Buchbesprechungen

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Mittlere ringe-XIII Die intramolekulare acylierung der ω-(1-naphthyl)-fettsäuren

The intramolecular Friedel-Crafts cyclisation of ω-arylalkanoic acids, which is in the benzene series a valuable synthetic route to bicyclic ketones with medium-sized and large rings, has been investigated with ω-(1-naphthyl)alkanoyl chlorides. The lower members, including naphthyl-caproic acid, close the ring at position 2 to form IV. The higher homologous acids show a preference for annellation at 7, making available a new type of heteronuclear naphthalene cyclic ketones (VII). During cyclisation of ω-(1-naphthyl) decanoic acid, the 1,4 ring closure competes with the 1,7 type.

Steric hindrance of resonance as a consequence of “medium ring torsion” was studied in different classes of naphthocyclenones.     

The stereochemistry of quaternary N-methyl sparteinium cations, their derivatives, stereoisomers and analogues : Part II. Molecular and crystal structure, and IR spectra of methiodide and methperchlorate of 2-oxosparteine

The crystal and molecular structures of two quarternary salts of 2-oxosparteine (II), the methiodide (IICH⁺₃ • I⁻) and the methperchlorate (IICH⁺₃ • ClO⁻₄) have been determined on the basis of X-ray and IR data. The studies were performed by analogy to previously investigated quaternary salts of sparteine (I), the methiodide (ICH⁺₃ • I⁻) and the methperchlorate (ICH⁺₃ • ClO⁻₄). As expected, the configurations and conformations of cationic parts within the two pairs of quaternary salts are identical, except for the structure of their A/B fragments, which in ICH⁺₃ cations have the character of tertiary amines, but in IICH⁺₃ that of lactams.

On the basis of accumulated X-ray and IR data the similarities and differences in the modes of interaction of perchlorate and iodide anions with quaternary cations, and especially with their N⁺---CH₃ groups are discussed. In this discussion are also included the methiodide and methperchlorate of -isosparteine: IIICH⁺₃ • X⁻ (X⁻ = I⁻ or ClO⁻₄) where N⁺---CH₃ groups are cisoidally oriented to the basic nitrogen atoms. The most interesting observations are as follows: (i) When N⁺---CH₃ groups are easily accessible for direct quasi hydrogen bonding interactions with counter anions and when other positive charged groups, for instance lactam groups, are absent in quaternary cations, perchlorate anions interact more strongly than the iodide anions and in consequence introduce conformational changes into the ring with N⁺---CH₃ group as well as into further rings. (ii) Perchlorate and iodide anions interact with N⁺---CH₃ groups similarly and very weakly if at all, when the N⁺---CH₃ groups are for steric reasons inaccessible to counter anions or when in quaternary cations there are additional groups which attract the counter anions electrostatically. The last mechanism operates in both quaternary salts of 2-oxosparteine and this is the reason why their monocrystals are isosteric and IR spectra almost identical. (iii) The sterically hindered N⁺---CD₃ groups in both IIICD⁺₃ • X⁻ salts give rise in their IR spectra to two doubles of sharp, well resolved bands which indicate the presence of two different rotamers stabilized by two modes of weak intramolecular hydrogen bonds with basic N atoms. (iv) In IIICH⁺₃ • X⁻ and IIICD⁺₃ • X⁻ salts the perchlorate and iodide anions do not interact at all with the rotating and vibrating N⁺---CH₃ (N⁺---CD₃) group but the structures of these salts are not isosteric since the perchlorate anions interact more strongly than iodide anions with the A/B fragment of the IIICH⁺₃ cations. This is visible from the shapes and intensities of the so-called “trans” band in the IR spectra of both salts.     

Critical dynamics of φ2n with random fields in the tree approximation

In the tree approximation, the critical relaxational dynamics of ²ⁿ with quenched random fields is calculated by renormalization near the upper critical dimensiond _u=4+2/(n–1). Although the relation between the characteristic frequency _c q and the wave-numberq is as usual,unusual results are obtained for the asymptotic decay of the order-parameter correlation functionS(q,t).Dedicated to Prof. Dr. W. Döring on the occasion of his 75th birthday     

Theory of diffuse neutron scattering in the high temperature phase of CsCuCl3 and related Jahn-Teller compounds

The hexagonal Jahn-Teller compounds ABCl₃ (A=Cs, Rb; B=Cu, Cr) in their common high temperature phase are modeled as a system of independent elastic dipoles dressed by a far reaching strain field. The diffuse elastic cross section for neutrons is derived as for Huang scattering. Isointensity contours and line widths (FWHM) are calculated for CsCuCl₃ and compared to experimental results, especially looking for correlations and precursor effects of the structural phase transition.     

Study of diffusion creep accompanying superplastic deformation of the alloy ZhS6KP

The development of diffusion creep (DC) accompanying superplastic deformation (SPD) of the highly doped nickel alloy ZhS6KP is studied based on an investigation of the redistribution of dispersed intragrain deposits of the phase of Ni₃(Al, Ti). Deposit-free zones (DFZ) are formed in the alloy, held at the temperature of SPD and accompanying deformation at the grain boundaries. The contribution of DC to the deformation was determined from a comparative analysis of the width of the DFZ in the deformed and undeformed parts of the samples for different grain sizes and rates of DC taking into account diffusion accommodation. It was established that for the optimum rate of SPD the upper limit of the contribution of DC to deformation for 2-m grains does not exceed 11%. It is concluded, based on the distribution of DFZ, that the effect of DC accompanying SPD is determined by diffusion fluxes, associated with the local concentration of stress accompanying the development of grain-boundary slipping.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 40–45, June, 1986.In conclusion, we thank Yu. M. Mishin for a useful discussion of the results.     

Optical frequency doubling of a single-mode dye laser in an external ring resonator

Optical frequency doubling of a single-mode cw Rhodamin 6G ring dye laser is performed with a thin angle-tuned LiIO₃ Brewster cut crystal in a stabilized passive ring resonator. A conversion efficiency of =5 mW uv/320 mW fundamental input power was achieved at =603 nm.     

Umsetzung von hydrobromiertem 1,4-Polybutadien mit lithiumorganischen Verbindungen

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