Über die Stereochemie der Hydrogenolyse von N-Benzyl-Bindungen I. Die Hydrogenolyse von Derivaten der 2-Amino-2-phenyl-propionsäure.

The stereochemistry of the hydrogenolysis of benzyl-N bonds was studied using S(+)-2-dimethylamino-2-phenyl-propionic acid (I) and its derivatives, and R(?)-2-anilino-2-phenyl-propionic acid (II). The configuration of I was confirmed, that of II established by ORD. measurements, after transformation of the phenyl into cyclohexyl groups. On a palladium catalyst the hydrogenolysis of I, its methyl and ethyl esters and its amide proceeded with 72 to 99% inversion of configuration, that of II with at least 66% inversion. The ester of the quaternary ammonium derivative of I gave as much inversion as retention (= racemisation).     

The effect of metal oxides on the oxidation of polybutadiene

Carboxy-terminated polybutadiene (CTPB) was oxidised as a coating on various metal oxides by heating in air on a thermobalance. The oxidation was found to be free from diffusion control and was catalysed by certain of the oxides. The catalysis was shown to be independent of semiconductor type and to be associated with those oxides for which the width of the forbidden zone between the valence and conduction bands (U) is less than 1.9 eV. In general, low values of U result in high catalytic activity. It is proposed that catalysis occurs by a redox mechanism, viz. RO₂H + p → RO₂^. + H⁺, RO₂H + e → RO^. + OH^?.     

Radical reactions involving esters of fumaric acid—III. Chain transfer processes

Model compounds have been used in studies at 60° in connection with transfer to polymer during the copolymerization of vinyl acetate with esters of fumaric acid. Succinate esters were used to simulate the fumarate ester units and ethyl acetate the vinyl acetate units in the copolymers. The succinate esters are much more reactive than ethyl acetate in transfer reactions with polyvinyl acetate radicals. Methyl isobutyrate and methyl propionate were also examined to assess the difference in reactivity in transfer of tertiary and secondary hydrogen atoms. It is concluded that branching is a very important reaction in the preparation of high conversion copolymers of fumarate esters with vinyl acetate.     

Synthesis and transformation of N-oxides of some imidazo[4,5-b]pyrazine derivatives

The Böckelheide reaction was accomplished with a number of imidazo[4,5-b]pyrazine N-oxides, and the N-oxidation of the resulting acetoxy(hydroxy)methyl derivatives of imidazo[4,5-b]pyrazine and 6-bromo-1-methylimidazo[4,5-b]pyrazine was studied. The hydrolytic cleavage of 6-bromo-1-methylimidazo[4,5-b]pyrazine and its 4-N-oxide was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 690–693, May, 1975.     

Reactions of Titanium Alkoxides with N-Methylaminoalcohols

N-methylaminoalkoxides of titanium of the type Ti(OR)_4?n(O · CHR′ · CH₂ · NR″R?)_n where R = Et and Pr¹; n = 1–4; and R′ = R″ = H, R? = Me; R′ = H, R″ = R? = Me; R′ = R″ = R? = Me, synthesized by the reactions of titanium alkoxides with aminoalcohols, show interesting variations in their properties like physical state, volatility and molecular complexity. I.r. and p.m.r. spectra of these derivatives have been recorded. A few interchange reactions with methanol and tert-butanol have also been carried out. These aminoalkoxides get cleaved with acetyl chloride and undergo insertion reactions with phenylisocyanate, thus providing the first examples of insertion reactions in such derivatives.     

Pyridylethylation of some heterocyclic thioamides and potential mercaptans

2-Pyridylethylation of benzazothiones-2 which are potential mercapto compounds (benzothiazolethione-2, benzoxazolethione-2, 1-methylbenzoimidazolethione-2, benzoimidazolethione-2, 5, 6-dimethylbenzoimidazolethione-2), is described, as well as preparation of 5, 6-dimethylbenzoimidazolethione-2 by direct oxidation of 5, 6-dimethylbenzoimidazole.     

Ab initio MO-SCF calculation on a model of anomalous water

Ab initio calculations are carried out on the planar hexamer model of anomalous water using a variety of basis sets. The results are compared to results of similar calculations on free water and water in the ice I-like puckered ring configurations.

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Zusammenfassung Es werden ab initio-Rechnungen für das planare Hexamer-Modell von anomalem Wasser unter Verwendung mehrerer BasissÄtze durchgeführt. Die Ergebnisse werden mit Resultaten Ähnlicher Rechnungen über freies Wasser und Wasser in der I-Eis Ähnlichen Konfiguration verzerrter Ringe verglichen.

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Résumé Calculs ab initio sur le modèle hexamérique plan de l'eau anormale en utilisant différentes bases. Les résultats sont comparés à ceux de calculs similaires sur l'eau libre et sur l'eau dans une configuration cyclique compacte analogue à celle de la glace I.

     

Structure and conformational isomerism of the major dimer of 2,3-naphthoquinodimethane

The major product from 2,3-naphthoquinodimethane formed by cyclisation of $\text{o}$-dipropadienylbenzene was found to be the dimer 5 containing an eight-membered ring, for which the inversion barrier was determined by dynamic ¹H NMR spectrometry, ΔG3 = 18 kcal/mole.     

Ultrasensitive polychromatic silver staining of sodium dodecyl sulfate-polyacrylamide gels with the Gelcode system using the PhastSystem Development Unit

The Gelcode color-based silver staining system, an improved formulation based on the original publication by Sammons et al. (Electrophoresis 1981, 2, 141-147) has been adapted to automated rapid staining in the PhastSystem Development Unit. The use of elevated temperatures in the fixation, washing, staining, and stabilization steps of the protocol reduces the total time of the process from 18 h to 1 h. The limit of detection, which is at least tenfold more sensitive than the silver staining protocol recommended for the PhastSystem, corresponds to 0.05-0.1 ng of protein per band. The method is applicable to both one- and two-dimensional polyacrylamide gels.