The Reaction of Maleic and Phthalic Anhydrides with 2-Methylimidazole

The reaction of maleic anhydride with 2-methylimidazole in acetonitrile and DMF is accompanied by the appearance of strong absorption bands in the visible part of the spectrum due to the formation of molecular complexes. In acetonitrile the reaction proceeds by two routes via the formation of an amide and the molecular complex. Phthalic anhydride reacts with 2-methylimidazole to give amide but not to form molecular complexes.     

Volumetric properties of H2O, D2O, and methanol in acetonitrile at 278.15—318.15 K

The densities of H₂O, D₂O, and MeOH solutions in acetonitrile with the solute concentrations up to 0.07 molar fractions at 278.15, 288.15, 298.15, 308.15, and 318.15 K were measured using vibrating-tube densimetry with an error 8·10^–6 g cm^–3. The limiting partial molar volumes for the H/D isotopomers of water and IaII in acetonitrile (V^– ₂ ) and the isotope effects in V^– ₂ and in excess molar volumes of acetonitrile—water mixtures were calculated. Molecules of H₂O, D₂O, and IaII form associates with acetonitrile molecules via hydrogen bonds. The associates have the packing volumes close to those in the individual solute. The water and methanol molecules were assumed to be incorporated into the acetonitrile structure without substantial changes in the latter. However, this process results in some compression of the system with a simultaneous increase in its expansibility.     

Synthesis and study of the light-stabilizing activity of some dithiocarbamates that include a heteroaromatic ring

A number of new dithiocarbamates of transition metals that contain thiophene, furan, benzo[b]thiophene, and benzo[b]selenophene rings were synthesized. The compounds obtained were investigated as light stabilizers for polymers. It is shown that the effectiveness of the light-stabilizing effect of the dithiocarbamate depends on the structure of the heterocyclic fragment included in its composition.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1482–1488, November, 1982.     

Computational study on the ring distortions of 1,4-dicyanobenzene in the gas phase and in the crystal

A molecular mechanics software enhanced to perform empirical energy calculations on crystals (KESSHOU) was further developed to handle intermolecular electrostatic interactions as well. The packing of the molecules of 1,4-dicyanobenzene and 1,4-diisocyanobenzene in the crystal was studied. The role of the van der Waals and the electrostatic interactions in the balance of nonbonded atom-atom interactions is analyzed. The packing forces are dominated by van der Waals forces. The electrostatic interactions have higher stabilizing contribution for the dicyano isomer than for the diisocyano form. The dependence of the results on the size of the crystal, the molecular mechanics force field (MM2 vs MM3), and the dielectric constant are also assessed. Ab initio MP2/6–311G** geometries of the isolated molecules are in accordance with the observed benzene ring distortions determined by electron diffraction.     

Experimental (NMR) and Computational (MD) Studies on the Inclusion Complexes of 1-Bromoadamantane with alpha-, beta-, and gamma-Cyclodextrin

The inclusion complexes between the most commonly used cyclodextrins (alpha-, beta-, and gamma-CD) and 1-bromoadamantane were prepared and studied experimentally by NMR methods and by molecular dynamics simulations (AMBER force field) with solvation. The NMR results suggest host/guest ratios of 2:1, 1:1, and 1:1 for the complexes with alpha-, beta-, and gamma-cyclodextrin, respectively, as well as defined geometries for the complexes. Averaged geometrical data from the molecular dynamics simulations agree with the complexation geometries deduced experimentally.     

Hydrolysis of bis(chloromethyl)phosphonic acid p-nitroanilide in aqueous micellar surfactant solutions

The hydrolysis of bis(chloromethyl)phosphonic acid p-nitroanilide has been studied in the pH range 6.86–13.0 and the effects of ionic surfactant micelles on this process have also been examined. The nature of the micellar effects of cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) on this reaction lead us to conclude that both the neutral and anionic forms of the substrate are reactive, and that in the range of pH > pK_a hydrolysis of the ionic form of the anilide predominates, while at pH < pK_a the reaction of the neutral form is predominant. The binding constants for both the neutral and anionic forms of bis(chloromethyl)phosphonic acid p-nitroanilide in micellar CTAB and SDS solutions have been determined using a kinetic method, as well as by measuring the changes in the acid-base properties of the substrate resulting from the influence of micelles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1718–1722, August, 1990.     

Synthesis of [1,2,3]Triazolo[4,5-d]pyrimidine 3-Oxides

[1,2,3]Triazolo[4,5-d]pyrimidine 3-oxides were synthesized by replacement of the amino group in 6-aminouracil by hydroxyamino, coupling of the resulting 6-hydroxyaminopyrimidine with benzenediazonium salts, and oxidation of 6-hydroxyamino-5-phenylazouracils with a solution of K₃[Fe(CN)₆] in water.     

Determination of Aluminum and Beryllium by Diffuse Reflectance Spectrometry with the Use of Chromaticity Functions

Immobilized Eriochrome Cyanine R was used for the direct determination of trace aluminum and beryllium by diffuse reflectance spectrometry. Anion exchanger AV-17, silica gel Silochrom C-120, Chromaton N-Super, octadecyl silica gel, and cellulose were examined as supports. Optimal sorption conditions were found. The dependence of chromaticity functions (chromaticity coordinates, lightness, color saturation, yellowness, and whiteness) on different factors was studied. Advantages of the use of chromaticity functions rather then the diffuse reflectance coefficient were demonstrated. A method is developed for the separate determination of aluminum and beryllium using cellulose as the support; the method was used for the analysis of real samples and tested with standard samples. When solution samples of 50 and 100 mL were used, the determination limit was 0.004 g/mL for aluminum and 0.0002 g/mL for beryllium.     

Molecular-dynamics simulation of model polymer nanocomposite rheology and comparison with experiment

The shear-rate dependence of viscosity is studied for model polymer melts containing various concentrations of spherical filler particles by molecular-dynamics simulations, and the results are compared with the experimental results for calcium-carbonate-filled polypropylene. Although there are some significant differences in scale between the simulated model polymer composite and the system used in the experiments, some important qualitative similarities in shear behavior are observed. The trends in the steady-state shear viscosities of the simulated polymer-filler system agree with those seen in the experimental results; shear viscosities, zero-shear viscosities, and the rate of shear thinning are all seen to increase with filler content in both the experimental and simulated systems. We observe a significant difference between the filler volume fraction dependence of the zero-shear viscosity of the simulated system and that of the experimental system that can be attributed to a large difference in the ratio of the filler particle radius to the radius of gyration of the polymer molecules. In the simulated system, the filler particles are so small that they only have a weak effect on the viscosity of the composite at low filler volume fraction, but in the experimental system, the viscosity of the composite increases rapidly with increasing filler volume fraction. Our results indicate that there exists a value of the ratio of the filler particle radius to the polymer radius of gyration such that the zero-shear-rate viscosity of the composite becomes approximately independent of the filler particle volume fraction.     

Comparison of reactivities of 1- and 4-oxotetrahydrocarbazoles in reactions with nucleophilic and electrophilic reagents

The half-wave potentials of polarographic reduction of the carbonyl group in unsubstituted and N-methyl- and N-phenylsulfonyl-substituted 1- and 4-oxotetrahydrocarbazoles and their reactivities in reactions with nucleophilic (NaBH₄, malonodinitrile, and cyanoacetamide) and electrophilic (DMF dimethyl acetal) reagents were compared. 4-Oxotetrahydrocarbazoles are much less reactive than 1-oxotetrahydrocarbazoles. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1832–1836, August, 2005.