Mechanism of the oxidation of cycloheptanone by chloramine-T

The oxidation kinetics of cycloheptanone by chloramine-T in alkaline media has been investigated. A mechanism involving the formation of an intermediate by the interaction between the enolic anion of cycloheptanone and chloramine-T in a slow step followed by its interaction with another molecule of chloramine-T in a fast step leading to products has been proposed. The scheme satisfactorily accords with the observed stoichiometry, negligible influence of ionic strength and a positive dielectric effect. Various rate parameters have been computed and 1.2-cycloheptanedione identified as the end product.With 2 Figures     

The reaction of 2-picoline N-Oxide with o-substituled benzoates and lsatoic anhydrides

The reaction of 2-picoline N-Oxide anion with o-substituted henzoates and isatoic anhydrides to give synthetically useful l-(2-methoxyphenyl)-2-(2-pyridinyl)ethanone N-oxides, I-(2-hydroxy-phenyJ)-2-(2-pyridinyl)ethanone N-oxides and I -(2-arninopheny])-2-(2-pyridinyl)ethanone N-oxides is described.     

Characterization of internal salts by laser mass spectrometry

An intermolecular alkyl transfer reaction (ATR) leading to ion-pair formation has been observed for internal salts by using laser mass spectrometry (l.m.s.). Positive- and negative-ion spectra both show evidence for alkyl transfer. Both the LAMMA-500 (transmission) and LAMMA-1000 (reflection) laser mass spectrometers were used. The positive-ion laser mass spectra obtained by these two instruments show some significant differences; no significant differences were observed in the negative-ion spectra. Results obtained for quaternary ammoniohexanoates as a function of laser power indicate that the extent of ATR is greater at high laser power. Addition of a small amount of p-toluenesulfonic acid to the ammoniohexanoates reduces fragmentation and enhances the intensity of the quasimolecular ion (M + H)⁺ relative to ATR. Results from deuterated sultaines were used to confirm intermolecular alkyl transfer and to elucidate some fragmentation processes. Field-desorption (f.d.) mass spectra of internal salts show similarities and differences from l.m.s.; not all internal salts showed the alkyl transfer reaction in f.d. Cluster ion formation was observed in f.d.m.s. but not in l.m.s.     

A statistical thermodynamic supermolecule-continuum study of ion hydration: Cell and shell methods

A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li⁺, Na⁺, K⁺, F^– and Cl^– each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties.     

Organosilicon compounds : LI. Further studies of the base-catalysed solvolysis of N-(triorganosilyl)anilines

Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC₆H₄NHSiEt₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO₂, 18; p-CN, ca. 43; p-NO₂, ca. 120. (ii) For PhNHSi(C₆H₄Y)₃ compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R₃ =) Et₃, 1.0; Et₂Me, 18 (at 30°); Me₂-i-Pr, 8 (at 30°);Me₂-t-Bu, 0.012 (at 50°);i-Pr₃, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ^?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed.     

Interfacial electrical properties of DNA-modified diamond thin films: intrinsic response and hybridization-induced field effects

We have investigated the frequency-dependent interfacial electrical properties of nanocrystalline diamond films that were covalently linked to DNA oligonucleotides and how these properties are changed upon exposure to complementary and noncomplementary DNA oligonucleotides. Frequency-dependent electrical measurements at the open-circuit potential show significant changes in impedance at frequencies of >10(4) Hz when DNA-modified diamond films are exposed to complementary DNA, with only minimal changes when exposed to noncomplementary DNA molecules. Measurements as a function of potential show that at 10(5) Hz, the impedance is dominated by the space-charge region of the diamond film. DNA molecules hybridizing at the interface induce a field effect in the diamond space-charge layer, altering the impedance of the diamond film. By identifying a range of impedances where the impedance is dominated by the diamond space-charge layer, we show that it possible to directly observe DNA hybridization, in real time and without additional labels, via simple measurement of the interfacial impedance.     

Kottamide E, the first example of a natural product bearing the amino acid 4-amino-1,2-dithiolane-4-carboxylic acid (Adt)

Kottamide E, a novel alkaloid containing dibrominated indole enamide, oxalic acid diamide and 4-amino-1,2-dithiolane-4-carboxamide moieties, has been isolated from the New Zealand ascidian Pycnoclavella kottae. Characterisation was achieved by interpretation of spectroscopic data.     

Anwendung mikroanalytischer Methoden zur Lösung kunst- und kulturgeschichtlicher Probleme

Zusammenfassung Mit bekannten mikroanalytischen Arbeitsmethoden — Oberflächenreaktionen, Abstrichuntersuchungen mit dem Korundstäbchen, Schutzschichtreaktionen sowie dem Abdruckverfahren — lassen sich archaeometrische Probleme einer Lösung näherbringen. Die Art der Korrosion kupferhaltiger Oberflächen wurde diskutiert.

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Application of microanalytical methods to the solution of artistic- and cultural historical problems

Summary Archeometrical problems are brought closer to a solution by means of known microanalytical procedures-surface reactions, surface scraping studies with the corundum rod, protective layer reactions as well as the imprint method. A discussion of the corrosion of copper-bearing surfaces is included.

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Vortrag anläßlich der Tagung Chemische Analysen — Kunst- und Kulturwissenschaften im Reiß-Museum in Mannheim, 19.–21. September 1974.     

The effects of molecular reorientation on the absorption of intense light by organic-dye solutions

Equations are presented for the spectral and orientational distribution of unexcited dye molecules in the field of an intense giant laser pulse. The solute dye molecules are linear oscillators that may be broadened either homogeneously or inhomogeneously, and may reorient by sudden jumps over large angles or by small angular steps (brownian rotational motion). The equations are employed to analyze the intensity dependence of fluorescence polarization observed by Mourou and Denariez-Roberge for the system cryptocyanine-glycerin. Their data are consistent with an excited-state deactivation time T₁ = 0.4 ± 1.0 ns and a rotational diffusion constant D = 20/T₁ = 5.0 × 10⁹ s⁻¹     

Improving catalyst scope: use of multiple aniline substrates to optimize a palladium-catalyzed bisdiene cyclization

[reaction: see text] Combinatorial screening of five catalyst precursors and nine ligands with three substituted aniline trapping reagents uncovered a catalyst system that promotes efficient palladium-catalyzed cyclization-trapping with a series of substituted anilines of varying steric and electronic character. The results of the parallel optimization study illustrate the interdependency of the key reaction variables.