Reaktionen mit phosphororganischen Verbindungen, 49. Synthese und 1H-NMR-Spektren von (3-Acylbicyclo[2.2.1]hept-5-en-2-yl)phosphonsäureestern

Reactions with Organophosphorus Compounds, 49. Synthesis and ¹H NMR Spectra of (3-Acylbicyclo[2.2.1]hept-5-en-2-yl)phosphonates Reaction of the (E)-(β-acylvinyl)phosphonates 1 with cyclopentadiene yields the isomeric norbornylphosphonates 2 (endo-acyl, exo-P) and 3 (exo-acyl, endo-P) in a 7:3 ratio. With 1,3-cyclohexadiene the corresponding bicyclooctenyl derivatives 7 and 8 are obtained from 1a . The (Z)-phosphinylacrylate 4 gives with cyclopentadiene the isomers 5 (exo-CO₂Me, exo-P) and 6 (endo-CO₂Me, endo-P) in nearly equal amounts. The configuration of the cycloadducts has been proved by ¹H NMR spectroscopy.     

A generalization of the Rouse-Zimm model

The idea of consistently averaging the hydrodynamic interaction and its various consequences for Hookean dumbbells are reviewed. For long chains this idea can be used to generalize the Rouse-Zimm model for polymer solutions. Unlike the usual Rouse-Zimm model, the new model for steady shear flow predicts a nonzero second normal stress coefficient and shear rate dependent material functions. In the limit of long chains, the viscosity and the normal stress coefficients are universal functions of the reduced shear rate.This paper was presented at the Frühjahrstagung des Fachausschusses Polymerphysik der Deutschen Physikalischen Gesellschaft at Kaiserslautern (West Germany), March 12–14, 1986.     

Electron propagator calculations of molecular electron affinities

An approximate electron propagator method for predictive calculations of molecular electron affinities is proposed. The self-energy accounts for relaxation effects to all orders Additional correlation effects are treated using a diagonal approximation with shifted denominators. Applications to CN, NH₂, and PH₂ are reported.     

Preparation and characterization of Co(II), Ni(II) and Cu(II) complexes of a ligand containing 1,3,4-thiadiazole groups

(1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazole-2-yl)ethane-1,2-diol (L) has been prepared by the reaction of thiosemicarbazide with (2R,3R)-(+)-tartaric acid (I) and phosphorous oxychloride, and its complexes with Co(II), Ni(II) and Cu(II) have been obtained. The structures of the ligand and its complexes have been established by i. r., ¹H- and ¹³C-n.m.r. spectra, u.v.–vis–nir spectroscopy, elemental analyses, T.g.-D.t.a. and magnetic susceptibility measurements.     

Vertical distribution of the natural and artificial radionuclides in various soil profiles to investigate soil erosion

Vertical distributions of ¹³⁷Cs and ²¹⁰Pb in soil profiles were examined to study their availability in soil erosion at Gökova region where there exists intensive agricultural activities on sloppy fields. Since the mobility of these radionuclides depend on soil characteristics, soil samples were analyzed also for their physical and chemical properties. From ¹³⁷Cs inventories measured, erosion rates for cultivated and disturbed (no cultivation) soils were calculated to range from 79.1 to 6.5 t^.ha^-1.y^-1 and from 79.9 to 3.5 t^.ha^-1.y^-1, respectively. The ²¹⁰Pb technique is found to be not suitable for erosion determination for this area, presumably due to the coal-fired power plants operating in the region.     

A new route for the functionalisation of wood through transesterification reactions

A novel transesterification reaction between acetylated maritime pine sapwood (Pinus pinaster Soland) and methyl benzoate (MB), in the presence of dibutyltin oxide (DBTO) as a catalyst, was performed. Reaction was confirmed by Fourier-transform infrared spectroscopy (FTIR) and ¹³C nuclear magnetic resonance cross-polarisation with magic-angle spinning (NMR CP MAS) analysis: signals corresponding to benzoylated wood were identified and, when transesterification was performed with ethyl trimethylsilylacetate (ETMSA), characteristic trimethylsilyl groups were detected. The acetyl/benzoyl exchange rate was found to increase with increasing amount of DBTO, temperature and reaction time and a concurrent deterioration of the woody material was evidenced.     

Computation of Rotation Matrices Making Lined‐Up to the Local Cartesian Coordinates

Rotation matrices were expressed in terms of Gaunt coefficients and complex spherical harmonics. The rotation matrices were calculated using two different ways. In the first, Gaunt coefficients and normalized complex spherical harmonics were directly calculated using binomial coefficients; in the second, Gaunt coefficients and complex spherical harmonics were recursively calculated. The methods were compared with respect to accuracy and computation time (CPU) for low and very high quantum numbers.     

Thermal decompositions of some divalent transition metal complexes of triethanolamine

The thermal behaviours of the Ti(II), Mn(II), Fe(II), Ni(II), Cu(II) and Zn(II) complexes of triethanolamine were studied by means of thermogravimetry, differential thermogravimetry, differential thermal analysis infrared spectrophotometry and elemental analysis. The sequence of thermal stability of the metal complexes, determined by using the initial decomposition temperature, was found to be Ti(II)?Mn(II)>Fe(II)>Ni(II)>Zn(II)>Cu(II). Some of the kinetic parameters, such as the activation energy and order of reaction for the initial decomposition reaction, were calculated and the relationship between the thermal stability and the chemical structure of the complexes is discussed.     

Preliminary Analyses of Radionuclides in Afşin-Elbistan Lignite Samples

This preliminary study describes the concentration of radionuclides ²³⁸U, ²³²Th, ⁴⁰K, and ²²⁶Ra in Afin-Elbistan lignite samples which are primarily used for power generation in the Afin-Elbistan Coal-Fired Power Plant. The results show that the concentration of ²³⁸U is higher in the Afin-Elbistan lignite compared to various world coals whereas the opposite is observed with ²³²Th and ⁴⁰K.