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  • 1
    facet.materialart.
    Unbekannt
    Publikationsdatum: 2020-12-11
    Beschreibung: Im Mai 2009 wurde Wolfram|Alpha gestartet, ein Service, der seinen Namen von seinem Entwickler, dem britischen Mathematiker Stephen Wolfram, ableitet. Dem Benutzer soll nicht nur eine Liste von Webseiten als Ergebnis auf Anfragen geliefert werden, sondern Antworten auf konkrete Fragen geben. In diesem Report soll gezeigt werden, warum sichWolframjAlpha von Suchmaschinen abgrenzt und was die Berechnung von Antworten auf natürlichsprachliche Fragen möglich machen kann.
    Beschreibung: Wolfram|Alpha was started in May 2009 and it's a service whose name derives from the british mathematician Stephen wolfram. As a result for a request the user is not just supported with a list of websites but with answers for concrete questions. In this report it will be shown why Wolfram|Alpha seperates from search engines and moreover what makes the computation of answers for natural language queries possible.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: reportzib , doc-type:preprint
    Format: application/pdf
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  • 2
    facet.materialart.
    Unbekannt
    Publikationsdatum: 2016-06-30
    Beschreibung: Executing applications in the Grid often requires access to multiple geographically distributed resources. In a Grid environment, these resources belong to different administrative domains, each employing its own scheduling policy. That is, at which time an activity (e.g., compute job, data transfer) is started, is decided by the resource's local management system. In such an environment, the coordinated execution of distributed applications requires guarantees on the quality of service (QoS) of the needed resources. Reserving resources in advance is an accepted means to obtain QoS guarantees from a single provider. The challenge, however, is to coordinate advance reservations of multiple resources. This work presents a system architecture and mechanisms to coordinate multiple advance reservations -- called co-reservations -- for delivering QoS guarantees to complex applications. We formally define the co-reservation problem as an optimization problem. The presented model supports three dimensions of freedom: the start time, the duration and the service level of a reservation. Requests and resources are described in a simple language. After matching the static properties and requirements of either side in a mapping, the reservation mechanism probes information about the future status of the resources. The versatile design of the probing step allows the efficient processing of requests, but also lets the resources express their preferences among the myriads of reservation candidates. Next, the best mapping is found through an implementation of the formal co-reservation model. Then, the mapping has to be secured, i.e., resources need to be allocated to a co-reservation candidate with all-or-nothing semantics. We study several goal-driven sequential and concurrent allocation mechanisms and define schemes for handling allocation failures. Finally, we introduce the concept of virtual resources for seamlessly embedding co-reservations into Grid resource management.
    Beschreibung: Die Ausführung von Anwendungen erfordert oft mehrere, geographisch verteilte Ressourcen. In Grid-Umgebungen gehören diese Ressourcen zu verschiedenen administrativen Organisationen, wobei jede ihre eigene Schedulingregeln verwendet. Das bedeutet, zu welcher Zeit eine Aktivität gestartet wird (z.B. ein Rechenjob), wird vom lokalen Ressourcenmanagementsystem entschieden. Die koordinierte Ausführung von verteilten Anwendungen erfordert Dienstgütegarantien für die benötigten Ressourcen. Das Reservieren von Ressourcen im Voraus ist ein Mittel, um Dienstgütegarantien von einem einzelnen Ressourcenanbieter zu erhalten. Die Herausforderung in dieser Arbeit ist, Vorausreservierungen von mehreren Ressourcen zu koordinieren. Es wird ein System für die Koordinierung mehrerer Vorausreservierungen -- Co-Reservierungen genannt -- für die Bereitstellung von Dienstgütegarantien vorgestellt. Wir definieren das Co-Reservierungsproblem als Optimierungsproblem. Das vorgestellte Modell unterstützt drei Freiheitsgrade: die Startzeit, die Dauer und die Dienstgüte einer Reservierung. Anfragen und Ressourcen werden in einer einfachen Sprache beschrieben. Nachdem statische Eigenschaften und Anforderungen beider Seiten überprüft wurden, ermittelt der Reservierungsmechanismus Informationen über den zukünftigen Zustand der Ressourcen. Dieser Schritt ist so allgemein gehalten, daß er sowohl ein effizientes Bearbeiten der Anfragen erlaubt als auch den Ressourcen ermöglicht ihre Präferenzen auszudrücken. Im Anschluss wird die optimale Zuweisung von Anfragen zu Ressourcen ermittelt. Im letzten Schritt muss diese Zuweisung umgesetzt werden, d.h., entweder alle oder keine Ressource wird allokiert. Es werden mehrere sequentielle und parallele Allokationsverfahren vorgestellt sowie deren Auswirkung auf verschiedene Metriken untersucht. Die Einbettung von Co-Reservierungen in das Grid-Ressourcenmanagement wird anhand des Konzeptes der virtuellen Ressource dargestellt.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
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  • 3
    Publikationsdatum: 2016-06-30
    Beschreibung: Aktuelle Entwicklungen zeigen, dass Peer-to-Peer (P2P) Anwendungen wie Skype oder Bittorrent im Internet immer mehr an Bedeutung gewinnen. In den letzten Jahren hat es einen explosionsartigen Anstieg an Nutzern und Daten in solchen Netzen gegeben. Dabei stellt der eigentliche Dateitransfer zwischen zwei Rechnern kein großes Problem mehr dar und auch der Speicherbedarf für die große Menge an Daten kann durch die Weiterentwicklung der Hardware gut gedeckt werden. Das eigentliche Problem liegt vielmehr darin, den Rechner zu finden, der die gewünschten Daten hat. Client-Server Architekturen, wie zum Beispiel Napster, haben sich als ungünstig herausgestellt. Wenige Server, die eine große Anzahl an Clients bedienen müssen, sind einerseits sehr anfällig gegenüber Angriffen und Ausfällen (Single Point of Failure)und kommen auch nicht mit der ständig wachsenden Anzahl an Nutzern zurecht. Verteilte Hashtabellen (DHT) bieten hier einen guten Lösungsansatz, der mit einer großen Anzahl an Nutzern skaliert und ausfallsicher ist. Andere dezentrale Lösungen, wie zum Beispiel das P2P Netzwerk Gnutella haben zwar das Problem des Single Point of Failure gelöst, jedoch haben sie starke Nachteile bei der Suche nach Keys. Bei einer Suche wird ein Broadcast verwendet (jeder schickt die Anfrage an jeden weiter) und damit ein enormer Netzwerkverkehr erzeugt. In "Why Gnutella Can't Scale. No, Really" wird erklärt, dass eine Suchanfrage bei Standardeinstellungen in der Clientsoftware einen Netzwerkverkehr von 17MB erzeugt. Deswegen wird zusätzlich eine Lösung benötigt, die Keys und Values geordnet verteilt, damit sie gezielt gesucht werden können. Aus diesem Grund beschäftigt sich die folgende Arbeit mit einer völlig dezentralen Architektur, die außerdem eine sinnvolle Platzierung der Keys vornimmt. Die dezentrale Architektur hat den Vorteil, dass die Endgeräte den Hauptteil des Dienstes selbst erbringen und damit jeder zusätzliche Teilnehmer seine eigenen Ressourcen beisteuert. Diese Arbeit präsentiert Chord#, eine dezentrale, skalierbare und selbstorganisierende verteilte Hashtabelle. Chord# wurde ausgewählt, da in dieser Arbeit auch Wert auf Bereichsabfragen gelegt wurde. Diese sind zum Beispiel bei dem Chord Algorithmus nicht möglich, da dieser eine Hashfunktion für die Keys verwendet und somit die Daten zwar gleichmäßig aber unsortiert auf die Teilnehmer verteilt. Es wird in dieser Arbeit gezeigt, dass mit Hilfe von Chord# auch ohne die Hashfunktion gute Ergebnisse erzielt werden. Außerdem können durch den Verzicht auf die Hashfunktion Bereichsabfragen ermöglicht werden. Dafür wird der Chord# Algorithmus in Java implementiert (ca. 1500 Zeilen Code) und in dem Forschungsnetz PlanetLab ausführlich auf Laufzeiten, Instandhaltungskosten und Skalierung getestet.
    Beschreibung: Recent developments show that peer-to-peer (p2p) applications, such as Skype or Bittorrent have become increasingly important in the internet. Over the last years there has been a rapid growth of both users and data in such networks. However, the actual file transfer between two peers is not really an issue anymore. The same holds true for data storage, since the new hardware grants users enough space to store their data. The real problem is finding the peers that possess the desired data. Client-server architectures like Napster have proven to be ineffective addressing that problem. One or few servers being responsible for many peers are vulnerable to attacks or failures (single point of failure). Additionally, they are unable to cope with the rapidly growing number of peers. Distributed hashtables (DHT) are a good approach to solve these problems, since they scale nicely with large numbers of peers and provide a high tolerance for errors. Other decentralized solutions like the p2p network Gnutella solved the problem of Single Point of Failure but show considerable disadvantages when searching for keys. The peers in Gnutella use a broadcast (sending the message to all peers they know)resulting in massive traffic. According to "Why Gnutella Can't Scale. No, Really.", each search using standard client settings yields 17MB traffc. This calls for a different solution, distributing keys and values to peers quickly and efficiently so they can be found fast. For that reason this thesis focuses on a fully distributed architecture using organized key placement. One major advantage of distributed architecture is the fact, that the peers do most of the work themselves. This way, new peers joining the network add resources to it. This thesis presents Chord#, a scalable, self-organizing and completely decentralized DHT. It has been chosen due to its capability to allow range queries. The regular Chord algorithm does not support range queries, because of the hashfunction it uses to evenly distribute the keys among the peers. This results in similar or logical coherent keys most likely not being close together in the network. This thesis shows Chord# achieving same results as Chord - regarding performance costs - without the hashfunction. In dropping the hashfunction this algorithm allows the use of range queries. The Chord# algorithm is implemented in Java (about 1500 lines of code) and thoroughly tested in the research network PlanetLab. The results are evaluated regarding performance, maintenance and scalability.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 4
    facet.materialart.
    Unbekannt
    Publikationsdatum: 2017-11-02
    Beschreibung: One of the biggest impacts on the performance of a Distributed Hash Table (DHT), once established, is its ability to balance load among its nodes. DHTs supporting range queries for example suffer from a potentially huge skew in the distribution of their items since techniques such as consistent hashing can not be applied. Thus explicit load balancing schemes need to be deployed. Several such schemes have been developed and are part of recent research, most of them using only information locally available in order to scale to arbitrary systems. Gossiping techniques however allow the retrieval of fairly good estimates of global information with low overhead. Such information can then be added to existing load balancing algorithms that can use the additional knowledge to improve their performance. Within this thesis several schemes are developed that use global information like the average load and the standard deviation of the load among the nodes to primarily reduce the number of items an algorithm moves to achieve a certain balance. Two novel load balancing algorithms have then been equipped with implementations of those schemes and have been simulated on several scenarios. Most of these variants show better balance results and move far less items than the algorithms they are based on. The best of the developed algorithms achieves a 15-30% better balance and moves only about 50-70% of the number of items its underlying algorithm moves. This variation is also very robust to erroneous estimates and scales linearly with the system size and system load. Further experiments with self-tuning algorithms that set an algorithm’s parameter according to the system’s state show that even more improvements can be gained if additionally applied. Such a variant based on the algorithm described by Karger and Ruhl shows the same balance improvements of 15-30% as the variant above but reduces the number of item movements further to 40-65%.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: masterthesis , doc-type:masterThesis
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  • 5
    Publikationsdatum: 2020-12-15
    Beschreibung: Entwurf und Entwicklung eines eingebetteten Hauptspeicher-Datenbanksystems mit Snapshot-Reads.
    Beschreibung: Design and implementation of an embedded main memory database with snapshot reads.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 6
    Publikationsdatum: 2016-06-30
    Beschreibung: Das Ziel dieser Arbeit ist die Schaffung einer Zugriffs-Komponente für das Grid-Datenmanagement-System ZIB-DMS, das dessen transparente Einbindung in den Verzeichnisbaum eines Linux-Systems erlaubt. Dazu wird unter Verwendung des FUSE-Rahmenwerkes ein Userspace-Dateisystem mit Anbindung an das ZIB-DMS konzipiert und implementiert. Im Fokus stehen dabei die Abbildung der erweiterten Verwaltungsmechanismen des Systems auf die limitierte Schnittstelle hierarchischer Dateisysteme und die dazu notwendigen Änderungen am ZIB-DMS.
    Beschreibung: The goal of this work is to create an access component for the Grid data management system ZIB-DMS, that allows a transparent integration into the directory tree of a Linux system. For this purpose the FUSE framework is used to design and implement a userspace file system with connections to the ZIB-DMS. The focus is on the mapping of the extended management mechanisms of the system to the limited interface of hierarchical file systems and the therefore necessary changes to ZIB-DMS.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 7
    Publikationsdatum: 2021-01-22
    Beschreibung: We present a framework for transactional data access on data stored in a DHT. It allows to atomically read and write items and to run distributed transactions consisting of a sequence of read and write operations on the items. Items are symmetrically replicated in order to achieve durability of data stored in the SON. To provide availability of items despite the unavailability of some replicas, operations on items are quorum-based. They make progress as long as a majority of replicas can be accessed. Our framework processes transactions optimistically with an atomic commit protocol that is based on Paxos atomic commit. We present algorithms for the whole framework with an event based notation. Additionally we discuss the problem of lookup inconsistencies and its implications on the one-copy serializability property of the transaction processing in our framework.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 8
    Publikationsdatum: 2020-12-11
    Beschreibung: When planning teams for projects with specific goals, employees of a company have to group together so well, that all necessary knowledge for conquering the project’s challenges are met within the member’s skills. A tool that facilitates semantic web technologies can support the team recruiter, who is responsible for chosing the members of the team, in terms of finding the most efficient combinations of the company’s employees based on their expertises.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 9
    Publikationsdatum: 2021-01-22
    Beschreibung: Key/value stores which are built on structured overlay networks often lack support for atomic transactions and strong data consistency among replicas. This is unfortunate, because consistency guarantees and transactions would allow a wide range of additional application domains to benefit from the inherent scalability and fault-tolerance of DHTs. The Scalaris key/value store supports strong data consistency and atomic transactions. It uses an enhanced Paxos Commit protocol with only four communication steps rather than six. This improvement was possible by exploiting information from the replica distribution in the DHT. Scalaris enables implementation of more reliable and scalable infrastructure for collaborative Web services that require strong consistency and atomic changes across multiple items.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 10
    Publikationsdatum: 2022-07-19
    Beschreibung: Basierend auf einem vorhandenen Ansatz zur Einführung von anisotropen Tetraedern im Randbereich eines reinen Tetraedergitters wird ein Gittergenerator für hybride Gitter implementiert. Das hybride Gitter besteht in Randnähe primär aus anisotropen Prismen und im Inneren der Geometrie aus isotropen Tetraedern. Eine erhöhte Auflösung im Randbereich soll zu besseren Ergebnissen von numerischen Strömungssimulationen führen, für welche eine problemangepasste Diskretisierung des zu untersuchenden Gebietes benötigt wird. In dem zuvor genannten Ansatz wird eine Reihe von Übergangselementen vorgeschlagen, die an scharfen Kanten der Oberfläche platziert werden sollen. Im Rahmen dieser Diplomarbeit wird die Idee der Übergangselemente aufgegriffen und bei hybriden Gittern eingesetzt, um auch komplexe Eingabegeometrien vergittern zu können. Der ursprüngliche Gittergenerierungprozess wird überarbeitet und erweitert. Eine neue Menge an Übergangselementen wird eingeführt, es werden gekrümmte Extrusionsvektoren verwendet und es wird die Auswertung der medialen Oberfläche vorgenommen, um Überschneidungen im hybriden Gitter zu vermeiden. Der Gittergenerator wird als Modul in das Visualisierungs- und Analyseprogramm Amira implementiert und die erstellten hybriden Gitter werden auf ihre Elementqualität und die Güte der Strömungssimulationsergebnisse hin überprüft.
    Beschreibung: Based on an existing approach for the introduction of anisotropic tetrahedra near the surface boundary of a tetrahedral grid a grid generator for hybrid grids is implemented. The hybrid grid consists near the surface boundary primarily of anisotropic prisms and inside the geometry of isotropic tetrahedra. An increased resolution near the boundary should lead to better results of numerical flow simulations, which needs a problem specific discretization of the analyzed domain. In the aforementioned approach a set of transition elements is suggested, which should be placed at sharp surface corners. As a part of this diploma thesis the concept of using transition elements is applied for creating hybrid grids even for very complex input geometries. The initial grid generation process is revised and enhanced. A new set of transition elements is introduced, curved extrusion vectors are used and the medial surface is evaluated to avoid intersections in the hybrid grid. The grid generator is implemented as a module for the visualization and analysis tool Amira and the element quality of the generated hybrid grids and the quality of flow simulations performed on the grids are tested.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 11
    Publikationsdatum: 2016-06-30
    Beschreibung: We study performance and scaling of the Berlin Quantum Chromodynamics Program (BQCD) on the SGI Altix 4700 at Leibniz Supercomputing Centre (LRZ). We employ different communication methods (MPI, MPI with two OpenMP threads per process, as well as the shmem library) and run the MPI version on the two types of nodes of that machine. For comparison with other machines we made performance measurements on an IBM p690 cluster and a Cray XT4.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 12
    Publikationsdatum: 2022-07-19
    Beschreibung: In dieser Arbeit wird eine Serie von Remeshing-Verfahren um die Berücksichtigung von nicht-mannigfaltigen Dreiecksvernetzungen und Merkmalskantenzügen erweitert. Die betrachteten Verfahren arbeiten im Wesentlichen lokal. Daher können die im Rahmen dieser Arbeit entwickelten Erweiterungen, die nicht-mannigfaltige Kantenzüge und Merkmalskantenzüge betreffen, separat beschrieben werden. Dabei wird ein Ansatz verfolgt, beide Arten von besonderen Kantenzügen aufgrund ihrer Gemeinsamkeiten einheitlich zu behandeln. Dieser besteht zum einen darin, eine Korrespondenz zwischen Kantenzügen auf der Eingabe- und der Ausgabefläche zu erhalten, indem die Remeshing-Operationen auf den Kantenzügen in entsprechend eingeschränkter Weise verwendet werden. Zum anderen wird beschrieben, wie die Abtastdichte der Kantenzüge dynamisch an die Abtastdichte der Umgebung angepasst werden kann, um für weitgehende Isotropie in der Nähe von Merkmalskantenzügen zu sorgen.
    Beschreibung: A unified approach for consistent remeshing of arbitrary non-manifold triangle meshes with additional user-defined feature lines is presented. The method is based on local operations only and produces meshes of high regularity and triangle quality while preserving the geometry as well as topology of the feature lines as well as the input mesh.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 13
    Publikationsdatum: 2022-07-19
    Beschreibung: This work introduces a novel streamline seeding technique based on dual streamlines that are orthogonal to the vector field, instead of tangential. The greedy algorithm presented here produces a net of orthogonal streamlines that is iteratively refined resulting in good domain coverage and a high degree of continuity and uniformity. The algorithm is easy to implement and efficient, and it naturally extends to curved surfaces.
    Beschreibung: In dieser Arbeit wird eine neue Strategie zur Platzierung von Stromlinien vorgestellt. Hierzu werden zusätzliche duale Stromlinien verwendet, die --im Gegensatz zur üblichen Definition-- orthogonal zum Vektorfeld verlaufen. Der vorgestellte Greedy-Algorithmus berechnet ein Netz aus orthogonalen Stromlinien, welches iterativ verfeinert wird, was zu einer guten Abdeckung der Domäne und einer gleichmäßigen Verteilung der Stromlinien führt. Es handelt sich um einen einfach zu implementierenden und effizienten Algorithmus, der direkt auf gekrümmten Oberflächen anwendbar ist.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 14
    Publikationsdatum: 2020-12-11
    Beschreibung: In dieser Diplomarbeit wird untersucht, wie auf der Basis von Literaturreferenzen ein Zitationsgraph durch ein automatisches Verfahren aufgebaut werden kann. Zur Lösung des Problems werden Probabilistische Relationale Modelle herangezogen. Eine problemspezifische Erweiterung des Modells ermöglicht es, dass bestehende Unsicherheiten im Zitationsgraphen mit Hilfe eines Inferenzverfahrens aufgelöst werden können. Zur Evaluierung des Verfahren werden Experimente auf dem Cora-Datensatz durchgeführt.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 15
    Publikationsdatum: 2016-06-30
    Beschreibung: Die Diplomarbeit präsentiert ein Transaktionsverfahren für strukturierte Overlay-Netzwerke, das an die Erfordernisse verteilter Informationssysteme mit relationalem Datenmodell angepasst ist. Insbesondere wird der Einsatz von Transaktionen für verteilte Wikis betrachtet, die moderne Funktionalitäten, wie Metadaten und zusätzliche Indexe für die Navigation, unterstützen. Konsistenz und Dauerhaftigkeit der gespeicherten Daten erfordert die Behandlung von Knotenausfällen. Die Arbeit schlägt dafür das Zellenmodell vor: Das Overlay wird aus replizierten Zustandsmaschinen gebildet, um Verfügbarkeit zu gewährleisten. Das Transaktionsverfahren baut darauf auf und verwendet Two-Phase-Commit mit Fehlererkennung und Widerherstellung von ausgefallenen Transaktionsmanagern. Anwendungen wird eine Auswahl an pessimistischen und hybrid-optimistischen Nebenläufigkeitskontrollverfahren geboten, die die Minimierung von Latenzeffekten und die schnelle Ausführung von Nur-Lese-Transaktionen ermöglichen. Für die Beispielanwendung Wiki wird der erforderliche Pseudocode angegeben und die verschiedenen Nebenläufigkeitskontrollverfahren hinsichtlich ihrer Nachrichtenkomplexität verglichen.
    Beschreibung: The diploma thesis presents a transaction processing scheme for structured overlay networks and uses it to develop a distributed Wiki application based on a relational data model. The Wiki supports rich metadata and additional indexes for navigation purposes. Ensuring consistency and durability requires handling of node failures. Such failures are masked by providing high availability of nodes. This in turn is achieved by constructing the overlay from replicated state machines (cell model). Atomicity is realized using two phase commit with additional support for failure detection and restoration of the transaction manager. The developed transaction processing scheme provides the application with a mixture of pessimistic, hybrid optimistic and multiversioning concurrency control techniques to minimize the impact of replication on latency and optimize for read operations. The pseudocode of the relevant Wiki functions is presented and the different concurrency control techniques are evaluated in terms of message complexity.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 16
    Publikationsdatum: 2016-06-30
    Beschreibung: Die Arbeit präsentiert ein Transaktionsverfahren für strukturierte Overlay-Netzwerke, das an die Erfordernisse verteilter Informationssysteme mit relationalem Datenmodell angepasst ist. Insbesondere wird der Einsatz von Transaktionen für verteilte Wikis betrachtet, die moderne Funktionalitäten, wie Metadaten und zusätzliche Indexe für die Navigation, unterstützen. Konsistenz und Dauerhaftigkeit der gespeicherten Daten erfordert die Behandlung von Knotenausfällen. Die Arbeit schlägt dafür das Zellenmodell vor: Das Overlay wird aus replizierten Zustandsmaschinen gebildet, um Verfügbarkeit zu gewährleisten. Das Transaktionsverfahren baut darauf auf und verwendet Two-Phase-Commit mit Fehlererkennung und Widerherstellung von ausgefallenen Transaktionsmanagern. Anwendungen wird eine Auswahl an pessimistischen und hybrid-optimistischen Nebenläufigkeitskontrollverfahren geboten, die die Minimierung von Latenzeffekten und die schnelle Ausführung von Nur-Lese-Transaktionen ermöglichen. Für die Beispielanwendung Wiki wird der erforderliche Pseudocode angegeben und die verschiedenen Nebenläufigkeitskontrollverfahren hinsichtlich ihrer Nachrichtenkomplexität verglichen.
    Beschreibung: The report presents a transaction processing scheme for structured overlay networks and uses it to develop a distributed Wiki application based on a relational data model. The Wiki supports rich metadata and additional indexes for navigation purposes. Ensuring consistency and durability requires handling of node failures. Such failures are masked by providing high availability of nodes. This in turn is achieved by constructing the overlay from replicated state machines (cell model). Atomicity is realized using two phase commit with additional support for failure detection and restoration of the transaction manager. The developed transaction processing scheme provides the application with a mixture of pessimistic, hybrid optimistic and multiversioning concurrency control techniques to minimize the impact of replication on latency and optimize for read operations. The pseudocode of the relevant Wiki functions is presented and the different concurrency control techniques are evaluated in terms of message complexit
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  • 17
    Publikationsdatum: 2016-06-30
    Beschreibung: Berlin als Stadtstaat ist Kommune und Land der Bundesrepublik zugleich und Standort vieler renommier-ter Wissenschafts- und Kultureinrichtungen. In enger Zusammenarbeit der Wissenschaftseinrichtungen mit dem IT-Dienstleistungszentrum Berlin (ITDZ, ehemals Landesbetrieb für Informationstechnik), der für die Behörden Berlins zuständigen Einrichtung, wurde seit 1993 ein landeseigenes Glasfasernetz mit einer derzeitigen Länge von 856 km Glasfaserkabel (je Kabel bis zu 144 Einzelfasern) zur gemeinsamen Nutzung von Wissenschaft und Verwaltung errichtet und weiter ausgebaut. 1994 erfolgte der offizielle Start des Berliner Wissenschaftsnetzes BRAIN (Berlin Research Area Information Network), als durch einen Beschluss des Senats von Berlin die Nutzung des landeseigenen Glasfasernetzes durch die Wissen-schaftseinrichtungen festgeschrieben wurde. Bereits 1995 wurden durch die Wissenschaftseinrichtungen auf diesem Glasfasernetz die ersten sieben Anschlüsse in ATM-Technik (Classical BRAIN-ATM) in Betrieb genommen, 1999 wurden anschließend auch erste Strecken in Ethernet-Technik (Classical BRAIN-GE) betrieben. Diese heterogenen Netze mit unterschiedlichen Netzgeräten wurden dezentral von den Netzadministratoren der beteiligten Einrichtungen nach globalen Absprachen betreut. Die dezentrale Administration erschwerte das Management und die Erweiterungen der Gesamtnetze. Basierend auf den vorliegenden Erfahrungen vereinbarten die Berliner Wissenschaftseinrichtungen, ein technisch neues Verbundnetz in Gigabit-Ethernet-Technik mit einheitlichen Geräten und einem zentralen Netzwerkmana-gement aufzubauen und zu betreiben. Seit November 2003 betreibt BRAIN auf dem landeseignen Glasfasernetz ein auf MPLS-Technik basie-rendes Gigabit-Ethernet-Netz, das „BRAIN-Verbundnetz“, mit den Diensten LAN-to-LAN-Kopplung der Einrichtungen, regionaler IP-Verkehr, Übergang zum Verwaltungsnetz und WiN-Backup. Das BRAIN-Verbundnetz löste die dezentral betreuten Vorläufernetze komplett ab. Von den derzeit 27 BRAIN-Teilnehmern nutzen 24 Einrichtungen an 53 in der Stadt verteilten Standorten die Dienste des BRAIN-Verbundnetzes, 18 Standorte sind mit 1000 Mbit/s und 35 Standorte mit 100 Mbit/s angeschlossen. Für verteilte Standorte einer Einrichtung besteht zudem die Möglichkeit, diese über dedizierte Fasern oder Bandbreiten miteinander zu vernetzen. Seit dem 2. Quartal 2007 wird im Rahmen eines Pilotprojekts der Nutzen eines zentral gemanagten Fibre Channel-Netzwerks "BRAIN-SAN" ermittelt, um Möglichkeiten einer verteilten Datenhaltung der Berliner Hochschulen und wissenschaftlichen Einrichtungen zu schaf-fen. Zusätzlich zu den vorgenannten Diensten nutzt der DFN-Verein die BRAIN-Struktur für die Verbindun-gen der X-WiN-Kernnetzknoten in Berlin und Potsdam untereinander und für Zugangsleitungen zu den Anwendern. Mit Stand 2007 nutzt das Berliner Wissenschaftsnetz BRAIN vom landeigenen Glasfasernetz 2100 km Einzelfasern und verbindet insgesamt 43 Einrichtungen (BRAIN-Teilnehmer und DFN-Anwender) aus Wissenschaft, Bildung und Kultur mit 129 Standorten. Der Betrieb von BRAIN wird im wesentlichen durch seine Nutzer finanziert. Das Land Berlin trägt aller-dings pauschal die überwiegenden Kosten für die Wartung des Glasfasernetzes, soweit es vom ITDZ be-reit gestellt wird. Zentrales Planungs- und Steuerungsorgan für BRAIN ist die von der Senatsverwaltung für Bildung, Wis-senschaft und Forschung eingerichtete BRAIN-Planungsgruppe. Sie besteht aus Mitarbeitern der Rechen-zentren der drei Berliner Universitäten und des ZIB. Nach außen wird BRAIN in rechtlicher und wirtschaftlicher Hinsicht treuhänderisch vom ZIB vertreten, die BRAIN-Geschäftsstelle befindet sich ebenfalls im ZIB.
    Beschreibung: Berlin as a city state is both local authority and federal state of the Federal Republic, as well as a location of many renowned institutions of research and culture. In close cooperation of the institutions of research with the IT service centre Berlin (ITDZ, the former Landesbetrieb für Informationstechnik) - which is the appropriate facility for the authorities of Berlin - a glass fibre network of a total extension of 856 kilome-tres of fibre optics (144 fibres each cable optic) for the common use of research and administration has been established and advanced since 1993. In 1994, when a resolution of the Senate of Berlin laid down the use of the appropriate fibre networks by the research facilities, this was the official beginning of the Berlin Research Area Information Network (BRAIN). The first seven interfaces in this fibre network in ATM technology (Classical BRAIN-ATM) were already established by the research facilities in 1995. In 1999, first systems run in Ethernet technology (Classical BRAIN-GE). These heterogeneous networks with different interfaces have been supported locally by the network administrators of the research facili-ties following global agreements. Management and advancement of the overall networks were encum-bered by these local administrations. Based on the existing experience, Berlin's research facilities agreed on the building and advancement of a technically new integrated network in gigabit Ethernet technology with standardised facilities and a centrally managed network. Since November 2003 the Berlin Research Area Information Network established a Gigabit Ethernet - called “BRAIN Integrated Network” - based on MPLS technology, including LAN to LAN linking of the facilities, local IP traffic, interface to the administration's network and WIN back-up. This BRAIN Inte-grated Network has completely replaced the locally administered predecessor networks. 24 of 27 BRAIN participants use the services of the BRAIN Integrated Network on 53 locations spread all over the city. 18 locations are connected with 1000 Mbit/s and 35 locations with 100 Mbit/s. Moreover, spread locations of a single facility have the possibililty to communicate by dedicated fibres or bandwidths. From the 2nd quarter 2007 within the scope of a pilot scheme, the advantage of a centrally administered fibre channel network "BRAIN-SAN" will be determined in order to accomplish possibilities of a spread data manage-ment of Berlin's universities and research facilities. In addition to the aforementioned services the DFN association makes use of BRAIN's structure for the connection of the X-WiN-core network nodes in Berlin and Potsdam und for access pathways to the us-ers. As from 2007, Berlin's research network BRAIN uses 2100 kilometres of single fibres from the country's fibre glass network and connects a total of 43 facilities (BRAIN participants and DFN users) from re-search, education and culture with 129 locations. The operations of BRAIN are funded basically by its users. However, the country of Berlin bears most of the costs for the maintenance of the glass fibre network, as far as it is provided by ITDZ. Central planning and steering body for BRAIN is the BRAIN planning group, which has been arranged by the administration of the Senatsverwaltung für Bildung, Wissenschaft und Forschung. It consists of staff from the computing centres of Berlin's three universities and of ZIB. BRAIN is represented legally and economically on a trust basis by the ZIB, where the BRAIN office is located also.
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  • 18
    Publikationsdatum: 2022-07-19
    Beschreibung: For medical diagnosis, visualization, and model-based therapy planning three-dimensional geometric reconstructions of individual anatomical structures are often indispensable. Computer-assisted, model-based planning procedures typically cover specific modifications of “virtual anatomy” as well as numeric simulations of associated phenomena, like e.g. mechanical loads, fluid dynamics, or diffusion processes, in order to evaluate a potential therapeutic outcome. Since internal anatomical structures cannot be measured optically or mechanically in vivo, three-dimensional reconstruction of tomographic image data remains the method of choice. In this work the process chain of individual anatomy reconstruction is described which consists of segmentation of medical image data, geometrical reconstruction of all relevant tissue interfaces, up to the generation of geometric approximations (boundary surfaces and volumetric meshes) of three-dimensional anatomy being suited for finite element analysis. All results presented herein are generated with amira ® – a highly interactive software system for 3D data analysis, visualization and geometry reconstruction.
    Schlagwort(e): ddc:004
    Sprache: Englisch
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  • 19
    Publikationsdatum: 2022-07-19
    Beschreibung: This work introduces novel internal and external memory algorithms for computing voxel skeletons of massive voxel objects with complex network-like architecture and for converting these voxel skeletons to piecewise linear geometry, that is triangle meshes and piecewise straight lines. The presented techniques help to tackle the challenge of visualizing and analyzing 3d images of increasing size and complexity, which are becoming more and more important in, for example, biological and medical research. Section 2.3.1 contributes to the theoretical foundations of thinning algorithms with a discussion of homotopic thinning in the grid cell model. The grid cell model explicitly represents a cell complex built of faces, edges, and vertices shared between voxels. A characterization of pairs of cells to be deleted is much simpler than characterizations of simple voxels were before. The grid cell model resolves topologically unclear voxel configurations at junctions and locked voxel configurations causing, for example, interior voxels in sets of non-simple voxels. A general conclusion is that the grid cell model is superior to indecomposable voxels for algorithms that need detailed control of topology. Section 2.3.2 introduces a noise-insensitive measure based on the geodesic distance along the boundary to compute two-dimensional skeletons. The measure is able to retain thin object structures if they are geometrically important while ignoring noise on the object's boundary. This combination of properties is not known of other measures. The measure is also used to guide erosion in a thinning process from the boundary towards lines centered within plate-like structures. Geodesic distance based quantities seem to be well suited to robustly identify one- and two-dimensional skeletons. Chapter 6 applies the method to visualization of bone micro-architecture. Chapter 3 describes a novel geometry generation scheme for representing voxel skeletons, which retracts voxel skeletons to piecewise linear geometry per dual cube. The generated triangle meshes and graphs provide a link to geometry processing and efficient rendering of voxel skeletons. The scheme creates non-closed surfaces with boundaries, which contain fewer triangles than a representation of voxel skeletons using closed surfaces like small cubes or iso-surfaces. A conclusion is that thinking specifically about voxel skeleton configurations instead of generic voxel configurations helps to deal with the topological implications. The geometry generation is one foundation of the applications presented in Chapter 6. Chapter 5 presents a novel external memory algorithm for distance ordered homotopic thinning. The presented method extends known algorithms for computing chamfer distance transformations and thinning to execute I/O-efficiently when input is larger than the available main memory. The applied block-wise decomposition schemes are quite simple. Yet it was necessary to carefully analyze effects of block boundaries to devise globally correct external memory variants of known algorithms. In general, doing so is superior to naive block-wise processing ignoring boundary effects. Chapter 6 applies the algorithms in a novel method based on confocal microscopy for quantitative study of micro-vascular networks in the field of microcirculation.
    Beschreibung: Die vorliegende Arbeit führt I/O-effiziente Algorithmen und Standard-Algorithmen zur Berechnung von Voxel-Skeletten aus großen Voxel-Objekten mit komplexer, netzwerkartiger Struktur und zur Umwandlung solcher Voxel-Skelette in stückweise-lineare Geometrie ein. Die vorgestellten Techniken werden zur Visualisierung und Analyse komplexer drei-dimensionaler Bilddaten, beispielsweise aus Biologie und Medizin, eingesetzt. Abschnitt 2.3.1 leistet mit der Diskussion von topologischem Thinning im Grid-Cell-Modell einen Beitrag zu den theoretischen Grundlagen von Thinning-Algorithmen. Im Grid-Cell-Modell wird ein Voxel-Objekt als Zellkomplex dargestellt, der aus den Ecken, Kanten, Flächen und den eingeschlossenen Volumina der Voxel gebildet wird. Topologisch unklare Situationen an Verzweigungen und blockierte Voxel-Kombinationen werden aufgelöst. Die Charakterisierung von Zellpaaren, die im Thinning-Prozess entfernt werden dürfen, ist einfacher als bekannte Charakterisierungen von so genannten "Simple Voxels". Eine wesentliche Schlussfolgerung ist, dass das Grid-Cell-Modell atomaren Voxeln überlegen ist, wenn Algorithmen detaillierte Kontrolle über Topologie benötigen. Abschnitt 2.3.2 präsentiert ein rauschunempfindliches Maß, das den geodätischen Abstand entlang der Oberfläche verwendet, um zweidimensionale Skelette zu berechnen, welche dünne, aber geometrisch bedeutsame, Strukturen des Objekts rauschunempfindlich abbilden. Das Maß wird im weiteren mit Thinning kombiniert, um die Erosion von Voxeln auf Linien zuzusteuern, die zentriert in plattenförmigen Strukturen liegen. Maße, die auf dem geodätischen Abstand aufbauen, scheinen sehr geeignet zu sein, um ein- und zwei-dimensionale Skelette bei vorhandenem Rauschen zu identifizieren. Eine theoretische Begründung für diese Beobachtung steht noch aus. In Abschnitt 6 werden die diskutierten Methoden zur Visualisierung von Knochenfeinstruktur eingesetzt. Abschnitt 3 beschreibt eine Methode, um Voxel-Skelette durch kontrollierte Retraktion in eine stückweise-lineare geometrische Darstellung umzuwandeln, die als Eingabe für Geometrieverarbeitung und effizientes Rendering von Voxel-Skeletten dient. Es zeigt sich, dass eine detaillierte Betrachtung der topologischen Eigenschaften eines Voxel-Skeletts einer Betrachtung von allgemeinen Voxel-Konfigurationen für die Umwandlung zu einer geometrischen Darstellung überlegen ist. Die diskutierte Methode bildet die Grundlage für die Anwendungen, die in Abschnitt 6 diskutiert werden. Abschnitt 5 führt einen I/O-effizienten Algorithmus für Thinning ein. Die vorgestellte Methode erweitert bekannte Algorithmen zur Berechung von Chamfer-Distanztransformationen und Thinning so, dass diese effizient ausführbar sind, wenn die Eingabedaten den verfügbaren Hauptspeicher übersteigen. Der Einfluss der Blockgrenzen auf die Algorithmen wurde analysiert, um global korrekte Ergebnisse sicherzustellen. Eine detaillierte Analyse ist einer naiven Zerlegung, die die Einflüsse von Blockgrenzen vernachlässigt, überlegen. In Abschnitt 6 wird, aufbauend auf den I/O-effizienten Algorithmen, ein Verfahren zur quantitativen Analyse von Mikrogefäßnetzwerken diskutiert.
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    Sprache: Englisch
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  • 20
    Publikationsdatum: 2022-07-19
    Beschreibung: One crucial step in virtual drug design is the identification of new lead structures with respect to a pharmacological target molecule. The search for new lead structures is often done with the help of a pharmacophore, which carries the essential structural as well as physico-chemical properties that a molecule needs to have in order to bind to the target molecule. In the absence of the target molecule, such a pharmacophore can be established by comparison of a set of active compounds. In order to identify their common features,a multiple alignment of all or most of the active compounds is necessary. Moreover, since the “outer shape” of the molecules plays a major role in the interaction between drug and target, an alignment algorithm aiming at the identification of common binding properties needs to consider the molecule’s “outer shape”, which can be approximated by the solvent excluded surface. In this thesis, we present a new approach to molecular surface alignment based on a discrete representation of shape as well as physico-chemical properties by points distributed on the solvent excluded surface. We propose a new method to distribute points regularly on a surface w.r.t. a smoothly varying point density given on that surface. Since the point distribution algorithm is not restricted to molecular surfaces, it might also be of interest for other applications. For the computation of pairwise surface alignments, we extend an existing point matching scheme to surface points, and we develop an efficient data structure speeding up the computation by a factor of three. Moreover, we present an approach to compute multiple alignments from pairwise alignments, which is able to handle a large number of surface points. All algorithms are evaluated on two sets of molecules: eight thermolysin inhibitors and seven HIV-1 protease inhibitors. Finally, we compare the results obtained from surface alignment with the results obtained by applying an atom alignment approach.
    Beschreibung: Die Identifizierung neuer Leitstrukturen (lead structures) zur Entwicklung optimierter Wirkstoffe ist ein äußerst wichtiger Schritt in der virtuellen Wirkstoffentwicklung (virtual drug design). Die Suche nach neuen Leitstrukturen wird oft mit Hilfe eines Pharmakophor-Modells durchgeführt, welches die wichtigsten strukturellen wie auch physiko-chemischen Eigenschaften eines bindenden Moleküls in sich vereint. Ist das Zielmolekül (target) nicht bekannt, kann das Pharmakophor-Modell mit Hilfe des Vergleiches aktiver Moleküle erstellt werden. Hier ist insbesondere die gleichzeitige Überlagerung (multiple alignment) aller oder nahezu aller Moleküle notwendig. Da bei der Interaktion zweier Moleküle die "äußere Form" der Moleküle eine besondere Rolle spielt, sollte diese von jedem Überlagerungsalgorithmus, der sich mit der Identifizierung von Bindungseigenschaften befasst, berücksichtigt werden. Dabei kann die "äußere Form" durch eine bestimmte Art von molekularer Oberfläche approximiert werden, die man als solvent excluded surface bezeichnet. In dieser Arbeit stellen wir einen neuen Ansatz zur Überlagerung molekularer Oberflächen dar, der auf einer diskreten Repräsentation sowohl der Form als auch der molekularen Eigenschaften mittels Punkten beruht. Um die Punkte auf der molekularen Oberfläche möglichst regulär entsprechend einer gegebenen Punktdichte zu verteilen, entwickeln wir eine neue Methode. Diese Methode ist nicht auf Moleküloberflächen beschränkt und könnte daher auch für andere Anwendungen von Interesse sein. Basierend auf einem bekannten Point-Matching Verfahren entwickeln wir einen Point-Matching Algorithmus für Oberflächenpunkte. Dazu erarbeiten wir u.a. eine effiziente Datenstruktur, die den Algorithmus um einen Faktor von drei beschleunigt. Darüberhinaus stellen wir einen Ansatz vor, der Mehrfachüberlagerungen (multiple alignments) aus paarweisen Überlagerungen berechnet. Die Herausforderung besteht hierbei vor allem in der großen Anzahl von Punkten, die berücksichtigt werden muss. Die vorgestellten Algorithmen werden an zwei Gruppen von Molekülen evaluiert, wobei die erste Gruppe aus acht Thermolysin Inhibitoren besteht, die zweite aus sieben HIV-1 Protease Inhibitoren. Darüberhinaus vergleichen wir die Ergebnisse der Oberflächenüberlagerung mit denen einer Atommittelpunktüberlagerung.
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  • 21
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The title compound, an analogue of [Leu5]-enkephalin with L-o-carboranylalanine replacing L-phenylalanine in position 4, was prepared by fragment condensation. The analogue has a 3-fold higher affinity for rat brain opiate receptors in the [3H]naloxone competition assay than natural [Leu5]-enkephalin. Like [Leu5]-enkephalin and Na-acetyl-[Leu5]-enkephalin, the N-terminal tripeptide fragment, H · Tyr-Gly-Gly · OH, had no melanotropic activity in the Rana pipiens frog skin assay.A convenient, direct synthesis of methyl t-butoxycarbonyl-L-propargylglycinate is described, and the 13C-NMR. spectra of L-o-carboranylalanine recorded. The procedure was extended to the preparation of BOC · Car-Leu · OMe from BOC · Pra-Leu · OMe. A number of new propargylglycine derivatives are reported.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 22
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The conversion of primary, secondary and vinylic halides to the two C-atoms homologated phenylselenomethyl ketones 8 is described. The method involves addition of the readily available phenylselenoacetaldehyde 5 to the Grignard reagents 9 and oxidation of the resulting β-hydroxy-selenides 10 (Scheme 3).
    Zusätzliches Material: 1 Tab.
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  • 23
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Preparation of Stilbenyl Derivatives of 1,2,4-OxadiazolesSchiffs bases derived from 3- and 5-(p-formylphenyl)-phenyl-1,2,4-oxadiazoles and chloroanilines are reacted with various p-tolyl substituted aromatic heterocycles in the presence of dimethylformamide and potassium hydroxide to yield the corresponding heterocyclic substituted stilbenes (‘Anil synthesis’). The reactivity of 5-[4-(chlorophenylimino-methyl)phenyl]-3-phenyl-1,2,4-oxadiazoles is very low and side reactions will predominate.
    Zusätzliches Material: 1 Ill.
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  • 24
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: (Perhalomethylthio)heterocycles. XIX. Mitt.: s. [1]. . Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activitiesIn the presence of C4F9SO3H the (perhalomethylthio)pyrroles 1a-c react with Cl3-nFnCSCl (n = 1-3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a-f and 3a-h. 2a and 3a react with CF3SCl (catalyst CF3SO3H) yielding 2,3,5-tris (trifloromethylthio)pyrrole (4a), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole (5). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole (4b) is formed. The pyrroles 2a, 4a and 5 form the mercury salts 6a-c; compound 5 yields also a silver salt 7. The 1H- and 19F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated.
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  • 25
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1451-1457 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new way to vinylic ethers from acetalsAcetals react at low temperatures in presence of a Lewis acid (aluminium chloride or magnesium bromide) with tertiary amine to give in good yields the vinylic ethers corresponding to the elimination of one molecule of alcohol.
    Zusätzliches Material: 4 Tab.
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  • 26
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Addition Reaction of 3-Dimethylamino-2,2-dimethyl-2H-azirine with Phenylisocyanate and Diphenylketene3-Dimethylamino-2,2-dimethyl-2H-azirine (1a) reacts with carbon disulfide and isothiocyanates with splitting of the azirine N(1), C(3)-double bond to give dipolar, fivemembered heterocyclic 1:1 adducts. In some cases, these products can undergo secondary reactions to yield 1:2 and 1:3 adducts. In this paper it is shown that the reaction of 1a with phenylisocyanate also takes place by cleavage of the N(1), C(3)-bond, whereas with diphenylketene N(1), C(2)-splitting is observed.The reaction of 1a and phenylisocyanate in hexane at room temperature yields the 1:3 adduct 2 in addition to the trimeric isocyanate 3 (Scheme 1). A mechanism for the formation of 2 is given in Scheme 5. Hydrolysis experiments with the 1:3 adduct 2, yielding the hydantoins 4-6 and the ureas 7 and 8 (Schemes 3 and 5), show that the formation of this adduct via the intermediates d, e and f is a reversible reaction.The aminoazirines 1a and 1b undergo an addition reaction with diphenylketene to give the 3-oxazolines 14 (Scheme 8), the structure of which has been established by spectral data and oxidative degradation of 14a to the 3-oxazolin-2-one 15 (R1 — R2 — CH3, Scheme 9).
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  • 27
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 1H-NMR. Spectroscopic Analysis of Prochiral Allenic Esters Using Optically Active Europium Shift ReagentsThe prochiral allenic methyl esters 1-4 (cf. Scheme) show in the presence of 1 mol-equiv. tris[3-(heptafluorobutyryl)-(+)-camphorato]europium (III) (Eu (hfc)3) in 1,1,2-trichloro-1,2,2-trifluoroethane (TCFE) induced unlike 1H-NMR. shift differences (ΔΔδ) for the enantiotopic protons and methyl groups on C(4), respectively (cf. Fig. 2 and 3). This effect allows to determine directly the 2JH,H coupling constants of the geminal protons on C(4) of the allenic esters 1 (15.5 Hz) and 2 (14.5 Hz) (cf. Table 2).
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 28
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1466-1474 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Heterocyclic anellated derivatives of strychnine: Imidazo-, oxazolo- and (1,3-dioxolo)strychnineThe synthesis of imidazo-, oxazolo- and dioxolo-strychnine derivatives, anellated at the 2,3-position of the aromatic nucleus is described. The spectroscopic properties of these compounds and of some intermediates are given.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 29
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1475-1484 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: UV.-irradiation of pivalic and isobutyric acid and their methyl esters as well as of α-hydroxy isobutyric and malonic acid in solution lead to chemically induced dynamic nuclear polarization (CIDNP.) of parent compounds and of various reaction products. CIDNP.-effects and product distributions confirm α-cleavage of the C(α), CO bond to be the major mode of photodecomposition. Scavenger experiments indicate that decomposition of the molecules from a triplet excited state is roughly equally or more probable than from a singlet excited state. Quantum yields of educt disappearance are also given for the methyl esters of pivalic and isobutyric acid.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 30
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Sodiumthiophenoxide and sodiumphenylselenide react with N-benzyl- and N-hexyl-di-p-toluenesulfonamides (1 and 2) via displacement at the C-atom to afford the corresponding organosulfides and selenides in yields of 68-96%. In contrast, sodium cyanide converts disulfonamides to monosulfonamides by attack on the S-atom. The different selectivities of phenylsulfide and selenide as compared to cyanide anions with respect to attack on the C- and S-atoms are rationalized on the grounds of the HSAB (hard and soft acids and bases) principle of Pearson.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 31
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1497-1500 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The recently proposed structure of the carotenoid pigment prolycopene as the 7,9,7′,9′-tetra-cis isomer of lycopene has been unambiguously confirmed by a series of homonuclear Overhauser 1H-NMR. experiments at 270 MHz. Comparative measurements are reported for lycopene.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 32
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The racemic sesquiterpene isocomene (1) has been synthesized starting from 1,7-octadien-3-one (2) in a stereoselective manner (Scheme 2). In the key step 4 → 5 the C(7), C(8)-bond was formed by an intramolecular thermal ene reaction. Further elaboration of 5 involved the ring contraction 6 → 7, the elimination 8 → 9 and the final olefin isomerization 9 → 1.
    Materialart: Digitale Medien
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  • 33
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Metabolites of Microorganisms. The Aspochalasins A, B, C, and DThe structures of the antibiotic aspochalasin B (asposterol) and its inactive co-metabolites aspochalasin A, C, and D from Aspergillus microcysticus (Tü 502) were elucidated by extended spectroscopic studies and chemical degradation. The structures are: aspochalasin A = 10-isopropyl-14-methyl[11]cytochalasa-6, 13-dien-1, 17, 18, 21-tetrone (32), aspochalasin B = 17-hydroxy-10-isopropyl-14-methyl-[11]cytochalasa-6, 13, 19-trien-1, 18, 21-trione (11), and aspochalasin C = 17, 18-dihydroxy-10-isopropyl-14-methyl[11]cytochalasa-6, 13, 19-trien-1, 21-dione (29). Aspochalasin D (1) is a diastereomer of aspochalasin C (different configuration at C (17) or C (18)).
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 34
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Metabolites of Microorganisms. Synthesis of 3-Isobutyl-4,5-dimethylisoindolin-1-one, a Degradation Product of Aspochalasin D3-Isobutyl-4,5-dimethylisoindolin-1-one (1) and 3-isobutyl-6, 7-dimethyl-isoindolin-1-one (6) were synthesized in a non-regioselective way. The structures could be assigned unequivocally by spectroscopic means. Compound 1 was identical with a degradation product of Aspochalasin D.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 35
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1531-1542 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Complexation in anhydrous methanol of Cu (II) and Zn (II) with diaza-polyoxamacrocyclic ligandsProtonation of five diaza-polyoxamacrocyclic ligands, (L = [2.1], [2.2], [2.1.1.], [2.2.1], [2.2.2]), and their complexing properties towards Cu2+ and Zn2+ cations have been studied in anhydrous methanolic solutions.Potentiometric measurements have been carried out at 25°, using 5 · 10-2MEt4N+ClO4- as support-electrolyte, in order to determine the nature of the species formed upon complexation and their stability constants. The results were confirmed by spectrophotometry, for the cupric complexes of [2.1] and [2.2.2], and the electronic spectra of the different complexes were calculated.Comparison between complexation in aqueous and methanolic solutions have been made: as in water, ML2+ species and sometimes protonated MHL3+ species, with higher stability constants, are present in methanol; but the main difference is the formation of dinuclear complexes M2L4+, between Cu2+ and all ligands except [2.1]. In these complexes the Cu2+ cations cannot be both ‘encaged’ in the ligand cavity because of its small size. The different possible structures are discussed in terms of the stability constants values. The protonation constants values and the existence of the binuclear complexes may indicate a possible conformational change in the complexing ligand on changing the solvent from water to methanol.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 36
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1549-1558 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: rac-1,2,10-Trimethoxy-aporphine (14) and rac-2-ethoxy-10,11-dimethoxyaporphine (27) have been synthesized from the 3-phenylphenethylamines 9 and 22 by a new route. The 8-phenyl-3,4-dihydroisoquinolines 11 and 24, the oxo-aporphines 12 and 25 and the rac-nor-aporphines 13 and 26 were obtained as intermediates.
    Materialart: Digitale Medien
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  • 37
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: (6aR)-1,2-(Methylenedioxy)aporphine-10, 11-diol (8) and (6aR)-aporphine-1, 1, 10, 11-tetrol (16) have been prepared from natural (S)-bulbocapnine (4). For both compounds, the partial synthesis included racemic intermediates which have been resolved into their enantiomers. Both compounds 8 and 16 showed dopaminergic activity in rats, although to a lower extent than (R)-apomorphine (1) itself.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 38
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1559-1565 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The self-ordered supramolecular structures formed by 5′-guanosine monophosphate (disodium salt) in aqueous solution at pH 7.8 show pronounced interaction with ammonium ions. Rather than competing with potassium ions for the central cavity in hydrogen-bonded guanine tetramers, ammonium ions bring about - in synergism with potassium ions - further aggregation. Glycine appears to destroy the aggregates, by competing with potassium ions for the core positions within the tetramers. Conversely, alanine does not interact significantly with the system. These conclusions follow from analysis, at various concentrations, of the microdynamics and of the mole fractions of sodium ions bound to self-assembled 5′-GMP--, obtained from relaxation rate measurements for the 23Na nucleus, as the 5′-GMP-- counter-ion.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 39
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1586-1602 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthetic application of epoxynitrones. II. Syntheses of steroidal α-methylidene-γ-lactonesThis communication describes the application of the epoxynitrone/CF3SO3SiR3 → 1,2-oxazine annelation-reaction [1] to the syntheses of steroidal α-methylidene-γ-lactones from olefines, e.g. 12 → 14a/b → 16a/b → 18a/b → 20 → 22 (Scheme 2).
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 40
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1603-1604 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Evidence is presented which demonstrates that 13C-NMR. spectroscopy can be used with confidence in evaluating the configuration of R1R2CHOH centers at C(6) and C(8) of iridoid glucosides.
    Zusätzliches Material: 1 Tab.
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  • 41
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1566-1569 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: XPS. and 1H-NMR. spectra of 1,3-diaryltriazenes complexes of Hg(II)The core binding energies C 1s, N 1s, Hg 4f7/2, Hg 4f5/2 in 7 symmetrical p-substituted 1,3-diphenyltriazenes complexes of Hg(II) have been measured by XPS. Within the limits of experimental error (± 0.2 eV) only one N 1s signal could be detected. This indicates the equivalence of the 3 N-atoms. Invariance of C 1s, N 1s, Hg 4f7/2, Hg 4d5/2 signals with the para substituents on the phenyl ring is explained on the basis of ionic character in the Hg, N bond. These results are corroborated by the 1H-NMR. spectra.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 42
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and reactivity of 3-aryl-1-(3,4-dimethyl-5-isoxazolyl)-triazenes and 4-arylazo-3,4-dimethylisoxazol-5-onesAccording to the experimental conditions and the nature of the substituents on the aromatic ring, aryldiazonium salts react with 5-amino-3,4-dimethylisoxazole (3) leading to either 3-aryl-1 (3,4-dimethyl-5-isoxazolyl)-triazenes (1A) or 4-arylazo-3,4-dimethylisoxazol-5-ones (4). Analyses of the products resulting from thermal decomposition of these triazenes in aromatic substrates and in DMSO and their behaviour in acidic medium show that it is essentially the arylazo form 1B which is reactive.
    Zusätzliches Material: 5 Tab.
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  • 43
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2282-2284 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The neurotoxin α-kainic acid (7) was synthesized from 1 via the thermal key step 5 → 6 in 41% overall yield.
    Materialart: Digitale Medien
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  • 44
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2276-2281 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Stereospecific synthesis of 6β,7β-methylene-20-spirox-4-ene-3,21-dioneA stereospecific synthesis of the highly active 6β,7β-methylene-20-spirolactone 4 (Prorenone) is described.
    Materialart: Digitale Medien
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  • 45
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2285-2302 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Chiral 2,2′-polyoxaalkano-9,9′-spirobifluorenesFrom 2,2′-diacetyl-9,9′-spirobifluorene (2), twelve chiral polyethers have been prepared as potential ion- and enantiomer-selective ionophores. The absolute configuration of the polyethers 15-17, 19-22, and 25 has been determined by chemical correlation with vespirenes [11] [29], by circular dichroism, and by X-ray analysis. The circular dichroism of 15-17, 19 and 21 depends on the size of the macrocycle and indicates that the fluorene chromophores of 19 and 21 with 13- and 16-membered rings respectively deviate considerably from orthogonality.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 46
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2325-2328 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Favorskii-rearrangement in the presence of 3,4-dimethoxyfuran: preparation of 3,4-dimethoxy 11endo-oxo-tricyclo [4.3.1.12,5]undec-3-en-10-one and any derivativesOn treatment with sodiumhydride of 2-chloro-cyclohexanone in the presence of 3,4-dimethoxyfuran, a possible intermediate of the Favorskii-rearrangement has been trapped as 3,4-dimethoxy-11endo-oxa-tricyclo [4.3.1.12,5]undec-3-en-10-one (3). This new compound contains a highly nucleophilic double bond. It can be cleaved in high yield by ozonolysis to 2exo, 4exo-bis (methoxycarbonyl)-3-oxabicyclo [3.3.1]nonan-9-one (4). Addition of chlorine to 3 occurs in stereoselective exo-cis-manner to the crystalline 3exo, 4exo-dichloro-3endo,4endo-dimethoxy 11endo-oxa-tricyclo [4.3.1.12,5]undecan-10-one (5). Silver ion assisted hydrolysis of 5, followed by thermal treatment of the intermediate hydrates, leads to the red 11endo-oxa-tricyclo [4.3.1.12,5]undecan-3,4, 10-trione (6), and methanolysis to 3,3,4,4-tetramethoxy-11endo-oxa-tricyclo [4.3.1.12,5]undecan-10-one (8). By photolytic decarbonylation, 8 is converted into 3,3,4,4-tetramethoxy-10-oxa-tricyclo-[4.3.12,5.0]decan (9).
    Materialart: Digitale Medien
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  • 47
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2350-2360 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Activated quinones: O- versus C-addition of phenols. New regiospecific syntheses of xanthones, thioxanthones and N-methyl-9-acridonesThe acid catalyzed reaction of phenols with activated quinones, e.g. 2-methoxycarbonyl-1, 4-benzoquinone or 2-acetyl-1, 4-benzoquinone, leads to substituted biphenylderivatives (C, C-addition) as has been previously described [1]. O, C-Addition of phenols has now been achieved by using 2-methoxypyridin or 4-dimethyl-aminopyridin [4] as basic catalysts. The resulting substituted diphenylethers can serve as convenient starting materials for regiospecific syntheses of substituted xanthones, especially for 1, 4-dimethoxyxanthones.Arylthiols and N-methyl-N-arylamines also react readily with activated quinones to give substituted di-aryl-thioethers and N-methyl-N, N-diarylamines respectively; both types of compounds are convenient materials for regiospecific syntheses of substituted thioxanthones and N-methyl-9-acridones.
    Materialart: Digitale Medien
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  • 48
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2361-2373 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cob(I)alamin as Catalyst. 5. Communication [1]. Enantioselective Reduction of α,β-Unsaturated Carbonyl DerivativesThe cob(I)alamin-catalyzed reduction of an α,β-unsaturated ethyl ester in aqueous acetic acid produced the (S)-configurated saturated derivative 2 with an enantiomeric excess of 21%. The starting material 1 is not reduced at pH = 7.0 in the presence of catalytic amounts of cob(I)alamin (see Scheme 2). It is shown that the attack of cob(I)alamin and not of cob(II)alamin, also present in Zn/CH3COOH/H2O, accounts for the enantioselective reduction observed. All the (Z)-configurated starting materials 1, 3, 5, 7, 9 and 11 have been transformed to the corresponding (S)-configurated saturated derivatives 2, 4, 6, 8, 10 and 12, respectively. The highest enantiomeric excess revealed to be present in the saturated product 12 (32,7%, S) derived from the (Z)-configurated methyl ketone 11 (see Scheme 3 and Table 1). The reduction of the (E)-configurated starting materials led mainly to racemic products. A saturated product having the (R)-configuration with a rather weak enantiomeric excess (5.9%) has been obtained starting from the (E)-configurated methyl ketone 23 (see Scheme 5 and Table 2). The allylic alcohols 16 and 24 have been reduced to the saturated racemic derivative 17.
    Zusätzliches Material: 3 Tab.
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  • 49
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Total Synthesis of Natural α-TocopherolTwo independent syntheses of (S)-6-hydroxy-2,5,7,8-tetramethylchroman-2-yl-methanol (8b), (Scheme 6 resp. 9) as optically active chroman moiety for the preparation of natural vitamin E via (S)-6-acetoxy-2,5,7,8-tetramethylchroman-2-carboaldehyde (2a) (Scheme 1) and a corresponding side chain are described. Both reaction sequences use trimethyl-hydroquinone as starting material; one approach employs an optically active C4 unit (10a) (Schemes 5 and 6) to introduce the required configuration at C(2), the other uses an optically active C5-synthon (11a) (Schemes 8 and 9) to build the optically active chroman unit. The correct configuration and optical purity of the chroman synthesized is established by correlation with optically pure material of known configuration from which natural vitamin E had already been derived [2].
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  • 50
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The crystal structure of the antibiotic hedamycin (1) has been solved by direct method and refined by least squares techniques to R = 0.091 for 2289 of 2643 independent reflexions. Crystals of C41H50N2O11 are orthorhombic, space group P212121 with lattice parameters a = 24.239 (12), b = 21.440 (10), c = 7.369 (4) Å, Z = 4. The structural features of hedamycin derived earlier by chemical and spectroscopical means are confirmed. Optical rotation and circular dichroism indicate that hedamycin (1) has the absolute configuration of the related antibiotic kidamycin (3). The conformation of ring F is a chair form with the aryl substituent almost axial. The bioxirane part of the antibiotic is in a synclinal conformation.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 51
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and Chirality of (5R, 6R)-5,6-Dihydro-β, ψ-carotene-5,6-diol, (5R, 6R, 6′R)-5,6-Dihydro-β, ε-carotene-5,6-diol, (5S, 6R)-5,6-Epoxy-5,6-dihydro-β,ψ-carotene and (5S, 6R, 6′R)-5,6-Epoxy-5,6-dihydro-β,ε-caroteneWittig-condensation of optically active azafrinal (1) with the phosphoranes 3 and 6 derived from all-(E)-ψ-ionol (2) and (+)-(R)-α-ionol (5) leads to the crystalline and optically active carotenoid diols 4 and 7, respectively. The latter behave much more like carotene hydrocarbons despite the presence of two hydroxylfunctions. Conversion to the optically active epoxides 8 and 9, respectively, is smoothly achieved by reaction with the sulfurane reagent of Martin [3]. These syntheses establish the absolute configurations of the title compounds since that of azafrin is known [2].
    Zusätzliches Material: 2 Ill.
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  • 52
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2517-2524 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ESR. and ENDOR. studies are reported for the radical anions of 1,2-diphenylcyclopentene (3) and its di(pe+deuteriophenyl)-derivative (3-D10). Comparison of the coupling constants of the phenyl protons in 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. with the analogous values for the radical anions of 1,2-diphenyl substituted cyclopropene (1) and cyclobutene (2) reveals regular changes in the sequence 1\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, 2\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, which are caused by an increasing twist of the phenyl groups about the C(1), C(1′)- and C(2), C(1″)-bonds linking them to the ethylene fragment. Such a twist is shown to be also responsible for the large difference in the coupling constants of the methylene β-protons in 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. (0.659 and 0.293 mT). It is suggested that - in order to minimize the losses caused by this twist in the π-delocalization energy - the 2 pz-axes at the centres 1 and 2 deviate from a perpendicular orientation to the mean plane of the cyclopentene ring. A deviation by 19° from such an orientation is required to account for the observed β-proton coupling constants in terms of their conventional cos2-dependence on the dihedral angles θ.
    Zusätzliches Material: 3 Ill.
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  • 53
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Sorelline and Hobartine, Two New Indole Alkaloids from Aristotelia peduncularis (LABILL.) HOOK. F.From Aristotelia peduncularis (LABILL.) HOOK. F. two new indole alkaloids, sorelline (1) and hobartine (2), have been isolated. Their structures were elucidated on the basis of spectroscopic data (the formulae represent their relative configurations). The alkaloids 1 and 2 have closely related structures with a monosubstituted indole moiety and an unrearranged monoterpene unit in the aliphatic part.
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  • 54
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and configuration of some spiro [indan-2,2′-pyrrolidine] and spiro [pyrrolidine-2,2′-tetraline] derivativesCatalytic hydrogenation of the nitrosoindan and nitrosotetralin derivatives 8 yielded trans-1-hydroxy-spiro [indan-2,2′-pyrrolidin]-5′-one (9) and trans-1′-hydroxy-spiro [pyrrolidine-2,2′-tetralin]-5-one (10) respectively, whilst the corresponding cis compounds 12 and 15 were prepared via the chlorides 11 and 14.The configurations of 10 and 13 were determined by X-Ray analysis.
    Zusätzliches Material: 2 Ill.
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  • 55
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions of valencepolaromeric ketenes of mesoionic heterocyles with 3-dimethylamino-2H-azirinesReactions of the 3-dimethylamino-2H-azirines 1a and 1b with the mesoionic oxazole 5 and the mesoionic dithiole 6 in acetonitrile at room temperature yield the 1:1 adducts 11, 12, 19 and 20, respectively (Schemes 5 and 8). These products can be formulated as adducts of the aminoazirines and the ketenes 5a and 6a, which are valence polaromeric forms of the mesoionic heterocycles 5 and 6 (Scheme 2).The structure of the adducts has been elucidated by spectral data and their comparison with the data of (Z)-11, the structure of which has been established by X-ray [19]. Oxidation of the 1:1 adducts with KMnO4 in a two-phase system yields 4-dimethylamino-3-oxazolin-2-ones (cf. Scheme 6) by clevage of the exocyclic C,C-double bond. A mechanism for the formation of the adducts is given in Scheme 9: Nucleophilic attack of 1 on the ketene leads to a primary adduct of type a, which undergoes clevage of the former N(1), C(2)-azirine bond to give adducts of type 11 or 19. The N(1), C(2)-ring opening of 1a in the reaction with ketenes contrasts with the N(1), C(3)-opening of 1a in the addition with, for instance, isothiocyanates. These different ring openings are explained by the difference in nucleophilicity of the heteroatoms X and Y in a′ (Scheme 10).
    Zusätzliches Material: 1 Ill.
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  • 56
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The spironaphthalen-2-ones 2, 10 and 18 were prepared by N-bromosuccinimide (NBS) oxidation of 1, 9 and 17 respectively, whereas spironaphthalen-1-ones 24 and 25 were obtained by treating 23 with NBS.The stereoisomeric reduction products 29, 30 and 32 obtained from 24 and 25, gave the pentacyclic compound 33 on treatment with polyphosphoric acid.
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  • 57
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cyclopeptide antibiotics from Aspergillus species. Structure of echinocandins C and DThe echinocandins B, C and D are antifungal antibiotics produced by a strain of Aspergillus rugulosus. All three metabolites are closely related representing cyclic oligopeptides composed of six amino acids and a linolic acid residue in an amide linkage. The complete structure of echinocandin B (1) has recently been established by X-ray analysis. Structural assignments to the new minor metabolites C and D have now been made by hydrolytic and oxidative cleavage reactions, formation of N-acyl-α-aminoethers as well as by chemical correlations and extensive NMR. examinations. Echinocandin C (2), C52H81N7O15, contains 3-hydroxyhomotyrosine in the place of 3, 4-dihydroxyhomotyrosine present in 1. Echinocandin D (3), C52H81N7O13, differs in two amino acids: 3, 4-dihyroxyhomotyrosine and 4, 5-dihydroxyornithine, unusual units of 1 being replaced by 3-hydroxyhomotyrosine and ornithine.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 58
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Compounds 2, 5 and 9 represent the first examples of isolable dichlorooxiranes formed by formal addition of dichloro carbene to a carbonyl group under phase transfer conditions. On heating, 2, 5 and 9 rearrange into α-chloroacid chlorides 3, 6 and 10, respectively.
    Materialart: Digitale Medien
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  • 59
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Aminoisoxazoles C-nucleosidesUpon treatment with bromocyanomethylenetriphenylphosphorane, a series of aldehydosugar derivatives gave in good to excellent yields the corresponding terminal gem-bromocyanoenoses 3, 7-10 and 16. Reacted with hydroxylamine, these unsaturated sugars led to the expected [3] 5-amino-3-glycosylisoxazoles 4, 11, 12 and 17, whereas using hydroxyurea as a binucleophile they gave the corresponding 3-amino-5-glycosylisoxazoles 13 and 14 as previously described in other series [3]. The major interest of these compounds rests in their being close analogs (or enantiomers of analogs) of important biological compounds as f.e. AICAR.
    Zusätzliches Material: 2 Tab.
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  • 60
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2613-2629 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Irradiation of 4-Allylated 2,6-Dimethylanilines in Methanol4-Allyl-, 4-(1′-methylallyl)-, 4-(2′-butenyl)-, and 4-(1′,1′-dimethylallyl)-2,6-dimethylaniline (14-17; cf. Scheme 3) were obtained by the acid catalysed, thermal rearrangement of the corresponding N-allylated anilines in good yields. Aniline 14, when irradiated with a high pressure mercury lamp through quartz in methanol, yielded as main product 4-(2′-methoxypropyl)-2,6-dimethylaniline (22; cf. Scheme 4) and, in addition, 2,6-dimethyl-4-propylaniline (18) and 4-cyclopropyl-2,6-dimethylaniline (23). The analogous products, namely erythro- and threo-4-(2′-methoxy-1′-methylpropyl)-2,6-dimethylaniline (erythro- and threo-24), 2,6-dimethyl-4-(1′-methylpropyl)aniline (19), trans- and cis-2,6-dimethyl-4-(2′-methylcyclopropyl)aniline (trans- and cis-25), as well as small amounts of 4-ethyl-2,6-dimethylaniline (26), were formed by irradiation of 15 in methanol (cf. Scheme 5). When this photoreaction was carried out in O-deuteriomethanol, erythro- and threo-24 showed an up-take of one deuterium atom in the side chain. The mass spectra of erythro- and threo-24 revealed that in 50% of the molecules the deuterium was located at the methyl group at C(1′) and in the other 50% at the methyl group at C(2′) (cf. Scheme 6). This is a good indication that the methanol addition products arise from methanolysis of intermediate spiro[2.5]octa-4,7-dien-6-imines (cf. Scheme 7). This assumption is further supported by the photoreaction of 17 in methanol (cf. Scheme 8) which led to the formation of 4-(2′-methoxy-1′,2′-dimethylpropyl)-2,6-dimethylaniline (28) as main product. The occurrence of a rearranged side chain in 28 can again be explained by the intervention of a spirodienimine 31 (cf. Scheme 9). In comparison with 14, 15 and 17, the 2′-butenylaniline 16 reacted only sluggishly on irradiation in methanol (cf. Scheme 10). It is suggested that all photoproducts - except for the cyclopropyl derivatives which are formed presumably via a triplet di-π-methane rearrangement - arise from an intramolecular singlet electron-donor-acceptor complex between the aniline and ethylene chromophor of the side chain. Protonation of this complex at C(3′) or C(2′) will lead to diradicals (e.g. 33 and 34, respectively, in Scheme 11). The diradicals of type 33 undergo ring closure to the corresponding spirodienimine intermediates (e.g. 31) whereas the diradicals of type 34 take up two hydrogen atoms to yield the photo-hydrogenated compounds (e.g. 21) or undergo to a minor extent fragmentation to side chain degraded products (e.g. 30; see also footnote 7).-Irradiation of 4-ally-2,6-dimethylaniline (14) in benzene or cyclohexane yielded the corresponding azo compound 38 (cf. Scheme 12), whereas its N,N-dimethyl derivative 41 was transformed into the cyclopropyl derivative 42. The allyl moiety in 14 is not necessary for the formation of azo compounds since 2,4,6-trimethylaniline (39) exhibited the same type of photoreaction in benzene solution.
    Zusätzliches Material: 1 Tab.
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  • 61
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2661-2672 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Conjugated cyclic divinyl ketones containing fifteen and seventeen membered rings have been prepared in a single step by condensation of 1,3-bis (dimethylphosphono)-2-propanone (10) with the dialdehydes 14, 17, 20, and 42 in the presence of hydrogencarbonate in aqueous t-butyl alcohol at reflux without using high dilution techniques. The more highly unsaturated aldehydes give better yields and ketones 34 and 36, or mixtures of the two, were transformed to muscone (1) and Exaltone® by standard procedures. Civetone (2) was prepared by hydrogenation of 43 in pyridine solution. Dienone 29 appears to be the first α, β-unsaturated ketone in which one of the β-vinyl proton resonates at higher field than the corresponding α-proton.
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  • 62
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Mechanism of the Photochemical Addition of Methanol to 2-Allylated AnilinesWe studied in methanol the photoreaction of the 2-allylated anilines, given in Scheme 3 (cf. also [1]). Irradiation of N-methyl-2-(1′-methylallyl)aniline (15) with a high pressure mercury lamp yielded trans- and cis-1,2,3-trimethylindoline (trans- and (cis-34) as well as erythro- and threo-2-(2′-methoxy-1′-methylpropyl)-N-methylaniline (erythro- and threo-35; Scheme 7). When the corresponding aniline d3-15, specifically deuterated in the 1′-methyl group, was irradiated in methanol, a mixture of trans- and cis-d3-34, and of erythro- and threo-d3-35 was obtained. Successive dehydrogenation of the mixture of cis/trans-d3-34 by Pd/C in boiling xylene and by MnO2 in boiling benzene lead to the corresponding indole d3-36 (cf. Scheme 9), the 1H- and 2H-NMR. spectra of which showed that both cis-d3- and trans-d3-34 had bound the deuterium labeled methyl group exclusively at C(3). The 1H- and 2H-NMR. analyses of the separated methanol addition products revealed that erythro-d3-35 contained the deuterium label to at least 95% in the methyl group at C(1′), and threo-d3-35 to 50% in CH3—C(1′) and to 50% in CH3—C(2′) (cf. Scheme 9). To confirm these results 2-(1′-ethylallyl)aniline (16) was irradiated in methanol, whereby a complex mixture of at least 6 products was obtained (cf. Scheme 11). Two products were identified as trans- and cis-3-ethyl-2-methylindoline (trans- and cis-37). The four other products represented erythro- and threo-2-(1′-ethyl-2′-methoxypropyl)aniline (erythro- and threo-39) as major components, and erythro- and threo-2-(2′-methoxy-1′-methylbutyl)aniline (erythro- and threo-40). These results clearly demonstrate that the methanol addition products must arise from spirodienimine intermediates of the type of trans-9 and cis-11 (R1 = CD3 or C2H5, R2 = CH3 or H; Scheme 2) which are opened solvolytically with inversion of configuration by methanol. Thus, cis-11 (R1 = CD3, R2 = CH3) must lead to a 1:1 mixture of threo-13 and threo-14 (i.e.) a 1:1 distribution of the deuterium labelled methyl group between C(1′) and C(2′) in threo-35) The formation of erythro-d3-35 with at least 95% of the deuterium label in the methyl group at C(1′) indicates that trans-9 (R1 = CD3, R2 = CH3) reacts with methanol regioselectively (〉 95%) at the C(2), C(3) bond. Similarly, the formation of the methanol addition products in the photoreaction of 16 (Scheme 11) can be explained. Since the indolines, formed in both photoreactions, show no alteration in the position of the subsituent at C(1′) with respect to the starting material we suppose that the diradical 7 (R1 = CD3 or C2H5, R2 = CH3 or H; Scheme 2) is a common intermediate which undergoes competetive 1.3 and 1.5 ring closure yielding the spirodienimines and the indolines.This conception is supported by irradiation experiments with N, 3,5-trimethyl-2-(1′-methylally)aniline (17) and 2-(2′-cyclohexenyl)-N-methylaniline (18) in methanol. In the former case the formation of spirodienimines is hindered by the methyl group at C(3) for steric reasons, thus leading to a ratio of the indoline to the methoxy compounds of about 6.3 as compared with ca. 1.0 for 15 (cf. Scheme 12). On the other hand, no methoxy compounds could be detected in the reaction mixture of 18 (cf. Scheme 13) which indicates that in this case the 1.3 ring closure cannot compete with the 1.5 cyclization in the corresponding cyclic diradical of the type 7 (R1-C(1′)-C(2′) is part of a six-membered ring; Scheme 2).We suppose that the diradicals of type 7 are formed by proton transfer in an intramolecular electron-donor-acceptor (EDA) complex arising from the excited single state of the aniline chromophor and the allylic side chain. This idea is supported by the fluorescence specta of 2-allylated N-methylanilines (cf. Fig.1-4) which show pronounced differences with respect to the corresponding 2-alkylated anilines. Furthermore, the anilines 18 and 20 when irradiated in methanol in the presence of an excess of trans-1,3-pentadiene undergo preferentially an intermolecular addition to the diene, thus yielding the N-(1′-methyl-2′-butenyl)anilines 52 and 51, respectively (Scheme 15), i.e. as one would expect the diene with its low lying LUMO is a better partner for an EDA complex than the double bond of the allylic side chain.
    Zusätzliches Material: 5 Ill.
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  • 63
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2673-2680 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new strategy for the synthesis of muscone (1) using the OH-assisted Prins reaction for macrocyclic ring closure has been developed. The monoacetal 4 of (Z,E)-4,8-dodecadienedial (3), easily obtainable from (Z,E,E)-1,5,9-cyclododecatriene (2), is treated with methallylmagnesium chloride, and the resulting C16-precursor 5 is subjected to acid-catalyzed cyclization in dilute (≤1%) solutions. This results in formation of the bicyclic dihydropyran derivatives 6 which directly yield muscone (1) on heating with a noble metal catalyst saturated with hydrogen. The five-step pathway proceeds with readily available starting materials in conventional steps and excellent overall yield (∼40%). This new principle of macrocyclic ring formation has also been used successfully for the preparation of 3-methylcyclotridecanone (34) and should be generally applicable for other suitable ring systems.
    Zusätzliches Material: 1 Tab.
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  • 64
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2681-2694 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A synthesis of (6 R, 7 R)-7-acylamino-2-oxocephem-4-carboxylic acids from penicillins is reported based on the formation of the 2-oxocephem system in an intramolecular Wittig condensation. An interesting steric effect of the acylamino grouping on the course of this key step was used to advantage. Some physical and biological properties of this new type of Δ3-cephem are described.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 65
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The chiral aminoethers 1-4, accessible from tartaric acid, are tested as complexing ligands in organolithium reactions. The tetramine 4 turns out to cause highest inductions [see Table 2 and Equations (1)-(4)].
    Zusätzliches Material: 2 Tab.
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  • 66
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Diglycosyl Derivatives. Preliminary communicationNovel types of diglycosyl compounds, some of them bearing a resemblance to natural di- or tri-saccharides are described: a diglycosyldiyne (1), a diglycosylthiophene (2), a diglycosylaziridine (3), a diglycosyldioxolane (4), as well as six C,N-diglycosylnitrones, 9b-9f and 14. These C,N-diglycosylnitrones, on treatment with an acetylenic Grignard reagent, led to the expected acetylenic diglycosyl-hydroxylamine 11, whereas diglycosylisoxazolines (f. ex. 10) were obtained when these nitrones underwent 1,3-dipolar cycloaddition to acetylenic compounds.
    Zusätzliches Material: 1 Tab.
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  • 67
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 882-893 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cob(I)alamin as Catalyst. 4. Communication. Reduction of α,β-Unsaturated NitrilesUsing catalytic amounts of cob (I)alamin and an excess of metallic zinc as source of electrons 1-naphthonitril (5) has been reduced to (1-naphthyl)methylamin (6) and in small amounts to (1-naphthyl)methanol (7) and (1,2,3,4-tetrahydro-1-naphthyl)methanol (8) (5 ½ h, CH3COOH/H2O; s. Scheme 3). Starting from cyclododecylideneacetonitrile (15) similar conditions (68 h, CH3COOH/H2O) produced the amines 16-19 as well as the nitrogen free saturated aldehyde 20, the corresponding allylic alcohol 21 and the saturated derivative 22 (s. Scheme 6). It is deduced that the first attack of cob (I)alamin on an α,β-unsaturated nitrile might occur on both the nitrile dipole as well as on the carbon atom in β-position. Cob (I)alamin in aqueous acetic acid saturates the isolated double bonds in allylic alcohols and amines. In a slow reaction the two different aromatic rings of (1-naphthyl)methanol (7) have been reduced giving the corresponding tetrahydronaphthalene derivatives 8 and 12, and in one case the production of the octahydroderivative 14 has been observed in a low yield (s. Scheme 5).
    Zusätzliches Material: 2 Tab.
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  • 68
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The wavelength range of the CD. spectra of some cyclohexapeptides containing different sequences of glycine, L- and D-alanine is extended down to 170 nm. This allows a relatively complete recording of the (n - π*) and (π° - π*) Cotton effects. Some striking spectral changes are observed on going from one molecule to another. The relative influence of L- and D-alanyl residues is discussed: Some spectra may be qualitatively related to each other by considering the effect of an L-residue at position q in the ring to cancel partially with the effect of a D-residue at position q ± 3. Assuming these cyclopeptides to occur in a hydrogen-bonded pleated sheet structure, certain dominant changes in the spectra are interpreted as reflecting a transition of the overall backbone conformation from one which is closer to the (optically inactive) symmetry Ci to another which is closer to the (optically active) symmetry C2. An attempt is made to relate the influence of L- and D-substituents within hairpin bends of the pleated sheet structure to an amide sector rule.
    Zusätzliches Material: 7 Ill.
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  • 69
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Lincomycin analogues. I. Chain-extensions of [1,2:3,4]-di-O-isopropylidene-α-D-galacto-hexodialdo-1,5-pyranoseThe title aldehydosugar 1 treated with Wittig reagents led in good to excellent yields to the unsaturated sugar derivatives 3-7 and 10-15, 8 having been prepared by condensation of 1 with malonic acid. The configuration (Z or E) of each compound obtained has been established by 1H-NMR. These chain-extensions constitute the first synthetic step towards the preparation of lincomycin analogues.
    Zusätzliches Material: 2 Tab.
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  • 70
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The photochemistry of optical active λ, δ-epoxy-enones. Racemization and cyclization of (-)-4-methylidene-5,6-epoxy-5,6-dihydro-β-ionone and of (-)-4-oxo-5,6-epoxy-5,6-dihydro-β-iononeUV.-irradiation (λ ≥ 347 nm as well as λ = 254 nm) converts the conjugated λ, δ-epoxy-enones (-)-2 and (-)-4 by cleavage of the C,C-oxirane bond to an intermediate ketonium ylide f which cyclizes giving the racemic starting materials. The degree of racemization depends on the length of the irradiation time.The formation of the optical active products (-)-3 and (+)-5 in these irradiations gives evidence, that the photocyclization of (-)-2 und (-)-4, respectively, is a one step reaction of a state g.
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  • 71
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The photoinduced cleavage of the C,C-oxirane bond of γ, δ-epoxy-enones: UV.-irradiation of 4-methylidene-5,6-epoxy-5,6-dihydro-β-iononeOn 1n, π*-excitation (λ ≥ 347 nm, pentane) 5 gives the isomeric bicyclic ether 10 in 75% yield (s. Scheme 2). In methanol the photoconversion of 5 to 10 is strongly reduced (12%) in favour of the formation of the methanol adduct 11 (43%). On photolysis in aqueous acetonitrile 5 is converted to the bicyclic ether 10 (9%), the dihydrofurane 12 (18%) as well as to the triketones 13A and 13B (7%), and 14 (23%).On 1π, π*-excitation (λ = 254 nm) in pentane no 10 is formed, but 5 isomerizes to the tricyclic cyclopropyl compound 16 (59%), the allenic product 17 (10%), and the cyclopropene compound 18 (12%; s. Scheme 3). Photolysis in methanol furnishes 11 (63%), and 18 (4%), but no tricyclic cyclopropyl compound 16. In a secondary photoreaction (λ = 254 nm) the dihydrofurane 12 is isomerized to the bicyclic cyclopropyl compound 20.Evidence is given that the products 11 and 13 are formed by solvent addition to an intermediate ketonium ylide b (s. Scheme 12). The presence of b is further proven by the formation of 12, a product of an electrocyclization of b. On photofragmentation of b carbenoids d and e are presumably formed (s. Scheme 14). 1,2-Hydrogen shift in d yields the allene derivative 17, and cyclization of d gives the cyclopropene compound 18. On the other hand, e cyclizes to the non isolated cyclopropene compound 69 which is transformed to 16 by an intramolecular [4 + 2]-cycloaddition.The present investigation shows that the photochemistry of 5 is determined by photoinduced C,C-bond cleavage of the oxirane ring. This is in sharp contrast to the photochemistry of conjugated γ, δ-epoxy-enones without the additional double bond in ε, ζ-position, where selective photocleavage of the C(λ), O-bond is observed.
    Zusätzliches Material: 1 Tab.
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  • 72
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979) 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 73
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Enantioselective 1,2-addition of Li-, Mg-, Zn-, and Cu-organic compounds and of Li-enolates to carbonyl derivatives in the chiral medium DDBDDB = 1,4-Dimethylamino-2,3-dimethoxybutan (= 2,3-Dimethoxy-N,N,N′,N′-tetramethyl-1,4-butandiamin).The (+)-enantiomer of the methoxyamine DDB is used as a chiral cosolvent in the title reactions. As evident from the results listed in the table, enantiotopic faces are generally differentiated with preferences ranging from 55:45 to 60:40.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 74
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1736-1744 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The influence of twenty substituents R on the solvolysis rates and products of tertiary chlorides R - CH2CH2C(CH3)2Cl (7) has been studied. H, CH3, (CH3)2NCH2, ClCH2, Cl, CN and NO2 exert an inductive effect only, as the good correlation of the rates with the corresponding inductive substituent constants σIq shows. Bulkier alkyl groups, i.e. isopropyl and t-butyl, lower the rate due to a Baker-Nathan effect, while the n-electron donors CH3S, CH3O, HO and (CH3)2N and the σ-electron donors (CH3)3Sn and HOCH2 cause rate increases based on σIq constants. These accelerations are attributed to C,C-hyperconjugative and inductomeric effects which arise in the transition state for ionization. A comparison of the reactivity of the acyclic chlorides 7 and the corresponding 1-R-substituted 3-bromoadamantanes 1a shows that polar substituent effects are more strongly transmitted in the rigid bicyclic compounds 1a than in the flexible acyclic compounds 7.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 75
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The intramolecular and dimensionless equilibrium constant, K′, for the equilibrium between open and aromatic-ring stacked isomers of ternary complexes formed between adenosine 5′-triphosphate, inosine 5′-triphosphate, or uridine 5′-triphosphate, Mg2+ or Zn2+, and L-tryptophanate, 2,2′-bipyridyl (bipy), or 1,10-phenanthroline (phen) have been estimated by 1H-NMR. shift measurements in D2O (I = 0.1M, NaNO3; 27°). The approximate equilibrium constants K′ are ≥ 20, ≥ 20, 1.2, 0.9, 0.7, 0.5, and 0.3 for the ternary complexes Zn (phen) (ATP)2-, Mg (phen) (ATP)2-, Zn (bipy) (ATP)2-, Zn (bipy) (ITP)2-, Zn (bipy) (UTP)2-, Zn (trp) (ATO) 3-, and Mg (trp) (ATP)3-, respectively. The percentages of the stacked isomers decrease in the order Zn (phen) (ATP)2- (≥ 95%) ≫ Zn (bipy) (ATP)2- (55%) 〉 Zn (bipy) (ITP)2- (48%) 〉 Zn (bipy) (UTP)2- (∼ 40%), which coincides with the order of stability of the binary metal-free adducts (phen) (ATP)4- 〉 (bipy) (ATP)4- ≃ (bipy) (ITP)4- 〉 (bipy) (UTP)4-; the corresponding stability constants are KABA = 28.2 ± 4.7, 8.1 ± 2.6, 8.8 ± 1.8, and ∼ 1 (M-1), respectively (D2O; I = 0.1 M, NaNO3; 27°): these series reflect the decreasing size of the aromatic-ring systems forming the stacks. The indole moiety of tryptophan resembles 2,2′-bipyridyl rather than 1,10-phenanthroline and K(trp)(ATP)(trp) = 6.2 ± 1.8 M-1 for (trp) (ATP)4-. Implications with respect to the stability of ternary complexes, and to biological systems are indicated briefly.
    Zusätzliches Material: 5 Ill.
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  • 76
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1763-1769 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Structural Modifications of Vitamin D3. Synthesis and Properties of the SO2-Adducts with (5Z)- and (5E)-Vitamin D3Treatment of (5Z)- and (5E)-vitamin D3 (4) with sulfur dioxide yields each quantitatively the cyclic sulfones 1a and 1b. Thermally induced elimination of sulfur dioxide leads to either isotachysterol3 (3) alone or mixtures of isotachysterol3 (3) and isovitamin D3 (2). On the other hand the extrusion of SO2 can be brought about by means of KOH/CH3OH or on an alumina surface affording (5E)-vitamin D3 (4). On treatment with CD3UD/tBuOK/D2O 1a and 1b are transformed (5E)-6, 19, 19′-trideuteriovitamin D3 (4a).
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 77
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: (E)-3α-Acetoxy-5, 10-seco-1(10)-cholesten-5-one (3) was synthesized by fragmentation of 3α-acetoxy-5α-cholestan-5-ol (1) using the photochemical version [3] of the lead tetraacetate reaction [4], and transformed into the corresponding 3-oxo-compound (5). Two conformations (A2α and B1α) were deduced for the 10-membered ring of 3 by analysis of the 1H- and 13C-NMR. spectra in toluene. The major conformation (A2α) corresponds to that found in the solid state by X-ray analysis. According to its NMR. spectra in toluene, the medium-sized ring of the diketone 5 exists also predominantly in two conformations, the major one being analogous to A1β (the solid-state conformation of the 3β-acetoxy isomer (9) [1]) and the minor one to A2α (see above). The stereochemistry of the acidcatalyzed and thermal cyclisations of 3 as well as of the corresponding 5-oxime is discussed in terms of conformational factors.
    Zusätzliches Material: 2 Ill.
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  • 78
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1016-1024 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The crystal structures of PdCl2[(-)-DIOP], PtCl2[(-)-DIOP] and of NiCl2-[(-)-DIOP] have been determined by X-ray analysis and refined by least-squares methods [(-)-DIOP=(-)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane]. The coordination around the nickel atom is tetrahedral, the coordination around palladium and platinum is square planar. The unit cell of the palladium complex contains two non-equivalent molecules with different conformations of the seven-membered chelate ring involving the metal and the two phosphorus atoms. PtCl2[(-)-DIOP] is isostructural with the corresponding palladium complex.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 79
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 1H-NMR. Spectroscopic Determination of Enantiomeric Purities of Allenic Esters Using Optically Active Europium Shift ReagentsThe racemic allenic methyl esters 3--7 and the racemic allenic diesters 8--10 (cf. Scheme 2) in 1,1,2-trichloro-1,2,2-trifluoroethane (TCFE) and CCl4 in the presence of optically active tris[3-(heptafluorobutyryl)-(+)-camphorato]europium(III) (Eu(hfc)3) have induced unlike 1H-NMR. shift differences (ΔΔδ) for the protons of the methoxycarbonyl groups of their enantiomers. In some allenic esters the shift reagent causes additional separation of resonance signals; thus, further substituents on the allenic framework may be differentiated in the racemic mixture. This finding provides a widely applicable method for the determination of absolute enantiomeric purities of allenic esters and their corresponding acids. Accordingly we found for optically pure (+)-(S)-2-methyl-2,3-pentadienoic acid ((+)-(S)-13; cf. Fig. 2) a calculated [α]58920 value of + 73.3 ± 1.8°. Finally, the substituent effects on ΔΔδ-values (cf. Table 1--3) are discussed.
    Zusätzliches Material: 2 Ill.
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  • 80
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Stereospecific Fragmentations in the Mass Spectra of Cyclohexanediamines and Bis(aminomethyl)cyclohexanesThe mass spectral behaviour, especially loss of NH3, of the six isomeric cyclohexanediamines 1--3 (cis and trans each, Scheme 1) as well as of the six isomeric bis(aminomethyl)cyclohexanes 4--6 (cis and trans each, Scheme 6) has been investigated. The cis- and trans-compounds of the 1,2-isomers 1 and 4 show very similar spectra, because of the ease of ring cleavage at C(1)--C(2) and the similar geometrical relations in all ring conformations. The cis- and trans-compounds of both the 1,3- and 1,4-isomers 2, 3, 5 and 6 show striking differences in their mass spectra due to stereospecific elimination of NH3 from the molecular ion.
    Zusätzliches Material: 6 Ill.
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  • 81
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 82
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The Mass Spectral Decomposition of Isomeric Diacetamido-cyclohexanes, their N-Phenethyl-Derivatives and Bis(acetamidomethyl)cyclohexanesIn the mass spectra of the six isomeric diacetamidocyclohexanes 2--4 (cis and trans each, Scheme 2) as well as of the six isomeric bis(acetamidomethyl)cyclohexanes 6--8 (cis and trans each, Scheme 5) are clear differences between the constitutional isomers, whereas cis/trans isomers show very similar spectra. The lack of stereospecific fragmentations is explained by loss of configurational integrity of the molecular ion before fragmentation.However, the mass spectral fragmentation of epimeric diamidocyclohexanes becomes very stereospecific by the introduction of a phenethyl group on one of the nitrogen atoms: this group avoids epimerization of the molecular ion prior to fragmentation. In the N-phenethyl derivatives 10, 11, 13 and 14 (Scheme 8) the typical fragmentations of the cis-isomer after loss of ·C7H7 from the molecular ion are the elimination of CH2CO by formation of cyclic ions, and the loss of p-toluenesulfonic acid or benzoic acid, respectively, with subsequent elimination of CH3CN (Scheme 9). In the trans-isomer the typical fragmentations are the loss of the side chain bearing a tertiary nitrogen atom, and the elimination of the tosyl or benzoyl radical, respectively, with subsequent loss of CH3CONH2 (Scheme 10).
    Zusätzliches Material: 4 Ill.
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  • 83
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The potentiometric study of the complexation of Cu2+ with 1,4,7-triazacyclononane (1), 1,4,8-triazacyclodecane (2) 1,5,9-triazacyclododecane (3) has shown that CuL, CuL2 and (CuLOH)2 are the main species present in solution. Their stabilities (Table 1) and their absorption spectra (Table 2) indicate facial coordination of the cyclic triamines in a distorted octahedral geometry.The formation and dissociation kinetics have been measured by stopped-flow techniques. The formation in acetate buffer can be described by the reaction of Cu2+ and CuAcO+ with the monoprotonated species of the ligand. The bimolecular rate constants for these complexations (Table 3) decrease when the ring size increases. In contrast the dissociation induced by acid is only little affected by the ring size. Thus for these complexes the rate of formation and not that of the dissociation determines the overall stability.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 84
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1096-1097 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The absolute configuration of the title compound, a minor constituent of civet, is shown to be S,S.
    Materialart: Digitale Medien
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  • 85
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1640-1644 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis of 22,23-methano-24-nor-cholest-5-en-3β-ol and comparison with cystosterol22,23-Methano-24-nor-cholest-5-en-3β-ol, a novel cyclopropane-containing sterol was synthesized from stigmasterol and found to be different from the isomeric, naturally occurring marine sterol cystosterol.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 86
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of the spin-labeled uridine and 2′-deoxyridine analogues RUGT 2, DUGT 3, l-RUGT 4, and l-DUGT 5 is described. DUGT 3 showed some activity against the leukemia P388 cell line.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 87
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1688-1688 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 88
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1682-1687 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The unique stabilization of the ester link in dialkyl succinyl succinates is explained and a facile route to known as well as to hitherto inaccessible succinyl succinates is suggested. New representatives of this series are described.
    Zusätzliches Material: 1 Tab.
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  • 89
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1689-1690 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 90
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1689-1700 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of ethylene oxidation by air over a supported silver catalyst were investigated in the temperature range 490-620 K. The reaction network was found to be triangular. Under virtually constant oxygen partial pressure (0.2 bar), the following rate relationships, (in mol g-1s-1) were found: (formulae in curved brackets denote partial pressures) where R is expressed in J · mol-1 · K-1.The given rate expressions are discussed in the framework of earlier kinetic investigations.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 91
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Enantioselective 1,4-additions of organometallic compounds to conjugated systems in the chiral medium DDBDDB = 1,4-Dimethylamino-2,3-dimethoxybutan (= 2,3-Dimethoxy-N,N,N′,N′-tetramethyl-1,4-butandiamin).The chiral methoxyamine DDB is used as a cosolvent to add achiral Li-, Cu-, and Zn-organic compounds enantioselectively to prochiral β-carbon atoms of α, β-unsaturated aldehydes, ketones, nitro compounds and ketene-thioacetals (Tables 1 and 2). The selectivity generally ranges from 55:45 to 63:27, in one case (9b) an enantiomeric excess of 43% was obtained.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 92
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 1745-1752 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The study of 16, 17, 18, 19, 28, 29-hexahydrorifamycin S by 1H-NMR. spectroscopy using INDOR at 100 MHz and homodecoupling at 270 MHz has shown that the conformation of the ansa fragment C(20)-C(27) and the position of this fragment relative to the naphthoquinone chromophore are practically the same as those of rifamycin S. This finding rules out the hypothesis that the lower activity of the hydrogenated rifamycins could be due to a different conformation.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 93
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Pyrazolo[1,5-a]indolesTreatment of 1-(2-heteroaroyl or aroyl-phenyl)-pyrazoles (3) with potassium hydroxide in 95% ethanol or with sodium ethanolate in ethanol produces a novel ring closure to new 4-hydroxy-4-(4-heteroaryl or aryl)-4H-pyrazolo [1,5-a]indoles 5 and 6 (Table 1). A 2, 3, or 4-pyridyl at position 4 is easily reduced yielding the 4-(2, 3, or 4-piperidyl)-derivatives 7 and 8 (Table 2). Water is split off from these piperidyl-derivatives 7 or 8 to give the piperidylidene derivatives 9 or 10 (Table 3) which may be considered as heterocyclic analogues to known tricyclic psychopharmaceuticals with antidepressant or neuroleptic activities.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 94
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The structure and configuration of gilmaniellin, a metabolite of Gilmaniella humicola BARRON, has been shown to be 2 by X-ray analysis. By comparison of spectral data structure 1 has been assigned to dechlorogilmaniellin.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 95
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2211-2217 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cycloadditions of 3,4-dimethoxyfuran with benzoquinonesCycloaddition of 3,4-dimethoxyfuran (3,4-DF, 1) with 1,4-benzoquinones furnishes isolable (2 + 4)-adducts in high yield. The crystalline products with benzoquinone, 2-methyl-benzoquinone, 2,3-dimethoxy-benzoquinone have endo-configuration, whereas 2,3-dimethyl-benzoquinone gives the exo-adduct 4c exclusively. Halogens (Cl2, Br2) add rapidly across the highly nucleophilic double bond of 3 or 4 in stereospecific cis-manner, and exclusively from the exo-side. The product 5c shows no sign of enolization to the hydroquinone; but with 3a and 3d the hydroquinones 6 were found. Methanolysis of 5 leads to the stable acetals 7 and 8. On oxidation of the hydroquinones 7 the thermolabile quinones 10 were obtained. Preparative pyrolysis of 10a under relatively mild conditions (N2, 200°, 0.1 Torr) gives tetramethoxy ethene (11) and isobenzofuran-4,7-quinone 12, a yellowish, crystalline and stable compound.
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  • 96
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2218-2229 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The acid-catalyzed hydrolysis of CF3CHN2 (1) follows an A2 mechanism of preequilibrium protonation and rate-determining solvolysis of the intermediate diazonium ion 4; this was demonstrated by: (a) the inverse kinetic isotope effect; (b) H-D exchange; (c) the unimportance of general acid catalysis; (d) strong rate acceleration by added nucleophiles. The activation parameters have been determined in two solvent systems. In contrast to 1 the secondary diazocompound CF3—CN2—CH3 (2) follows the normal A-SE2 mechanism of rate-determining proton transfer.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 97
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Lithium- and copper-derivatives of α,α-doubly deprotonated nitroalkanes. Generation, properties and reactions with alkyl- and allylhalidesAus der Dissertation von F.L., ETH Zürich, 1979; Nr. 6356. Die Arbeiten wurden teilweise am Institut für Organische Chemie der Justus-Liebig-Universität Giessen durchgeführt. Vorläufige Mitteilungen siehe [1] und [2].Primary nitroalkanes are deprotonated twice in the α-position when treated with two mol-equiv. of butyllithium at -78° to -100° in THF containing HMPT to give dilithium derivatives 15 (the compound with R = C2H5 is stable up to -30°). The acidity of the nitronate proton of 13 is estimated to be in the same range as that of diisopropylamine. The C-nucleophilicity of the novel reagents 15 is dramatically increased as compared with that of simple nitronates 5: C,C-bond-forming reactions readily take place with alkylhalides (→22c-e,g,h,j-m) and benzylbromide (→22b,f,i); allylations are possible via nitroalkycopper-lithium-derivatives (→27-29).
    Zusätzliches Material: 6 Tab.
    Materialart: Digitale Medien
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  • 98
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Electrochemical Investigations of the Enantiomer Selectivity of Chiral Ionophores in Liquid MembranesThe enantiomer selectivity of a series of chiral neutral ionophores was investigated by electrochemical methods using ionophore-solvent-polymer membranes and chiral ammonium salts as substrates. The potentiometrically determined enantiomer selectivities are in good agreement with the results of electrodialytic transport studies.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 99
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Die vier diastereomeren Thioanalogen des (±)-MuscarinsIm Zusammenhang mit pharmakologischen Arbeiten über die chemische Natur des cholinergischen Rezeptors haben wir die reinen (±)-Thiomuscarinjodide 4a-d hergestellt und ihre relativen Konfigurationen an C(2), C(3) und C(5) an den nor-Basen 3a-d in 1H-NMR.-Spektren mit Lanthanidverschiebung aufgeklärt. Auf der Stufe der 3-Hydroxymide 2 wurden die vier Diastereomere chromatographisch voneinander getrennt.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 100
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Monomolecular fragmentations of butadiyne- and 1,3-pentadiyne radical cations in their electronically excited states have been investigated by use of the photoelectron-photoion coincidence technique. Breakdown curves for the molecular and various fragment ions have been recorded over the ionization energy range of 9 to 17 eV. These breakdown curves reveal the extent of the competition between the radiative relaxation (ion fluorescence) and the non-radiative internal conversion followed by fragmentation for the decay of the first excited electronic states. Extensive hydrogen scrambling and/or ionic-carbon-skeleton isomerization takes place prior to fragmentation, as revealed by the breakdown curves obtained for the site specifically deuteriated 1,3-pentadiynes.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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