Total synthesis of (+)-pederine. A simple synthetic method for N-(1-methoxyalkyl)amides

A mild one-pot method for the synthesis of acyclic N-(1-methoxyalkyl)amides starting from carboxylic acids and methyl imidates had been developed and applied to the total synthesis of the insect poison pederine $\text{1}$.     

Isothermal titration calorimetric studies of surfactant interactions with negatively charged, ‘hairy’ latex nanoparticles

Isothermal titration calorimetry (ITC) measurements of the mixture of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) with negatively charged, hairy copolymer latices (poly-(2,3-epoxypropylmethacrylate-co-methacrylic acid) in different ratio) at high water excess indicate a monomer adsorption mechanism of CTAB by the polymer particles. The number of adsorbed CTAB molecules at saturation corresponds approximately to the number of negative elementary charges bound at the surface of the latices. The mixing enthalpy is the sum of demicellization and sorption enthalpies. At 25 °C for CTAB the demicellization enthalpy amounts to 10 kJ/mol, whereas the adsorption enthalpy varies from –7 kJ/mol (surface charge density of the latices =–0.37 C/m²) to +3 kJ/mol (=–0.085 C/m²). The hydrodynamic radius R_H of the latex particles upon titration of cationic detergent and salt (NaBr) decreases by about 2 nm until the onset of aggregation near the isoelectric point. Titration of nonionic or anionic detergents has much less influence on the hydrodynamic radius and produces no measurable adsorption heat. The results are consistent within a model of latex particles with extended negatively charged polymer chains interacting predominantly via Coulombic forces with detergents.     

The Influence of Cobalt (II) in Carboxymethyl Cellulose Processing

Controlling the reduction in molecular weight of the cellulose chains is essential in the production of carboxymethyl cellulose (CMC). Such a reduction can be achieved by the addition of cobalt during the process of cobalt(II) ions, which act as a catalyst for oxidative cleavage, and the influence thereof has been studied under a variety of conditions. This study has resulted in a model that summarises the effects of the added amount of cobalt, the time for the cobalt reaction, the temperature in the mercerisation stage of the CMC-manufacturing process and finally the effect of the temperature in the etherification stage. It is shown that it is important for cobalt to be present during the mercerisation stage in order to achieve the desired viscosity.     

Medicinal flowers. II. Inhibitors of nitric oxide production and absolute stereostructures of five new germacrane-type sesquiterpenes, kikkanols D, D monoacetate, E, F, and F monoacetate from the flowers of Chrysanthemum indicum L

The methanolic extract and ethyl acetate-soluble portion from the flowers of Chrysanthemum indicum L., Chrysanthemi Indici Flos, were found to show inhibitory activity against nitric oxide (NO) production in lipopolysaccharide-activated macrophages. Five new germacrane-type sesquiterpenes, kikkanols D, D monoacetate, E, F, and F monoacetate, were isolated from the ethyl acetate-soluble portion. Their absolute stereostructures were elucidated on the basis of chemical and physicochemical evidence, which included application of the modified Mosher's method. The effects of fifteen principal components from the ethyl acetate-soluble portion of this medicinal flower against NO production were examined and, among them, acetylenic compounds and flavonoids were found to show potent inhibitory activity.     

Theoretical and Experimental Studies on a Metallorganic Complex of (Isopropylxanthato)(Phenyl)Mercury(I) [Hg(I)(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)(C<Subscript>4</Subscript>H<Subscript>7</Subscript>OS<Subscript>2</Subscript>)]

The title compound, (isopropylxanthato)(phenyl)mercury(I), was synthesized and characterized by elemental analysis, IR and thermogravimetric analysis. Density functional theory (DFT) method calculations were performed at B3LYP/CEP-121G and B3LYP/CEP-31G levels of theory, respectively. Vibrational frequencies were predicted, assigned, compared with the experimental values, and they are supported each other. The calculated results show that the strength of bond Hg—C is stronger than that of Hg—S, which is good agreement with the experimental data. The calculations of the second order optical nonlinearity and electronic absorption spectra are also performed.     

Host-guest complexes of cucubit[8]uril with phenanthrolines and some methyl derivatives

Cucurbituril a molecular container (or host) has a rigid hollow interior cavity which is large enough to accommodate, one or more, smaller molecules (or guests). The cavity is accessible through two carbonyl portal openings. Molecules or guests enter the …     

Solvation Phenomena of Potassium Thiocyanate in Methanol–Water Mixtures

This paper reports the results of a variety of experiments carried out for understanding the solvation behavior of potassium thiocyanate in methanol–water mixtures. Electrical conductivity, speed of sound, viscosity, and FT-Raman spectra of potassium thiocyanate solutions in 5 and 10% methanol–water (w/w) mixtures were measured as functions of concentration and temperature. The conductivity and structural relaxation time suggest the ion–solvent and solvent-separated ion–ion associations increase as the salt concentration increases in the mixtures. The Raman band shifts due to the C–O stretching mode of methanol for the solvent mixtures reveal the formation of methanol–water complexes. The significant changes in the Raman bands for the C–N, C–S and O–H stretching modes indicate the presence of SCN⁻−solvent interactions through the N-end, “free” SCN⁻ and the solvent-shared ion pairs as potassium thiocyanate is added to the methanol–water mixtures. The relative changes corresponding to H–O–H bending and C–O stretching frequencies indicate that K⁺ is preferentially solvated by water in these solvent mixtures. The appearance and increase of the intensity of a broad band at ≈940 cm⁻¹ upon salt addition was attributed to the SCN⁻–H₂O–K⁺ solvent-shared ion pairs. No Raman spectral evidence for K⁺(H₂O)_n species was observed. The preferential solvation of K⁺ and SCN⁻ in the methanol−water mixtures was verified by the application of the Kirkwood−Buff theory of solutions. This theory confirms that K⁺ is strongly preferentially solvated by water, whereas SCN⁻ is preferentially solvated by the methanol component.     

Equilibrium Studies of Binary and Ternary Complexes Involving Tricine and Some Selected α-Amino Acids

Summary. The formation equilibria for the binary complexes of Co^II, Ni^II, Cu^II, Zn^II, Cd^II, Mn^II, Pb^II, Th^IV, UO₂^II, and Ce^III with tricine and for the ternary complexes involving some -amino acids (glycine, -alanine, proline, serine, asparagine, and aspartic acid) were investigated using pH-metric technique. The formation of binary and ternary complexes was inferred from the pH-metric titration curves. It was deduced that tricine acts as a primary ligand in the ternary complexes involving the monocarboxylic amino acids (glycine, -alanine, proline, serine, and asparagine), whereas it behaves as a secondary ligand in the ternary systems containing the dicarboxylic aspartic acid. The ternary complex formation was found to take place in a stepwise manner. The stability constants of the complexes formed in aqueous solutions were determined potentiometrically under the experimental conditions (t=25°C, I=0.1moldm^–3 NaNO₃). The order of stability of the ternary complexes in terms of the nature of the amino acids is investigated and discussed. The values of log K for the ternary complexes have been evaluated and discussed. Evaluation of the effects of ionic strength and temperature of the medium on the stability of the ternary system M^II-tricine--alanine (M^II=Co^II, Ni^II, and Cu^II) has been studied. The thermodynamic parameters were calculated and discussed.     

A Chiral Coordination Polymer of Silver(I) with Saccharinate and Pyridine: Synthesis,Spectral, Thermal,and Structural Characterization of [Ag(sac)(py)]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

The first silver(I) complex of saccharinate (sac) with pyridine (py), [Ag(sac)(py)]_n has been synthesized and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffractometry. The complex crystallizes in chiral, trigonal space group P3₁21 (No. 152) with unit cell parameters of a = 11.2605(2) Å, c = 17.3300(4) Å, V = 1903.02(6) ų and Z = 6. [Ag(sac)(py)]_n contains monomeric [Ag(sac)(py)] units linked into infinite helices by way of Ag⋅sAg interactions [d(Ag⋅sAg) = 2.909(2) and 2.985(1) Å]. The distorted square-planar environment of Ag is completed by an N-bonded sac [Ag—N = 2.084(2) Å] and a py molecule [Ag—N = 2.116(2) Å]. The N_sac—Ag—N_py angle is 173.85(10)^∘. The one-dimensional chains are crosslinked by C—H⋅sO interactions involving the carbonyl and sulfonyl O atoms of sac and aromatic-ring hydrogen atoms of both sac and py. The thermal stability of the title complex was investigated using thermogravimetry and differential thermal analysis in a static atmosphere of air. The first decomposition stage between 90 and 160^∘C corresponds to removal of the py molecule in a single stage, while the degradation of the sac moiety occurs at two stages in the temperature range 370–515^∘C, giving an end product of metallic Ag.