Benzothiazolium derivatives. III. Nucleophilic substitution reactions of benzothiazolium salts

The reactions of 2,3-dihydrothiazolo[2,3-b]benzothiazolium bromide 1 (A^? ?Br^?) with certain nucleophilic reagents have been performed for the purpose of ascertaining the reaction pathways and identifying the group that is displaced from the central carbon atom of the dithiocarbamate system. The nature of complex salt-like intermediates formed initially from 1 (A^? ?Br^?) has been studied and confirmed. For comparison, a number of nucleophilic substitution reactions of 2-methylthio-3-methylbenzothiazolium iodide 17 and 2-dimethylamino-3-methylbenzothiazolium perchlorate 18 have been examined.     

Relations between subclasses of greedoids

In previous papers many different classes and constructions of greedoids have been defined and studied. This paper documents inclusion relations among all subclasses of greedoids which are known so far. It will be shown that all inclusion relations are proper and that all but one subclasses of interval greedoids are distinct.

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Zusammenfassung In früheren Arbeiten wurden viele verschiedene Klassen und Konstruktionen für Greedoide eingeführt und studiert. In dieser Arbeit werden alle bekannten Inklusionsbeziehungen zwischen Unterklassen von Greedoiden dokumentiert. Es wird gezeigt, daß alle Inklusionsbeziehungen echt und alle Unterklassen mit einer Ausnahme tatsächlich verschieden sind.

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Supported by the joint research project Algorithmic Aspects of Combinatorial Optimization of the Hungarian Academy of Sciences (Magyar Tudományos Akadémia) and the German Research Association (Deutsche Forschungsgemeinschaft, SFB 21). Part of this research was done while the first author was visiting the Department of Combinatorics and Optimization, University of Waterloo.     

Lösungsmitteleinfluß auf das Redoxverhalten von Bistriphenylphosphinquecksilber(II)-perchlorat

The influence of solvents on the redox behaviour of bistriphenylphosphinomercury perchlorate has been investigated by polarographic, voltammetric and potentiometric methods. The electrode process was found to be reversible in acetonitrile, propylene carbonate, N,N-dimethylformamide and dimethyl sulfoxide. An irreversible process was observed in nitromethane employing the dropping mercury electrode as well as in N,N-dimethylthioformamide and N-methyl-2-thiopyrrolidinone employing the rotating platinum electrode. Half wave potentials and diffusion coefficients have been measured. A linear relationship between theE _1/2 and the donor number (DN) of the solvent has been found for the reversible electrode reactions. Ligand replacement occurs in N,N-dimethylthioformamide and N-methyl-2-thiopyrrolidinone.

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Mit 1 Abbildung     

Complexing effects in the solvent extraction of thallium(I) 2-mercaptobenzothiazole

Studies of the extraction of thallum(l) from aqueous solution in the absence and presence of aqueous complexing agents into chloroform containing 2-mercaptobenzothiazole are described. Fluoride, chloride, bromide, iodide, thiocyanair, cyanide, and sulfate were employed as aqueous complexing agents. A number of the participating species were identified and association constants are estimated.     

Semiclassical study of collision-induced predissociation: Comparison of the Landau-Zener model with the method of analytic continuation

Semiclassical calculations are carried out by two methods for the problem of collision-induced predissociation of electronically excited I₂. The first method is that of surface-hopping with the Landau-Zener model. The second method is similar to surface-hopping, except that analytic continuation of the adiabatic potential energy surfaces replaces the Landau-Zener model. Results of the calculations by the two methods compare favorably with each other and with experiment. The possible advantages of the second method are discussed.Camille and Henry Dreyfus Teacher-Scholar, Alfred P. Sloan Research Fellow.     

Selective initiation of nonconjugated dienes containing electron donor–electron acceptor systems. II. Polymerization studies of vinyl ether–β-nitrostyrenes

The monomer series, o-, m-, and p-(2-vinyloxyethoxy)-β-nitrostyrenes, was studied. All three monomers were selectively polymerized through the electron-donating vinyloxy group via cationic initiation. The linear polymers from the meta and para isomers containing the electron-accepting nitrovinyl group were readily crosslinked via anionic initiation. The polymer derived from the ortho isomer was not crosslinked by this mechanism, an observation in accord with results previously reported from these laboratories in which it was shown that all o-substituted-β-nitrostyrenes having ortho substituents larger than fluorine exhibited a sterically inhibited propagation step. The meta and para isomers of this series were selectively polymerized through the electron-accepting nitrovinyl group via anionic initiation. Because of the fact that the resulting polymers were soluble only in highly polar solvents, subsequent crosslinking of these polymers via cationic initiation could not be accomplished. However, these polymers showed strong tendencies to undergo crosslinking upon long exposure to air. Because of the sterically induced ortho effect referred to above, no significant polymerization occurred in the case of the ortho isomer of this series via anionic initiation. However, it was shown in this case that initiation via the anion was rapid, and that the slow step was propagation.     

Searching of chemical structure data bases with parallel computer hardware

The use of two types of parallel computer hardware for increasing the efficiency of processing in chemical structure data bases is discussed. The distributed array processor can be used for the clustering of 2-D chemical structure data bases by using the Jarvis—Patrick clustering method and for the ranking of output in an experimental system for substructure searching in the 3-D macromolecules in the Protein Data Bank. The Inmos transputer can be used in the construction of PC-based systems for 2-D substructure searching and in the identification of the maximal substructures common to pairs of 3-D molecules.     

Phytochemicals from Echinacea and Hypericum: A Direct Synthesis of Isoligularone

Reaction of trienes with α,β-unsaturated aldehydes produces bicyclic products via a tandem Diels-Alder/ene reaction. The adduct from tiglic aldehyde was converted into isoligularone by conversion to a furan followed by benzylic oxidation.     

Development and validation of routine analysis methods for the determination of essential, nonessential, and toxic minor and trace elements in cereal and cereal flour samples by inductively coupled plasma-atomic emission spectrometry

Various digestion procedures were carefully investigated and accurately evaluated with respect to their effect on the analysis of cereals and cereal flours. Multielement methods were selected and well developed for the determination of essential (Cr, Cu, Fe, Mg, Mn, and Zn), nonessential (Ag, Al, Ba, Bi, In, and Ga), and toxic (Cd and Pb) minor and trace elements by inductively coupled plasma-atomic emission spectrometry. Only Ag could be determined, either with aqueous standard or standard addition calibration methods, while the standard addition methods were more accurate for the determination of other elements. The recoveries were mostly within the range of 84.1-113% for the expected values of all analytes with respect to certified reference material NIST SRM 1586a (rice flour). The results proved that, for cereals and cereal flours, the use of H2O2 for wet digestion and HNO3 for dry ashing were not necessary. Linear regression analysis and Student's paired t-test were applied to evaluate the significant differences between different procedures and type of samples.     

Dynamics of self-assembled chaining in magnetorheological fluids

The aggregation dynamics of paramagnetic spherical particles embedded in a viscous fluid is investigated via numerical simulations using a fully coupled three-dimensional model. Particles experience simultaneously Brownian motion, dipolar magnetic attraction, and multibody hydrodynamic interactions. When the dipole strength characterizing the ratio of magnetic attraction to random diffusion exceeds a critical value, particles join together forming supraparticle structures. As time evolves, particle/chain and chain/ chain interactions lead to a continuous increase of the cluster size. The mean length of particle chains has a power-law dependence with respect to time, as predicted by the theory of diffusion-limited aggregation. Both the exponent and the characteristic time scale agree very well with the experimental results of Promislow et al.