Über die gemeinsame Umsetzung von α-Mercaptoketonen mit Oxoverbindungen und α-Aminocarbonsäureestern

Zusammenfassung Bei der Umsetzung von -Mercaptoketonen mitSchiffschen Basen aus Glykokolläthylester und Oxoverbindungen (Aldehyden, Cyclohexanon) bzw. bei der gemeinsamen Einwirkung derSchiffschen Base-Komponenten Glykokolläthylester und Oxoverbindungen auf -Mercaptoketone entstehen in glatter Reaktion ⁴-Thiazolin-3-yl-essigsäureäthylester.Als cyclische Enamine lassen sich diese ⁴-Thiazoline mit Ameisensäure zu den entsprechenden beständigen Thiazolidinyl-3-essigsäureäthylestern hydrieren.Die ⁴-Thiazolin-3-yl-essigsäureäthylester, die in 2-Stellung monosubstituiert sind, erleiden beim Erhitzen auf etwa 150° Thermolyse, wobei es unter Abspaltung von Essigsäureäthylester zur Bildung von Thiazolen kommt.

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-Mercapto ketones react with aldehydes (or cyclohexanone) and esters of -amino acids (or their hydrochlorides) or with theSchiff bases formed by these compounds to form esters of ⁴-thiazolin-3-ylacetic acids. These esters can be hydrogenated with formic acid to the corresponding thiazolidines.Esters of ⁴-thiazolinylacetic acids which have a H atom in position 2, can be pyrolysed by heating at about 150° to form the corresponding thiazoles and alkyl acetate. These reactions are illustrated for the case of 2-mercaptopentan-3-on as -mercapto ketone, glycinethylester as amine component and various aldehydes or cyclohexanone as oxo compound.

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60. Mitt.:F. Asinger, W. Schäfer, H. Kersten undA. Saus, Mh. Chem.98, 1841 (1967).

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Teil der DiplomarbeitC. Dudeck, Techn. Hochschule Aachen, 1967.     

Zur Kenntnis der Reaktionsfähigkeit alkylsubstituierter Thiomorpholine, 1. Mitt.

Zusammenfassung Die Darstellung einigerMannichbasen (3 a-f) bzw.Mannich-basen-hydrochloride (2 a-f) und zahlreicher s-Triazin-Derivate (4 a-d, 5 a–m, 6 a–w, 7 a–e, 8 a–d, und9 a–l) auf Basis des unsubstituierten Thiomorpholins (1 a) sowie C-mono-[2-Methylthiomorpholin (1 b) und 2-Äthylthiomorpholin (1 c)] und C-dialkylierter Thiomorpholine [2-Methyl-3-äthylthiomorpholin (1 d)] wird beschrieben.

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Concomitant action of elementary sulfur and gaseous ammonia upon ketones, LXXIX: On the reactivity of alkyl substituted thiomorpholines, I

The preparation of someMannichbases (3 a-f) andMannich base hydrochlorides (2 a-f), resp., and numerous s-triazine derivatives (4 a-d, 5 a–m, 6 a–w, 7 a–e, 8 a–d, and9 a–l) based upon unsubstituted thiomorpholine (1 a) as well as C-mono-[2-methylthiomorpholine (1 b) and 2-ethylthio-morpholine (1 c)] and C-dialkylated thiomorpholines [2-methyl-3-ethylthiomorpholine (1 d)] is described.

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HerrE. Wilms dankt der Deutschen Texaco AG. für die Gewährung eines Stipendiums herzlichst.     

Laser ablation in a running hall effect thruster for space propulsion

Hall Effect Thrusters (HETs) are promising electric propulsion devices for the station-keeping of geostationary satellites (more than 120 in orbit to date). Moreover, they can offer a cost-effective solution for interplanetary journey, as proved by the recent ESA SMART-1 mission to the Moon. The main limiting factor of the HETs lifetime is the erosion of the annular channel ceramics walls. In order to provide a better understanding of the energy deposition on the insulated walls, a laser irradiation study has been carried out on a PPS100-ML thruster during its run in the PIVOINE-2G ground test facility (CNRS Orléans, France). Two distinct approaches have been followed: continuous wave fiber laser irradiation (generation of thermal defects) and nanosecond pulsed laser ablation (generation of topological defects). The irradiated zones have been monitored in situ by IR thermography and optical emission spectroscopy and further investigated ex situ by scanning electron microscopy and profilometry.     

First nucleation steps during deposition of SiO2 thin films by plasma enhanced chemical vapour deposition

The initial nucleation stages during deposition of SiO₂ by remote plasma enhanced chemical vapour deposition (PECVD) have been monitored by XPS inelastic peak shape analysis. Experiments have been carried out on two substrates, a flat ZrO₂ thin film and a silicon wafer with a native silicon oxide layer on its surface. For the two substrates it is found that PECVD SiO₂ grows in the form of islands. When the SiO₂ particles reach heights close to 10 nm they coalesce and cover completely the substrate surface. The particle formation mechanism has been confirmed by TEM observation of the particles grown on silicon substrates. The kinetic Monte Carlo simulation of the nucleation and growth of the SiO₂ particles has shown that formation of islands is favoured under PECVD conditions because the plasma species may reach the substrate surface according to off-perpendicular directions. The average energy of these species is the main parameter used to describe their angular distribution function, while the reactivity of the surface is another key parameter used in the simulations.     

Plasma-wall interactions in DC discharges and sheath of Langmuir probes

The plasma-wall interactions in various DC discharges and sheath of Langmuir probe are analyzed and discussed. The methods of their investigations are discussed including fluid and PIC MC. Various assumptions used in fluid models e.g. plasma neutrality, Bohm criterion, Boltzmann electrons approximation, etc. are analyzed. Ion heating and electron cooling effect at the DC plasma wall is discussed and explained. Langmuir probes measurements in high-temperature and ion thruster plasma are analyzed. The secondary electron emission influences the IV characteristic of Langmuir probe especially at positive voltages. However, only elastic reflection processes really contribute significantly to the probe current. The elastic SEE processes reflect electrons from probe with the same relatively high speed. It was observed that the axial magnetic field influences probe characteristics and floating potential more significantly than radial field. The axial field deflects all electrons approaching probe.     

Al2O3 ceramics under high-fluence irradiation: plasma plume dynamics through space- and time-resolved optical emission spectroscopy

The expansion in vacuum of the plume generated by the UV ablation of a LiYF₄ crystal was analysed as a function of several parameters: distance from the target along the plume axis, laser fluency and angular dislocation with respect to the plume axis. The study was carried out by the optical time of flight technique. Time-resolved signals of the optical emission of the neutral as well as ionised species in the plume were recorded and analysed for different experimental situations. The most probable velocity for each species was calculated and confirmed by the Maxwell-Boltzmann distribution fits of the relative emission temporal profiles. An angular distribution of the ablated species could also be provided.     

Thermal evolution of defects produced by implantation of H, D and He in Silicon

Despite decades of study, voids in silicon produced by implantation of H or He followed by annealing continue to be a topic of interest. There are two key applications: gettering of heavy metal impurities, and “ion cutting” used in silicon-on-insulator fabrication. Positron annihilation is one of the few techniques that can probe the vacancies and vacancy clusters that are the precursors to void formation. Data from recent studies will be discussed, including (I) isotopic substitution, in which comparisons of H vs. D implantation permit examination of the impact of primary point defects vs. chemical effects. Remarkable differences exist between H and D in blistering of silicon - ion doses 2-3 times higher are required for blistering with D than with H, despite a higher rate of primary defect production for D; (II) the effect of annealing temperature ramp-rate, in which we show that ramp-rate has a significant impact on residual defects, despite which it is so disregarded as to often be omitted from published reports; and (III) comparisons with electron microscopy which suggest that positron annihilation can be insensitive to large voids. In these studies, positron annihilation augments data from techniques including ion channelling, Raman scattering and electron microscopy; the suite of techniques allows elucidation of the interplay between implanted impurities and the vacancies and interstitials created by implantation.     

Modification of silicon waveguide structures using ion implantation induced defects

The structure of re-crystallized silicon films is investigated using transmission electron microscopy, spectroscopic ellipsometry and positron annihilation spectroscopy. Samples were prepared via amorphization of the silicon overlayer of silicon-on-insulator substrates, and subsequent thermal annealing. For an annealing temperature of 650 °C we show that the silicon film has a poly-crystalline structure. Its refractive index measured at 1550 nm is comparable to that of crystalline silicon following re-crystallization at 750 °C. Positron measurements indicate a high concentration of open-volume point defects in the re-crystallized films. We discuss the potential importance of these structures with regard to defect engineering for silicon photonic devices.     

Effect of Eshelby twist on core structure of screw dislocations in molybdenum: atomic structure and electron microscope image simulations

This paper addresses the question as to whether the core structure of screw dislocations in Mo in the bulk can be obtained from high-resolution electron microscopy (HREM) images of such dislocations viewed end-on in a thin foil. Atomistic simulations of the core structure of screw dislocations in elastically anisotropic Mo were carried out using bond order potentials. These simulations take account automatically of the effects of the surface relaxation displacements (anisotropic Eshelby twist). They show that the differential displacements of the atoms at the surface are different with components perpendicular to the Burgers vector about five times larger than those in the middle of the foil, the latter being characteristic of the bulk. Nye tensor plots show that the surface relaxation stresses strongly affect the incompatible distortions. HREM simulations of the computed structure reflect the displacements at the exit surface, modified by interband scattering and the microscope transfer function. Nye tensor plots obtained from the HREM images show that interband scattering also affects the incompatible distortions. It is concluded that it would be very difficult to obtain information on the core structure of screw dislocations in the bulk Mo from HREM images, even under ideal experimental conditions, and that quantitative comparisons between experimental and simulated images from assumed model structures would be essential.