The molecular and crystal structures of two diastereomeric 3,4-dihydropyrromethenones

The molecular and crystal structures of the two racemic diastereomeric 3,4-dihydropyrromethenone derivatives1 and2 of configurations (Z) and (E) were determined at 93 K (1, 2) and at room temperature (1). From an analysis of the crystallographically observed temperature coefficients a pseudorotation flexibility of the pyrrolidinone ring in the crystal is deduced. In both compounds a nearly orthogonal arrangement between the two heterocyclic ring systems is observed, which is ascribed to the steric bulk of the substituents in positions 1 and 3 of the pyrrolidinone ring.Herrn Prof.Josef Schurz zum 60. Geburtstag gewidmet.     

Über die Anwendung der Kohlepaste-Elektrode zur inversvoltammetrischen Bestimmung kleiner Quecksilbermengen

The applicability of the carbon paste electrode to the determination of trace quantities of mercury has been investigated in a base electrolyte of 0.1 N KSCN + 0.025 N HCl containing 25 ng/ml copper. The detection limit of the mercury determination has a value near 2.5 ng/ml (1.25×10^?8 M), if pre-electrolysis is carried out 10 min at ?1.0 V and the current voltage curve is registered with a scan rate of 16.7 mV/sec between ?0.5 and +0.5 V. The peak height is directly proportional to the concentration in the range from 1.25×10^?8 to 1.25×10^?6 M. With appropriate preconditioning the carbon paste electrode can be used for several measurements without renewing the surface.     

Mass-selected resonance-enhanced multiphoton ionisation spectra of laser-desorbed molecules for environmental analysis: 16 representative polycyclic aromatic compounds

Mass-selected gas-phase UV spectra of laser-desorbed molecules at room temperature have been measured via resonance-enhanced multiphoton ionisation (REMPI) and time-of-flight mass selection. The wavelength range of 260 to 320 nm is optimal for detection of polycyclic aromatic hydrocarbons (PAHs) using REMPI-mass spectrometry. A new laser desorption/laser ionisation source has been used which features a compact size and thermal equilibrium of the desorbed molecules. 16 PAHs have been investigated which have been selected by the US Environmental Protection Agency (EPA). These 16 EPA-PAHs are commonly used world-wide to characterise the PAH-load of environmental samples.     

Femptovoltmeter (10−15 Volt) based on a double Josphson junction resistive interferometer

A voltmeter of sensitivity is based on direct conversion of the voltage to be measured into a frequency according to the Josephson voltage-frequency relation. Selfpumped parametric amplification in a d.c. biased loop containing two Josephson junctions and a measuring resistanceR _s=4.7×10^–9 amplifies the femptovolt level voltages acrossR _s to microvolt levels that can be observed with a room temperature amplifier. The sensitivity of the femptovoltmeter is determined by Johnson-Nyquist noise voltages at 4.2 K in the 4.7×10^–9 resistance.     

A theoretical study of the electromagnetic properties of ferrocene and the ferrocenium ion

An iterative extended Hückel molecular orbital calculation was used to obtain wave functions for the ground state of ferrocene and several low lying states of the ferrocenium ion. Photoemission spectra in terms of relative ionization potentials and the electric field gradient at the iron nucleus were calculated for ferrocene andg values and the electric field gradient were calculated for the ferrocenium ion. These values are in good agreement with experiment. The nature of the molecular orbitals was compared with results of previous semi-empirical andab initio calculations.     

Beiträge zur Chemie der Silicium—Stickstoff-Verbindungen, 16. Mitt.: N-Silyl-carbonamide und N-Silyl-carbamidsäureester

Zusammenfassung Die durch direkte Silylierung von Carbonamidgruppen mit Halogensilanen nicht zugänglichen Verbindungen der Gruppierung R-CONHSiR₃ konnten durch Umsetzung von Säureamiden oder Säurechloriden mit Hexamethyldisilazan gewonnen werden. So wurden Derivate mit R=CH₃, C₂H₅, C₆H₅, CONHSiR₃ , OCH₃, OC₂H₅, OCH(CH₃)₂; R=CH₃ (vgl. Tab. 1) dargestellt und in ihren physikalischen und chemischen Eigenschaften näher studiert.Herrn Prof. Dr.A. Zinke zum 70. Geburtstag gewidmet.15. Mitt.:U. Wannagat undH. Kuckertz, Angew. Chem.74, 117 (1962).Auszug aus der DissertationJ. Pump, Techn. Hochsch. Aachen 1962.     

Conformational analysis3̄CXXIV: The conformation of ring A in the 4,4-dimethyl-3-androstanone system. The crystal structure of 4,4-dimethylandrostan-3-on-17β-yl benzoate

Molecular mechanics calculations indicate that the deformed chair and twisted-boat conformations are similar in energy for a 4,4-dimethyl-3-keto steroid. Earlier dipole moment work on such compounds is discussed. The crystal structure of 4,4-dimethylandrostan-3-on-17β-yl benzoate has been determined. The crystals are orthorhombic, P2₁2₁2₁, a = 17.096 (2), b = 22.136 (e), c = 6.217 (1) A. The structure was solved by direct methods and refined by least squares to R ? 0.039, R_XXX = 0.038, based on 2168 observed reflections. Ring A is shown to exist in a chair form, deformed as indicated by the calculations.     

Synthese von „Dithio-Oxolinsäure“

5-Amino-benzo-1,3-dithiol, available by reduction of 5-amino-benzo-1,3-dithiol-2-thion, was elaborated into dithio-oxolinic Acid (6 a).

     

3-Chloropropyltrialkoxysilanes—Key Intermediates for the Commercial Production of Organofunctionalized Silanes and Polysiloxanes

Silicon and carbon may be looked upon as the two fundamental antipodes with respect to the naturally occurring forms of matter and life on earth: Silicon plays the key role in the “petrification” of inanimate matter, while carbon is the representative element for the “incarnation” of living organisms. If a scientist were to search for a highly efficient method of uniting inorganic and organic matter, he would, at a very early stage of attempting to solve this problem, combine these two natural principles of matter and think of “bireactive” molecules containing a silicon functionality for bonding to inorganic material on the one hand and a carbon functionality for anchoring to an organic counterpart on the other. The title compounds and their derivatives epitomize such molecules: they are wanderers between both (chemical) worlds. Owing to their bifunctionality they are capable of binding to inorganic (especially siliceous) systems as well as to organic polymers. Whether their commercial application concerns the strengthening of polyester resins with glass fibers for use in boatbuilding or the incorporation of silica as a filler in rubber mixtures for the manufacture of wear-resistant tires or even the immobilization of enzymes on glass spheres for carrying out reactions in enzyme reactors—in all cases organofunctionalized silanes guarantee a reliable and permanent union between two otherwise “incompatible” material systems.     

Crystal structure, morphology and composition of magnetron sputtered tungsten carbide films

Summary It is shown that small variations of the deposition parameters during magnetron sputtering of tungsten carbide thin films may result in drastic changes of film properties. An increasing working gas pressure for example lowers stress and hardness values. Simultaneously, the texture of the WC_1–x cristallites turns from 200 preferential orientation to 111, whereas the composition of the films does not change. In reactive sputtering with a tungsten target there is a narrow range from 2 to 3% C₂H₂ gas admixture to the working gas where the films are stochiometric (WC) and hard, and grain size and morphology are similar to that of non-reactively sputtered films. The generation of different crystallite structures and orientations in the range of 0–3% C₂H₂ admixtures are used to produce a multiphase thin film with extremely low crack propagation.