Metalation of Biginelli compounds. A general unprecedented route to C-6 functionalized 4-aryl-3,4-dihydropyrimidinones

4-Aryl-6-methyl-3,4-dihydro-2(1H)-pyrimidinone esters (DHPMs) readily undergo metalation at the C-6 methyl (vinylogous ester) position on treatment with lithium diisopropylamide at -10 degrees C. The resulting anion intermediates can be treated with electrophilic reagents to afford functionalized DHPMs that have been chemically elaborated mainly at the C-6 position. Di- and trianion formation is also possible at both the vinylogous methyl and NH positions when reactions are performed with excess equivalents of the base.     

Collapse dynamics of liquid bridges investigated by time-varying magnetic levitation

Using a novel technique that facilitates temporal control over the total body force on a liquid, an unexpected scaling relationship was discovered for the collapse time of a liquid bridge. A paramagnetic liquid was suspended between the tips of two collinear rods in a strong magnetic field gradient that was adjusted to compensate gravity. A sudden change of the magnet current, corresponding to a change of Bond number, resulted in a deformation and ultimate collapse of the liquid bridge. The collapse time was found to be independent of the bridge length when other parameters were held constant.     

Resonance Raman and electronic absorption study of free‐base tetraphenylporphine diacid dispersed in polymethylcyanoacrylate

We report a resonance Raman study on free‐base tetraphenylporphine (H₂TPP) and its chemically prepared diacid dispersed in polymethylcyanoacrylate (PMCA). Photoexcitation of the neutral porphine by laser light leads irreversibly to the formation of the diacid, with the π‐cation radical as intermediate species. Resonance Raman (RR) spectra of the diacid dispersed in the polymer obtained with 441.6 nm in the wavenumber region of 100–1650 cm⁻¹ are recorded. Wavenumbers with other excitation lines are also reported for the diacid species. Some bands assigned to out‐of‐plane vibrational modes and forbidden under ideal D_2h symmetry are also observed in the resonance Raman spectra of the diacid. These bands arise from the out‐of‐plane distortions, which reduce the symmetry of the molecule. These findings are supported by the electronic absorption studies of the diacid in the polymer. Copyright © 2007 John Wiley & Sons, Ltd.     

Thermodynamic Properties of Binary Liquid Mixtures of n-Dodecane with an Alkan-1-ol or an Alkan-2-ol at 298.15 K: A Comparative Study

Experimental densities (ρ), viscosities (η), and speeds of sound (u) of the binary mixtures of n-dodecane with an alkan-1-ol (hexan-1-ol, heptan-1-ol, octan-1-ol) or an alkan-2-ol (hexan-2-ol, heptan-2-ol and octan-2-ol) were measured over the whole mixture composition range at T = 298.15 K. From these data, the excess molar volume ( $ V_{\text{m}}^{\text{E}} $ V m E ), deviations in viscosity (Δη), and excess isentropic compressibility ( $ \kappa_{S}^{\text{E}} $ κ S E ) have been calculated. The results were fitted by means of the Redlich–Kister equation, in order to estimate the binary coefficients and standard errors. Differences among these binary systems are ascribed to the different association abilities of the alkan-1-ols and alkan-2-ols. Experimental data on the constituted binaries were analyzed using McAllister’s multi-body interaction model, the Jouyban–Acree model, the Prigogine–Flory–Patterson theory, and the Bloomfield and Dewan model. The experimental and calculated quantities are used to study the nature of mixing behavior among the mixtures.     

Solubility and dissolution enhancement of saquinavir mesylate by inclusion complexation technique

The objective of the present study was to formulate inclusion complex of saquinavir mesylate to improve the aqueous solubility and dissolution rate. Saquinavir mesylate is a BCS class II drug having low aqueous solubility and therefore low oral bioavailability. In the present study, inclusion complex of saquinavir mesylate with hydroxypropyl-β-cyclodextrin were prepared by kneading method. Inclusion complex were characterized by differential scanning calorimetry (DSC), X-ray diffractometry (XRD), ¹H NMR studies, and Fourier transform infrared spectroscopy and evaluated for in vitro dissolution, and phase solubility studies. DSC and XRD study demonstrated that there was a significant decrease in crystallinity of pure drug present in inclusion complex, which resulted in an increased dissolution rate of saquinavir mesylate and ¹H NMR studies strongly, confirmed that the inclusion complex has formed. Inclusion complexation results in improvement in solubility and dissolution rate. The inclusion complexation would be suitable method for dissolution and bioavailability enhancement of saquinavir mesylate.     

Synthesis,Spectroscopic Characterization,and In Vitro Antimicrobial Potency of Sulfur-Bonded Complexes of Boron(III)

The present article describes the synthesis and characterization of tetracoordinated boron (III) complexes with monobasic bidentate ligands (L ¹ H, L ² H, L ³ H, L ⁴ H, L ⁵ H, and L ⁶ H) having the general formulae PhB(L)(OH) and PhB(L) ₂ . The 1:1 and 1:2 reactions of phenyl boronic acid with monobasic bidentate ligands resulted in the formation of colored solids. The complexes have been characterized by elemental analysis, molecular weight determinations, and IR and NMR ( ¹ H, ¹³ C and ¹¹ B) spectroscopy, as well as UV-vis spectral studies. Based on these studies, a tetrahedral geometry has been proposed for the resulting complexes. The ligands, along with their complexes, have been screened in vitro against a number of pathogenic fungal and bacterial strains. The studies indicate that the boron chelates are more potent than the parent ligands.     

Alternating current electrolysis for organic synthesis

Electrochemical organic synthesis has recently attracted much attention because of its unique reactivity and environmentally benign approach. Conventional electrosynthesis uses either constant current or constant potential, known as direct current electrolysis. However, recently, alternating current electrolysis has begun receiving more attention. The purpose of this study is to give a short overview of the history and recent advances in the field of alternating current electrolysis for organic synthesis.     

Vibrational spectroscopic and density functional theory studies of chloranil-imidazole interaction

The present work reports vibrational spectra and density functional theory calculations for chloranil, imidazole and their complexes. The experimentally observed infrared and Raman bands have been assigned with the help of calculated vibrational frequencies and potential energy distribution analysis. Some bands of chloranil and imidazole have been found to shift on the complex formation due to partial electronic charge transfer from imidazole to chloranil. The charge transfer between these molecules is also corroborated by the electronic absorption spectroscopy and calculations. The theoretical values of the interaction energy of various possible chloranil-imidazole interactions suggest that the two molecules interact preferably via N and H atoms of imidazole and CO group of chloranil with their molecular planes almost perpendicular to each other.