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  • 1
    Publication Date: 2019-01-29
    Description: We consider an optimal control problem from hyperthermia treatment planning and its barrier regularization. We derive basic results, which lay the groundwork for the computation of optimal solutions via an interior point path-following method. Further, we report on a numerical implementation of such a method and its performance at an example problem.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 2
    Publication Date: 2016-06-09
    Description: Optical technologies are ubiquitously used in hi-tech devices. As a common feature of such devices one finds structures with dimensions in the order of the wavelength of the used light. To design and produce such devices, the wave nature of light must be taken into account. Accordingly, robust simulation tools are required which are based on rigorously solving Maxwell's equations, the governing equations of light propagation within macroscopic media. This thesis contributes to the modeling and the numerical computation of light scattering problems: Light scattering problems are typically posed on the entire space. The Perfectly-Matched -Layer method (PML) is widely used to restrict the simulation problem onto a bounded computational domain. We propose an adaptive PML method which exhibits a good convergence even for critical problems where standard PML implementations fail. Besides the computation of the near field, that is the electromagnetic field within the computational domain, it is of major interest to evaluate the electromagnetic field in the exterior domain and to compute the far field. So far, this was numerically only possible for simple geometries such as homogeneous exterior domains or layered media. To deal with more complicated devices, for example with waveguide inhomogeneities, we develop an evaluation formula based on the PML solution which allows for an exterior domain field evaluation in a half space above the device. Finally, we generalize the PML method to problems with multiply structured exterior domains. The term “multiply structured exterior domain” is defined in this thesis and means that the exterior domain exhibits several half-infinite structures. Mathematically, this gives rise to various complications. For example, no analytical solutions to Maxwell's equations for standard light sources are available in the exterior domain, which are needed to describe the incoming field in a light scattering problem. To tackle this we propose a new light scattering problem formulation which fits well into the PML method framework and which may be regarded as an extension of classical contributions by Sommerfeld, Wiener and Hopf. An exterior domain evaluation formula for multiply structured exterior domains with an extended illumination is derived as well.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 3
    Publication Date: 2020-08-05
    Description: We introduce the coolest path problem, which is a mixture of two well-known problems from distinct mathematical fields. One of them is the shortest path problem from combinatorial optimization. The other is the heat conduction problem from the field of partial differential equations. Together, they make up a control problem, where some geometrical object traverses a digraph in an optimal way, with constraints on intermediate or the final state. We discuss some properties of the problem and present numerical solution techniques. We demonstrate that the problem can be formulated as a linear mixed-integer program. Numerical solutions can thus be achieved within one hour for instances with up to 70 nodes in the graph.
    Keywords: ddc:510
    Language: English
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  • 4
    Publication Date: 2021-08-05
    Description: Given a general mixed integer program (MIP), we automatically detect block structures in the constraint matrix together with the coupling by capacity constraints arising from multi-commodity-flow formulations. We identify the underlying graph and generate cutting planes based on cuts in the detected network. Our implementation adds a separator to the branch-and-cut libraries of SCIP and CPLEX. We make use of the complemented mixed integer rounding framework (cMIR) but provide a special purpose aggregation heuristic that exploits the network structure. Our separation scheme speeds-up the computation for a large set of MIPs coming from network design problems by a factor of two on average.
    Keywords: ddc:510
    Language: English
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  • 5
    Publication Date: 2022-03-14
    Description: Pseudo-Boolean problems lie on the border between satisfiability problems, constraint programming, and integer programming. In particular, nonlinear constraints in pseudo-Boolean optimization can be handled by methods arising in these different fields: One can either linearize them and work on a linear programming relaxation or one can treat them directly by propagation. In this paper, we investigate the individual strengths of these approaches and compare their computational performance. Furthermore, we integrate these techniques into a branch-and-cut-and-propagate framework, resulting in an efficient nonlinear pseudo-Boolean solver.
    Keywords: ddc:510
    Language: English
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  • 6
    Publication Date: 2020-08-05
    Description: Every day, millions of people are transported by buses, trains, and airplanes in Germany. Public transit (PT) is of major importance for the quality of life of individuals as well as the productivity of entire regions. Quality and efficiency of PT systems depend on the political framework (state-run, market oriented) and the suitability of the infrastructure (railway tracks, airport locations), the existing level of service (timetable, flight schedule), the use of adequate technologies (information, control, and booking systems), and the best possible deployment of equipment and resources (energy, vehicles, crews). The decision, planning, and optimization problems arising in this context are often gigantic and “scream” for mathematical support because of their complexity. This article sketches the state and the relevance of mathematics in planning and operating public transit, describes today’s challenges, and suggests a number of innovative actions. The current contribution of mathematics to public transit is — depending on the transportation mode — of varying depth. Air traffic is already well supported by mathematics. Bus traffic made significant advances in recent years, while rail traffic still bears significant opportunities for improvements. In all areas of public transit, the existing potentials are far from being exhausted. For some PT problems, such as vehicle and crew scheduling in bus and air traffic, excellent mathematical tools are not only available, but used in many places. In other areas, such as rolling stock rostering in rail traffic, the performance of the existing mathematical algorithms is not yet sufficient. Some topics are essentially untouched from a mathematical point of view; e.g., there are (except for air traffic) no network design or fare planning models of practical relevance. PT infrastructure construction is essentially devoid of mathematics, even though enormous capital investments are made in this area. These problems lead to questions that can only be tackled by engineers, economists, politicians, and mathematicians in a joint effort. Among other things, the authors propose to investigate two specific topics, which can be addressed at short notice, are of fundamental importance not only for the area of traffic planning, should lead to a significant improvement in the collaboration of all involved parties, and, if successful, will be of real value for companies and customers: • discrete optimal control: real-time re-planning of traffic systems in case of disruptions, • model integration: service design in bus and rail traffic. Work on these topics in interdisciplinary research projects could be funded by the German ministry of research and education (BMBF), the German ministry of economics (BMWi), or the German science foundation (DFG).
    Keywords: ddc:510
    Language: English
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  • 7
    Publication Date: 2020-08-05
    Description: The steel mill slab design problem from the CSPLib is a binpacking problem that is motivated by an application of the steel industry and that has been widely studied in the constraint programming community. Recently, several people proposed new models and methods to solve this problem. A steel mill slab library was created which contains 380 instances. A closely related binpacking problem called multiple knapsack problem with color constraints, originated from the same industrial problem, were discussed in the integer programming community. In particular, a simple integer programming for this problem has been given by Forrest et al. [3]. The aim of this paper is to bring these different studies together. Moreover, we adopt the model of [3] for the steel mill slab problem. Using a state of the art integer program solver, this model is capable to solve all instances of the steel mill slab library, mostly in less than one second, to optimality. We improved, thereby, the solution value of 76 instances.
    Keywords: ddc:510
    Language: English
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  • 8
    Publication Date: 2020-08-05
    Description: Nowadays most data networks use shortest path protocols such as OSPF or IS-IS to route traffic. Given administrative routing lengths for the links of a network, all data packets are sent along shortest paths with respect to these lengths from their source to their destination. One of the most fundamental problems in planning shortest path networks is to decide whether a given set of routing paths forms a valid routing and, if this is not the case, to find a small subset of the given paths that cannot be shortest paths simultaneously for any routing lengths. In this paper we show that it is NP-hard to approximate the size of the smallest shortest path conflict by a factor less than 7/6.
    Keywords: ddc:510
    Language: English
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  • 9
    Publication Date: 2020-08-05
    Description: The Vehicle Positioning Problem (VPP) consists of the assignment of vehicles (buses, trams or trains) of a public transport or railway company to parking positions in a depot and to timetabled trips. Such companies have many different types of vehicles, and each trip can be performed only by vehicles of some of these types. These assignments are non-trivial due to the topology of depots. The parking positions are organized in tracks, which work as one- or two-sided stacks or queues. If a required type of vehicle is not available in the front of any track, shunting movements must be performed in order to change vehicles' positions, which is undesirable and should be avoided. In this text we present integer linear and non-linear programming formulations for some versions of the problem and compare them from a theoretical and a computational point of view.
    Keywords: ddc:510
    Language: English
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  • 10
    Publication Date: 2020-03-11
    Description: The understanding of geometric structures and dynamical properties of molecular conformations gives insight into molecular long-term behavior. The identification of metastable conformations together with their life times and transition patterns is the intention of conformation dynamics. Conformation dynamics is a multi-scale approach that leads to a reduced description of the dynamical system in terms of a stochastic transition probability matrix. The present thesis deals with the error analysis of computed matrices and the resulting matrix functions. Since conformational membership vectors, as they are computed by the Robust Perron Cluster Analysis (PCCA+), form an invariant subspace of the transition matrix, subspace-based error estimators are of particular interest. The decomposition of the state space into basis functions and the approximation of integrals by Monte-Carlo quadrature give rise to row-wise correlated random matrices, for which stochastic norms are computed. Together with an appropriate statistical model for the distribution of matrix rows, this allows for the calculation of error bounds and error distributions of the invariant subspace and other variables of interest. Equilibration of errors among the basis functions can be achieved by enhanced sampling in regions where the trajectories are mixing slowly. Hierarchical refinement of such basis functions systematically improves the clustering into metastable conformations by reducing the error in the corresponding invariant subspace. These techniques allow for an evaluation of simulation results and pave the way for the analysis of larger molecules. Moreover, the extension of PCCA+ to non-reversible Markov chains, verified by the corresponding perturbation theory, and the modification of the objective function for the case of soft membership vectors represent a further generalization of the clustering method, thus continuing the development from PCCA over PCCA+ to PCCA++. The methods developed in this thesis are useful for but not limited to conformation dynamics. In fact, they are applicable to a broader class of problems which combine domain decomposition with Monte-Carlo quadrature. Possible application areas may include the chemical master equation or quantum dynamical systems.
    Description: Das Verständnis von geometrischen Strukturen und dynamischen Eigenschaften molekularer Konformationen ist essentiell für die Vorhersage des Langzeitverhaltens von Molekülen. Die Identifikation metastabiler Konformationen sowie die Bestimmung von Übergangswahrscheinlichkeiten und Haltezeiten sind Bestandteil der Konformationdynamik. Dabei handelt es sich um eine Mehrskalenmethode, die auf eine reduzierte Beschreibung des Systems mittels einer stochastischen Übergangsmatrix führt. In der vorliegenden Dissertation wurde untersucht, wie man die Genauigkeit der Matrizen sowie der daraus berechneten Größen quantifizieren kann. Im Mittelpunkt stehen dabei Fehlerschätzer für den invarianten Unterraum, da die rechten Eigenvektoren als Grundlage der Robusten Perron Cluster Analyse (PCCA+) zur Identifizierung der metastabilen Konformationen dienen. Die Zerlegung des Zustandsraumes in Basisfunktionen sowie die Approximation der Matrixeinträge mittels Monte-Carlo-Quadratur führen zu zeilenweise korrelierten Zufallsmatrizen. Mit Hilfe einer stochastischen Norm sowie einem geeigneten statistischen Modell für die Verteilung der Matrixzeilen können u.a. Fehlerschranken und -verteilungen für den invarianten Unterraum brechnet werden. Eine Equilibrierung des Fehlers zwischen den Basisfunktionen kann durch erweitertes Sampling in solchen Regionen erreicht werden, in denen die Trajektorien nur langsam mischen.Eine hierarchische Zerlegung dieser Basisfunktionen verbessert systematisch die Zerlegung in metastabile Konformationen, indem sie den Fehler im invarianten Unterraum reduziert. Diese Techniken gestatten eine Evaluierung der Simulationsergebnisse und ebnen den Weg zur Behandlung komplexerer Moleküle. Desweiteren wurden Verallgemeinerungen der PCCA+ untersucht. Die Erweiterung der PCCA+ auf nicht-reversible Markov-Ketten sowie die Modifizierung der Zielfunktion für den Fall der weichen Clusterung setzen die Entwicklung von der PCCA über PCCA+ zu PCCA++ fort. Somit können neue Anwendungsfelder für dieses Cluster-Verfahren erschlossen werden. Die Methoden wurden zwar in Rahmen der Konformationsdynamik entwickelt, jedoch lassen sie sich auf eine weite Problemklasse anwenden, in der Gebietszerlegungsverfahren mit Monte-Carlo-Quadratur kombiniert werden. Mögliche Anwendungsgebiete umfassen die chemische Master-Gleichung oder quantenchemische Systeme.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 11
    Publication Date: 2020-08-05
    Description: The Vehicle Positioning Problem (VPP) is a classical combinatorial optimization problem in public transport planning. A number of models and approaches have been suggested in the literature, which work for small problems, but not for large ones. We propose in this article a novel set partitioning model and an associated column generation solution approach for the VPP. The model provides a tight linear description of the problem. The pricing problem, and hence the LP relaxation itself, can be solved in polynomial resp. pseudo-polynomial time for some versions of the problems.
    Keywords: ddc:510
    Language: English
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  • 12
    Publication Date: 2020-08-05
    Description: Since the initial application of mathematical optimisation methods to mine planning in 1965, the Lerchs-Grossmann algorithm for computing the ultimate pit limit, operations researchers have worked on a variety of challenging problems in the area of open pit mining. This thesis focuses on the open pit mining production scheduling problem: Given the discretisation of an orebody as a block model, determine the sequence in which the blocks should be removed from the pit, over the lifespan of the mine, such that the net present value of the mining operation is maximised. In practise, when some material has been removed from the pit, it must be processed further in order to extract the valuable elements contained therein. If the concentration of valuable elements is not sufficiently high, the material is discarded as waste or stockpiled. Realistically-sized block models can contain hundreds of thousands of blocks. A common approach to render these problem instances computationally tractable is the aggregation of blocks to larger scheduling units. The thrust of this thesis is the investigation of a new mixed-integer programming formulation for the open pit mining production scheduling problem, which allows for processing decisions to be made at block level, while the actual mining schedule is still computed at aggregate level. A drawback of this model in its full form is the large number of additional variables needed to model the processing decisions. One main result of this thesis shows how these processing variables can be aggregated efficiently to reduce the problem size significantly, while practically incurring no loss in net present value. The second focus is on the application of lagrangean relaxation to the resource constraints. Using a result of Möhring et al. (2003) for project scheduling, the lagrangean relaxation can be solved efficiently via minimum cut computations in a weighted digraph. Experiments with a bundle algorithm implementation by Helmberg showed how the lagrangean dual can be solved within a small fraction of the time required by standard linear programming algorithms, while yielding practically the same dual bound. Finally, several problem-specific heuristics are presented together with computational results: two greedy sub-MIP start heuristics and a large neighbourhood search heuristic. A combination of a lagrangean-based start heuristic followed by a large neighbourhood search proved to be effective in generating solutions with objective values within a 0.05% gap of the optimum.
    Keywords: ddc:510
    Language: English
    Type: masterthesis , doc-type:masterThesis
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  • 13
    Publication Date: 2019-01-29
    Description: In dieser Arbeit wird ein neuer Ansatz zur Modellierung von thermal signifikanten Gefäßsträngen im Hyperthermie-Kontext betrachtet. Ausgehend von einer Konvektions-Diffusions-Gleichung wird durch Reskalierung des Massenflussterms eine Reduktion des Adergebietes auf eine 1D-Struktur erreicht. Nach numerischen Vorbetrachtungen wird die Grenzgleichung innerhalb einer verallgemeinerten Sobolev-Algebra formuliert. Die Untersuchung der Lösungsfamilie in klassischen Funktionenräumen zeigt, dass deren schwacher Grenzwert die Lösung der korrespondierenden Diffusions-Gleichung ist. Die Diskretisierung einer formalen Grenzgleichung mit Linienstromanteil stellt jedoch eine gute Approximation an die Diskretisierung des ursprünglichen Problems dar, wenn man die lokale Maschenweite an die Gefäßradien koppelt und bei erhöhtem Genauigkeitsbedarf auf ein vollständiges 3D-Modell umschaltet.
    Keywords: ddc:510
    Language: German
    Type: masterthesis , doc-type:masterThesis
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  • 14
    Publication Date: 2022-03-14
    Description: We present Undercover, a primal heuristic for mixed-integer nonlinear programming (MINLP). The heuristic constructs a mixed-integer linear subproblem (sub-MIP) of a given MINLP by fixing a subset of the variables. We solve a set covering problem to identify a minimal set of variables which need to be fixed in order to linearise each constraint. Subsequently, these variables are fixed to approximate values, e.g. obtained from a linear outer approximation. The resulting sub-MIP is solved by a mixed-integer linear programming solver. Each feasible solution of the sub-MIP corresponds to a feasible solution of the original problem. Although general in nature, the heuristic seems most promising for mixed-integer quadratically constrained programmes (MIQCPs). We present computational results on a general test set of MIQCPs selected from the MINLPLib.
    Keywords: ddc:510
    Language: English
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  • 15
    Publication Date: 2020-08-05
    Description: We consider a system with Poisson arrivals and i.i.d. service times. The requests are served according to the state-dependent processor sharing discipline, where each request receives a service capacity which depends on the actual number of requests in the system. The linear systems of PDEs describing the residual and attained sojourn times coincide for this system, which provides time reversibility including sojourn times for this system, and their minimal non negative solution gives the LST of the sojourn time $V(\tau)$ of a request with required service time $\tau$. For the case that the service time distribution is exponential in a neighborhood of zero, we derive a linear system of ODEs, whose minimal non negative solution gives the LST of $V(\tau)$, and which yields linear systems of ODEs for the moments of $V(\tau)$ in the considered neighborhood of zero. Numerical results are presented for the variance of $V(\tau)$. In case of an M/GI/2-PS system, the LST of $V(\tau)$ is given in terms of the solution of a convolution equation in the considered neighborhood of zero. For bounded from below service times, surprisingly simple expressions for the LST and variance of $V(\tau)$ in this neighborhood of zero are derived, which yield in particular the LST and variance of $V(\tau)$ in M/D/2-PS.
    Keywords: ddc:510
    Language: English
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  • 16
    Publication Date: 2020-12-11
    Description: Eigentlich war der erste Autor nur zu einem Grußwort zur Tagung „GML² 2009 - Grundfragen Multi¬medialen Lehrens und Lernens“ eingeladen. Daraus wurde ein E-Learning-bezogener Vortrag, der – basierend auf Erfahrungen im Fach Mathematik – einen kritischen Blick auf die E-Learning-Szene in Deutschland wirft und diese mit entsprechenden Aktivitäten weltweit vergleicht. Dies ist die in seinen mathematischen Teilen gekürzte, in den E-Learning-Anteilen ein wenig erweiterte schriftliche Fassung des Vortrags. Der Artikel stammt nicht von E-Learning-Spezialisten sondern von Personen, die sich seit fast zwanzig Jahren mit elektronischer Information und Kommunikation (kurz: IuK) – insbesondere in der Mathematik – beschäftigen. Nach einer Definition von Michael Kerres kennzeichnet der Begriff E-Learning (electronic learning – elektronisch unterstütztes Lernen) alle Formen von Lernen, bei denen digitale Medien für die Präsentation und Distribution von Lernmaterialien und/oder zur Unterstützung zwischenmenschlicher Kommunikation zum Einsatz kommen, siehe z.B. http://de.wikipedia.org/wiki/E-Learning. IuK und E-Learning haben nach dieser Begriffsbildung viele Berührungspunkte. Deswegen wagen wir es, unsere positiven und negativen Erfahrungen im Bereich IuK in diesem Eröffnungsvortrag zu berichten, einige Entwicklungslinien zu vergleichen und eine eigene Kurzversion der Definition von E-Learning (besser E-Teaching and -Learning) voranzustellen: „Lehren und Lernen mit Unterstützung elektronischer Hilfsmittel“.
    Keywords: ddc:510
    Language: German
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  • 17
    Publication Date: 2020-08-05
    Description: Telecommunication transport networks consist of a stack of technologically different subnetworks, so-called layers, which are strongly interdependent. For example, one layer may correspond to an Internet (IP) backbone network whose links are realized by lightpath connections in an underlying optical fiber layer. To ensure that the network can fulfill its task of routing all communication requests, the inter-layer dependencies have to be taken into account already in the planning phase of the network. This is particularly important with survivability constraints, where connections in one layer have to be protected against cable cuts or equipment failures in another layer. The traditional sequential planning approach where one layer is optimized after the other cannot properly take care of the inter-layer dependencies; this can only be achieved with an integrated planning of several network layers at the same time. This thesis provides mathematical models and algorithmic techniques for the integrated optimization of two network layers with survivability constraints. We describe a multi-layer network design problem which occurs in various technologies, and model it mathematically using mixed-integer programming (MIP) formulations. The presented models cover many important practical side constraints from different technological contexts. In contrast to previous models from the literature, they can be used to design large two-layer networks with survivability requirements. We discuss modeling alternatives for various aspects of a multi-layer network and compare different routing formulations under multi-layer survivability constraints. We solve our models using a branch-and-cut-and-price approach with various problemspecific enhancements. This includes a presolving technique based on linear programming to reduce the problem size, combinatorial and sub-MIP-based primal heuristics to compute feasible network configurations, cutting planes which take the multi-layer survivability constraints into account to improve the lower bound on the optimal network cost, and column generation to generate flow variables dynamically during the algorithm. We develop techniques to speed up computations in a Benders decomposition approach and compare this approach to the standard formulation with a single MIP. We use the developed techniques to design large survivable two-layer networks by means of linear and integer programming methods. On realistic test instances with up to 67 network nodes and survivability constraints, we investigate the algorithmic impact of our techniques and show how to use them to compute good network configurations with quality guarantees. Most of the smaller test instances with up to 17 nodes can be solved to near-optimality. Moreover, we can compute feasible solutions and dual bounds even for large networks with survivability constraints, which has not been possible before.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 18
    Publication Date: 2020-08-05
    Description: In the simplex algorithm, solving linear systems with the basis matrix and its transpose accounts for a large part of the total computation time. We investigate various methods from modern numerical linear algebra to improve the computation speed of the basis updates arising in LPs. The experiments are executed on a large real-world test set. The most widely used solution technique is sparse LU factorization, paired with an updating scheme that allows to use the factors over several iterations. Clearly, small number of fill-in elements in the LU factors is critical for the overall performance. Using a wide range of LPs we show numerically that after a simple permutation the non-triangular part of the basis matrix is so small, that the whole matrix can be factorized with (relative) fill-in close to the optimum. This permutation has been exploited by simplex practitioners for many years. But to our knowledge no systematic numerical study has been published that demonstrates the effective reduction to a surprisingly small non-triangular problem, even for large scale LPs. For the factorization of the non-triangular part most existing simplex codes use some variant of dynamic Markowitz pivoting, which originated in the late 1950s. We also show numerically that, in terms of fill-in and in the simplex context, dynamic Markowitz is quite consistently superior to other, more recently developed techniques.
    Keywords: ddc:510
    Language: English
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  • 19
    Publication Date: 2020-03-11
    Description: We compute expectation values for the solution of the nuclear Schrödinger equation. The proposed particle method consists of three steps: sampling of the initial Wigner function, classical transport of the sampling points, weighted phase space summation for the final computation of the expectation values. The Egorov theorem guarantees that the algorithm is second order accurate with respect to the semiclassical parameter. We present numerical experiments for a two-dimensional torsional potential with three different sets of initial data and for a six-dimensional Henon-Heiles potential. By construction, the computing times scale linearly with the number of initial sampling points and range between three seconds and one hour.
    Keywords: ddc:510
    Language: English
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  • 20
    Publication Date: 2022-03-14
    Description: This paper discusses how to build a solver for mixed integer quadratically constrained programs (MIQCPs) by extending a framework for constraint integer programming (CIP). The advantage of this approach is that we can utilize the full power of advanced MIP and CP technologies. In particular, this addresses the linear relaxation and the discrete components of the problem. For relaxation, we use an outer approximation generated by linearization of convex constraints and linear underestimation of nonconvex constraints. Further, we give an overview of the reformulation, separation, and propagation techniques that are used to handle the quadratic constraints efficiently. We implemented these methods in the branch-cut-and-price framework SCIP. Computational experiments indicates the potential of the approach.
    Keywords: ddc:510
    Language: English
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  • 21
    Publication Date: 2016-06-09
    Description: Supercomputers can simulate complex molecular systems. However, there is a very large gap between the fastest oscillations of covalent bonds of a molecule and the time-scale of the dominant processes. In order to extract the dominant time-scales and to identify the dominant processes, a clustering of information is needed. This thesis shows that only the subspace-based Robust Perron Cluster Analysis (PCCA+) can solve this problem correctly by the construction of a Markov State Model. PCCA+ allows for time-extrapolation in molecular kinetics. This thesis shows the difference between molecular dynamics and molecular kinetics. Only in the molecular kinetics framework a definition of transition rates is possible. In this context, the existence of an infinitesimal generator of the dynamical processes is discussed. If the existence is assumed, the Theorem of Gauß can be applied in order to compute transition rates efficiently. Molecular dynamics, however, is not able to provide a suitable statistical basis for the determination of the transition pattern.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 22
    Publication Date: 2020-08-05
    Description: We consider a system with Poisson arrivals and general service times, where the requests are served according to the State-Dependent Processor Sharing (SDPS) discipline (Cohen's generalized processor sharing discipline), where each request receives a service capacity which depends on the actual number of requests in the system. For this system, denoted by $M/GI/SDPS$, we derive approximations for the squared coefficients of variation of the conditional sojourn time of a request given its service time and of the unconditional sojourn time by means of two-moment fittings of the service times. The approximations are given in terms of the squared coefficients of variation of the conditional and unconditional sojourn time in related $M/D/SDPS$ and $M/M/SDPS$ systems, respectively. The numerical results presented for $M/GI/m-PS$ systems illustrate that the proposed approximations work well.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 23
    Publication Date: 2020-08-05
    Description: We consider a system with Poisson arrivals and i.i.d. service times and where the requests are served according to the state-dependent (Cohen's generalized) processor sharing discipline, where each request in the system receives a service capacity which depends on the actual number of requests in the system. For this system we derive asymptotically tight upper bounds for the moments of the conditional sojourn time of a request with given required service time. The bounds generalize corresponding results, recently given for the single-server processor sharing system by Cheung et al. and for the state-dependent processor sharing system with exponential service times by the authors. Analogous results hold for the waiting times.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 24
    Publication Date: 2020-11-13
    Description: The Dynamic Multi-Period Routing Problem DMPRP introduced by Angelelli et al. gives a model for a two-stage online-offline routing problem. At the beginning of each time period a set of customers becomes known. The customers need to be served either in the current time period or in the following. Postponed customers have to be served in the next time period. The decision whether to postpone a customer has to be done online. At the end of each time period, an optimal tour for the customers assigned to this period has to be computed and this computation can be done offline. The objective of the problem is to minimize the distance traveled over all planning periods assuming optimal routes for the customers selected in each period. We provide the first randomized online algorithms for the DMPRP which beat the known lower bounds for deterministic algorithms. For the special case of two planning periods we provide lower bounds on the competitive ratio of any randomized online algorithm against the oblivious adversary. We identify a randomized algorithm that achieves the optimal competitive ratio of $\frac{1+\sqrt{2}}{2}$ for two time periods on the real line. For three time periods, we give a randomized algorithm that is strictly better than any deterministic algorithm.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 25
    Publication Date: 2021-08-05
    Description: This thesis introduces the novel paradigm of "constraint integer programming" (CIP), which integrates constraint programming (CP) and mixed integer programming (MIP) modeling and solving techniques. It is supplemented by the software SCIP, which is a solver and framework for constraint integer programming that also features SAT solving techniques. SCIP is freely available in source code for academic and non-commercial purposes. Our constraint integer programming approach is a generalization of MIP that allows for the inclusion of arbitrary constraints, as long as they turn into linear constraints on the continuous variables after all integer variables have been fixed. The constraints, may they be linear or more complex, are treated by any combination of CP and MIP techniques: the propagation of the domains by constraint specific algorithms, the generation of a linear relaxation and its solving by LP methods, and the strengthening of the LP by cutting plane separation. The current version of SCIP comes with all of the necessary components to solve mixed integer programs. In the thesis, we cover most of these ingredients and present extensive computational results to compare different variants for the individual building blocks of a MIP solver. We focus on the algorithms and their impact on the overall performance of the solver. In addition to mixed integer programming, the thesis deals with chip design verification, which is an important topic of electronic design automation. Chip manufacturers have to make sure that the logic design of a circuit conforms to the specification of the chip. Otherwise, the chip would show an erroneous behavior that may cause failures in the device where it is employed. An important subproblem of chip design verification is the property checking problem, which is to verify whether a circuit satisfies a specified property. We show how this problem can be modeled as constraint integer program and provide a number of problem-specific algorithms that exploit the structure of the individual constraints and the circuit as a whole. Another set of extensive computational benchmarks compares our CIP approach to the current state-of-the-art SAT methodology and documents the success of our method.
    Description: Diese Arbeit stellt einen integrierten Ansatz aus "Constraint Programming" (CP) und Gemischt-Ganzzahliger Programmierung ("Mixed Integer Programming", MIP) vor, den wir "Constraint Integer Programming" (CIP) nennen. Sowohl Modellierungs- als auch Lösungstechniken beider Felder fließen in den neuen integrierten Ansatz ein, um die unterschiedlichen Stärken der beiden Gebiete zu kombinieren. Als weiteren Beitrag stellen wir der wissenschaftlichen Gemeinschaft die Software SCIP zur Verfügung, die ein Framework für Constraint Integer Programming darstellt und zusätzlich Techniken des SAT-Lösens beinhaltet. SCIP ist im Source Code für akademische und nicht-kommerzielle Zwecke frei erhältlich. Unser Ansatz des Constraint Integer Programming ist eine Verallgemeinerung von MIP, die zusätzlich die Verwendung beliebiger Constraints erlaubt, solange sich diese durch lineare Bedingungen ausdrücken lassen falls alle ganzzahligen Variablen auf feste Werte eingestellt sind. Die Constraints werden von einer beliebigen Kombination aus CP- und MIP-Techniken behandelt. Dies beinhaltet insbesondere die "Domain Propagation", die Relaxierung der Constraints durch lineare Ungleichungen, sowie die Verstärkung der Relaxierung durch dynamisch generierte Schnittebenen. Die derzeitige Version von SCIP enthält alle Komponenten, die für das effiziente Lösen von Gemischt-Ganzzahligen Programmen benötigt werden. Die vorliegende Arbeit liefert eine ausführliche Beschreibung dieser Komponenten und bewertet verschiedene Varianten in Hinblick auf ihren Einfluß auf das Gesamt-Lösungsverhalten anhand von aufwendigen praktischen Experimenten. Dabei wird besonders auf die algorithmischen Aspekte eingegangen. Ein weiterer Hauptteil der Arbeit befasst sich mit der Chip-Design-Verifikation, die ein wichtiges Thema innerhalb des Fachgebiets der "Electronic Design Automation" darstellt. Chip-Hersteller müssen sicherstellen, dass der logische Entwurf einer Schaltung der gegebenen Spezifikation entspricht. Andernfalls würde der Chip fehlerhaftes Verhalten aufweisen, dass zu Fehlfunktionen innerhalb des Gerätes führen kann, in dem der Chip verwendet wird. Ein wichtiges Teilproblem in diesem Feld ist das Eigenschafts-Verifikations-Problem, bei dem geprüft wird, ob der gegebene Schaltkreisentwurf eine gewünschte Eigenschaft aufweist. Wir zeigen, wie dieses Problem als Constraint Integer Program modelliert werden kann und geben eine Reihe von problemspezifischen Algorithmen an, die die Struktur der einzelnen Constraints und der Gesamtschaltung ausnutzen. Testrechnungen auf Industrie-Beispielen vergleichen unseren Ansatz mit den bisher verwendeten SAT-Techniken und belegen den Erfolg unserer Methode.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 26
    Publication Date: 2020-08-05
    Description: In this paper we investigate the fare planning model for public transport, which consists in designing a system of fares maximizing the revenue. We discuss a discrete choice model in which passengers choose between different travel alternatives to express the demand as a function of fares. Furthermore, we give a computational example for the city of Potsdam and discuss some theoretical aspects.
    Keywords: ddc:510
    Language: English
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  • 27
    Publication Date: 2020-08-05
    Description: This extended abstract is about algorithms for controlling elevator systems employing destination hall calls, i.e. the passenger provides his destination floor when calling an elevator. We present the first exact algorithm for controlling a group of elevators and report on simulation results indicating that destination hall call systems outperform conventional systems.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 28
    Publication Date: 2019-01-29
    Description: The paper proposes goal-oriented error estimation and mesh refinement for optimal control problems with elliptic PDE constraints using the value of the reduced cost functional as quantity of interest. Error representation, hierarchical error estimators, and greedy-style error indicators are derived and compared to their counterparts when using the all-at-once cost functional as quantity of interest. Finally, the efficiency of the error estimator and generated meshes are demonstrated on numerical examples.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 29
    Publication Date: 2016-06-09
    Description: The paper considers the time integration of frictionless dynamical contact problems between viscoelastic bodies in the frame of the Signorini condition. Among the numerical integrators, interest focuses on the contact-stabilized Newmark method recently suggested by Deuflhard et al., which is compared to the classical Newmark method and an improved energy dissipative version due to Kane et al. In the absence of contact, any such variant is equivalent to the Störmer-Verlet scheme, which is well-known to have consistency order 2. In the presence of contact, however, the classical approach to discretization errors would not show consistency at all because of the discontinuity at the contact. Surprisingly, the question of consistency in the constrained situation has not been solved yet. The present paper fills this gap by means of a novel proof technique using specific norms based on earlier perturbation results due to the authors. The corresponding estimation of the local discretization error requires the bounded total variation of the solution. The results have consequences for the construction of an adaptive timestep control, which will be worked out subsequently in a forthcoming paper.
    Keywords: ddc:510
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  • 30
    Publication Date: 2020-08-05
    Description: The mathematical treatment of planning problems in public transit has made significant advances in the last decade. Among others, the classical problems of vehicle and crew scheduling can nowadays be solved on a routine basis using combinatorial optimization methods. This is not yet the case for problems that pertain to the design of public transit networks, and for the problems of operations control that address the implementation of a schedule in the presence of disturbances. The article gives a sketch of the state and important developments in these areas, and it addresses important challenges. The vision is that mathematical tools of computer aided scheduling (CAS) will soon play a similar role in the design and operation of public transport systems as CAD systems in manufacturing.
    Description: Die mathematische Behandlung von Planungsproblemen im öffentlichen Verkehr hat im letzten Jahrzehnt große Fortschritte gemacht. Klassische Probleme wie die Umlauf- und die Dienstplanung können heutzutage routinemäßig mit kombinatorischen Optimierungsmethoden gelöst werden. Die Behandlung von Problemen der Angebotsplanung und der Betriebssteuerung sind dagegen noch nicht ganz auf diesem Stand. Dieser Artikel gibt einen Überblick über den Stand der Forschung, über wichtige Entwicklungen und einige Herausforderungen in diesem Gebiet. Die Vision ist, dass mathematische Planungswerkzeuge im öffentlichen Verkehr (Computer Aided Scheduling, CAS) in Zukunft eine ähnliche Rolle spielen werden wie CAD-Systeme in der industriellen Fertigung.
    Keywords: ddc:510
    Language: English
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  • 31
    Publication Date: 2022-07-19
    Description: The reconstruction of geometric shapes plays an important role in many biomedical applications. One example is the patient-specific, computer-aided planning of complex interventions, which requires the generation of explicitly represented geometric models of anatomical structures from medical image data. Only solutions that require minimal interaction by medical personnel are likely to enter clinical routine. Another example is the planning of surgical corrections of deformities where the target shape is unknown. Surgeons are often forced to resort to subjective criteria. These applications still pose highly challenging reconstruction problems, which are addressed in this thesis. The fundamental hypothesis, pursued in this thesis, is that the problems can be solved by incorporating a-priori knowledge about shape and other application-specific characteristics. Here, we focus mainly on the aspect of geometric shape analysis. The basic idea is to capture the most essential variations of a certain class of geometric objects via statistical shape models, which model typical features contained in a given population, and restrict the outcome of a reconstruction algorithm (more or less) to the space spanned by such models. A fundamental prerequisite for performing statistical shape analysis on a set of different objects is the identification of corresponding points on their associated surfaces. This problem is particularly difficult to solve if the shapes stem from different individuals. The reason lies in the basic difficulty of defining suitable measures of similarity. In this thesis, we divide the correspondence problem into feature and non-feature matching. The feature part depends on the application, while the non-feature part can be characterized by a purely geometric description. We propose two different approaches. The first approach has proved useful in many applications. Yet, it suffers from some practical limitations and does not yield a measure of similarity. Our second, variational, approach is designed to overcome these limitations. In it, we propose to minimize an invariant stretching measure, constrained by previously computed features. An important property, which sets our method apart from previous work, is that it does not require the computation of a global surface parameterization.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 32
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 1-2 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 33
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 3-8 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird die Synthese des geschützten Pentapeptids Boc - Orn(MOA)-Thr - Orn(Z) - Thr - Orn(Z) - OMe [3] beschrieben. Dazu wurden die beiden Dipeptide Boc - Thr - Orn(Z) - OH und Thr - Orn(Z) - OMe nach der Carbodiimid- und Azid-Methode zum Tetrapeptid gekuppelt und dieses mit Boc - Orn(MOA) - ONP zum Pentapeptid umgesetzt.
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  • 34
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969) 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 35
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 9-14 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die aus 4-Amino-1,2,4-triazol bzw. 3,5-Dimethyl-4-amino-1,2,4-triazol erhältlichen 1-Al-kyl-4-amino- bzw. 1-Alkyl-3,5-dimethyl-4-amino-triazolium-Salze gehen beim Erhitzen mit verdünnter Natronlauge durch Ringspaltung, Wanderung der gebildeten Acylgruppe und erneuten Ringschluß in die entsprechenden 4-Alkylamino-1,2,4-triazole über, deren Struktur bewiesen wird.Die Acylwanderung verläuft intermolekular, wie sich aus dem Kreuzungsexperiment ergibt.
    Additional Material: 2 Tab.
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  • 36
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 15-35 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der elektrophilen Halogenierung von Olefinen in Gegenwart organischer Cyanverbindungen, wie RCN, RSCN, R2NCN, CICN und ROCN werden neben den 1,2-Dihalogenalkanen N-(β-Haloalkyl)-imidhalogenide erhalten, die bei Hydrolyse die entsprechenden Amide ergeben. So sind N-(β-Haloalkyl)-amide, N-(β-Haloalkyl)-thiolurethane, N-(β-Haloalkyl)-N′,N′-dialkylharnstoffe und N-(β-Haloalkyl)-urethane zugänglich.Die primär entstehenden Verbindungen mit Imidhalogenidstruktur sind teils zersetzliche, teils in Substanz isolierbare Verbindungen.
    Additional Material: 2 Ill.
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  • 37
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 40-44 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Amino-3-halogen-pyrazine werden mit Brom in Bromwasserstoffsäure leicht bromiert. Der Eintritt des Broms erfolgt in 5-Stellung. Die Darstellung von 2,3,5-Trihalogen- sowie 2,5-Dihalogen-3-hydroxy-pyrazinen aus 2-Amino-3,5-dihalogen-pyrazinen wird beschrieben.
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  • 38
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 61-70 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4,6-Diphenyl-2H-thiopyranthion-(2) 1, ist am Thionschwefel zu Thiopyryliumsalzen des Typs 2, alkylierbar und acylierbar. Bei der Umsetzung von Oxalylhalogeniden mit 1, oder 4,6-Diphenyl-2H-thiopyranon-(2) 4 fragmentiert das Acylierungsprodukt A zu den reaktiven 2-Halogen-thiopyryliumsalzen 3.Die Hydrolyse der 3, führt zu Gemischen von 1, und 4,6-Diphenyl-2H-thiopyranon-(2) 4, die Sulfhydrolyse zu reinem 1.1 und 2 sind zu 4 hydrolysierbar, mit primären Aminen bilden 1,2 und 3 die Azomethine 5. Am Stickstoff aliphatisch substituierte 5 werden durch Methyljodid zu 2-Dialkylamino-thiopyrylium-jodiden 6 alkyliert. Aliphatische Amine bewirken bei 4 einen Austausch des Ringschwefels gegen Stickstoff unter Bildung von 4,6-Diphenyl-pyridonen-(2) 9. Kupferbronze reagiert mit 1 unter Bildung von 4,4′,6,6′-Tetraphenyl-2,2′-dithiodipyrylen 10.
    Additional Material: 3 Tab.
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  • 39
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 36-39 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Am cis-4-Phenyl-4-hydroxy-cycloheptanol, cis-1,4-Dimethyl- und cis-1,4-Dibutylcycloheptandiol-(1,4) können infrarotspektroskopisch transanulare H-Brücken nachgewiesen werden. In den entsprechenden trans-Verbindungen findet keine transanulare Assoziation statt.
    Additional Material: 1 Tab.
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  • 40
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 71-77 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Hydrazino-pyridin- bzw. -chinolin-hydrochlorid (1 bzw. 2) reagiert mit 2-Amino-5-aryl-1.3.4-oxdiazolen 3 in Äthanol-Pyridin unter Abspaltung von Ammoniak zu Produkten, denen die Struktur von 3-(Nβ-Aroyl-hydrazino)-s-triazolo[4,3-a]pyridinen 4 bzw. 1-(Nβ-Aroyl-hydrazino)-s-triazolo[4,3-a]chinolinen 5 zugesprochen wird, da die Verbindungen 4 in einer für dieses Ringsystem typischen Oxydationsreaktion 1.2.4-Triazol ergeben.
    Additional Material: 2 Tab.
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  • 41
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 78-81 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Umsetzung von o-[p-Tosylamino]-benzoylchlorid mit ätherischer Diazomethan-lösung entsteht o-[p-Tosylamino]-ω-diazoacetophenon 5 in guter Ausbeute, aus dem über N-Tosyl-indoxyl 6 Indigo gewonnen werden kann.
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  • 42
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 91-96 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In Lösungsmitteln unterschiedlicher Polarität wird die Umsetzung des trans-1-Phenyl-2-cyclohexyl-äthylens mit Brom und Chlor sowie komplexen Halogenierungsmitteln untersucht. Aus der IR-spektroskopischen Produktanalyse der Diastereomerenbildung ergeben sich Schlußfolgerungen über die Natur des Zwischenzustandes bei der elektrophilen Halogenaddition.
    Additional Material: 1 Ill.
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  • 43
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 97-101 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Umsetzung von 2,5-Methylen-1,2,5,6-tetrahydrobenzaldehyd 1 bzw. 2,5-Methylenhexahydrobenzaldehyd 2 mit Acetophenonen liefert Chalkone, während Aceton vornehmlich zum Aldol-Additionsprodukt führt. KNOEVENAGEL-Kondensationen mit Malonsäure und ihren Derivaten verlaufen in der bicyclischen Reihe im allgemeinen glatt.
    Additional Material: 2 Tab.
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  • 44
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 45-60 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die charakteristischen UV-S-Absorptionen einiger Aryldithiocarbonsäureester werden mitgeteilt. Die längstwelligen Banden werden auf der Basis der HMO - SC-Übergangsenergien diskutiert. Die ersten intensiven Absorptionsmaxima von Dithiobenzoesäureestern, die in p-Stellung mit Elektronendonatoren substituiert sind, dienen zur Ableitung spektroskopischer Substituentenkonstanten. Diese sind auch für andere Serien brauchbar.Schon die einfache HÜCKELsche MO - LCAO - (kurz HMO-) Methode erlaubt eine Beschreibung der Anregungsenergien der längstwelligen Absorptionsbanden heterocyclischer Schwefelverbindungen im ultravioletten und sichtbaren Spektrabereich [1-5].Diese quantenchemische Methode geht von sinnvollen Annahmen über die Eigenschaften der einzelnen Atome μ und Bindungen μν in den π-Elektronensystemen aus, die als empirische Parameter αμ = αC + hμβCC (COULOMB-Integral) und βμν = kμνβCC (Resonanzintegral) in die Rechnung eingehen (vgl. [6]).In welchem Umfang die bisher verwendeten Schwefelparameter auch für die Berechnung acyclischer Schwefelverbindungen geeignet sind, ist bisher nicht eingehend geprüft worden. Ein anderes offenes Problem ist das Verhältnis der Schwefelparameter zu denen anderer Heteroatome. Dithiocarbonsäureester, deren Präparation und Reduktion Gegenstand einer früheren Veröffentlichung war [7], bieten eine Möglichkeit, diesen Fragenkomplex in Angriff zu nehmen und das experimentelle spektroskopische Material zu systematisieren.
    Additional Material: 8 Ill.
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  • 45
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 102-104 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Interaction of uranyl nitrate with potassium-molybdocyanide has been investigated spectrophotometrically. The reaction occurs in the molar ratio of 1:1. This is further supported by conductometric titrations performed in aqueous and aqueous-alcoholic media. Formation constant and free energy of formation has been calculated.
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  • 46
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 105-117 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mit einem anisothermen Mischungskalorimeter, das auf dem Prinzip der thermometrischen Titration beruht, und einem Verdampfungskalorimeter, das nach der Inertgas-Durchströmungsmethode arbeitet und die isotherme differentielle Verdampfungswärme zu bestimmen gestattet, wurde das Enthalpie-Konzentrations-Diagramm (MOLLIER-PONCHON-Diagramm) des Systems Nitromethan/Wasser für 50° in einer für technische Zwecke ausreichenden Güte bestimmt. Die experimentellen Ergebnisse konnten mit theoretischen Voraussagen von SCHUBERTH [2] unter Verwendung des zweiseitigen PORTERschen Ansatzes, der für die Beschreibung des Phasengleichgewichtsverhaltens des genannten Systems eine gute Näherung darstellt [3], verglichen werden; die Übereinstimmung war im Rahmen des zu Erwartenden zufriedenstellend.
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  • 47
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 130-134 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wurde die Nitrierung von 2,3-diarylsubstituierten Indonen 1 mit einer Methyl- bzw. Methoxylgruppe am 3-Phenylrest untersucht. Die anfallenden Nitroprodukte wurden durch Säulenchromatographie an Aluminiumoxid gereinigt und ihre Struktur durch IR-Spektroskopie und oxydativen Abbau ermittelt.
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  • 48
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 82-90 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die N2O4-Oxydation von Thioäthern R1 - S - R2 in Tetrachlorkohlenstoff als Lösungsmittel wurde nach der Methode der Konkurrenzreaktion kinetisch verfolgt. Die relativen RG-Konstanten von 6 kernsubstituierten Thioanisolen genügen der Hammett-Gleichung mit ϱ = -2,71; die relativen RG-Konstanten von 30 aliphatischen Sulfiden genügen der Taft-Gleichung mit ϱ* = -1,68 und δ = 0,85. Zwischen den RG-Konstanten der N2O4-Oxydation und denen der H2O2-Oxydation besteht eine lineare Freie-Energie-Beziehung. Alle Befunde deuten darauf hin, daß bei der untersuchten Reaktion ein nucleophiler Angriff des Sulfid-S-Atoms auf ein O-Atom des N2O4 stattfindet. Da die N2O4-Oxydation nach einem Geschwindigkeitsgesetz \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm RG = k}_{\rm 3} \left[{{\rm Thio}\mathop {\rm a}\limits^{..} {\rm ther}} \right]\left[{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } \right]^2 $$\end{document} verläuft, muß ein cyclischer Übergangszustand angenommen werden, der zwei Moleküle N2O4 und ein Molekül Thioäther enthält.
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  • 49
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 135-140 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Hydrierungsgeschwindigkeit unverzweigter Δ1-Olefine des Kettenlängenbereiches C6—C17 in Äthanol in Gegenwart von Pt, Pd- und Rh-haltigen Trägerkontakten sinkt mit steigender Kettenlänge des Olefins. Geschwindigkeitsbestimmend ist die Reaktion an der Katalysatoroberfläche an Pt-haltigen Trägerkonstanten.
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  • 50
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 141-146 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wurde gezeigt, daß eine Reinigung des bei der Perjodatoxydation des Dextrans gebildeten Oxydextrans vom Jodat in einfacher Weise mittels Ionenaustauschern auch im präparativen Maßstab erfolgen kann. An Stelle des in der Literatur für analytische Arbeiten zur Abtrennung von Perjodat beschriebenen Austauschers Amberlite IRA - 400 (Acetatform) konnten mit Erfolg Austauscher der DDR-Produktion eingesetzt werden (Wofatit SBW und Wofatit L 150 des VEB Farbenfabrik Wolfen). Wofatit L 150 ist wegen seiner höheren Kapazität und seines universelleren Anwendungsbereiches (pH 1 - 14) dem Wofatit SBW vorzuziehen. Die Abtrennung des Oxydextrans vom Jodat gelingt quantitativ bei einer Rückgewinnung des Jodats von 99,0 ± 0,7%. Ist in der zu reinigenden Oxydextranlösung neben Jodat noch Natriumsulfat in größeren Mengen vorhanden, wie es für die Regeneration des Jodats zu Perjodat durch anodische Oxydation erforderlich ist, muß zweistufig adsorbiert/eluiert werden.
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  • 51
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 118-129 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird die Benzonitriloxid-Addition an die semicyclische CC-Doppelbindung der 2-Methylen-cycloalkanone-(1), der benzokondensierten und bicyclischen α-Methylenketone sowie der α,α′-Dimethylen-cycloalkanone beschrieben. Die erhaltenen Spiro-isoxazoline wurden NMR-spektroskopisch untersucht und daraus die Additionsrichtung festgelegt. Die LiAlH4-Reduktion vom Benzonitriloxid-Addukt des 2-Methylen-cycloheptanons-(1) liefert 1,2-Dihydroxy-2-(β-amino-β-phenyl-äthyl)-cycloheptan.
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  • 52
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 153-158 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Als Testsubstanzen zur Untersuchung der Abbauprodukte von Diacetylen-MANNICH-Basen-methojodiden mit wäßriger Kalilauge wurden die isomeren Octendiine und Nonendiine 1-3 synthetisiert und deren gaschromatographische Identifizierung untersucht.
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  • 53
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 159-161 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 54
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 165-167 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 55
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 168-170 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 56
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 162-164 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 57
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Peroxygenierungsgeschwindigkeiten bei Alkoholen, Essigsäureestern und Methyläthern mit olefinischen und aromatischen Gruppen werden verglichen. Die substituierten Essigsäureester und Methyläther bilden Hydroperoxide, deren Struktur bewiesen wurde. C—H-Bindungen mit benachbarten sauerstoffhaltigen funktionellen Gruppen und olefinischen oder aromatischen Resten reagieren leicht mit molekularem Sauerstoff. Enthält die funktionelle Gruppe Carbonylsauerstoff, so verläuft die Reaktion nach dem α-Methylen-Mechanismus; ist der Sauerstoff Brückenatom, so tritt keine Wanderung der Doppelbindung ein.
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  • 58
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 171-171 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 59
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 172-173 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 60
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 174-177 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 183-186 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 62
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 178-182 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 63
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 187-189 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 64
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969) 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 190-192 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 66
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 193-200 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird eine Reihe von Theophyllinderivaten beschrieben, welche zu den Diphenylpropylaminen gehören.
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  • 67
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 213-218 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Acyl-5-[(3-phenyl)-1.2.4-triazolyl-(5)]-diaminoguanidine sowie 1-Benzoyl-5-[(3-phenyl)-1.2.4-thiodiazolyl-(5)]- und 1-Benzoyl-5-[pyridyl-(4)]-diaminoguanidin cyclisieren in siedender Alkalilauge durch intramolekulare Wasserabspaltung und gleichzeitige Oxydation durch Luftsauerstoff zu in Nβ-Stellung durch Heterocyclen substituierten 3-Aryl(alkyl)-5-azo-1.2.4-triazolen, die durch Zinn (II)-chlorid in saurem oder durch Natrimdithionit in alkalischem Milieu zu den korrespondierenden Hydrazoverbindungen reduziert werden können.
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  • 68
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 201-212 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Temperaturabhängigkeit des endo/exo-Isomerenverhältnisses bei der Umsetzung von Cyclopentadien mit Acrolein wird untersucht; in dieser kinetisch kontrollierten Reaktion fällt der Gehalt an endo-Form von 76% bei 20°C (in Dioxan) auf 71% bei 101°C. Für die Bildung der endo-Form wird bei etwa gleicher Aktivierungsentropie eine geringere Aktivierungsenthalpie benötigt (ΔΔH≠ 650 cal/Mol). Beim Erhitzen von 2,5-Methylen-1,2,5,6-tetrahydrobenzaldehyd 1 erfolgt Isomerisierung, wobei der Gleichgewichtswert bei 170°C nach wenigen Stunden erreicht wird; unter 100° bleibt die Ausgangszusammensetzung erhalten.Die Äquilibrierung mit Basen liefert den Gleichgewichtswert bereits nach wenigen Minuten: Kexo/endo = 0,695 (20°C); 0,925 (100°C). Die Basenkonzentration muß niedrig sein. da beim Aldehyd 1 leicht CANNIZZARO-Reaktion eintritt.Äquilibrierungsversuche mit Säuren schlugen infolge Nebenproduktbildung fehl.Durch alkalische Hydrolyse des Enolacetats 5 wird das thermodynamisch, durch saure Spaltung von 5 sowie des Enoläthers 6 oder der Enamine 7 wird das kinetisch bestimmte endo/exo-Verhältnis (∼ 75/25) erhalten.Reaktivitätsunterschiede der beiden Formen des Aldehyds 1 machen sich nicht bemerkbar.
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  • 69
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 219-227 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, some dyeing, and fastness properties of several new dispersed and acid dyes derived from the amino-benzotriazoles 1 & 3 and the aminobenzimidazoles 2a, 2b & 4 are described. The suitability of the amino derivatives 1, 2a, 2b, 3 & 4 as bases for azoic dyeing has also been studied. Several interesting observations between the properties of some synthesised dyes and the corresponding benzene or naphthalene analogues are cited.
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  • 70
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 228-230 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Auswertung der IR-Spektren einiger substituierter Schwefelsäurediamide konnten für die SO2-Gruppe dieser Amide folgende Moleküldaten nach GILLESPIE berechnet werden: Bindungsabstand, Bindungswinkel, Kraftkonstante sowie Bindungsabstand.
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  • 71
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 231-237 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzylhydrazin reagiert analog dem Phenylhydrazin und im Gegensatz zu aliphatischen Hydrazinen mit in 5-Stellung substituierten 2-Amino-1,3,4-oxdiazolen zu Diamino-guanidinen, die sich zu 1,2,4-Triazolen cyclisieren lassen.
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  • 72
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 256-259 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden neue Methoden zur Herstellung von phosphororganischen Isocyanaten durch Umsetzung von phosphororganischen Amidsalzen mit Phosgen oder Oxalylchlorid und aus N-Diphenyl-phosphinsäureureiden mit Phosgen beschrieben. Phosphonsäurediureide liefern mit Phosgen Dioxo-triazaphosphorinane.
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  • 73
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 260-265 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Drei in 2,6-Stellung des aromatischen Kernes disubstituierte β-Methylstyrole wurden mit NOCl/HCl in α-Chloroxime überführt; diese lieferten mit Triäthylamin in Äther relativ stabile monomere Nitrosoolefine, die durch ihre Spektren sowie durch ihre Reaktion mit Piperidin zu α-Piperidinooximen charakterisiert wurden.
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  • 74
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 238-255 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Additionen von Jodthiocyanat (JSCN), 2,4-Dinitrobenzolsulfenylchlorid (ArSCl) und Nitrosylchlorid (NOCl) an Olefine verschiedener Strukturtypen wurden teils durch maßanalytische Verfolgung der Konzentrationen, teils durch gaschromatographische Auswertung von Konkurrenzreaktionen kinetisch untersucht. Die Reaktionen sind untereinander und mit der Brom-Addition verwandt. Die Additionsgeschwindigkeiten von JSCN, ArSCl und NOCl an kernsubstituierte Styrole geben eine gute Korrelation mit der HAMMETT-Gleichung, die Additionsgeschwindigkeiten an offenkettige aliphatische Olefine folgen der TAFT-Gleichung befriedigend. Die relativen Reaktionsgeschwindigkeiten von cis/trans-isomeren Olefinen sowie die von Cycloolefinen werden diskutiert. Offenbar läßt sich aus kinetischen Daten allein nicht sicher ableiten, ob der Übergangszustand elektrophiler Olefin-Additionen einem offenkettigen Carbeniumion, einem verbrückten. Ion oder einem Vierring ähnlich ist. Die Additionsgeschwindigkeiten von Quecksilberacetat (Hg(OAc)2) an Olefine zeigen eine völlig andere Abhängigkeit von der Struktur des Substrats als die Additionsgeschwindigkeiten von Br2, JSCN, ArSCl und NOCl.
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 266-270 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of glutaric anhydride with benzene and toluene has been thoroughly studied. 4,4-Diphenyl-pent-4-enoic acid and 1,3-dibenzoyl propane were isolated as by-products of the reaction with benzene. The mechanism of formation of the by-products has been proved. In case of toluene no by-products were detected.
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  • 76
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 271-277 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung der beiden Tripeptid-Derivate Boc - Gly - Ile - Cys(Bzl) - Azid und Ser - Leu - Tyr - OMe [3] wird das geschützte Hexapeptid Boc - Gly - Ile - Cys(Bzl) - Ser - Leu - Tyr - OMe erhalten. Dieses Peptid entspricht der Aminosäuresequenz 9-14 der A-Kette des Pferdeinsulins.
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 278-285 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird die Synthese des vollständig geschützten Pentapeptid-Derivates Boc - Dab(Z) - D - Leu - Ile - Dab(Z) - Dab(Z) - NHNH2 [2] beschrieben. Es entspricht einer Teilsequenz der bisher für das Circulin B angenommenen Struktur. Der Aufbau erfolgte stufenweise vom Carboxylende her unter Benutzung der Nitrophenylester und der gemischten Anhydride.
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  • 78
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 296-301 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An 12 Alkylcycloheptanonen wurde die Verschiebung der Protonensignale im Kernresonanzspektrum beim Übergang vom Lösungsmittel CDCl3 zu C6H6 untersucht. Die erhaltenen Ergebnisse lassen sich zur Konformation der Cycloheptanone in Beziehung setzen und weisen auf das Vorliegen dieser Verbindungen als axialsymmetrische Sesselkonformation hin.
    Additional Material: 1 Tab.
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  • 79
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 286-295 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das neuerdings leicht zugängliche 3-Amino-4-hydroxy-6-methy1-pyridazin 1 [1] erschließt einen neuen Zugang zu Derivaten des Pyridazins. Die Umsetzung mit salpetriger Säure liefert in verdünnter Schwefelsäure 3,4-Dihydroxy-6-methyl-pyridazin 3, in konz. Salzsäure dagegen 3-Chlor-4-hydroxy-6-methylpyridazin 2. Das Chloratom in 2 ist leicht nucleophil ersetzbar unter Bildung der 3-Hydroxy-, 3-Amino- bzw. 3-Phenylthio-Verbindungen 3, 7a-i. Noch leichter reagieren die entsprechenden 4-Methoxyverbindungen, so daß auch die interessanten3-Arylsulfonylamino-4-methoxy-Derivate 8k, l gut zugänglich sind.Mit Phosphoroxidchlorid liefert 2 das 3,4-Dichlor-6-methyl-pyridazin 10, das - ebenso wie 2 - in Gegenwart von Palladium reduktiv enthalogeniert werden kann, wobei 3-Methyl-pyridazin 11 bzw. das bisher unbekannte 4-Hydroxy-6-methyl-pyridazin 9 entstehen. Die Umsetzung des 3-Amino-4-hydroxy-6-methyl-pyridazins 1 mit Dimethylsulfat führt nur zum 4-Methoxy-Derivat 4. In gleicher Weise reagieren die 4-Hydroxy-6-methylpyridazine 7a-i und 2. Die Struktur der dargestellten Verbindungen wird gesichert. Die Verbindungen mit 4-Hydroxygruppe zeichnen sich durch hohe Schmelzpunkte, relativ geringe Löslichkeiten in Wasser und damit zusammenhängend sehr stark assoziierte IR-Banden der OH-Gruppe aus.
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  • 80
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 328-335 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preliminary studies on the different chelates of PGR and BPGR with a number of metal ions have been made. Different conditions under which these chelates are formed have been evaluated.
    Additional Material: 6 Ill.
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  • 81
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 302-327 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nickel cyanide-ammonia forms clathrate compounds with a variety of organic molecules such as aniline, benzene, pyridine, pyrrole, and thiophene. The present results suggest that there is a definite indication of captured molecules and the absorption characteristics of molecules in their environment in nickel cyanide-ammonia cage are similar to those of the molecules in liquid state. In accepting the guest molecules, the nickel cyanide-ammonia structure is not changed, since apart from the appearance of bands due to the trapped molecules, the bands due to pure nickel cyanide-ammonia remain virtually unchanged. The infrared spectra of nickel cyanide-ammonia clathrates in the 100-4000 cm-1 region are described in this investigation.
    Additional Material: 26 Ill.
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  • 82
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 336-349 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 7 Tab.
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  • 83
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 350-352 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Tab.
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  • 84
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969) 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 363-369 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Umsetzung von 3-Methylpyrazol-5-carbonsäureäthylester mit Dialkylaminoalkylhalogeniden entstehen Isomerengemische der 1,3- und 1,5-dialkylierten Ester. Bei der α-Aminomethylierung erhält man ausschließlich den 1,5-dialkylierten Ester.
    Additional Material: 1 Ill.
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  • 86
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 353-362 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Verschiedene Cyanacetylamino-Verbindungen wurden mit p-Nitroso-N.N-bis-(β-chloräthyl)-anilin und p-Nitroso-N.N-bis-(β-hydroxyäthyl)-anilin zu den entsprechenden Cyananilen umgesetzt. Bromcyanacetamid lieferte analoge Nitrone. Aus Cyanacetylverbindungen, deren Amidsubstituent in einer zum Ringschuluß geeigneten Stellung ein reaktionsfähiges H-Atom besitzt, bildeten sich unter HCN-Abspaltung Anile cyclischer Verbindungen.
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  • 87
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 370-378 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbonsäureester R—CH2—COOMe werden durch MeONO/NaOMe in aprotischen Lösungsmitteln α-nitrosiert; man erhält in Ausbeuten zwischen 14 und 34% die entsprechenden α-Oximinocarbonsäureester. α-Verzweigte Carbonsäureester werden durch MeONO/NaOMe nitrosierend gespalten: Die primär gebildeten Ketoxime lassen sich wegen des Auftretens von Folgereaktionen nur in Ausbeuten unter 10% isolieren.
    Additional Material: 6 Tab.
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  • 88
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 379-382 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die aus 2-Oxolävulinsäureäthylester mit Aminen und Aldehyden gebildeten 3-Acetyl-4.5-dioxopyrrolidine 1 reagieren mit Arylhydrazinen zu entsprechenden 6-Oxo-1.4.5.6-tetrahydropyrrolo[3.4-c]pyrazolen 2.
    Additional Material: 1 Tab.
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  • 89
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 438-444 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus 1-Methyl-7-amino-6-azalumazinen werden substituierte 3,5-Diamino-as-triazin-carbonsäuren-6 dargestellt. Durch Erhitzen über den Schmelzpunkt entstehen daraus substituierte Diamino-as-triazine. Die alkalische Verseifung von 1-Methyl-7-äthylmercapto-6-azalumazin ergab 1-Methyl-7-hydroxy-6-azalumazin.
    Additional Material: 2 Tab.
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  • 90
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei 25°C wurden an den binären Systemen Methanol/Dimethylformamid, Aceton/Dimethylformamid, Äthanol/Diäthylformamid und Aceton/Diäthylformamid mittlere molare Zusatzenthalpien und mittlere molare Zusatzvolumina bestimmt. Die kalorimetrischen Messungen erfolgten vorwiegend im mittleren, die pyknometrischen im gesamten Molenbruchgebiet. Die experimentell gefundenen Zusatzeffekte ergaben sich bei äquimolarer Zusammensetzung in der genannten Reihenfolge der Systeme wie folgt: -26,5; +8,8; +72,5; +10,2 cal/Mol bzw. -0,385; -0,26; -0,095 und +0,036 cm3/Mol. Ihre Konzentrationsabhängigkeiten zeigten schwache bis mäßige Asymmetrie.Diese Ergebnisse führten zusammen mit früher ermittelten molaren freien Zusatzenthalpien zu qualitativen Modellvorstellungen über molekularstrukturell bedingte Nahordnungszustände in den vier Mischphasen.
    Additional Material: 4 Ill.
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  • 91
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 445-454 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird die Synthese von 6-Azido- und 6-Amino-17 α-acetoxy-progesteron und von 6-Azido- und 6-Amino-testosteronacetat beschrieben. Die Einführung der Stickstoffunktion kann durch Aufspaltung des entsprechenden Epoxides mit Natriumazid erfolgen. Die Aminoverbindungen werden aus den Azidoverbindungen durch Reduktion mit Hydrazinhydrat/Raney-Nickel erhalten.
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  • 92
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 455-462 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Umsetzung von Caprolactam mit Sulfurylchlorid in CCl4 wird ein bicyclisches, chlorhaltiges Amidin (1-[3,3-Dichlor-azacyclohepten-(1)-yl (2)]-2-oxo-3,3-dichlorazacycloheptan) 2 gebildet, dessen Struktur durch NMR-Spektroskopie aufgeklärt wurde. Die Bildungsweise von 2 aus Caprolactam, α, α-Dichlor-caprolactam und dem bisher als Dicaprolactimäther bezeichneten 1-[Azacyclohepten-(1)-yl-(2)]-2-oxo-azacycloheptan 5 wurde untersucht.
    Additional Material: 4 Ill.
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  • 93
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 463-471 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird über die Reaktionen von Bi- und Cyclopoly-phosphinen mit P-substituierten Lithiumphosphiden berichtet. Die Umsetzung von Tetraphenylbiphosphin mit LiPR2 (R = C2H5; c-C6H11) und Li2PR′ (R′ = C6H5) führt zunächst zu unsymmetrischen Biphosphinen R′2P-PR2 bzw. R′(Li)P-PR′2, die mit weiterem LiPR2(Li2PR′) die symmetrischen Biphosphine R2P-PR2 bzw. R′(Li)P-P(Li)R′ bilden. Aus „Phenylphosphor“ und Li2PC6H5 entstehen Verbindungen des Typs Li-(PC6H5)x-Li (x = 2, 3, 4). Versuche, Lithium-phosphide der Zusammensetzung Li-(PC6H5)x-P(C6H5)2 (x 〉 1) aus „Phenylphosphor“ und Lithium-diphenylphosphid herzustellen, blieben ohne Erfolg. Es gelang nur, ihre Zerfalls- bzw. Abbauprodukte 1.4-Dilithium-1.2.3.4-tetraphenyl-tetraphosphin, Tetraphenylbiphosphin und 1-Lithium-1.2.2-triphenylbiphosphin zu isolieren.
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  • 94
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 472-476 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Anwendbarkeit der jodometrischen Titration zur Bestimmung von Enthiolgehalten einiger Thiocarbonylverbindungen wird geprüft. Verläßliche Ergebnisse lassen sich nur bei völlig wasserfreier Arbeitsweise erzielen, anderenfalls wird ein Enthiolgehalt nur vorgetäuscht. Die Endpunktsanzeige kann optisch oder besser potentiometrisch erfolgen. Rücktitrationsverfahren mit wäßrigen Lösungen sind ungeeignet. Beim potentiometrischen Verfahren vermögen einige CH-acide Thion- und Dithioester mit basischen Leitsalzen Enthiolate zu bilden, die wie freie Enthiole reagieren, weshalb die Methode bei diesen Verbindungen nicht brauchbar ist.
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  • 95
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 96
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969) 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 97
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 527-528 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 98
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 529-538 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Umsetzung von Äthylendiamin mit Chlormethylphosphonat in alkalischem Medium führte zur Bildung von β-Aminoäthyl-aminomethylphosphonsäure 1, Äthylendiamin-N,N′-di(methyl-phosphonsäure) 2, Äthylendiamin-N,N,N′-tri(methylphosphonsäure) 3 und Äthylendiamin-N,N,N′,N′-tetra(methylphosphonsäure) 4. Durch potentiometrische pH-Titration wurden die pK-Werte der Säuren 1 bis 4 bestimmt. Aus den pK-Werten wurden Dissoziationsschemata abgeleitet und mit denen von Aminopolycarbonsäuren verglichen.
    Additional Material: 2 Ill.
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  • 99
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 539-548 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Einwirkung von Hydrazinhydrat auf 2-Arylamino-5-alkyl-1,3,4-oxdiazole entstehen neben 3-Alkyl-4-aryl-s-triazolonen-(5) 4 die 3-Alkyl-4-amino-5-arylamino-s-triazole 3, deren Eigenschaften untersucht werden.
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  • 100
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    Journal für Praktische Chemie/Chemiker-Zeitung 311 (1969), S. 563-570 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird über die Darstellung von α-trimethylammoniumsubstituierten Phosphonaten 2 berichtet. In Abhängigkeit von der Nucleophilie des Anions und der Natur des Phosphonat-alkyls geben sie mehr oder weniger glatt Alkyl-phosphonobetaine 3. Durch Deprotonierung entstehen aus 2 stabile N-Ylide 4, deren Struktur durch Kernresonanz-Spektroskopie eindeutig sichergestellt werden konnte.
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