Melt-polymerizable bisimido-bisphthalonitriles containing silicon,fluoro, and ether groups: Synthesis,characterization, and NMR study

Various melt-polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with bis(3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), and 3,3′, 4,4′-tetracarboxylichenzophen+ne dianhydride (BTDA) in an aprotic solvent. The synthesized monomers showed crystalline melting at 269 and 271°C. Elemental analysis, differential thermal analysis (DTA), infrared (IR), nuclear magnetic resonance (¹H-NMR) and mass spectral studies were carried out to characterize the synthesized monomers. Thermogravimetric analysis (TGA) of the synthesized monomers showed their thermal stability at 410–400°C. A detailed study and NMR investigation of the first step of condensation reaction was carried out and indicated the formation of a transient charge transfer complex. Thermal cyclization of the formed intermediate, however, gave the required monomers. A preliminary study demonstrated that melt-polymerization of the synthesized monomers gave thermallystable, tough polymers.     

Interaction of heterocyclic thioamides with tellurium(II) and tellurium(IV). Syntheses and crystal structures of bis[2-(2-thioxo-1,3- thiazolidin-3-yl)-4,5-dihydro-1,3- thiazolium]hexabromotellurate(IV) and tris(1- methylimidazole-2-(3H)-thione)tellurium(II) bromide

Reaction of 1,3-thiazolidine-2-thione with tellurium(IV) in hydrobromic acid medium gave the hexabromotellurate, [C₆H₉N₂S₃]₂²⁺[Te^IVBr₆]²⁻ (3). Reaction of 1-methylimidazoline-2-(3H)-thione (L″) with tellurium(IV), in hydrobromic acid medium, gave the mixed-ligand tellurium(II) complex [Te^IIL″₃Br]⁺Br⁻ (4). The structures of [C₆H₉N₂S₃]₂²⁺[Te^IVBr₆]²⁻ (3) and [Te^IIL″₃Br]⁺Br⁻ were determined by single crystal X-ray diffraction methods. In 3 the unit cell contains [TeBr₆]²⁻ anions and two [C₆H₉N₂S₃]⁺ cations. There is no direct bonding between the metal atom and the cations. In the anion only slight angular deviations from the perfect octahedral geometry are observed. The lone pair of electrons on tellurium(IV) is found to be stereochemically inert. In the cation the two five-membered heterocyclic rings adopt different conformations. In complex 4, in the solid state, the planar [Te^IIL″₃Br]⁺ cation and Br⁻ anion are held together by ionic interactions. In the cation, L″ is bonded to the central tellurium atom through the sulphur atom.     

Synthetic reactions catalyzed by immobilized lipase from oilseed rape (Brassica napus L.)

Lipase from rape (Brassica napus L., immobilized onto celite, catalyzes esterification and transesterification reactions in hexane. The activity of the lipase is stimulated up to 35 fold by the addition of water (1.3% w/v). The activity of the lipase in hydrolysis is about 8 times higher than in the esterification reactions in hexane. Interesteri-fication reactions between mono- and diacylglycerols and transesterification reactions of mono- and diacylglycerols with alcohols were also catalyzed at relatively high rates but transesterification/esterification of these acylglycerols with fatty acids was comparatively slow. In transesterification reactions, triacylglycerols reacted rather slowly.     

Alkalimetric determination of mercaptans through trithiocarbonic acid formation

A simple and rapid alkalimetric method for the determination of mercaptans through trithiocarbonic acid formation is described. The mercaptans are titrated in tert.-butanol in the presence of carbon disulphide with standard aqueous sodium hydroxide, with phenolphthalein as indicator. The -SH group is smoothly, rapidly and quantitatively transformed into the group under the specified conditions. The method has been extended to the analysis of mercaptan-carboxylic acid and mercaptan-trithiocarbonate mixtures.     

Amperometric determination of organic isothiocyanates

An amperometric titration method is described for the determination of 1-5 mg of organic isothiocyanates, based on their quantitative reaction with n-butylamine in dimethylfonnamide to form N,N-disubstituted thioureas which are then titrated amperometrically in aqueous ammonia-ammonium nitrate buffer with silver nitrate (dropping mercury electrode at -0.56V). The end-point corresponds to a silver:thiourea ratio of 2:1, with precipitation of silver sulphide. The method is simple, accurate, widely applicable, and gives reproducible results.     

Bismuthiol II as an analytical reagent

Summary Silver can be separated as its Bismuthiol II complex from OsO_{4 4} ^2– , Os⁴⁺, Ir⁴⁺, Ru³⁺, Rh³⁺ with thiosulphate or complexone III as the masking agent at a p_H between 5 and 9. Au³⁺ can be kept in solution only by thiosulphate at a p_H 8–9 and cyanide complexes palladium at a P_H of about 6. Separation from platinum in presence of a mixture of tartaric acid and complexone III is possible only to a limited extent.Part VI see Z. analyt. Chem. 155, 86 (1957)     

Bis-salicylaldehyde-ethylenediamine as an analytical reagent

Summary Copper has been determined gravimetrically as its bis-salicylaldehyde-ethylenediamine complex of the composition C₁₆H₁₄O₂N₂ · Cu, dried at 100–120° C. The complex is completely precipitated in theph range of 10.5–13.5, adjusted with ammonia or caustic alkali. It is stable in presence of excess ammonia, 0.1 N alkali, ammonium salts and complexing agents as tartrate, citrate, sodium-thiosulphate, fluoride, thiourea, triethanolamine and EDTA. In presence of tartrate and ammonia the ions of alkali metals, alkaline earths, Ag⁺, Tl⁺, Tl³⁺, Pb²⁺, Cd²⁺, Co²⁺, Mn²⁺, Pd²⁺, Al³⁺, Cr³⁺, La³⁺, Ce³⁺, Au³⁺, Pt⁴⁺, Ti⁴⁺, Zr⁴⁺, Th⁴⁺, UO₂ ²⁺ and anions as VO₃ ^–, MoO₄ ^2–, WO₄ ^2–, CrO₄ ^2–, PO₄ ^3–, AsO₄ ^3– do not interfere. Ni²⁺ and Hg²⁺ are masked by tartrate, EDTA and ammonia; As³⁺, Sb³⁺ and Sn²⁺ are separated using fluoride as the complexing agent; at an alkalinity of 0.1 N caustic alkali in presence of tartrate As³⁺, Sb³⁺, Sn²⁺, Bi³⁺, Zn²⁺ and Fe³⁺ are separated. Fe³⁺ can also be separated using triethanolamine as the masking agent at aph of about 13.0. Copper can be separated from almost all the ions, thus affording a highly selective method for the determination of copper.

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Zusammenfassung Es wird eine gravimetrische Methode zur Bestimmung von Kupfer beschrieben, die auf der Bildung des Bis-salicylaldehyd-äthylendiaminkomplexes beruht. Dieser hat die Zusammensetzung C₁₆H₁₄O₂N₂ · Cu. Die Fällung wird imph-Bereich 10,5–13,5 (mit Ammoniak oder Alkalilauge eingestellt) vorgenommen und der Niederschlag bei 100°–120° C getrocknet. Der Komplex ist beständig in Gegenwart von überschüssigem Ammoniak, 0,1 n Alkali, Ammoniumsalzen sowie Tartrat, Citrat, Natriumthiosulfat, Fluorid, Thioharnstoff, Triäthanolamin und ÄDTA. In Gegenwart von Tartrat und Ammoniak stören nicht: Alkalien, Erdalkalien, Ag⁺, Tl⁺, Tl³⁺, Pb²⁺, Cd²⁺, Co²⁺, Mn²⁺, Pd²⁺, Al³⁺, Cr³⁺, La³⁺, Ce³⁺, Au³⁺, Pt⁴⁺, Ti⁴⁺, Zr⁴⁺, Th⁴⁺, UO₂ ²⁺ sowie VO₃ ^–, MoO₄ ^2–, WO₄ ^2–, CrO₄ ^2–, PO₄ ^3– und AsO₄ ³⁺. Ni²⁺ und Hg²⁺ können mit Tartrat, ÄDTA und Ammoniak maskiert werden, As³⁺, Sb³⁺ und Sn²⁺ mit Fluorid. In 0,1 n ätzalkalischer Lösung in Gegenwart von Tartrat können As³⁺, Sb³⁺, Sn²⁺, Bi³⁺, Zn²⁺ und Fe³⁺ abgetrennt werden. Fe³⁺ kann ebenfalls mit Triäthanolamin beiph 13,0 maskiert werden. Das beschriebene Verfahren erlaubt somit eine Abtrennung des Kupfers von fast allen anderen Ionen.

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Part I: Singh, B. R., and S. Kumar: Z. analyt. Chem. 185, 211 (1962).     

A LASER FLASH PHOTOLYSIS STUDY OF PYRENE-1-ALDEHYDE. INTERSYSTEM CROSSING EFFICIENCY, PHOTOREACTIVITY AND TRIPLET STATE PROPERTIES IN VARIOUS SOLVENTS

Abstract— Triplet-and singlet-related photoprocesses of pyrene-1-aldehyde (PA) in various solvents have been investigated in detail using 337.1 and 355 nm laser flash photolysis in conjunction with time-correlated determination of fluorescence lifetimes (τ_F) and steady-state photochemical and absorption-emission spectral measurements. In benzene, the lowest triplet of PA (43 < E_T < 46 kcal/mol) has a lifetime of about 50 µs (τ_T) and displays the absorption maximum at 443 nm with a maximum extinction coefficient (ε_max) of 21000 M ^-1cm^-1; the corresponding ketyl radical has a sharp absorption maximum at 428 nm (ε_max≥ 25000 M ^-1cm^-1). The quantum yields (φ_T) of lowest triplet occupation are high in nonprotic solvents (0.6–0.8), decrease in protic solvents (alcohols) as the polarity of the latter is increased, and maintain a complementary relationship with the quantum yields (φ_F) of fluorescence. Quantum yields (φ_PC) of loss of PA due to photoreactions in some solvents have also been determined under conditions of steady irradiation at 366 nm; φ_PC is in the range 0.1–0.2 in electron-rich olefinic solvents such as cyclohexene and tetramethylethylene. These results concerning τ_F, τ_T, φ_F. φ_T and φ_PC as well as the effects of 1,2,4-trimethoxybenzene and 2,5-dimethyl-2,4-hexadiene as quenchers for fluorescence, triplet yield, and photochemistry are discussed in the light of possible state orders for PA in polar and nonpolar environments.     

Kinetics of stepwise oxidation of manganese(II) by peroxodisulphate in phosphoric acid medium

Summary The oxidation of Mn^II by S₂O₈ ^2– to Mn^VII in phosphoric acid medium proceeds via a stable Mn^III and Mn^IV species. The reaction is catalysed by Ag⁺ and exhibits first order dependence on [S₂O₈ ^2–], [Ag⁺] and, is independent of [Mn^II]. The [H⁺] has no significant effect on the reaction. It is observed that the PO₄ ^3– ion stabilises the transient manganese(III) and manganese(IV) species by forming a stable and soluble phosphato-complexes. The activation parameters for the two stages of oxidation, namely Mn^II Mn^IV and Mn^IVMn^VII at 25° C are E_a=52 ±4 kJ mole^–1, S^*=–57±2 JK^–1 mole^–1 and E_a =56±4 kJ mole^–1, S^*=–44±2 JK^–1 mole^–1, respectively. A mechanism consistent with the experimental observations is proposed.Presented at the National Symposium on Reaction Kinetics and Mechanism, Department of Chemistry, University of Jodhpur, Jodhpur, India, Nov. 15–18, 1986.     

Structural Transitions of Self-Nanoemulsifying Drug Delivery System of Glibenclamide,Carvedilol, and Lovastatin upon Progressive Aqueous Dilution

The dynamics of morphological transition in amphiphillic systems such as self-nanoemulsifying drug delivery system (SNEDDS) has become an increasingly active field of research in colloidal science. The present contribution deals with the morphological transition of selected optimized SNEDDS formulations of glibenclamide, carvedilol, and lovastatin on progressive aqueous dilution using transmission electron microscopy. The study emphasizes the structural aspects of the systems and stresses the effect of aqueous dilution under which the systems transform from water-in-oil (L₂) phase into bicontinuous structure and, finally, in oil-in-water (L₁) nanodroplets.