Obtention de selenopysultones lors de l'oxydation de thio-1 chromenes par le dioxyde de selenium

Selenium dioxide oxidation of 1-thiochromene leads to 3-formyl (5,6)benzo-1,2 thiaseleninne-1,1-dioxide, which is a representative of a hitherto unknown class of heterocyclic compounds. Pyrolysis of this compound leads to 2-formyl benzo(b)selenophen, by loss of sulphur dioxide. The reaction can be applied to other 1 thiochromenes but no similar behaviour has been observed for their selenium isologues.     

Koordinationschemie von Dinitroresorcin mit Kupfer-, Kobalt-, Nickel-, Eisen- und Zinksalzen

The reactions of the bidentate dinitrosoresorcinol (DNR) with copper, cobalt, nickel, iron and zinc salts were investigated. This ligand was found to react with these metal salts in aqueous media where hydrogen ion was confirmed to be liberated except in case of iron. The solid complexes were prepared in alcoholic media. Chemical analyses, magnetic and spectral data were compatible to determine the structure of these complexes and their mode of chelation.

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Beiträge zur Chemie der Pyrrolpigmente, 19. Mitt.: Die elektrochemische Oxidation von Pyrromethenonen und Pyrromethenen (Gallenpigment-Partialstrukturen)

The electrochemical oxidation of arylmethylene-pyrrolinones, pyrromethenones and pyrromethenes as representative bile pigment partial structure models was investigated by means of a rotating disc platinum electrode using acetonitrile as the solvent. Two different oxidation reactions were found. The first reaction being a reversible one-electron oxidation with compounds of the arylmethylene-pyrrolinone series and pyrromethenones which are unsubstituted in position 5 of the pyrrole ring. A two step reaction (the first one reversible, the second irreversible) on the other hand was found to be typical for pyrromethenones bearing a methyl group in this position.Through protonation the first step is at a higher potential, whereas the second one is lowered and becomes reversible. The resulting oxidation pattern can be interpreted analogous to the oxidation of hydroquinones in aprotic solvents.The geometrical isomers of a pyrromethenone were oxidized at appr. the same potential, but there is a strong dependence of the potential of the first oxidation step on the substitution: a higher degree of alkylation favours oxidation by lowering the oxidation potential.

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Oxidative addition of some geminal halonitroalkanes to iridium(I) and platinum(0) compounds

Oxidative addition of 1-chloro-1-nitroethane to trans-IrCl(CO)-[P(CH₃)₂C₆H₅]₂ followed by treatment of the initial product with pyridine yields a new iridium(III) complex IrCl(py)[COC(NO₂)CH₃][P(CH₃)₂C₆H₅]₂, whose structure has been confirmed by X-rays crystallography. Two intermediate products have been observed by NMR spectroscopy; their structures have been tentatively assigned. The reaction of the corresponding bromine derivatives yields two isomers of the composition IrBr₂(CO)[CH(NO₂)CH₃][P(CH₃)₂C₆H₅]₂, and these are not affected by pyridine. The reaction of 1-chloro-1-nitroethane with Pt[P(C₆H₅)₃]₄ takes a completely different course in that yields nitrorethane and cis-PtCl₂[P(C₆H₅)₃]₂ as the main products, with no detectable formation of the products of oxidation addition. A brief mechanistic investigation points towards the participation of radicals and radical anions as transient intermediates and a mechanism is proposed which explains most of the experimental results.     

Implementation of an expert system for the qualitative interpretation of X-ray fluorescence spectra

The implementation of an expert system for the automated qualitative interpretation of energy-dispersive x-ray spectra is discussed. The first step in the interpretation process is the extraction of the relevant data from the spectrum, which is done by a preprocessor program, written in FORTRAN. The expert system itself consists of three parts. The knowledge base contains specific information on energy-dispersive x-ray fluorescence spectrometry presented in the form of IF/THEN rules. The data base contains the reduced spectral data and an array of certainty factors associated with each element; the certainty factor for an element represents the probability of its being present in the sample from which the spectrum was taken. Finally, the inference engine performs manipulation of the knowledge. For a particular state of the data base, the certainty factors for all the elements are iteratively modified until convergence is reached by using the rules from the knowledge base. During each cycle, the inference engine selects one rule from the knowledge base and executes it. Rules are selected on the basis of the chemical elements contained in their IF part and according to their previously assigned focus levels. Execution of the THEN part of the selected rule modifies the certainty factors of a number of elements. At the end of the interpretation session, the system lists the elements which have a high probability of being present in the sample. Optionally, the user can be provided with explanations of the reasoning steps taken during the interpretation. Application of the expert system to a particular spectrum shows that it is useful for the reliable interpretation of spectral data obtained from electron microprobe analysis of industrial aerosol particles.     

N-Monobromamide: Darstellung durch Bromierung mit „Dibromisocyanursäure”, Eigenschaften

By reaction of primary carboxamides with “dibromoisocyanuric acid” (DBI) N-monobromoamides can be readily obtained as well as the N,N-dibromoamides described in an earlier paper¹. Reactions, some of them new, and properties of these compounds are described and compared with those of the N,N-dibromoamides. Like other compounds bearing the NHBr group^{2, 3} the N-monobromocarboxamides disproportionate at room temperature according to: 2 RCONHBr ? ? RCONH₂+RCONBr₂. For CH₃CONHBr the equilibrium constant was found to beK=0.02. In aqueous solution they behave as weak acids. The dissociation constants of eight compounds [R=?CH₃, ?C₂H₅, ?CH₂Cl, ?CHCl₂, ?CCl₃, ?CF₃, ?C(CH₃)₃ and ?C₆H₅] were measured: they differ from those of the corresponding carboxylic acids by about three powers of ten.     

Dérivés propargyliques,XII et dérivés de la décahydroquinoléine,II Alkynyl-4, alkényl-4 et alkyl-4-décahydroquinolinols-4 N-substitués

The authors describe the synthesis of decahydro-4-quinolinones and N-substituted 4-alkynyl-, 4-allyl- and 4-alkyldecahydro-4-quinolinols and discuss the stereochemical problems of this compounds.     

Zum Mechanismus der Hydrogenolyse aromatisch gebundenen Halogens

The selective chlorination of a m/p-xylene mixture, followed by distillation of the unreacted p-xylene, leaves a residue containing up to 90% of monochlorinated m-xylenes. m-Xylene is recovered from the latter by heterogeneous catalytic hydrogenolysis in the gas-phase. It was found that the hydrogenolysis on certain noble metal catalysts proceeds according to an ionic reaction mechanism at temperatures below a definite temperature range. At temperatures above this range hydrogenolysis follows a radical reaction mechanism.     

Effect of pressure on free-radical copolymerization kinetics. I. A concept of additivity of partial molar volumes of activation

A short review of the effect of pressure on copolymerization kinetics shows the necessity of simple models for a better understanding of activation volumes. Therefore, a simple concept, possibly generally valid for free-radical polymerization, is proposed, based on the assumption that molar volumes of activation can be expressed as an addition of a characteristic radical and a monomer contribution, regardless of the combination involved. The scheme may facilitate the visualization of the transition state and contribute to the understanding of reaction mechanisms of radical polymerizations. Ethylene–vinyl acetate copolymerization at 62°C with tert-butyl alcohol as solvent agrees with the proposed scheme, appearing from the pressure independence of the product of reactivity ratios at the different levels (35,600, and 1200 kg/cm²). Implicitly it can be shown that an ethylene monomer contributes about 2 cm³/mole more to the activation volumes of the propagation reactions than does the vinyl acetate monomer, whereas for the radicals the difference of the respective contributions to the activation volumes is opposite in sign.     

Selenium in environmental waters: Determination, speciation and concentration levels

This article reviews the different methods used for the determination of selenium species in all types of environmental waters. Basic difficulties are discussed and the efficiency of the methods is explained in view of the sub-mug/1. concentration levels. Special attention is paid to preconcentration steps. Published data on speciation and concentration levels in various water samples are critically reviewed.