compare our simulated spectra to previously published action spectra in the first and second OH-stretching overtone regions. In addition we have recorded the spectrum in the OH-stretch and OOH-bend combination region around 7700 cm-1 and we also compare to this. Our simulated spectrum is in qualitative agreement with experiment in the first and second OH-stretching overtone and in the stretch-bend regions.     

A convenient and new approach to the synthesis of ω-heterocyclic amino acids from carboxy lactams through ring-chain-transformation. Part 2: Synthesis of (2R)-/(2S)-2-aminomethyl-3-(1-aryl-/1,5-diaryl-1H-pyrazol-3-yl)-propionic acid

Making use of amide activation, a convenient and short path synthesis of optically pure ω-heterocyclic-β-amino acids has been achieved from (1R,3R)- and (1R,3S)-5-oxo-1-(1-phenyl-ethyl)-pyrrolidine-3-carboxylic acid methyl ester. The key step of the synthesis involves a regiospecific ring-chain-transformation of the enaminones when subjected to 1,2-binucleophilic attacks. The method is illustrated by the synthesis of (2R)-/(2S)-2-aminomethyl-3-(1-aryl-/1,5-diaryl-1H-pyrazol-3-yl)-propionic acid.     

Microwave-Assisted Minutes Synthesis of Bioactive Phenylbutanoids Occurring in <Emphasis Type="Italic">Zingiber cassumunar</Emphasis>

Microwave-assisted condensation of benzaldehyde (3a,b) with acetone in aqueous sodium hydroxide adsorbed on basic alumina provides phenylbutenone (4a–4b) in 68–71% yield within 4 min, which upon further reduction with sodium borohydride and basic alumina gives phenylbutenol (5a,b) in 91–94% yield within 2 min. Dehydration of 5 with anhydrous copper (II) sulfate gives phenylbutadiene (1a,b), a metabolite of Zingiber cassumunar, within 3 min in 42–48% yield, respectively. All the steps involve environmental friendly solvents and reagents, mild reaction conditions, and overall formation of product 1a,b from 3a,b in 34–38% yield within 9 min under microwave irradiation. __________ Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 300–302, July–August, 2005.     

Dipole-induced chiral smectic-C phase in a eutectic mixture of cholesterol esters

Both cholesteryl oleate (CO) and cholesteryl oleyl carbonate (COC) are thermotropic mesogens with a general cooling phase sequence: isotropic → cholesteric → smectic → crystal. They are almost identical with respect to molecular structure and the central location of molecular dipole. However, the orientation of the latter is axial for CO and transverse for COC. A eutectic mixture of these components shows a phase sequence like the above but involving an induced smectic-C* phase. We explain this discovery on the basis of computer simulation results involving rigid core-dipole-flexible tail model of a mesogen and argue in favor of a ferroelectric liquid crystal model of the induced phase.     

Trapped two-dimensional condensates with synthetic spin-orbit coupling

We study trapped 2D atomic Bose-Einstein condensates with spin-independent interactions in the presence of an isotropic spin-orbit coupling, showing that a rich physics results from the nontrivial interplay between spin-orbit coupling, confinement and interatomic interactions. For low interactions two types of half-vortex solutions with different winding occur, whereas strong-enough repulsive interactions result in a stripe-phase similar to that predicted for homogeneous condensates. Intermediate interaction regimes are characterized for large enough spin-orbit coupling by an hexagonally-symmetric phase with a triangular lattice of density minima similar to that observed in rapidly rotating condensates.     

Catalytic enantioselective aziridoarylation of aryl cinnamyl ethers toward synthesis of trans-3-amino-4-arylchromans

Catalytic enantioselective one-pot aziridoarylation reaction of aryl cinnamyl ethers has been demonstrated in detail. Combination of suitable copper catalyst and chiral bis-oxazoline ligand was found to be very efficient for asymmetric aziridination followed by intramolecular arylation (Friedel-Crafts) reaction to provide a general and direct method for the synthesis of trans-3-amino-4-arylchromans with high regio-, diastereo- (dr > 99:1), and enantioselectivity (up to 95% ee) with moderate yield. trans-3-Amino-4-arylchroman is an advanced intermediate for the synthesis of chromenoisoquinoline compounds such as doxanthrine, a potent and selective full agonist for the dopamine-D(1) receptor.     

PVT properties of UNEX/HCCD-PEG diluent phenyl trifluoromethyl sulfone (FS-13) and experimental measurement of vapour pressure in 283.15–363.15?K range

Phenyl trifluoromethyl sulfone (FS-13) is a polar diluent, proposed in literature as an alternate to nitrobenzene, in UNEX/HCCD-PEG processes for better physical properties. Its PVT properties and accurate expression for estimation of its vapour pressure are not available in the literature. Recently PVT properties of FS-13 were estimated by authors and its vapour pressure was experimentally measured at temperatures ranging from 263.15 to 363.15 K. In this paper, results of these studies are presented.