Diene synthesis with 2-pyrones and 2-pyridones XIV. 1,4-Cycloadducts of 1-alkyl-2-pyridones with N-phenylmaleinimide and maleinimide

1-Alkyl-2-pyridones react with N-phenylmaleinimide and maleinimide stereoselectively via the scheme of the diene synthesis to give imides of 8-alkyl-8-azabicyclo[2.2.2]-4-octen-7-one-1,2-dioic acid. 3-Unsubstituted 2-pyridones form adducts with an endo configuration, whereas 1,3-dimethyl-2-pyridone gives an exo adduct under the same conditions. The endo- and exo-bridge adducts readily undergo retrograde diene disintegration on heating.     

Low temperature absorption spectra of TcO 4 − and ReO 4 − in KClO4

The low temperature spectra of TcO ₄ ^– and ReO ₄ ^– both show two band systems with pronounced vibrational structures. The bands are identified as¹ A ₁¹ T ₂ transitions. No other bands are observed with certainty. It seems likely that the KClO₄ crystals contain KReO₄ crystallites. They are therefore not pure mixed crystals. It is concluded that the virtual orbital (2e) used in the construction of the low lying states resembles an atomic nd orbital more and more when going from n=3, Mn to n=5, Re.

---

Zusammenfassung Die Tieftemperaturspektren von TcO ₄ ^– und ReO ₄ ^– zeigen beide zwei Bandensysteme mit ausgeprägten Schwingungsstrukturen. Die Banden werden als ¹ A ₁¹ T ₂-Übergänge identifiziert. Keine anderen Banden werden mit Sicherheit beobachtet. Es scheint wahrscheinlich, daß die KClO₄-Kristalle KReO₄-Kristallite enthalten und deswegen keine reinen Mischkristalle sind. Es wird geschlossen, daß das virtuelle Orbital (2e), welches zur Konstruktion der tiefliegenden Zustände gebraucht wird, in der Reihe n=3, Mn bis n=5, Re immer weitgehender einem nd-Atomorbital ähnelt.

---

---

Nachwuchsstipendiat, Schweizerischer Nationalfonds.     

Purine N-oxides—XLI : The 3-acyloxypurine 8-substitution reaction: On the mechanism of the reaction

The 3-acyloxypurine 8-substitution reaction involves elimination of the 3-acyloxy group and nucleophilic substitution at C-8 to yield 8-substituted xanthines or guanines. In aqueous solutions the reaction of 3-acetoxyxanthine proceeds slowly below pH 2, but is greatly accelerated with an increase of the pH from 3 to 7. It is proposed that the slow reaction involves heterolytic cleavage of the 3-acetoxy moiety from 3-acetoxyxanthine to yield a nitrenium ion at N-3 followed by intermolecular nucleophilic substitution of the incipient carbonium ion at the allylic C-8 position, also the most probable mechanism in polar aprotic solvents. The beginning of the fast reaction coincides with the beginning of ionization of the imidazole hydrogen of 3-acetoxyxanthine. It is proposed that this ionization induces a similar but more rapid departure of the 3-acetoxy group from the anion of 3-acetoxyxanthine to produce dehydroxanthine. The latter, upon protonation, yields the same reactive carbonium ion at C-8 that is formed in the slow reaction. Some reduction of 3-acetoxyxanthine to xanthine accompanies the fast reaction. That reduction has the characteristics of a free-radical mediated reaction. It is proposed that reduction results from a homolytic cleavage of the NO bond in the 3-acetoxyxanthine anion to produce a radical-anion, which abstracts hydrogen from water to yield xanthine. These reaction mechanisms and possible alternatives are evaluated.     

Studies in sesquiterpenes—LVI: Isolongifolene (part 7): mechanism of rearrangement of longifolene to isolongifolene—II

The question of possible neutral intermediates which may lie on the reaction pathway in going from longifolene to isolongifolene has been investigated using BF₃·Et₂O-AcOD and D₃PO₄-dioxane, as reagents. It has been found that longicyclene is not an obligatory intermediate. The mode of cleavage of cyclopropane ring in longicyclene has been investigated.     

Dialkylindiumacetate R2InOOCCH3 (R = CH3, C2H5) Darstellung,Eigenschaften und Struktur

Dialkylindium Acetates R₂InOOCCH₃ (R = CH₃, C₂H₅). Preparation, Properties, and Structure. Dimethyl- and diethylindium acetate were prepared and the vibrational spectra (IR and RAMAN ) discussed. The X-ray structure determination shows that diethylindium acetate belongs to the orthorhombic space group Pnma. The unit cell with lattice constants a = 8.40, b = 7.41, c = 15.13 Å contains four molecules. Each indium atom forms with an acetate group a planar four-membered ring. The indium-oxygen distance within such a ring is only a little shorter than the distance of this oxygen to the indium of the next neighboured ring. Indium has therefore the coordination number six.     

Ab initio SCF Calculation of the Fluoronium Ion: Geometry,electronic structure and vibrational constants

An ab initio SCF calculation of 42 points of the energy hypersurface of the fluoronium ion is presented using a contracted F(5s/3p), H(2s) gaussian basis set. In its equilibrium structure a bond length of 1.812 a.u. and a HFH bond angle of 127.2° are predicted. The calculated vibrational frequencies for H₂F⁺, HDF⁺, and D₂F⁺ are in good agreement with the experimental data.     

On an Asymptotics of the Number of Representations of a Pair of Integers by Quadratic and Linear Forms with Congruential Condition

Mathematical Notes - Asymptotic formulas with remainder for the number of representations of a pair of integers by quadratic and linear forms with a congruential condition are proved.     

Coincidence experiments with electrons

Coincidence experiments with electrons provide new information on the structure of nucleons and nuclei. Using new CW accelerators, kinematic regions can be explored with high precision which have not been accessible previously. The equipment and the necessary steps in the analysis of (e,ep) experiments will be discussed and illustrated with new data taken at the MAMI facility.Lectures given at the Indian-Summer School on Electron Scattering of Nucleons and Nuclei, Prague (Czech Republic), September 1994.     

Domain wall theory of elementary excitations in anisotropic antiferromagneticS=1 chains

We present a theoretical investigation of elementary excitations in anisotropic antiferromagneticS=1 chains using the concept of domain walls in string (hidden) order. Domain walls are classified by the internal spin projectionS _dw ^z . We calculate energies and string correlation functions of low lying excited states of the domain wall type in the Haldane phase and compare the results to those of numerical computations. The boundaries of the Haldane phase are determined from the instability of these excitations with respect to the ground state. The interaction between two domain walls is found to be proportional to the productS _dw ^z , S _dw ^z ₂, it is effectively repulsive for equal spin projections.     

A matrix approach to grazing-incidence X-ray diffraction in multilayers

A method for computation of X-ray grazing-incidence diffraction (GID) in multilayers and superlattices is presented. The method is based on X-ray dynamical diffraction theory and a matrix from a boundary equations and provides a simple numerical solution of the problem. The application of the method to simulating GID measurements taken from A1As/GaAs superlattice (20 periods of 14.6 nm A1As and 6.8 nm GaAs) demonstrates the principal validity of the theory. A perfect matching between the theory and the experiment requires the real-structure effects of sample to be taken into account.