Synthesis in the 2-mercaptobenzothiazole series

The reduction of some dihydrothiazolobenzothiazolium salts with sodium borohydride may take place in two directions: with the formation of thiazolidino[2, 3-b]benzathiazolines and with the cleavage of the C-S bond to give N-(-mercaptoethyl)benzothiazolines. The behavior of thiazolidino[2, 3-b]benzothiazoline under the conditions of acid and alkaline hydrolysis has been studied.For communication VI, see [1].     

Thermodynamics of Lithium Intercalates in Carbonized Fabric

The method of quasi-equilibrium galvanostatic curves was applied to study the thermodynamics of lithium deintercalation from the system Li _x C₆ (solid phase)/Li⁺ (solution) in the interval 293-323 K and the thermodynamic characteristics (G, S, H) of lithium intercalation compounds in a carbonized fabric in relation to the degree of intercalation x.     

Spin-spin coupling of77Se and31P nuclei in cyclic organophosphorous compounds

We have established that direct phosphorus-selenium spin-spin coupling constants in cyclic compounds with P=Se exocyclic and P-C endocyclic bonds are found in the range¹J_PSe=–708 to –859 Hz; in this case, it is greater for the axial orientation of P=Se than for the equatorial orientation.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 776–780, April, 1990.     

Investigation of N-nitrohydrazines by the NMR method

Functionally substituted N-nitrohydrazines were studied by heteronuclear NMR. It was shown that all the investigated products from nitration of the trimethylsilyl derivatives of functionally substituted hydrazines contain the N-NO₂ fragment. The chemical shift of the nitrogen atoms of the hydrazine fragment in the¹⁵N NMR spectra and the spin-spin coupling constants were used as the main tests for structural identification. It was established that the number of recordable conformers decreases in the transition from the trimethylsilyl phenylhydrazine derivatives to the nitrohydrazines as a result of the conformational flexibility of the N(NO₂)CO fragment.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2024–2031, September, 1991.     

Ductile-to-ductile transition in dispersely filled composites based on thermoplastic polymers

The fracture mechanism for rubber-filled composites based on gutta-percha, LDPE, medium-density PE, and rubber particles has been studied. An increase in the concentration of filler particles leads to a change in the stress-strain behavior of the composites from neck propagation to homogeneous plastic deformation. For the filled composites, the criterion for the ductile-to-ductile transition is the equality of yield and draw stresses. The critical concentration of rubber particles at the ductile-to-ductile transition is controlled by the ratio between the yield stress of matrix polymer and the neck propagation stress. Transition from neck propagation to homogeneous plastic flow of the material is accomplished under two conditions: the breaking strength of the polymer matrix should be higher than the yield stress, and stretching of the composite should not be accompanied by the formation of diamond cracks. The latter condition is fulfilled when the dimensions of rubber particles are below a certain critical value, which is determined by the ductility of the matrix.     

Reactivity of Cage-Like Amines toward p-Toluenesulfonyl Chloride and Diphenyl Chlorophosphate in Acetonitrile

The nucleophilic reactivity of amines of the norbornane, norbornene, and adamantane series toward ptoluenesulfonyl chloride and diphenyl chlorophosphate in acetonitrile at 25°C is determined mainly by the steric factor. Parameters characterizing spatial accessibility of the reaction center in the amine molecule have been determined. Cage-like substituents show no appreciable effect on the amine reactivity, as compared to common alkyl groups.     

Chemiluminescent determination of reactive hydrocarbons

Summary Chemiluminescent reactions of ozone with several classes of compounds at different temperatures are described. In a reaction chamber in front of a photomultiplier ozone is mixed with the compounds studied such as alkanes, olefins, alcohols, aromatics, C₂H₂, NO, vinyl chloride or H₂S. The chemiluminescent emission is proportional to the concentration of the compound involved. At room temperature only olefinic hydrocarbons respond but at temperatures above 150°C also a response for alkanes, alcohols, CO etc. is obtained. It is suggested that next to the ozonide-excited formaldehyde mechanism the CO-CO ₂ ^* mechanism is responsible for the chemiluminescent emission at high temperature. A detection limit of a few ppb is achieved. Possible applications are a selective gas-chromatographic detector, an air pollution monitor for instance for CO, and a photochemical reactivity monitor.

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Bestimmung reaktiver Kohlenwasserstoffe durch Chemiluminescenz

Zusammenfassung Chemiluminescenzreaktionen von Ozon mit verschiedenen Verbindungsgruppen (hauptsächlich Kohlenwasserstoffe) bei unterschiedlichen Temperaturen werden beschrieben. In einer Reaktionskammer werden die Verbindungen vor einem Photomultiplier mit Ozon vermischt. Es handelt sich u. a. um folgende Verbindungstypen: Alkane, Olefine, Alkohole, Aromaten, C₂H₂, NO, Vinylchlorid, H₂S. Die Emissionsintensität ist proportional der Konzentration. Bei Raumtemperatur sprechen nur Olefine an, die übrigen Verbindungen erst über 150°C. Die Emission bei höherer Temperatur wird neben der Bildung von Formaldehyd auf die Reaktion CO-CO ₂ ^* zurückgeführt. Die Nachweisgrenze beträgt wenige ppb. Als mögliche Anwendungsgebiete werden ein selektiver GC-Detektor, ein Monitor für Luftverunreinigungen (z.B. für CO) sowie ein Monitor zur Messung photochemischer Reaktivität der Luft genannt.

Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria.