ALBERT

Notes: Spectroscopic Investigations on the Acidity of O,O′-Dithiophosphoric Acid Esters in Nonpolar Aprotic Solvents

Notes: Me3SiCl bildet mit N-Methylimidazol (NMI) eine bei Raumtemperatur beständige, kristalline 1:1 Verbindung. Nach der Röntgenstrukturanalyse entsteht unter Spaltung der Si—Cl-Bindung und Anlagerung eines NMI-Rings eine Verbindung ionischer Struktur [Me3Si(NMI)]+Cl- 1. Die Reaktion von Me2HSiCl mit NMI (Molverhältnis 1:2) führt unter Spaltung der Si—Cl-Bindung und Koordination von zwei NMI-Ringen zur Verbindung [Me2HSi(NMI)2]+Cl- 2. Bei der analogen Umsetzung von Me2SiCl2 mit NMI (Molverhältnis 2:1) entsteht eine Verbindung, die Me2SiCl2 und NMI im Molverhältnis 1:2 enthält. Bei der Sublimation werden Einkristalle der Verbindung [Me2Si(NMI)3]2+ 2 Cl-· NMI 3 erhalten.

Notes: One of the basic prerequisites for rational and high quality production of plastic parts is a tool layout tailored to the production process. To date, both design and construction have generally been based on values acquired by experience. This first, necessitates highly qualified personnel and second, involves what is frequently time consuming and costly finishing work. Experience acquired so far with computer-aided layout of injection molds shows that even a designer with little experience reaches the target more quickly and more reliably. At the same time he is able to draw on the results of intricate calculation and simulation methods which he was unable to apply in the past for reasons of time alone. This paper thus sets out the possibilities currently open and the experience available for computer-aided mold layout. The chief point of focus here is a system for the layout of injection molds. Working on from this system, however, the potentials for computer application are presented for blow mold- and foaming mold-design. After finding the mold principle, mold layout essentially divides up into two major areas, namely dimensioning calculations (CAE) and compilation of production documents (CAD). In dimensioning, the different functional elements of the mold are calculated. The aids that have been developed and the potentials of computer-aided dimensioning are presented with examples from the fields of rheological, thermal, and mechanical mold layout. Computer-aided rheological layout divides up into two steps. The first gives information on qualitative filling behavior (filling picture, flow paths) and the second provides quantitative results (pressures, shear stresses, temperatures). Computer-aided thermal layout similarly divides up into part steps. These are a rough overall energy balance, a rough layout of the tempering system, a segmented layout, and a homogeneity check, which involves simulating the temperature conditions in the mold by means of difference methods. When it comes to mechanical layout of the mold, programs are available for deformation calculations on basic cases and these will frequently be sufficient. For more complex cases of loading and deformation, a finite element program is used. Graphic data processing units can be used to supply extra facilities - first, to provide an aid for the simulation programs in dimensioning and second, to rationalize the compilation of the production documents. An illustration of a CAD workplace is given, incorporating the necessary computer configuration and peripherals. Compiling production documents is essentially a problem of variant design. The variants in this case are the individual components of the mold and a number of standardized accessories that can be called up as “standardized components.” The mold cavity, however, always has to be a free design. All programs are dialogue driven and are in a standardized manner so that even designers with no data processing experience can use the computer as an aid. The CAD/CAE system presented duly fulfils all these requirements. It allows the designer, at a single computer work station, to carry out both simulation and dimensioning calculations, to obtain information on material data, and to compile production documents on the basis of variant and free design. This provides the designer with a readily manageable aid and makes a considerable contribution towards improving the design result. Finally, the capacity of different computer concepts and the CAE/CAD/CAM systems on the market are discussed. For the future it will be possible to establish a computer-aided link between the different areas of design, from development of the molded part, via mold design and production, through setting the processing parameters of the injection molding machine.

Notes: As masked 1,3-dicarbonyl compounds, 1,1-dioxo-2H-1,2-thiazine-4-carbaldehydes (2a-e, 7) undergo ring transformations with nucleophilic hydrazines to produce 4-[1-methyl-2-(arylsulfamoyl)vinyl]pyrazoles (9a-i). For 9h, an X-ray structural analysis is reported. With less nucleophilic semicarbazide and p-nitrophenylhydrazine the hydrazones (11a, b) were isolated. The carbaldehydes 2a-e, 7 and 8a, b were synthesized by formylation of the 1,1-dioxo-2H-1,2-thiazines 1a-e, 5 and 6a, b with dichloromethyl methyl ether/TiCl4. In the case of 1a-e mixtures of 4- and 6-carbaldehydes (2a-e/3a-e) were obtained, which, however, could be used for the synthesis of pyrazoles.

Notes: Structure of Basic Zinc-O,O′-2-ethylhexyldithiophosphates in Apolar Aprotic SolventsA sample of technically used Zinc-O,O′-2-ethylhexyldithiophosphate enriched by basic Zinc-O,O′-2-ethylhexyldithiophosphates (i-C8-ZnDTP) was investigated in aprotic apolar solvents by integral and structure specific analytical methods. The results let us suppose that the structure of basic i-C8-ZnDTP in apolar aprotic solvents can be described by an Zn3-complex of type ZnO(ZnDTP)2.

Notes: Bis-(1-chloro-3-phenoxy-prop-2-yl)-sulfanes - Nucleophilic Displacement and Regiochemistry. Separation and Assignment of Diastereomers. Synthesis of Diastereomerically Pure TrithiacyclesThe title compounds 1 were substituted by a series of O-, N- and S-nucleophiles (H2O solvolysis, AgOAc, NaN3, KSCN, NaSPh, thiourea). A strong tendency to β-elimination of HCl depending on the kind of the attacking nucleophile was found. In most cases no regioisomerization could be detected in the isolated products of the nucleophilic displacement. Best results were obtained with sulfur nucleophiles. The separation of the diastereomeric mixture of the p-kresyl derivative 1b into the individual diastereomers 1bA and 1bB in a preparative scale was achieved. These 3-thia-1,5-dichlorides and several products of substitution could be assigned to the meso- or (±)-form by examination of the stereochemistry and symmetry of the corresponding sulfoxides.The 1,5-dimercapto derivatives 8 are convenient as structural units for the synthesis of diastereomerically pure cis- or trans-disubstituted trithiacycles e.g. 15bA, 15bB. The (±)-form of the 4,6-disubstituted 2,5,8-trithia[9]-(2,6)-pyridinophane 16bA was characterized by X-ray crystal structure determination.

Notes: Untersuchungen zum Schwingungsrißkorrosionsverhalten des weichmartensitischen Stahles X4CrNiMo 16 5 1 ESU und des Martensitaushärters X5CrNiCuNb 17 4 PH in NaCl-haltigen Lösungen im Temperaturbereich zwischen 20° und 150 °C. Bestimmung der Korrosionseigenschaften und der Rißeinleitungsmechanismen. Vergleich zwischen einem Elektro-Schlacke-umgeschmolzenen Weichmartensiten und einer Charge, die nicht ESU-behandelt worden ist. Mikrofraktographische Bruch- und Rißverlaufsbeurteilung zur Deutung der Versuchsergebnisse.Die fraktographischen Untersuchungen ergaben, daß bei dem hochreinen weichmartensitischen und dem martensitaushärtenden Stahl oxidische Einschlüsse bei der Rißeinleitung keine Rolle spielen. Beim martensitaushärtenden Stahl wurden Cu-haltige Einschlüsse im Rißausgangsbereich nachgewiesen. In konzentrierter Salzlösung trat bei beiden Stählen Lochfraß auf, der rißinitiierend wirkte.