Convolution voltammetry of metal complexes

The application of convolution potential voltammetry to questions of metal complexation is described. Theoretical relations are derived to show that the stability constants may be directly related to the shift in the peak potential of the semiderivative wave, provided the complexes are labile. Equations are also given for inert and quasilabile complexes. Stability constants for the PbCl_x and CdCl_x systems are reported, illustrating the use of convolution techniques with linear scan voltammetry and with linear scan anodic stripping voltammetry. Advantages of convolution techniques are discussed.     

Synthesis of 2,4′-dioxospiro[indoline-3,2′-thiazolidine]-5′-acetic acids: X-ray structure of 1-benzyl-3′-(4-chlorophenyl)-2,4′-dioxospiro- [indoline-3,2′-thiazolidine]-5′-acetic acid

The title compounds have been prepared by the cyclocondensation of mercaptosuccinic acid with isatin-3-imines. The 1-benzyl derivatives have been synthesized by simultaneously reacting 1-benzylisatin, substituted anilines and mercaptosuccinic acid. The structure of the products has been confirmed by X-ray diffraction measurements.     

Synthesis of homoallylic chiral tertiary alcohols via chelation-controlled diastereoselective nucleophilic addition on alpha-alkoxyketones: application for the synthesis of the C(1)-C(11) subunit of 8-epi-fostriecin

[reaction: see text] Chiral beta-syn-alkoxyhomoallylic alcohols derived from alkoxyallylboration of aldehydes upon oxidation provided the corresponding chiral ketones. Chelation-controlled nucleophilic addition to these ketones occurred in a highly stereoselective manner to afford anti-homoallylic tertiary alcohols. This methodology has been applied for the synthesis of the C(1)-C(11) subunit of C(8)-epi-fostriecin.     

Facile synthesis of unsymmetrical benzotetrathiafulvalenes via cleavage of the corresponding hexathioorthooxalates

Unsymmetrical hexathioorthooxalates of types ($\text{1}$) and ($\text{2}$) undergo elimination of dialkyl disulfide on heating in an organic solvent; the reaction, which is catalyzed by acid, proceeds without fission of the central C:C bond and provides the first general, high yield synthesis of unsymmetrical benzotetrathiafulvalenes of types ($\text{3}$) and ($\text{4}$).     

The mass spectra of some phenyl pyridyl ketones

The mass spectra of phenyl 2-pyridyl, phenyl 3-methoxy-2-pyridyl, phenyl 4-methoxy-2-pyridyl, phenyl 5-methoxy-2-pyridyl, phenyl 6-methoxy-2-pyridyl ketones, phenyl 3-pyridyl and phenyl 6-methoxy-3-pyridyl ketones, and phenyl 4-pyridyl ketone were studied. The major fragmentation pathway of all the ketones results in the formation of[C₆H₅CO]⁺ and [C₅H₄NCO]⁺ type ions. Another fragmentation path is the loss of carbon monoxide with formation of an [M ? CO]⁺ ion after skeletal rearrangement.     

The thermal decomposition of ammonium metavanadate,I

The stoichiometry of the various stages involved in the thermal decomposition of ammonium metavanadate has been shown to correspond to a stepwise decrease in the ratio of ammonia and water to V₂O₅, with V₂O₅ being the final product in vacuum, in air and in argon. In ammonia, VO₂ is formed. The actual stages and intermediates are dependent upon the prevailing atmosphere. Chemical analyses, together with infrared absorption spectra and X-ray powder data, have enabled the intermediates and products to be characterized and the structural changes involved in the decomposition to be discussed.

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Zusammenfassung Es wurde gezeigt, daß die verschiedenen Stufen in der thermischen Zersetzung von Ammoniummetavanadat dem stufenweisen stöchiometrischen Verlust von Ammonia und Wasser entsprechen. In Vakuum, Sauerstoff und Argon ist V₂O₅, in Ammoniak VO₂ das Endprodukt. Die Zwischenprodukte der einzelnen Stufen sind von der umgebenden Gasatmosphäre abhängig. Durch chemische, infrarot- und röntgenspektroskopische Analyse gelang es, diese zu charakterisieren und so die durch die Zersetzung hervorgerufenen strukturellen Umlagerungen zu deuten.

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Résumé On montre que les différentes étapes de la décomposition thermique du métavanadate d'ammonium correspondent à la diminution progressive de l'eau et de l'ammoniac par rapport à V₂O₅; cet oxyde constitue le produit final dans le vide, dans l'air et dans l'argon. Dans l'ammoniac, c'est VO₂ qui se forme. Les étapes respectives et les intermédiaires dépendent de l'atmosphère qui prévaut. A l'aide de l'analyse chimique, des spectres d'absorption infrarouge et des données de rayons X sur poudre, on a pu caractériser les intermédiaires et les produits formés, ainsi que les changements structuraux provoqués par la décomposition.

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, V₂O₅. , V₂O₅. . , , .

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We wish to acknowledge helpful comments from Prof. L. Glasser and Dr. N. H. Agnew and financial support from the National Institute for Metallurgy, Johannesburg, South Africa.     

Organoboranes—34 : General synthesis of chiral boronic and borinic esters via asymmetric hydroboration-displacement. carbenoidation of chiral borinic esters to acyclic ketones of high enantiomeric purities

Asymmetric hydroboration of appropriate alkenes with diisopinocampheylborane (Ipc₂BH) or monoisopinocampheylborane (IpcBH₂) produces intermediates that readily eliminate α-pinene on treat- ment with acetaldehyde, providing a direct, convenient route to chiral boronic esters of high enantiomeric purities. Mixed chiral trialkylboranes, readily prepared by stepwise hydroboration of appropriate alkenes with IpcBH₂, eliminate α-pinene on treatment with acetaldehyde under very mild conditions. The procedure makes readily available chiral borinic esters of high enantiomeric purities. The synthetic utility of chiral borinic esters is demonstrated by converting them into acyclic ketones including an alarm pheromone of the ant Monica mutica.     

Separation techniques for biotechnology in the 1990s.

Scientists are constantly looking for better and cheaper separation techniques to replace or complement the current technology. Over the past few decades, and in particular the last 10 years, new separation techniques or modifications of existing techniques have become available for separating compounds from complex sample matrices. There are many areas, however, where the separation technology is not sufficient to achieve high purity and yield while remaining cost effective. In the area of biotechnology, separation techniques are urgently needed to meet demands for ultra-high purity and yield. Thus, a variety of techniques are being developed to address these needs. Generally, biological compounds for the pharmaceutical and biotechnology industries must be obtained at greater than 99.9% purity (sometimes greater than 99.99%) while maintaining high yield. In any area of chemistry this degree of purity would cause problems; in biotechnology it is even more difficult to achieve because of the complex sample matrices. In addition, the compounds of interest may be very similar to impurities or contaminants in the sample matrix, and the compounds could be denatured (or even destroyed) by certain solvents and/or high temperature. In particular, three areas of biotechnology have presented scientists with problems in separations: cell separations, DNA-RNA separations, and protein-peptide separations. The current technology available and possible future trends in these areas are discussed, and also problems to be solved in the future.