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  • Cell & Developmental Biology  (5,878)
  • Inorganic Chemistry  (5,043)
  • Aerodynamics
  • Aircraft Design, Testing and Performance
  • ddc:330
  • 2020-2024  (50)
  • 1985-1989  (8,674)
  • 1950-1954  (2,424)
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  • 1
    Publication Date: 2023-12-20
    Description: Striving to mitigate climate change, the European Union has adopted net-zero greenhouse gas emissions as a target for 2050. In this paper, European chemical industry roadmaps from the past six years are assessed and compared to uncover how the industry envisions its role in the transition to net-zero emissions. The roadmaps are assessed in terms of ambition level, technology and feedstock strategies, investment needs and costs, agency and dependency on other actors, as well as timeline and concretion. Although net-zero pathways are often drawn out in the roadmaps, some also choose to emphasize and argue for less ambitious pathways with emission reductions of only 40-60 %. The roadmaps vary widely in terms of the importance they assign to mechanical and chemical recycling, switching to biogenic carbon and carbon dioxide as feedstock, electrification and hydrogen, and carbon capture and storage. A commonality though, is that low-tech or near-term mitigation pathways such as demand reduction, reuse or material efficiency are seldom included. High investment needs are generally highlighted, as well as the need for policy to create enabling conditions, whereas the agency and responsibility of the chemical industry itself is downplayed. Our analysis highlights that the chemical industry does not yet have a strong and shared vision for pathways to net-zero emissions. We conclude that such a future vision would benefit from taking a whole value chain approach including demand-side options and consideration of scope 3 emissions.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
    Type: article , doc-type:article
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  • 2
    Publication Date: 2024-04-04
    Description: Die schnelle und umfassende Emissionsminderung in der Energie- und Kreislaufwirtschaft ist der Schlüssel für die Begrenzung der Erderwärmung auf unter 2 °C. In Deutschland werden entsprechende Politiken seit den 1990er-Jahren verfolgt, allerdings erst in jüngster Vergangenheit mit dem notwendigen Nachdruck und der notwendigen Orientierung hin zu mehr Marktmechanismen. Wesentliche Handlungsfelder sind Energieeinsparung und erhöhte Energieeffizienz, Umstieg auf erneuerbare Energien, Bepreisung von Klimagasen sowie eine Reduzierung und Schließung der Stoffkreisläufe. In allen Handlungsfeldern sind Grundlagen geschaffen, es bleibt jedoch der Großteil des Weges noch zu gehen, um Klimaneutralität zu erreichen. Für einen schnellen Fortschritt spielen neben der Überwindung der technischen, ökonomischen und organisatorischen Herausforderungen auch Verteilungsfragen und die Einbettung in internationale Maßnahmen eine zunehmende Rolle.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 3
    Publication Date: 2024-03-13
    Description: Deutschlands Haushalte werden, zu Beheizungszwecken, zu 70 % leitungsgebunden versorgt: 50 % mit Erdgas und 14 % mit Fernwärme; 5 % mit Elektrizität, davon je die Hälfte noch mit Nachtspeicherheizung, die andere Hälfte mit Wärmepumpen. So war es 2021. So wird es in Zukunft nicht sein, denn Erdgas ist ein Energieträger fossiler Herkunft. Dessen Nutzung geht in den nächsten beiden Jahrzehnten gen Null. Die Frage ist, was das für die Erdgasleitungen in Deutschland bedeutet.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 4
    Publication Date: 2024-03-13
    Description: The petrochemical industry is among the most relevant sectors from an economic, energetic and climate policy perspective. In Western Europe, production occurs in local chemical parks that form strongly connected and densely integrated regional clusters. This paper analyzes the structural characteristics of the petrochemical system in Germany and investigates three particularly distinct clusters regarding their challenges and chances for a transition towards climate-neutrality. For this, feedstock and energy supply, product portfolios and process integration as well as existing transformation activities are examined. We find that depending on their distinct network characteristics and location, unique and complex strategies are to be mastered for every cluster. Despite the many activities underway, none of them seems to have a strategic network to co-create a tailored defossilization strategy for the cluster - which is the core recommendation of this paper to develop.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
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  • 5
    Publication Date: 2024-03-07
    Description: Demand-side mitigation strategies have been gaining momentum in climate change mitigation research. Still, the impact of different approaches in passenger transport, one of the largest energy demand sectors, remains unclear. We couple a transport simulation model to an energy system optimisation model, both highly disintegrated in order to compare those impacts. Our scenarios are created for the case of Germany in an interdisciplinary, qualitative-quantitative research design, going beyond techno-economic assumptions, and cover Avoid, Shift, and Improve strategies, as well as their combination. The results show that sufficiency - Avoid and Shift strategies - have the same impact as the improvement of propulsion technologies (i.e. efficiency), which is reduction of generation capacities by one quarter. This lowers energy system transformation cost accordingly, but requires different kinds of investments: Sufficiency measures require public investment for high-quality public services, while efficiency measures require individuals to purchase more expensive vehicles at their own cost. These results raise socio-political questions of system design and well-being. However, all strategies are required to unleash the full potential of climate change mitigation.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
    Type: article , doc-type:article
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  • 6
    Publication Date: 2024-02-09
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
    Type: report , doc-type:report
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  • 7
    Publication Date: 2024-02-09
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
    Type: contributiontoperiodical , doc-type:contributionToPeriodical
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  • 8
    Publication Date: 2024-05-13
    Description: Energy performance contracting (EPC) as a market instrument has been effective in promoting energy efficiency worldwide, but it has encountered many insurmountable obstacles in rural energy management. In this study, based on the characteristics of energy management in rural areas, three EPC modes are designed and tested in 24,000 rural households. The test results show that two adapted EPC modes of local government involvement and energy payment directly from the national grid can effectively overcome the barriers encountered in the traditional EPC modes and work well under the economic and social environmental conditions in rural areas. The key to the adaptation of the traditional EPC modes is the introduction of the local government as the third party. Participation of the third party can effectively reduce and remove the barriers and risks and increase the mutual trust between the clients (households) and the energy service companies (ESCOs). Based on the testing results, this study suggests that governmental departments should formulate relevant EPC policies and technical guidelines within the rural context. This research recommends that farmers should not manage their energy services by themselves and it is suggested to out-contracting ESCOs by applying the modes developed and tested by this paper.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
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  • 9
    Publication Date: 2024-06-07
    Description: North Rhine-Westphalia (NRW) is the industrial center of Germany and one of the most important industrial locations in Europe. It is a key location for the energy-intensive basic materials industry like the production of steel and non-ferrous metals, (petro)chemicals, cement and lime, bricks, glass and ceramics, and paper. Around 20 % of NRW's total greenhouse emissions derive from industrial processes. By 2045, industry must achieve climate-neutrality, which requires a massive transformation effort. Technologically, this needs large-scale utilization of green hydrogen, carbon management, consequent circular economy, and climate-neutral production of process heat. Furthermore, various adjustments to the policy framework are essential.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
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  • 10
    Publication Date: 2024-06-07
    Description: The goal of this dissertation is to facilitate the assessment of impacts from sustainable measures and projects with an emphasis on impact reporting for Green, Social or Sustainability Bonds in the Sustainable Finance market. It does so by providing analysts with the means to develop, depict, formulate, and assess a causal hypothesis between an intervention and its subsequent effects in an impact-chain, represented by desired environmental (E), social (S) or governance (G) changes. This is achieved by developing a methodology for so-called ESG Logic Models or ESG-LM, that combine heuristic Theories-of-Change with propositional logic and Bayesian Reasoning. Three research questions are investigated and responded to. Research Question 1 asks how such Theories-of-Change can be developed for any type of ESG-related issue and how the different process steps in a causal chain can be classified, hierarchised, and prioritised regarding their efficacy towards overarching sustainability goals and their plausibility. Research Question 2 studies (a) the means by which the analyst or any other interested third party might be warranted in believing the causal claims from an ESG-LM, and (b) how an ESG-LM can be improved if this credence is low. Research Question 3 then looks at the reporting of impacts themselves regarding indicator selection, indicator assessment and indicator quantification as well as the provision of information on the contributions and attributions by different actors. The dissertation draws on a variety of theories and adapts existing methods to achieve that. It operationalises concepts from empirical Sustainable Finance research and already existing impact assessment methodologies. It adapts scholarly and practitioner approaches for theory-based evaluation and applies a qualitative social science perspective towards theory-building and evaluation, while some of the assessment tools in the dissertation are grounded in Logic, Set Theory and Bayesian Epistemology. Examples for such tools include rules for the Attribution by actors, heuristics for the abduction of plausible outcome pathways, or a four-stage Argument and Decision-Tree to assess the credibility of ESG-LM claims (based on Bayes Theorem). My assessment of the entire methodology is positive overall, as it provides solutions to each of the three research areas. Limitations of the approach, and thus opportunities for further research, are the additional expertise and time required by analysts compared to the existing, and somewhat more pragmatic, solutions in the current market. However, this is outweighed in my opinion by the ability of the framework to strongly mitigate impact washing by actors in the financial markets as well as biases by analysts. Its overall methodology also provides opportunities for new research angles in the area of sustainability indicators and assessments.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 11
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    MDPI - Multidisciplinary Digital Publishing Institute
    Publication Date: 2023-11-30
    Description: Active flow control (AFC) utilizes local active perturbations to induce changes in global flow behavior that result in aero/hydrodynamic performance improvement. It has been a vibrant research area with potential applications in a wide range of engineering fields. This Special Issue is a collection of 11 excellent research papers published in Actuators, showcasing and discussing new advances in both fundamental and applied AFC technologies.
    Keywords: Active flow control ; Actuators ; Aerodynamics ; Synthetic jets&nbsp ; bic Book Industry Communication::T Technology, engineering, agriculture::TB Technology: general issues
    Language: English
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  • 12
    Publication Date: 2023-10-02
    Description: Die verheerenden Mengen an Abfall am Ende des Lebenszyklus von Produkten zu bewältigen, gilt als eine der größten Herausforderungen auf dem Weg zu einer Circular Economy. Die negativen Folgen, die sich aus dem Missmanagement von Kunststoffabfällen aufgrund fehlender oder nicht funktionierender Abfallwirtschaftsstrukturen in weiten Teilen der Erde ergeben, werden zunehmend deutlich. Bei der Circular Economy als elementarer Lösungsansatz sollen Stoffströme geschlossen und Produktlebenszyklen verlängert werden. Ein Instrument zur Annäherung an dieses Modell ist der Handel mit sogenannten Plastic Credits - ein Mittel, um den Ausbau regionaler Infrastrukturen für die Sammlung und das Recycling von Kunststoffabfällen zu finanzieren. Die Abnehmer von Plastic Credits sind die treibende Kraft hinter dem Mechanismus. Es ist weiterführende Forschung notwendig, insbesondere in Bezug auf die Frage, wie Unternehmen das Instrument der Plastic Credits nutzen und in ihre Gesamtstrategie integrieren. Diese Masterarbeit widmet sich der dabei vorgelagerten Frage: Existieren bestimmte Profile bei Unternehmen, die in Plastic Credits investieren, und lassen sich hierbei spezifische Cluster bilden? Im Rahmen der Beantwortung dieser Frage wurden Expert*innen-Interviews mit Hilfe der qualitativen Inhaltsanalyse nach Mayring ausgewertet. Dabei haben sich drei konkrete Unterfragen ergeben, die sich auf die Motivation, Branchenzugehörigkeit und räumliche Verortung der Abnehmer beziehen. Die Ergebnisse zeigen, dass sich die Abnehmer von Plastic Credits bereits umfangreich mit der Kunststoffabfallproblematik und der damit verbundenen Auswirkung auf die Umwelt beschäftigen. Offen bleibt, inwiefern Maßnahmen zur Vermeidung von neuartigem Kunststoff, der Verbesserung der Recyclingfähigkeit der Produkte oder der Einsatz von Rezyklaten in der Herstellung dem Weg der Kompensation vorangestellt werden. In Bezug auf die Branchenzugehörigkeit legen die Ergebnisse nahe, dass vorrangig Unternehmen, die mit einem erschwerten Rezyklate-Einsatz konfrontiert sind, in Plastic Credits investieren. Welche Auswirkungen Maßnahmen wie die Entbürokratisierung der Zulassungsverfahren für neue Recyclingprozesse oder verpflichtende Anteile an recycelten Materialien in bestimmten Produkten auf die Investition in Plastic Credits haben, wird sich in Zukunft zeigen. Die Analyse der räumlichen Verortung gab Aufschluss darüber, dass zurzeit im Wesentlichen Unternehmen aus dem globalen Norden in Plastic Credits investieren - jedoch verbunden mit dem Ziel, eine Finanzierung aus den Projektländern heraus zu intensivieren.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
    Type: masterthesis , doc-type:masterThesis
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  • 13
    Publication Date: 2023-10-02
    Description: Förderbanken vergeben in Deutschland jährlich mindestens 200 Milliarden Euro an Mitteln für Investitionen, die sonst nicht oder sehr viel später umgesetzt werden könnten. Sie arbeiten im öffentlichen Auftrag und richten ihre Tätigkeit an gesellschaftlichen Zielen aus. Diese Ziele haben sich weiterentwickelt. Angesichts von Klimawandel, Energiekrise und den Herausforderungen einer Kreislaufwirtschaft wollen sowohl die Länder als auch die Bundesregierung ihre Förderbanken umbauen. Gerade die Förderbanken der Länder müssen sich darum jetzt bereit machen für die "Weiterentwicklung von Förderbanken zu Transformationsbanken". Für die erfolgreiche Gestaltung dieses gesellschaftlichen Umbruchs brauchen sie Unterstützung. Wie dies gelingt, zeigt dieser Zukunftsimpuls.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
    Type: workingpaper , doc-type:workingPaper
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  • 14
    Publication Date: 2023-12-05
    Description: The transition to a greener and more circular economy has been a European policy priority for several years. The Circular Economy Action Plan of 2020 underlines the ambition. The following EEA initiatives are meant to support the transition process: - Bellagio Process on circular economy monitoring principles (EPA network); - Enhancement of EEA indicators on circular economy (ETC/WMGE); - Explorative work on novel data streams (FWC); - Co-creation work - knowledge sharing of monitoring experience (ETC/Eionet). The scope of the present task was to report on the co-creation process that was undertaken at the end of 2020. The co-creation process was organised to identify: (i) best practices on monitoring strategies, data sources and target setting; and (ii) areas of circularity measuring and monitoring that remain challenging and require additional investment. The co-creation process partially built on the work done during the Bellagio Process/Initiative which was run in parallel. This ETC report presents and documents the evidence gathered throughout the co- creation process as well as providing a retrospective analysis of the links to the Bellagio Principles.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
    Type: report , doc-type:report
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  • 15
    Publication Date: 2023-12-21
    Description: In Deutschland werden jährlich über sieben Millionen gebrauchte Matratzen entsorgt, die überwiegend verbrannt und nur zu einem Bruchteil recycelt werden. Dieser lineare Ansatz belastet die Ressourcen, erhöht die Emissionen und birgt Umweltrisiken. Um diesen Herausforderungen zu begegnen, kann die erweiterte Herstellerverantwortung (Extended Producer Responsibility, EPR) als Instrument zur Umsetzung einer Kreislaufwirtschaft dienen. In dieser Masterarbeit wird daher untersucht, wie ein EPR-System für Matratzen in Deutschland gestaltet sein sollte, um Kreisläufe effizient zu schließen. Gleichzeitig zielt diese Thesis darauf ab, die damit verbundenen Anforderungen und Herausforderungen bei der Umsetzung eines solchen Systems zu identifizieren. Zur Beantwortung der Forschungsfragen wurden mithilfe von Expert*innen-Interviews und einer umfassenden Literaturrecherche drei EPR-Modelle entwickelt und anhand von ausgewählten Kriterien bewertet. Die Ergebnisse der Bewertung ergaben, dass ein Modell präferiert werden sollte, in dem eine sogenannte Producer Responsibility Organisation (PRO) gebündelt die Verantwortung der Hersteller übernimmt. Ein solches System würde unter anderem eine angemessene Kontrolle ermöglichen und Anreize für Forschung und Entwicklung im Bereich der Recyclingtechnologien und des zirkulären Designs der Matratzen schaffen. Obwohl die Datenlage über Altmatratzen und deren Verwertung in Deutschland derzeit noch begrenzt sind und die hier präsentierten Ergebnisse von der gewählten Methodik abhängen, dient diese Masterarbeit als erste Grundlage für die weitere Entwicklung eines EPR-Systems für Matratzen in Deutschland.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
    Type: masterthesis , doc-type:masterThesis
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  • 16
    Publication Date: 2023-12-22
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
    Type: contributiontoperiodical , doc-type:contributionToPeriodical
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  • 17
    Publication Date: 2023-12-22
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 18
    Publication Date: 2023-12-22
    Description: Die Transformation der bisher linearen Strukturen von Produktion und Konsum ("take-make-dispose") hin zu einer Circular Economy (CE) - im Sinne einer weiterentwickelten Kreislaufwirtschaft - gilt als zentrales Konzept zur Steigerung der Ressourceneffizienz und Kreislaufführung von Materialien und Produkten, zur Stärkung der Wettbewerbsfähigkeit der einheimischen Industrie sowie zur Schaffung neuer Arbeitsplatzpotenziale. Ziel dieses Forschungsmoduls ist es, die bisherige Umsetzung dieses Konzepts im Rahmen der Nachhaltigkeitsstrategie NRW zu analysieren und durch geeignete Impulse zu begleiten. Durch die Entwicklung eines Leitbilds für eine nachhaltige Circular Economy und zu seiner Messung geeigneter Indikatoren soll das noch an vielen Stellen unscharfe Konzept präzisiert und insbesondere an die spezifischen Ausgangsbedingungen und Herausforderungen von Nordrhein-Westfalen angepasst werden. Dazu sollen Bausteine für ein mittel- und langfristiges Leitbild (2030) entworfen werden, das einen konsistenten Entwicklungspfad für diesen komplexen Transformationsprozess beschreiben soll. Die bestehenden stark abfallwirtschaftlich geprägten Indikatoren zum Thema Kreislaufwirtschaft sollen durch Vorschläge für zusätzliche Indikatoren zur Nachhaltigkeit im Rahmen der Kreislaufwirtschaft (Circular Economy, CE) ergänzt werden.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
    Type: report , doc-type:report
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  • 19
    Publication Date: 2023-12-22
    Description: Although small and medium-sized enterprises (SMEs) contribute considerably to Germany's carbon emissions, regional savings and cooperative banks - SMEs' most important financiers - hardly consider this aspect in lending to these businesses. However, given Germany's commitment to climate neutrality by 2045, suitable approaches for injecting climate finance into these SME lending processes are greatly required. Against this background, the paper at hand aims to introduce the specific case of regional banks into the debate on green finance and green banking and suggest future research in this context. In discussing the state of research on the peculiarities of regional savings and cooperative banks, we outline the resulting opportunities and limitations for climate impact assessments in SME lending. We argue that while the dual bottom-line orientation of regional banks in Germany precludes them from applying simple positive or negative screenings, their in-depth knowledge about local clients and circumstances enables them to be active and engaging partners for the green transformation of SMEs. Nonetheless, we explain why developing solutions to utilise this knowledge for climate finance by integrating climate impact assessments into routine lending processes remains a particularly challenging task.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 20
    Publication Date: 2023-03-24
    Description: In der Chemiebranche macht sich mittlerweile die Erkenntnis breit, dass sie zukünftig geschlossene Stoffkreisläufe brauchen wird, wenn sie weiter Gewinne machen will. Doch der Weg dahin ist noch ziemlich weit. Deshalb wird es ohne langfristig angelegte und klare gesetzgeberische Vorgaben nicht gehen.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 21
    Publication Date: 2023-05-15
    Description: The Digital Product Passport (DPP) is a concept for collecting and sharing product-related information along the life cycle of a product. DPPs are currently the subject of intense discussion, and various development efforts are being undertaken. These are supported by regulatory activities, especially in the case of the battery passport. The aggregation of product life-cycle data and their respective use, as well as the sharing of these data between companies, entrepreneurs, and other actors in the value chain, is crucial for the creation of a resource-efficient circular economy. Despite the urgent need for such a solution, there is currently little attention given to the digital infrastructure for the creation and handling of the DPPs (i.e., the so-called DPP system). Moreover, there is so far no common understanding of what the requirements for a DPP system are. This is the background and underlying motivation of our paper: we identify the requirements for a DPP system in a structured way, i.e., based on stakeholder involvement and current literature from science and industry. In addition, we compose, categorize, and critically analyze the results, i.e., the list of requirements for DPP systems, in order to identify gaps. Summarized, our research provides insights into the criteria to be considered in the creation of an actual DPP system.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: English
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  • 22
    Publication Date: 2023-08-02
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
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  • 23
    Publication Date: 2023-04-03
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 24
    Publication Date: 2023-04-03
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 25
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    München : Siedler
    Publication Date: 2023-04-21
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 26
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    München : Siedler
    Publication Date: 2023-04-21
    Keywords: ddc:330
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  • 27
    Publication Date: 2023-04-21
    Description: Ob die Rückführung von industriellen und gewerblichen Sekundärkunststoffen, das heißt von Abfällen bzw. von bereits wiederaufbereiteten Kunststoffrezyklaten, gelingen kann, ist von mehreren Faktoren wie insbesondere den spezifischen Materialeigenschaften, den Mengen, in denen sie anfallen, den aktuellen Marktpreisen (auch gegenüber Neuware) und auch der räumlichen Nähe von Sortier- bzw. Wiederaufbereitungsinfrastruktur abhängig. Trotz eigentlich guter Voraussetzungen für ein werkstoffliches Recycling, gelangen einzelne in Unternehmen anfallende Abfallchargen häufig in eine thermische Verwertung, weil sich ein Recycling wirtschaftlich nicht lohnt. Grund hierfür ist unter anderem, dass der Informationsaustausch zu den oben genannten Faktoren für Unternehmen häufig noch sehr mangelhaft ist. Aktuell in Entwicklung befindliche digitale Plattformen und Applikationen sowie zugehörige Geschäfts- und Betreibermodelle, welche Kunststoffverarbeiter untereinander sowie Wertstofferzeuger und -verwerter vernetzen sollen, können künftig höhere Recyclingquoten ermöglichen und ökologische Einsparpotenziale heben. Der Artikel führt Entwicklungen und Ergebnisse aktueller Forschungsprojekte zu solchen Vernetzungen zusammen, zeigt die aktuelle Situation des werkstofflichen Recyclings von industriellen und gewerblichen Kunststoffabfällen auf und beleuchtet welche Voraussetzungen für eine erfolgreiche Kreislaufführung von industriellen Kunststoffen gegeben sein müssen. Es wird insbesondere analysiert, in welcher Weise digitale Technologien und die durch sie erzielbare Informationstransparenz eine verbesserte Kreislaufwirtschaft bewirken können und in welcher Weise dies Wertschöpfungsnetzwerke räumlich beeinflussen kann.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 28
    Publication Date: 2024-01-29
    Description: Fortschreitende Digitalisierung und zunehmende Internationalisierung von Märkten bergen Herausforderungen für Unternehmen mit traditionell geprägten Arbeits- und Fertigungsstrukturen. Um den steigenden Anforderungen gerecht zu werden, sollten in diesen Unternehmen die digitale Arbeitsfähigkeit und Kompetenzen für Agilität ausgebaut werden. Dieser Beitrag beschreibt die Konzeption einer digitalen Plattform zur Steigerung derartiger Kompetenzen in kleinen und mittelständischen Unternehmen (KMU). Die digitale Kompetenzplattform soll insbesondere produzierenden KMU strukturschwacher Regionen helfen, ihre Agilität zu steigern und so zur Innovations- und Zukunftsfähigkeit des Unternehmens beitragen.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 29
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-11
    Description: Some sixty years after the experimental flights of the North American X-15 hypersonic rocket-powered aircraft, sustained hypervelocity travel is still the next frontier in high-speed transportation. Today, there is much excitement and interest regarding hypersonic vehicles. In fact, many aerospace agencies, large industries, and several start-ups are involved in design activities and experimental campaigns both in wind tunnels and in-flight with full-scale experimental flying test beds and prototypes to make hypersonic travel almost as easy and convenient as airliner travel. Achieving this goal will radically revolutionize the future of civil transportation. This book contains valuable contributions that focus on various design issues related to hypersonic aircraft.
    Keywords: Aerodynamics ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science::TGMF Engineering: Mechanics of fluids::TGMF1 Aerodynamics
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  • 30
    Publication Date: 2023-12-08
    Description: Die Stärkung der Digitalisierung im Nachhaltigkeitsmanagement und das Schaffen einer einheitlichen sowie konsistenten Datenbasis können Unternehmen maßgeblich unterstützen, steigenden Nachhaltigkeitsanforderungen zu entsprechen und die Transparenz zur Nachhaltigkeit des Wirtschaftens zu gewährleisten. Dieser Beitrag stellt Anforderungen und einen serviceorientierten Ansatz zur Entwicklung einer Plattform für datengestütztes Nachhaltigkeitsmanagement in produzierenden Unternehmen vor.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 31
    Publication Date: 2023-03-24
    Description: At the end of March 2022, the European Commission published its new EU Strategy for Sustainable and Circular Textiles. Its ambitious vision is to reduce textile waste, promote circular measures and minimise the negative environmental impacts of the textile industry. But what would a textile industry that keeps textiles in a closed loop look like, and what political conditions would be required in Germany? This Zukunftsimpuls paper by the Wuppertal Institute points to the role that Germany could play in the transformation towards a circular textile industry.
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    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
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  • 32
    Publication Date: 2023-03-24
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 33
    Publication Date: 2023-03-24
    Keywords: ddc:330
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    Language: German
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  • 34
    Publication Date: 2023-03-24
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 35
    Publication Date: 2023-03-24
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 36
    Publication Date: 2023-02-08
    Description: Although smart energy technologies (SETs) can fulfill multiple tasks in increasingly decarbonized and digitalized energy systems, market diffusion is still limited. This study investigates which beliefs influence consumers' intention to adopt two smart-energy offerings, whether the rapid growth of the smart home market will now drive SET adoption, and if consumer-driven diffusion will lead to sustainability potentials being realized. Building on UTAUT2, a new theoretical model is proposed, and a consumer acceptance survey was conducted in Germany (n = 700). Results indicate that a growing smart home market will not increase SET adoption and that "adjustable green defaults" should be introduced.
    Keywords: ddc:330
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  • 37
    Publication Date: 2023-07-07
    Description: Innerhalb des Projekts "Digitalisierung gestalten - Transformation zur Nachhaltigkeit ermöglichen" werden die besonderen Transformationspotenziale der Digitalisierung herausgearbeitet und für Deutschland am Beispiel der ausgewählten Handlungsfelder Mobilität, Circular Economy sowie Landwirtschaft und Ernährung diskutiert. Dieser Bericht adressiert das Handlungsfeld einer klimaschonenden und ressourceneffizienten Kreislaufwirtschaft, die Circular Economy. Bisher wird Kreislaufwirtschaft dabei vor allem mit Fokus auf Recycling und Wiederverwertung von Materialien diskutiert. Das greift jedoch zu kurz - es muss um die Skalierung von neuen, ressourcenschonenden Geschäftsmodellen und der umfassenden Transformation von Wertschöpfungsketten und Industriestrukturen gehen. Die Analyse zeigt: richtig eingesetzt ist Digitalisierung unverzichtbar für diesen Wandel. Der vorliegende Bericht möchte Anstöße für diesen Weg liefern und neue Impulse für eine klima- und ressourcenschonende Industrietransformation in Deutschland setzen. Der Bericht verarbeitet dabei Ergebnisse eines interdisziplinären Workshops zum Thema "Die digital-ökologische Industrietransformation gestalten - Geschäftsmodelle und politische Rahmenbedingungen für Klima- und Ressourcenschutz" mit Expertinnen und Experten aus Forschung, Zivilgesellschaft, Behörden und Privatunternehmen.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 38
    Publication Date: 2023-07-07
    Description: Das Wirtschafts- und Strukturprogramm für das Rheinische Zukunftsrevier enthält eine Reihe von Zielen, die demonstrieren sollen, wie der European Green Deal modellhaft im Rheinischen Revier bis 2038 umgesetzt werden kann. Das Konzept der "Ressourcenwende" stellt dabei einen Lösungsweg für die erfolgreiche Umsetzung dieser Transformation dar. Das Wuppertal Institut hat vor diesem Hintergrund gemeinsam mit der Prognos AG die vorliegende Studie zu einer regionalen Ressourcenwende im Rheinischen Revier erarbeitet. Das Rheinische Revier ist geprägt durch die Gewinnung, Verstromung und Veredelung von Braunkohle. Darüber hinaus haben sich hier - aufgrund der Nähe zu bedeutenden europäischen Transportwegen und einer zentralen Lage zu wichtigen Märkten in Europa - viele weitere Branchen angesiedelt, wie etwa die Metall-, Chemie- und Aluminiumbranche. Im Hinblick auf den von der Bundesregierung und Nordrhein-Westfalen (NRW) beschlossenen Braunkohleausstieg 2030 und den European Green Deal wird die Notwendigkeit eines Wandels der energie- und ressourcenintensiven Industrien hin zu einer treibhausgasneutralen und ressourcenleichten Wirtschaft im Rheinischen Revier mehr als deutlich. Welchen Fußabdruck hinterlässt das Rheinische Revier, welche innovativen Ressourcenstrategien sollte die Region verfolgen und wie kann dies gemessen werden? Zu dieser Fragestellung haben die Forschenden ein methodisches Konzept einer regionalen Ressourcenwende für das Rheinischen Revier erarbeitet. Die Ressourcenwende selbst begrenzt sich dabei nicht nur auf Primärrohstoffe, sondern nimmt auch die Aspekte wie Bodennutzung bzw. Flächenverbrauch und Biodiversität bzw. Ökosystemleistungen in den Blick und setzt diese in den Kontext eines regionalen Kreislaufwirtschaftssystems.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
    Language: German
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  • 39
    Publication Date: 2023-04-24
    Description: Innovative digital technologies open up new opportun­ ities for small and medium-sized enterprises (SMEs) to improve energy efficiency and energy management behavior. The question is: How far will SMEs be capable of profiting from the benefits of these new technologies? Using technology screening, this study identifies smart metering and mobile energy monitoring as digital technologies best addressing SMEs' specific demands. In addition, potentials and limitations of the technologies are investigated in two qualitative in-depth field trials. Barriers to adopting digitally enabled energy management practices are examined. The results indicate that visualising energy data enables SMEs to pursue new energy management practices for reducing energy consumption and costs (such as peak load analysis). SMEs need extensive guidance to identify and pursue these strategies. In conclusion, an exploratory adoption model for digitally enabled energy management practices is developed. Hypotheses for future experimental studies and policy implications are derived.
    Keywords: ddc:330
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  • 40
    Publication Date: 2024-01-18
    Description: The project "Plastic Credits - Financing the Transition to the Global Circular Economy" supports the implementation of a waste management structure in India's rural regions. By that it aims to improve the current waste collection and treatment structures in the pilot regions Goa, Maharashtra, and Kerala. Herein, the project focuses on low value plastics (LVP), and especially multi-layer plastics (MLP), that have no market value. In order to analyze the environmental impacts of the project, an Environmental Impact Assessment (EIA) was conducted. The considered environmental components comprise: greenhouse gas emissions, usage of primary resources, impacts on marine and terrestrial wildlife, standard of living, and economic costs.
    Keywords: ddc:330
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  • 41
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    Frontiers Media SA
    Publication Date: 2024-04-04
    Description: The Frontiers in Chemistry Editorial Office team are delighted to present the inaugural “Frontiers in Chemistry: Rising Stars” article collection, showcasing the high-quality work of internationally recognized researchers in the early stages of their independent careers. All Rising Star researchers featured within this collection were individually nominated by the Journal’s Chief Editors in recognition of their potential to influence the future directions in their respective fields. The work presented here highlights the diversity of research performed across the entire breadth of the chemical sciences, and presents advances in theory, experiment and methodology with applications to compelling problems. This Editorial features the corresponding author(s) of each paper published within this important collection, ordered by section alphabetically, highlighting them as the great researchers of the future. The Frontiers in Chemistry Editorial Office team would like to thank each researcher who contributed their work to this collection. We would also like to personally thank our Chief Editors for their exemplary leadership of this article collection; their strong support and passion for this important, community-driven collection has ensured its success and global impact.
    Keywords: Green and Sustainable Chemistry ; Analytical Chemistry ; Theoretical and Computational Chemistry ; Polymer Chemistry ; Medicinal and Pharmaceutical Chemistry ; Organic Chemistry ; Nanoscience ; Catalysis and Photocatalysis ; Supramolecular Chemistry ; Electrochemistry ; Inorganic Chemistry ; Chemical Biology ; thema EDItEUR::P Mathematics and Science::PD Science: general issues
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  • 42
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-11
    Description: Aerodynamics, the study of air motion around solid objects, allows us to understand and measure the dominating forces acting on aircrafts, buildings, bridges, automobiles, and other structures. The forces that result in an aircraft overcoming gravity and drag are called thrust and lift. Various parameters such as geometrical configurations of objects, as well as physical properties of air, which may be functions of position and time, affect those forces. This book covers some of the latest studies regarding the application of the principles of aerodynamics to the design of many different engineered objects. This book will be of interest to mechanical and aerospace engineering students, academics, and researchers who are looking for new insights into this fascinating branch of fluid mechanics.
    Keywords: Aerodynamics ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 43
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-11
    Description: Aerodynamics, from a modern point of view, is a branch of physics that study physical laws and their applications, regarding the displacement of a body into a fluid, such concept could be applied to any body moving in a fluid at rest or any fluid moving around a body at rest. This Book covers a small part of the numerous cases of stationary and non stationary aerodynamics; wave generation and propagation; wind energy; flow control techniques and, also, sports aerodynamics. It's not an undergraduate text but is thought to be useful for those teachers and/or researchers which work in the several branches of applied aerodynamics and/or applied fluid dynamics, from experiments procedures to computational methods.
    Keywords: Aerodynamics ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 44
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-11
    Description: This book is intended to be a valuable addition to students, engineers, scientists, industrialists, consultants and others providing greater insight into wind tunnel designs and their enormous research potential. It is a compilation of works from world experts on subsonic and supersonic wind tunnel designs, applicable to a diverse range of disciplines. The book is organised in two sections. The first section comprises of three chapters on various aspects of stationary and portable subsonic wind tunnel designs, followed by one chapter on supersonic wind tunnel and the final chapter discusses a method to address unsteadiness effects of fan blade rotation. The second section contains four chapters regarding wind tunnel applications across a multitude of engineering fields including civil, mechanical, chemical and environmental engineering.
    Keywords: Aerodynamics ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 45
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-11
    Description: This book reports the latest development and trends in the low Re number aerodynamics, transition from laminar to turbulence, unsteady low Reynolds number flows, experimental studies, numerical transition modelling, control of low Re number flows, and MAV wing aerodynamics. The contributors to each chapter are fluid mechanics and aerodynamics scientists and engineers with strong expertise in their respective fields. As a whole, the studies presented here reveal important new directions toward the realization of applications of MAV and wind turbine blades.
    Keywords: Aerodynamics ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 46
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    IntechOpen
    Publication Date: 2024-04-04
    Description: Spacecraft attitude maneuvers comply with Euler's moment equations, a set of three nonlinear, coupled differential equations. Nonlinearities complicate the mathematical treatment of the seemingly simple action of rotating, and these complications lead to a robust lineage of research. This book is meant for basic scientifically inclined readers, and commences with a chapter on the basics of spaceflight and leverages this remediation to reveal very advanced topics to new spaceflight enthusiasts. The topics learned from reading this text will prepare students and faculties to investigate interesting spaceflight problems in an era where cube satellites have made such investigations attainable by even small universities. It is the fondest hope of the editor and authors that readers enjoy this book.
    Keywords: Science ; Mechanics ; Aerodynamics ; bic Book Industry Communication::P Mathematics & science::PH Physics::PHD Classical mechanics::PHDF Fluid mechanics ; thema EDItEUR::P Mathematics and Science::PH Physics::PHD Classical mechanics::PHDF Physics: Fluid mechanics
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  • 47
    facet.materialart.
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-11
    Description: Although great advances in computational methods have been made in recent years, wind tunnel tests remain essential for obtaining the full range of data required to guide detailed design decisions for various practical engineering problems. This book collects original and innovative research studies on recent applications in wind tunnel tests, exhibiting various investigation directions and providing a bird’s eye view on this broad subject area. It is composed of seven chapters that have been grouped in two major parts. The first part of the book (chapters 1–4) deals with wind tunnel technologies and devices. The second part (chapters 5–7) deals with the latest applications of wind tunnel testing. The text is addressed not only to researchers but also to professional engineers, engineering lecturers, and students seeking to gain better understanding of the current status of wind tunnels. Through its seven chapters, the reader will have an access to a wide range of works related to wind tunnel testing.
    Keywords: Aerodynamics ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 48
    facet.materialart.
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-11
    Description: Spacecraft attitude maneuvers comply with Euler's moment equations, a set of three nonlinear, coupled differential equations. Nonlinearities complicate the mathematical treatment of the seemingly simple action of rotating, and these complications lead to a robust lineage of research. This book is meant for basic scientifically inclined readers, and commences with a chapter on the basics of spaceflight and leverages this remediation to reveal very advanced topics to new spaceflight enthusiasts. The topics learned from reading this text will prepare students and faculties to investigate interesting spaceflight problems in an era where cube satellites have made such investigations attainable by even small universities. It is the fondest hope of the editor and authors that readers enjoy this book.
    Keywords: Aerodynamics ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 49
    Publication Date: 2023-05-15
    Description: More than 150 municipal utilities (so-called Stadtwerke) were established in Germany from the beginning of the millennium, bringing the total number of Stadtwerke currently established within the country to approximately 900. With responsibility for more than half of the supply of electricity, gas and heat in Germany, these Stadtwerke play a central role in the transformation of the energy sector, or Energiewende. In addition, due to their local and regional ties, Stadtwerke have a particular role to play in energy politics, the economy and across society. This article focuses on the motives behind, and grounds for, the current wave of newly established Stadtwerke. Further, it discusses the factors that were critical to the successful formation of new Stadtwerke in recent years. The results of our survey indicate that the establishment of municipal Stadtwerke is a suitable measure to implement the energy transition at the local level, whereby the concept of public value has a high level of importance for the local decision-makers. Collaboration and cooperation, as well as a resilience-oriented strategy, are important success factors for new Stadtwerke.
    Keywords: ddc:330
    Repository Name: Wuppertal Institut für Klima, Umwelt, Energie
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  • 50
    Publication Date: 2023-05-15
    Description: The need for a transition towards a circular economy (CE) is evident, as the current economic model is based on the exploitation of far more resources than the planet can replenish sustainably. A significant part of this economic transition is the inception of new, CE-oriented startups and business activities. While business model frameworks (BMF), such as the Business Model Canvas (BMC), were at the center of discussions about structuring business ideas in the beginning of the millennium, the conversation must now shift towards circular BMFs (CBMF). This paper follows the Design Research Methodology (DRM) for an empirical approach to devising a novel CBMF, including expert interviews as well as a first application of the framework with a startup. Throughout this process, a new and innovative tool called Circular Business Framework (CBF) was created and tested based on CE principles.
    Keywords: ddc:330
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  • 51
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    In:  CASI
    Publication Date: 2019-08-14
    Description: A compression pylon for an aircraft with a wing-mounted engine, that does not cause supersonic airflow to occur within the fuselage-wing-pylon-nacelle channel is presented. The chord length of the pylon is greater than the local chord length of the wing to which it is attached. The maximum thickness of the pylon occurs at a point corresponding to the local trailing edge of the wing. As a result, the airflow through the channel never reaches supersonic velocities.
    Keywords: Aircraft Design, Testing and Performance
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  • 52
    Publication Date: 2019-07-13
    Description: As a result of the continued interest in designing efficient low Reynolds number systems, the University of Notre Dame decided to organize a Conference on Low Reynolds Number Aerodynamics in June 1989. This Conference followed the 1986 International Conference in London by about three years and the first Conference on Low Reynolds Number Airfoil Aerodynamics at Notre Dame in 1985 by four years. The emphasis of the 1989 Conference was to assess the state-of-the-art in the chord Reynolds number range from about 10,000 to about 700,000. Applications of current interest include high altitude remotely or robotically piloted vehicles, ultra-light, and human powered vehicles as well as mini-RPVs at low altitudes. Other examples include small axial-flow fans used to cool electronic equipment in the unpressurized sections of high-altitude aircraft and gas turbine blades. High Reynolds number airfoil design strategies attempt to control the onset and development of turbulent boundary layers. This is difficult at low Reynolds numbers because of the increased stability of attached laminar boundary layers. Therefore, laminar separation is common even at small angles of attack at low Reynolds numbers. Under these conditions, the development of a turbulent boundary layer usually depends on the formation of a transitional separation bubble. The purpose of this Conference on Low Reynolds Number Aerodynamics was to bring together those researchers who have been active in areas closely related to this subject. It is clear from the papers presented that a great deal of progress has been made in understanding the occurrence and behavior of laminar separation and transition as well as their overall effect on the performance of airfoils at low chord Reynolds numbers. This progress has brought us closer to our goal of improving analytical methods for the design and evaluation of a variety of practical applications.
    Keywords: Aerodynamics
    Type: Jun 05, 1989 - Jun 07, 1989; Notre Dame, IN; United States
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  • 53
    facet.materialart.
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    In:  Other Sources
    Publication Date: 2019-07-10
    Description: New aircraft technologies are presented that have the potential to expand the air transportation system and reduce congestion through new operating capabilities while also providing greater levels of safety and environmental compatibility. These new capabilities will result from current and planned civil aeronautics technology at the NASA Ames, Lewis, and Langley Research Centers and will cover the complete spectrum of current aircraft and new vehicle concepts including rotorcraft (helicopters and tilt rotors), vertical and short takeoff and landing (V/STOL), and short takeoff and landing (STOL) aircraft, subsonic transports, high-speed transports, and hypersonic/transatmospheric vehicles. New technologies will improve efficiency, affordability, safety, and environmental compatibility of current aircraft and will enable the development of new transportation system. The new capabilities of vehicles could lead to substantial market opportunities and economic growth and could improve the competitive position of the U.S. aerospace industry.
    Keywords: Aircraft Design, Testing and Performance
    Type: SAE-1989-1642 , SAE Transactions; SAE-1989-1642
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  • 54
    facet.materialart.
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    In:  CASI
    Publication Date: 2019-07-12
    Description: A balance ring (18) which is shrunk fit within each disk (12) of a rotor is selectively ground for detail balance. A plurality of openings (20) through the outer edge of the balance ring receive weights during the asssembly balance of the rotor. A snap ring (42) retains the weights within the openings.
    Keywords: Aerodynamics
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  • 55
    Publication Date: 2019-07-13
    Description: Flight experiments were conducted on a 30 degree swept wing with a perforated leading edge by systematically varying the location and amount of suction over a range of Mach number and Reynolds number. Suction was varied chordwise ahead of the front spar from either the front or rear direction by sealing spanwise perforated strips. Transition from laminar to turbulent flow was due to leading edge turbulence contamination or crossflow disturbance growth and/or Tollmien-Schlichting disturbance growth-depending on the test configuration, flight condition, and suction location. A state-of-the-art linear stability theory which accounts for body and streamline curvature and compressibility was used to study the boundary layer stability as suction location and magnitude varied. N-factor correlations with transition location were made for various suction configurations.
    Keywords: Aerodynamics
    Type: AIAA Paper 89-1893 , AIAA 20th Fluid Dynamics, Plasma Dynamics and Lasers Conference; Jun 12, 1989 - Jun 14, 1989; Buffalo, NY; United States
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  • 56
    Publication Date: 2019-07-13
    Description: Three-dimensional viscous flow computations are presented for the F/A-18 forebody-LEX geometry. Solutions are obtained from an algorithm for the compressible Navier-Stokes equations which incorporates an upwind-biased, flux-difference-splitting approach along with longitudinally-patched grids. Results are presented for both laminar and fully turbulent flow assumptions and include correlations with wind tunnel as well as flight-test results. A good quantitative agreement for the forebody surface pressure distribution is achieved between the turbulent computations and wind tunnel measurements at Mach number of 0.6. The computed turbulent surface flow patterns on the forebody qualitatively agree well with in-flight surface flow patterns obtained on an F/A-fS aircraft at Mach number of 0.34.
    Keywords: Aerodynamics
    Type: AIAA Paper 89-0338 , 27th Aerospace Sciences Meeting; Jan 09, 1989 - Jan 12, 1989; Reno, NV; United States
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  • 57
    Publication Date: 2019-07-13
    Description: A patched-grid algorithm for the analysis of complex configurations with an implicit, upwind-biased Navier-Stokes solver is presented. Results from both a spatial-flux and a time-flux conservation approach to patching across zonal boundaries are presented. A generalized coordinate transformation with a biquadratic geometric element is used at the zonal interface in order to treat highly stretched viscous grids and arbitrarily-shaped zonal boundaries. Applications are made to the F-18 forebody-strake configuration at subsonic, high-alpha conditions. Computed surface flow patterns compare well with ground-based and flight-test results; the large effect of Reynolds number on the forebody flow-field is shown.
    Keywords: Aircraft Design, Testing and Performance
    Type: AIAA Paper 89-0121 , 27th Aerospace Sciences Meeting; Jan 09, 1989 - Jan 12, 1989; Reno, NV; United States
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  • 58
    Publication Date: 2019-07-13
    Description: Flight boundary-layer transition experiments were conducted on a 30 degree swept wing with a perforated leading-edge suction panel. The transition location on the panel was changed by systematically varying the location and amount of suction. Transition from laminar to turbulent flow was due to leading-edge turbulence contamination or crossflow disturbance growth and/or Tollmien-Schlichting disturbance growth, depending on flight condition and suction variation. Amplification factor correlations with transition location were made for various suction configurations using a state-of-the-art linear stability theory which accounts for body and streamline curvature and compressibility.
    Keywords: Aircraft Design, Testing and Performance
    Type: IUTAM Third Symposium on Laminar-Turbulent Transition; Sep 11, 1989 - Sep 15, 1989; Toulouse; France
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  • 59
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 19-24 
    ISSN: 0009-2940
    Keywords: Bis(diorganoboryl)chalcogenides ; Pyrazaboles ; Pyrazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Neuartige Substituierte B2ElVIN2 HeterocyclenDie Bis(diorganoboryl)chalkogenide (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], und (R2B)2Se [R2 = 1,5-C8H14 (7)] reagieren mit Pyrazol (Pz) und dessen Derivaten 3-Methylpyrazol (3-MePz) und Indazol (benzo-Pz) in hohen Ausbeuten (65-92%) zu stabilen 1:1-Additionsverbindungen [z. B. 2 (El = O), 4 (El = O), 6 (El = S), 8 (El = Se)]. 1H-, 13C-, 11B-NMR-Spektren und Röntgenstrukturanalysen (von 2 und 6) zeigen eine Grundstruktur mit einem zentralen B2ElN2-Heterocyclus (El = O, S, Se). Die Reaktion von 2 mit R2BH und die Thermolyse von 4 führen zu den dimeren 1-Pyrazolylboranen 9a bzw. 9b.
    Notes: The bis(diorganoboryl) chalcogenides (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], and (R2B)2Se [R2 = 1,5-C8H14 (7)] react with pyrazole (Pz) and its derivatives 3-methylpyrazole (3-MePz) and indazole (benzo-Pz) to form in high yields (65-92%) stable 1:1 adducts [e.g. 2 (El = O), 4 (El = O), 6 (El = S) and 8 (El = Se)]. 1H-, 13C-, 11B-NMR spectra and X-ray analyses (of 2 and 6) show a basic structure with a central B2ElN2 (El = O, S, Se) heterocycle. The reaction of 2 with R2BH and the thermolysis of 4 give the dimeric 1-pyrazolylboranes 9a and 9b, respectively.
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  • 60
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 31-36 
    ISSN: 0009-2940
    Keywords: Mercury - mercury contacts ; Naphthalenediylmercury compounds ; Organomercury compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Extremely Short Mercury-Mercury Contacts in peri-Dimercurated Naphthalene Compounds1-Naphthylmercury chloride (1) and 1,8-naphthalenediylbis(mercury chloride) (2) were prepared from the corresponding naphthyllithium precursors and HgCl2 in ca. 80% yield. In an alternative route, 2 can be obtained from 1,8-naphthalenediyldiboric acid anhydride and HgCl2 in 85% yield. The structure of 2·DMSO has been determined by X-ray diffraction methods. The lattice contains discrete adducts in which the two mercury atoms are bridged by the DMSO oxygen atom. The HgCl moieties are bent away from each other through distortions of the naphthalene framework and of the C—Hg—Cl axes, which results in a Hg ‥ Hg distance of 3.102(1) Å. - Symmetrization of 2, induced by treatment with NaI in aqueous ethanol, affords bis(μ-1,8-naphthalenediyl)dimercury (3). In the X-ray structure determination of this compound the shortest „non-bonding“ Hg·Hg contact reported in the literature has been detected: Hg1··Hg2 = 2.797(1) Å. The molecule also shows distortions in the naphthalene framework and in the C—Hg—C axes [C—Hg—C = 173.3(5)°].
    Notes: 1-Naphthylquecksilberchlorid (1) und 1,8-Naphthalindiylbis-(quecksilberchlorid) (2) werden aus den zugehörigen Naphthyllithium-Verbindungen und HgCl2 mit ca. 80% Ausbeute erhalten. Alternativ kann 2 auch aus 1,8-Naphthalindiyldiborsäureanhydrid und HgCl2 gewonnen werden (Ausbeute 85%). Von 2·DMSO wurde die Kristallstruktur bestimmt. Es liegen diskrete Addukte vor, in denen die beiden Hg-Atome durch das O-Atom des DMSO überbrückt werden. Die HgCl-Einheiten sind durch Verzerrungen im Naphthalingerüst, durch Winkelung der Achsen C—Hg—Cl und durch deren Auslenkung aus der Naphthalinebene voneinander weggebogen, so daß ein Hg·· Hg-Kontakt von 3.102(1) Å resultiert. - 2 symmetrisiert sich bei der Einwirkung von NaI in wäßrigem Ethanol unter Bildung von Bis(μ-1,8-naphthalindiyl)diquecksilber (3). Bei der Strukturanalyse dieser im Kristall zentrosymmetrischen Verbindung wurde der bisher kürzeste „nichtbindende“ Hg··Hg-Kontakt von 2.797(1) Å gefunden. Auch in 3 sind die C—Hg—C-Achsen abgewinkelt [C—Hg—C = 173.3(5)°], und das Naphthalingerüst ist verzerrt.
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 59-61 
    ISSN: 0009-2940
    Keywords: N-Butyl-N′-dansylthiourea ; Complexing agent, fluorescent ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Butyl-N′-dansylthiourea as Fluorescent Broad-Band Complexing AgentN-Butyl-N′-dansylthiourea (2) [dansyl = 5-(dimethylamino)-1-naphthylsulfonyl] is obtained by the reaction of dansylamide (1) with butyl isothiocyanate. The compound is a stable, fluorescent complex agent for a broad spectrum of metal ions. The UV spectra and fluorescence of the ligand and some metal complexes are discussed. The fluorescence of the dansyl group is strongly affected by metal ions.
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  • 62
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 83-94 
    ISSN: 0009-2940
    Keywords: Enaminecarbaldehydes ; Enamino ketones ; hetero Diels-Alder reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Struktur von Enaminecarbaldehyden und Enamino KetonenDie Synthese der Enamincarbaldehyde 1a-s und 17a-c sowie der Enamino-Ketone 2a-k und deren N-Acyl-Derivate 19a-k und 21-t mit Elektronenacceptor-Substituenten an C-2 bzw an der CO-Gruppe wird beschrieben. Kondensation von 2-Formyl-3-oxopropansäure-methylester (13) mit Ammoniak und den Aminen 14b-s ergab die Enamincarbaldehyde 1a bzw. 1b-s in einer Ausbeute von 72-93%. Die Enamincarbaldehyde 17 konnten durch Formylierung von 15 mit dem gemischten Ameisensäureessigsäureanhydrid erhalten werden. Die Synthese der Enamino-Ketone 2a-k erfolgte mit einer Ausbeute von 61-97% durch Kondensation von Ammoniak und Aminen mit den Enolethern 24a-f, die durch Umsetzung reaktiver Acylchloride 23 mit Ethylvinyl-ether dargestellt wurden. Die für hetero-Diels-Alder-Reaktionen benötigten N-Acyl-Derivate 19a-k und 21-t wurden durch Acylierung des Enamincarbaldehyds 1a und der Enamino-Ketone 2a-k gebildet.
    Notes: The synthesis of enaminecarbaldehydes 1a-s and 17a-c as well as enamino ketones 2a-k, and their N-acyl derivatives 19a-k and 21-t with electron accepting substituents at C-2 and at the CO group, respectively, is described. Condensation of methyl 2-formyl-3-oxopropanoate (13) with ammonia and the amines 14b-s gave the enaminecarbaldehydes 1a and 1b-s, respectively, in 72-93% yield. The enaminecarbaldehydes 17 were obtained by formylation of 15 with acetic formic anhydride. The synthesis of the enamino ketones 2a-k was accomplished in 61-97% yield by reaction of ammonia and amines with the enol ethers 24a-f, which were formed by treatment of reactive acyl chlorides 23 with ethyl vinyl ether. The enaminecarbaldehyde 1a as well as the enamino ketones 2a-k could be acylated to give 19a-k and 2l-t, respectively, which can be used in the hetero Diels-Alder reaction.
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  • 63
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 119-122 
    ISSN: 0009-2940
    Keywords: Bis(phosphonium) salts ; Pyridylphosphonium salts, tri-n-butyl- and triphenyl- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry of Triphenyl-(or Tri-n-butyl-)pyridylphosphonium salts, 2. - 2,4-Pyridinediylbis(phosphonium) Salts2,4-Pyridinediylbis(phosphonium) salts 1 react with nucleophiles to give 4-substituted products 6-8. Under radical reaction conditions the 5-position in 1a is attacked to yield 9. sodium azide transforms 1a into 8. This salt is used as starting material for 11. The removal of the phosphonium groups in 1 and in the resulting products can be carried out selectively.
    Notes: 2,4-Pyridindiylbis(phosphoniumsalze) 1 lassen sich mit nucleophilen Reaktionspartnern in die 4-substituierten Produkte 6-8 überführen. Unter radikalischen Bedingungen wird selektiv die 5-Position in 1a unter Bildung von 9 angegriffen. Nach Umsetzung mit Natriumazid entsteht zunächst das Salz 8, das als Ausgangsverbindung für 11 dient. Die Substitution der Phosphoniumgruppen aus den Edukten 1 und Produkten kann selektiv durchgeführt werden.
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  • 64
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 145-149 
    ISSN: 0009-2940
    Keywords: Cycloalkenes, 1-methyl- ; Ozonolysis ; Peroxyhemiacetals, cyclic ; Rubber, natural ; Tetrahydrofurans, 2-hydroperoxy- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ozonolyses of 1-Methylcyclopentene, 1-Methylcyclobutene, 5-Hexen-2-one and Natural Rubber in the Presence of MethanolOzonolyses of 1-methylcyclopentene (8a) and of 1-methylcyclobutene (8b) in methanol proceeded in each case in the two possible directions. The resulting methoxyperoxides 13 and 14 afforded the corresponding peroxyhemiacetals 15 and 19 by intramolecular reactions of the OOH with the corresponding carbonyl groups. Ozonolysis of 1-methylcyclobutene (8b) additionally gave the corresponding ozonide 17b and 2-hydroperoxy-5-methoxy-2-methyl-as well as 5-hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b and 18b). The mode of formation of these hydroperoxy compounds has been elucidated by ozonolyses of 5-hexen-2-one (25) and of natural rubber (28) in the presence of methanol.
    Notes: Ozonolysen von 1-Methylcyclopenten (8a) und von 1-Methylcyclobuten (8b) in Methanol verliefen jeweils nach beiden möglichen Spaltungsrichtungen. Die dabei gebildeten Methoxyhydroperoxide 13 und 14 ergaben durch intramolekulare Reaktionen der OOH- mit den Carbonylgruppen die entsprechenden Peroxyhalbacetale 15 bzw. 19. Bei der Ozonolyse von 1-Methylcyclobuten (8b) wurden zusätzlich das entsprechende Ozonid 17b sowie 2-Hydroperoxy-5-methoxy-2-methyl- und 5-Hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b und 18b) gebildet. Die Bildungsweise dieser Hydroperoxy-Verbindungen wurde durch Ozonolysen von 5-Hexen-2-on (25) und von Naturkautschuk (28) im Beisein von Methanol aufgeklärt.
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  • 65
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 169-174 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of New 3-substituted PyrrolesThe synthesis of 3-alkyl- (4), 3-(ω-bromoalkyl)- (5), 3-iodo- (6), 3-formyl- (9a), 3-acetyl-1-(triisopropylsilyl)pyrrole (9b), of 2-[1-(triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(triisopropylsilyl)-3-pyrrolecarboxylic acid (8), and 7-[1-(triisopropylsilyl)-3-pyrrolyl]heptanoic acid (10) as well as the desilylation of these products to the corresponding 3-substituted pyrroles 11 is described. Intermediates in these syntheses are 1-(triisopropylsilyl)pyrrole (1), 3-bromo- (2), and 3-lithio-1-(triisopropylsilyl)pyrrole (3).
    Notes: Die Synthese von 3-Alkyl- (4), 3-(ω-Bromalkyl)- (5), 3-Iod- (6), 3-Formyl- (9a) und 3-Acetyl-1-(triisopropylsilyl)pyrrol (9b), von 2-[1-(Triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(Triisopropylsilyl)-3-pyrrolcarbonsäure (8) und 7-[1-(Triisopropylsilyl)-3-pyrrolyl]heptansäure (10) sowie die Desilylierung dieser Produkte zu den entsprechenden 3-substituierten Pyrrolen 11 wird beschrieben. Zwischenstufen der Darstellung sind 1-(Triisopropylsilyl)pyrrol (1), 3-Brom- (2) und 3-Lithio-1-(triisopropylsilyl)pyrrol (3).
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 223-230 
    ISSN: 0009-2940
    Keywords: Gold(I) silyl complexes ; Transition-metal silyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition-Metal Silyl Complexes, 26. - Gold(I) Silyl ComplexesComplexes of type L-Au-SiR3 with L = PR′3 or PhNC and SiR3 = Si(aryl)3, Si(SiMe3)3, or SiPh2Me are prepared by reaction of L-Au-Cl with LiSiR3. Depending on L and R, their stability decreases, in the order R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Reaction of R′3P-Au-CH3 or R′3P-Au-OAc with HSiR3 does not yield silyl complexes. However, using chlorinated silanes like HSiR2Cl, CH3/Cl or OAc/Cl exchange takes place. The Mössbauer spectrum of MePh2P-Au-SiPh3 (6) and NMR- and IR-spectroscopic investigations show that silyl groups act as strong σ donors towards the gold atom. MePh2P-Au-SiPh3 (6) and MePh2P-Au-Si(SiMe3)3 (7) have been characterized by X-ray structure analyses [Au—Si 235.4(4) and 235.6(2) pm]. The Au-Si bond in MePh2P-Au-SiPh2Tol (5) is cleaved by X2 (X = Cl, Br, I), HCl or MeI, but not by H2O or MeOH.
    Notes: Komplexe des Typs L-Au-SiR3 mit L = PR′3 oder PhNC und SiR3 = Si(aryl)3, Si(SiMe3)3 oder SiPh2Me wurden durch Umsetzung von L-Au-Cl mit LiSiR3 dargestellt. Ihre Stabilität sinkt in Abhängigkeit von L und R in der Reihenfolge R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Umsetzung von R′3P-Au-CH3 oder R′3P-Au-OAc mit HSiR3 ergibt keine Silyl-Komplexe, bei Verwendung chlorierter Silane, HSi-R2Cl, findet lediglich CH3/Cl- bzw. OAc/Cl-Austausch statt. Das Mößbauer-Spektrum von MePh2P-Au-SiPh3 (6) sowie NMR- und IR-spektroskopische Untersuchungen zeigen, daß Silylreste als starke σ-Donor-Liganden gegenüber dem Goldatom wirken. MePh2P-Au-SiPh3 (6) und MePh2P-Au-Si(SiMe3)3 (7) wurden durch Röntgenstrukturanalysen charakterisiert [Au—Si 235.4(4) und 235.6(2) pm]. Die Au—Si-Bindung in MePh2P-Au-SiPh2 Tol (5) wird durch X2 (X = Cl, Br, I), HCl oder MeI, nicht aber durch H2O oder MeOH gespalten.
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 245-252 
    ISSN: 0009-2940
    Keywords: Germylenes ; Germanium nitrogen compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Germylenes with Azides: Iminogermanes, Azidogermanes, Tetrazagermoles and HexaazadigermadispirododecanesGermylenes, X2Ge, stabilized by steric blocking and/or incorporation into five-membered ring systems, react with azido compounds YN3 depending on the steric requirements of the substituents X and Y to give iminogermanes, X2Ge=NY (1, 2) azidogermanes X2Ge(N3)NY2 (6-8) tetrazagermoles, X2Ge(— NY — N =)2 (10-16), and hexaazadigermadispirododecanes, [(— NR — CH2 — CH2 — NR —)Ge(μ-NY -)]2 (17, 18). NMR (1H, 13C, 14N, 15N, and 29Si), MS data, and X-ray structure analyses of the compounds 8, 9, 16, and 18 are reported.
    Notes: Durch sterische Blockierung und/oder Einbau in fünfgliedrige Ringsysteme stabilisierte Germylene, X2Ge, reagieren mit Azidoverbindungen, YN3, in Abhängigkeit von der Raumerfüllung der Substituenten X und Y zu Iminogermanen X2 Ge=NY (1, 2), Azidogermanen, X2Ge(N3)NY2 (6′8), Tetrazagermolen, X2Ge-(-NY-N=)2 (10-16), bzw. Hexaazadigermadispirododecanen, [(—NR—CH2—CH2—NR— )Ge(μ-NY-)]2 (17, 18). NMR-(1H, 13C, 14N, 15N und 29Si), MS-Daten und Röntgenstrukturanalysen für die Verbindungen 8, 9, 16 und 18 sind angegeben.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 271-277 
    ISSN: 0009-2940
    Keywords: Chalcogenogermanes, (trifluoromethyl)- ; Disilaselenanes ; Germachalcogenanes, bis(trifluoromethyl)- ; Germanes, (trifluoromethyl)- ; Germatranes, (trifluoromethyl)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (Trifluormethyl)germanes, III. - Preparation of New (Trifluormethyl)germanium Chalcogene CompoundsStarting with the dihalogenobis(trifluoromethyl)germanes (CF3)2-GeX2 (X = Cl, or I), halogen-chalcogen exchange leads to corresponding chalcogen derivatives of the general type [(CF3)2GeE]n (6, 7) (E = O, NH, S, or Se). The resulting compounds differ in their degree of polymerisation. [(CF3)2GeO]x and the corresponding sesquioxane [(CF3)GeO1, 5]x are highly polymeric, quite in contrast to the corresponding germathianes and -selenanes. The crystal structure of [(CF3)2GeO]x (6a) was determined by X-ray single crystal diffraction. The reaction of CF3GeCl3 with triethanolamine results in the formation of 1-(trifluoromethyl)germatrane (13). Disilaselenane (10) reacts at low temperatures with chloro-(trifluoromethyl)germanes (CF3)nGeCl4-n under retention of one Si—Se bond to give (CF3)nGe(SeSiH3)4-n (11) and H3SiCl. Compounds with n = 3 and 2 could be isolated. Exchange of iodine by ECF3 takes place with iodogermanes (CF3)nGeI4-n and Hg(ECF3)2 (E = S, Se) with formation of a complete series of (trifluoromethyl)(trifluoromethylchalcogeno)germanes (CF3)nGe-(ECF3)4-n (3, 5).
    Notes: Durch Halogen-Chalkogen-Austauschreaktionen an (CF3)2)GeX2 (X = Cl, I) wurden Bis(trifluormethyl)germachalkogenane [(CF3)2GeE]n (6, 7) E = O, NH, S, Se) von unterschiedlichem Oligomerisierungsgrad erhalten. Die Germoxane [(CF3)2GeO]x und (CF3GeO1,5)x sind im Gegensatz zu den homologen Germathianen und -selenanen polymer, wobei die Struktur von [(CF3)2GeO]x (6a) durch eine Kristallstrukturanalyse ermittelt wurde. Durch Umsetzung von CF3GeCl3 mit Triethanolamin wird 1-(Trifluormethyl)germatran (13) erhalten. Disilaselenan (10) reagiert bei tiefen Temperaturen mit den Chlor (trifluormethyl)-germanen (CF3)nGeCl4-n monofunktionell unter Erhalt einer Si—Se-Bindung zu (CF3)nGe(SeSiH3)4-n (11) und H3SiCl, von denen die Verbindungen mit n = 3 und 2 isoliert werden konnten. Reaktionen der Iodgermane (CF3)nGeI4-n(1) mit Hg(ECF3)2) (E = S, Se) führen unter Substitution des Iods gegen die ECF3-Gruppen zur vollständigen Reihe der (Trifluormethyl)(trifluormethylchalkogeno)germane (CF3)nGe(ECF3)4-n (3, 5).
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 291-292 
    ISSN: 0009-2940
    Keywords: (Phthalocyaninato)copper complex, substituted with crown ethers ; Alkali metal extraction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A soluble (phthalocyaninato)copper(II) complex containing eight symmetrical benzo-15-crown-5 substituents, namely {2,3,9,10,16,17,23,24-octakis[[benzo-15-crown-5)-4′ -yl]oxymethyl]phthalocyaninato}copper(II) (2) from 1,2-bis{[benzo-15-crown-5)-4′-yl]oxymethyl}-4,5-dibromobenzene (1) and CuCN in quinoline or pyridine was synthesized. The crown-ether groups in 2 were shown to prefer intramolecular complexation with alkali metal ions.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 463-466 
    ISSN: 0009-2940
    Keywords: C—C Rotation ; Sterical hindrance by SF5 groups ; Rotational barriers ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterical Hindrance of the C—C Rotation by two SF5 GroupsAddition of SF5Cl to SF5CH=CF2 gives products carrying two SF5 groups on one carbon atom. As a consequence, C—C single bond rotation is strongly hindered. The highest rotational barrier observed is 61.7 kJ mol-1, rotational isomers are hence detectable at room temperature.
    Notes: Die Addition von SF5Cl an SF5CH=CF2 ergibt Produkte, die zwei SF5-Gruppen an einem Kohlenstoff tragen. In diesen kommt es zu einer starken Hinderung der Rotation um die C—C-Einfachbindung. Die höchste Rotationsbarriere wird mit 61.7 kJ mol-1 gefunden, d. h. Rotationsisomere sind bei Raumtemperatur getrennt nachweisbar.
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  • 72
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 467-472 
    ISSN: 0009-2940
    Keywords: Tetracarbonylchromium complexes ; 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Structure, and Reactions of 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine DerivativesThe 1,2,3,6-tetrahydro-1,2,3,6-diphosphadiborine derivatives 3a and 3b are obtained by cyclocondensation of 1,2-bis[chloro(dialkylamino)boryl]ethenes 2 and 1,2-dipotassium 1,2-di-tert-butyldiphosphanediide. As in the case of 2,5-dihydro-1H-1,2,5-phosphadiborole derivatives 1 the temperature-dependent 1H-NMR spectra of 3b exhibit a lowered barrier of inversion at phosphorus. The X-ray structure analysis of 3b shows, that the six-membered C2B2P2 ring is nonplanar and the P atoms are coordinated pyramidally. Attempts to substitute the dialkylamino groups at the boron atoms of 3a and 3b with HCl·Et2O or tBuLi lead to cleavage of the B—P bonds. Reaction between 3a or 3b and Cr(CO)3(MeCN)3 does not result in the formation of tricarbonylchromium complexes but of tetracarbonylchromium complexes 6a and 6b with pentahapto-bonded ligands 3a and 3b.
    Notes: Die 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborin-Derivate 3a und 3b entstehen durch Cyclokondensation aus 1,2-Bis[chlor(dialkylamino)boryl]ethenen 2 und 1,2-Dikalium-1,2-di-tert-butyldiphosphandiid. Die Temperaturabhängigkeit der 1H-NMR-Spektren von 3b dokumentiert wie bei 2,5-Dihydro-1H-1,2,5-phosphadiborol-Derivaten 1 eine erniedrigte Phosphor-Inversionsbarriere. Die Röntgenstrukturanalyse von 3b zeigt, daß der C2B2P2-Sechsring im Kristall nicht eben ist und daß die P-Atome pyramidal koordiniert sind. Versuche zur Substitution der Dialkylaminogruppen an den Boratomen von 3a und 3b mit HCl·Et2O oder tBuLi führen zur Spaltung der B—P-Bindungen. Die Umsetzung von 3a bzw. 3b mit Cr(CO)3(MeCN)3 ergibt keine Tricarbonylchrom-Komplexe, sondern die Tetracarbonylchrom-Komplexe 6a bzw. 6b, in denen die Liganden 3a und 3b pentahapto gebunden sind.
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  • 73
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Synthesis via Transition Metal Complexes, 34. - Novel Formation of C=C Bonds by Condensation of Acid Amides with Carbene Complexes Involving an Insertion of C2 Units into M=C BondsCarben complexes LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] and acid amides RCH2CONMe2 2 undergo a novel condensation reaction in presence of POCl3/Et3N to give alkenyl aminocarbene complexes 3. The reaction involves an insertion of a C2 unit of 2 into the M=C bond of 1 to give a C=C bond. It can be achieved with open-chain and cyclic amides like N-methyl-2-pyrrolidone (8). the structures of the complexes have been determined spectroscopically. A mechanism of the reaction is suggested.
    Notes: Carbenkomplexe LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] lassen sich mit Säureamiden RCH2CONMe2 2 und POCl3/Et3N zu Alkenyl-Aminocarben-Komplexen 3 kondensieren. Dabei wird eine C2-Einheit von 2 in die M=C-Bindung von 1 eingeschoben und eine C=C-Bindung neu geknüpft. Die Reaktion gelingt mit offenkettigen und cyclischen Amiden wie N-Methyl-2-pyrrolidon (8). Die Strukturen der Komplexe wurden spektroskopisch ermittelt und Vorschläge zur Deutung des Reaktionsablaufs gemacht.
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  • 74
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 711-714 
    ISSN: 0009-2940
    Keywords: Azulenes ; 1,6-Methano[10]annulenes ; 1,2,4,5-Tetrazine ; [4 + 2] Cycloadditions, „inverse“ ; Pyridazines, annulated ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azulene and 1,6-Methano[10]annulene as Dienophiles in the Diels-Alder Reaction with 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazineThe LUMO-diene-controlled [4 + 2] cycloadditions of azulene (2) and 1,6-methano[10]annulene (14) with the electron-deficient s-cisfixed diazadiene system of 3,6-bis(trifluoromethyl)-1,2,4,5-tetrazine (1) are described. Contrary to expectation, 1 reacts under unusually mild conditions with 2 (or its valence tautomer 3) to yield the adduct 4 which after N2 elimination rearranges to the benzo[f]phthalazine 11. The Diels-Alder reaction of 1 with 14 (or its valence tautomer 13) leads to the annulated dihydropyridazines 15 and 16, which can be dehydrogenated by silver(I) oxide to the methano-bridged aromatic cyclodecapyridazine 17 and the olefinic phthalazino[5,6-f]phthalazine 18, respectively. Besides, the methano-bridged cyclodeca[d]pyridazine 24 is prepared.
    Notes: LUMO-Dien-kontrollierte [4 + 2]-Cycloadditionen von Azulen (2) und 1,6-Methano[10]annulen (14) an das elektronenarme, s-cis-fixierte Diazadiensystem von 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazin (1) werden beschrieben. Wider Erwarten reagiert 1 unter ungewöhnlich milden Bedingungen mit 2 (oder dessen Valenztautomerem 3) zum Addukt 4, das nach N2-Eliminierung und nachfolgender Umlagerung das Benzo[f]phthalazin 11 liefert. Die Diels-Alder-Reaktion von 1 mit 14 (oder dessen Valenztautomer 13) führt zu den beiden anellierten Dihydropyridazinen 15 und 16, die mit Silber(I)-oxid zu dem Methano-überbrückten aromatischen Cyclodecapyridazin 17 bzw. dem olefinischen Phthalazino[5,6-f]phthalazin 18 dehydriert werden können. Daneben wird das Methano-überbrückte Cyclodeca[d]pyridazin 24 dargestellt.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 715-719 
    ISSN: 0009-2940
    Keywords: Alkyne ; Carbene ; Cycloisomerization ; Pyrolysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Über die thermische Cycloisomerisierung langkettiger Alkylacetylene in der GasphaseDie thermische Cycloisomerisierung einiger Alkylacetylene wurde in einem Laborrohrreaktor aus Quarzglas untersucht. 1-Hexin (1) wird dabei durch 1,2-H-Verschiebung und 1,5-C,H-Insertion des intermediär gebildeten Pentylidencarbens (vgl. Schema 1) in 3-Methyl-1-cyclopenten (5) umgelagert. 5-Methyl-1-hexin (2) reagiert analog; es entsteht 3,3-Dimethyl-1-cyclopenten (6). Im Gegensatz zur Bildung von in 3-Stellung methylierten Cyclopentenen aus 1-Alkinen ensteht aus 2-Hexin (3) 1-Methyl-1-cyclopenten (7). Offenbar ist die Acetylen-Vinyliden-Umlagerung nicht auf 1,2-H-Verschiebung beschränkt. Der Mechanismus der Cycloisomerisierung von Alkylacetylenen wird durch Untersuchungen mit D-markierten Alkinen bestätigt. Die Ergebnisse lassen den Schluß zu, daß die Cycloisomerisierung ohne weiteres mit dem überwiegend nach einem Radikalketten-Mechanismus verlaufenden thermischen Zerfall konkurrieren kann.
    Notes: The thermal cycloisomerization of some alkylacetylenes was investigated in a tubular quartz reactor. At 570°C 1-hexyne (1) rearranges to 3-methyl-1-cyclopentene (5) with a selectivity of about 27 by a reaction sequence including an acetylene-vinylidene rearrangement and 1,5-C,H insertion of the intermediately formed alkylidenecarbene species. 5-methyl-1-hexyne (2) behaves analogously forming 3,3-dimethyl-1-cyclopentene (6), while 2-hexyne (3) provides 1-methyl-1-cyclopentene (7) indicating that the acetylene-vinylidene rearrangement is obviously not restricted to 1,2-H shifts. The mechanism of the cycloisomerization of alkylacetylenes is investigated by means of D-labeled parent alkynes. The results show that the unimolecular cycloisomerization via alkylidenecarbenes obviously can be an important channel despite the dominance of a radical chain course.
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  • 76
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 745-748 
    ISSN: 0009-2940
    Keywords: Flash Pyrolysis ; Matrix IR spectroscopy ; Photolysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Methoxy- und AminoisocyanatMethoxyisocyanat (1) kann durch Photolyse von Azidoameisensäure-methylester (3) oder Pyrolyse von N-Methoxycarbonyl-O-methylhydroxylamin (4) dargestellt werden. Aminoisocyanat (2) ist auf ähnliche Weise durch Photolyse von Carbamoylazid (12) und Pyrolyse von Carbazinsäure-methylester (13) oder 3,4-Diaminofurazan (14) zugänglich. Die IR-Spektren von 1 und 2, aufgenommen in einer Argon-Matrix bei 10 K, werden diskutiert.
    Notes: Methoxyisocyanate (1) can be prepared by photolysis of methyl azidoformate (3) or pyrolysis of N-methoxycarbonyl-O-methyl-hydroxylamine (4). Aminoisocyanate (2) is similarly formed on photolysis of carbamoyl azide (12) and pyrolysis of either methyl carbazate (13) or 3,4-diaminofurazan (14). The infrared spectra of 1 and 2 in an argon matrix at 10 K have been measured, and some of their properties are discussed.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 749-752 
    ISSN: 0009-2940
    Keywords: Matrix isolation ; Photochemistry ; Theoretical vibrational spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Infrarot-Spektren und Photochemie von Isodiazen und seinen deuterierten IsotopomerenDie Matrixisolation von Aminoisocyanat eröffnet einen neuen ergiebigen Weg zur Darstellung von Isodiazen (Aminonitren). Damit ist es möglich geworden, nicht nur sein IR-Spektrum eindeutig festzulegen und mit Hilfe von ab-initio-Rechnungen zu interpretieren, sondern auch seine Photochemie zu untersuchen.
    Notes: The matrix isolation of aminoisocyanate opens a new efficient route for the preparation of isodiazene (aminonitrene). Its infrared spectrum can now, with the help of ab initio calculations, be interpreted, and its photochemistry can be studied.
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  • 78
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 795-796 
    ISSN: 0009-2940
    Keywords: Thiochalcones ; Thienylchalcones ; Fries rearrangement ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new thienylchalcones (1, 4, 5, and 6) were synthesized by condensing hydroxy-nitroacetophenones with 2-thiophene and 3-thiophenecarboxaldehydes in the presence of dilute NaOH.
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 767-779 
    ISSN: 0009-2940
    Keywords: Molecular twisting ; cis-9,10-Dihydronaphthalenes, persubstituted ; Valence isomerizations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Valence Isomerizations, 17. - Persubstituted cis-9,10-Dihydronaphthalenes and their Valence IsomerizationsThe tricyclic diester 10 is available from 2-butyne in a six-step synthesis with an overall yield of 10%. Thermolysis of 10 gives the bicyclic diester 11 which upon UV irradiation yields 12 as the first persubstituted cis-9,10-dihydronaphthalene. X-ray analysis of 12 shows the molecule considerably twisted along the central bond. In addition, the planes of the ester groups are at an angle of approximately 60° to the „planes“ of the six-membered rings so that conjugation of the diene systems with the carbonyl functions is virtually interrupted, an effect which is reflected by the unusual spectroscopic properties of 12. The same structural features can be found in decamethyl-cis-9,10-dihydronaphthalene (16). When heated slightly, 12 is converted to the tetracyclic valence isomer 34. On reduction of 12 with diisobutylaluminum hydride both, dihydronaphthalene dicarbinol 25 as well as its unexpected positional isomer 26, are formed depending on the reaction conditions. Etherification of the reduction products with CH2N2/Et2O—BF3 furnishes a mixture of the three isomeric bis(methoxymethyl) compounds 31, 32 and 33. They can be separated by chromatography in the cold, but revert to the mixture of the three isomers at room temperature. We consider diradical 38 to be the intermediate of this intriguing valence isomerization.
    Notes: Der tricyclische Diester 10 ist in sechs Stufen in einer Gesamtausbeute von 10% aus 2-Butin zugänglich. Thermolyse von 10 liefert den Bicyclus 11, bei dessen UV-Bestrahlung das erste persubstituierte cis-9,10-Dihydronaphtalin 12 gebildet wird. Eine Röntgenstrukturanalyse von 12 beweist die starke Verdrillung des Moleküls um die zentrale Bindung. Die Ebenen der Ester-Gruppen stehen ungefähr in einem 60°-Winkel zu den Sechsring-„Ebenen“, so daß die Konjugation der Dien-Systeme mit den Carbonyl-Funktionen praktisch unterbrochen ist, ein Effekt, der sich in den ungewöhnlichen spektroskopischen Eigenschaften von 12 widerspiegelt. Analoge Strukturmerkmale gelten auch für das Decamethyl-cis-9,10-dihydronaphthalin (16). Bicyclus 12 wandelt sich bei leichtem Erwärmen in den valenzisomeren Tetracyclus 34 um. Reduktion von 12 mit Diisobutylaluminiumhydrid gibt je nach den Reaktionsbedingungen das Dihydronaphthalindicarbinol 25 bzw. das unerwartete Stellungsisomere 26. Veretherung der Reduktionsprodukte mit CH2N2/Et2O—BF3 liefert ein Gemisch der drei isomeren Bis(methoxymethyl)-Verbindungen 31, 32 und 33, die chromatographisch in der Kälte trennbar sind, aber schon bei Raumtemperatur wieder das Gemisch der drei Isomeren zurückbilden, wobei das Diradikal 38 als Zwischenprodukt dieser erstaunlichen Valenzisomerisierung anzunehmen ist.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 803-808 
    ISSN: 0009-2940
    Keywords: Bismuth organic compounds ; Fluorinated aromatic rings ; Square pyramidal bismuth ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structures of Pentaarylbismuth CompoundsPentaarylbismuth compounds were synthesized by the known reaction Ar3BiX2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2. Whenever possible they were characterized by single-crystal X-ray structure determination. In two cases almost ideal square-pyramidal geometry was found, in a third case there were two different molecules in the unit cell, both again with square-pyramidal geometry. None of these novel bismuth pentaaryls exhibit the deep coloration and the dichroism of Bi(C6H5)5.
    Notes: Pentaarylbismut- Verbindungen wurden durch die bekannte Reaktion BiAr3X2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2 hergestellt und, soweit möglich, durch Röntgenbeugung an Einkristallen strukturell untersucht. In zwei Fällen erwies sich die Struktur als nahezu ideal quadratisch-pyramidal, in einem dritten Fall wurden zwei unterschiedliche Moleküle im Kristall gefunden, die aber beide wiederum quadratisch-pyramidal sind. Keines der hier vorgestellten neuen Bismutpentaaryle zeigt die tiefe Färbung und den Dichroismus von Bi(C6H5)5.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 533-535 
    ISSN: 0009-2940
    Keywords: Free radicals ; Triphenylmethyl radicals ; ESR measurements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Hindered Free Radicals, XIX. - Stable 4,4′,4″-Trisubstituted Triphenylmethyl RadicalsThe title radicals (4-R—C6H4)3C. (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, have been prepared, the latter four for the first time, and the ESR spectra have been recorded. aoH, amH, and apR are listed. The intensities of the ESR signals remain constant within the accessible range of -30 to + 100°C. Within this range these radicals are kinetically stable and do not dimerize like other trityls by, e.g., α,p-, α,o-, α,α -recombinations.
    Notes: Die Titelradikale (4-R—C6H4)3C· (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, wurden dargestellt, davon die vier letzten erstmalig, und mittels ESR-Spektroskopie vermessen. aoH, amH und apR werden angegeben. Die ESR-Signale bleiben im gesamten zugänglichen Temperaturbereich - 30 bis + 100°C in ihrer Intensität unverändert. Daraus folgt, daß alle diese Radikale im genannten Temperaturbereich kinetisch stabil sind, also nicht wie andere Trityle zu Dimerisierungen, etwa α,p-, α,o-, α,α-, neigen.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 523-531 
    ISSN: 0009-2940
    Keywords: Dicyclopenta-s-indacene ; 2-Osxa[3.3.3]propellane derivatives ; Pentalene derivatives ; [3.3.3]Propellane-3,7-dione ; Weiss reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel Products in the Weiss Reaction of 1,2-Cyclopentanedione. Improved Preparation of [3.3.3]Propellane-3,7-dioneThe reaction of 1,2-cyclopentanedione (1c, 9) with the 3-oxoglutarate 4 in methanol/water in the presence of sodium bicarbonate followed by hydrolysis and decarboxylation of the product mixture affords the oxa[3.3.3]propellane ester 11c in addition to the [3.3.3]propellanedione 6c. The alkali enolates of 4 react with 9 in boiling methanol to yield the yellow, poorly soluble alkali dihydropentalenolates 12M and the [3.3.3]propellane tetraester 5c, which on hydrolysis and decarboxylation yields 53% of 6c. The dihydropentalenol 12H equilibrates with the tautomeric β-oxodiester 13, the proportion of which increases with solvent polarity. In methanol solutions, 12H and 13 add diastereoselectively forming the dicyclopenta-s-indacene tetraester syn-14, which is derived from a novel pentacyclic ring system. The configuration of syn-14 is determined by X-ray diffraction analysis. The mechanisms of formation are discussed for 11c, 12M, and syn-14.
    Notes: Nach Umsetzung von 1,2-Cyclopentandion (1c, 9) mit dem 3-Oxoglutarsäureester 4 in Methanol/Wasser in Gegenwart von Natriumhydrogencarbonat, saurer Hydrolyse und Decarboxylierung des Produktgemischs erhält man neben dem [3.3.3]Propellandion 6c den Oxa[3.3.3]propellanester 11c. Die Alkali-Enolate von 4 reagieren mit 9 in siedendem Methanol zu den gelben, schwer löslichen Dihydropentalenolaten 12M und dem [3.3.3]Propellantetraester 5c, der nach Hydrolyse und Decarboxylierung 53% 6c ergibt. Das Dihydropentalenol 12H liegt im Gleichgewicht mit dem tautomeren β-Oxodiester 13 vor, dessen Anteil mit der Polarität des Lösungsmittels zunimmt. In Methanol addieren sich 12H und 13 diastereoselektiv und bilden den Dicyclopenta-s-indacentetraester syn-14, der sich von einem neuartigen, pentacyclischen Ringsystem ableitet. Die Konfiguration von syn-14 wird durch Röntgenstrukturbestimmung aufgeklärt. Die Mechanismen der Bildung von 11c, 12M und syn-14 werden diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 553-559 
    ISSN: 0009-2940
    Keywords: Amino acids ; Diastereoselective addition ; 1-(Methacryloyl)proline derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Amino Acids, 15. - Diastereoselective Addition of Thiocarboxylic Acids to 1-(Methacryloyl)proline and-prolinol DerivativesThiocarboxylic acids 6 add to 1-(methacryloyl)-substituted proline and prolinol derivatives stereoselectively to give the 1-[3-(acylthio)-2-methylpropionyl]proline and -prolinol derivatives 7,7′ and 9. The less soluble (2S,2′R)-diastereomers are obtained in optical yields ≥ 98% by digestion of the crude products, the configuration of which was determined by acid hydrolysis of (2S,2′R)-7,7′ to (R)-3-mercapto-2-methylpropionic acid [(R)-8]. The stereoselectivity of the additions may be explained by a sevenmembered ring intermediate with an intramolecular H bridge, to which the S-nucleophiles add preferentially to give the compounds with the (2′R)-configuration.
    Notes: Thiocarbonsäuren 6 addieren stereoselektiv mit hohen optischen Ausbeuten an 1-(Methacryloyl)-substituierte Prolin- und Prolinol-Derivate zu den 1-[3-(Acylthio)-2-methylpropionyl]prolin-und -prolinol-Derivaten 7,7′ und 9. Durch Digerieren der Rohprodukte mit Diethylether werden die schwerer löslichen (2S,2′R)-Diastereomeren in optischen Ausbeuten ≥98% erhalten, deren Konfiguration durch Acidolyse von (2S,2′R)-7,7′ zu (R)-3-Mercapto-2-methylpropansäure [(R)-8] bewiesen wurde. Die Stereoselektivität der Additionen wird über einen Siebenring mit intramolekularer H-Brücke als Zwischenstufe, an die Schwefelnucleophile bevorzugt unter Bildung der (2′R)-Konfiguration addieren, gedeutet.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 545-551 
    ISSN: 0009-2940
    Keywords: Amino acids ; Diastereoselective addition ; 1-Acryloylproline esters ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Amino Acids, 14. - Diastereoselective Addition of Benzenesulfenyl Chloride to 1-Acryloylproline Esters(S)-Proline esters (S)-1 react with acryloyl chloride (2) to give 1-acryloylproline esters (S)-3 in good yields. Addition of benzenesulfenyl chloride (6) to (S)-3 at -95°C in dichloromethane results in 1-[2-chloro-3-(phenylthio)propionyl]proline esters (2S,2′R/2S,2′S)-7. The diastereoselectivity of the addition depends on the conformer ratio 3′/3″ of the starting material (S)-3. The diastereomers are separated by MPLC. Configuration at C-2′ of the resulting main products (2S,2′S)-7 was proved by independent synthesis. The diastereoselectivity of the addition of 6 to (S)-3 is interpreted to result from formation of a complex of the benzenesulfenyl cation with the proline ester group and subsequent electrophilic addition to a thiiranium intermediate B with (2S,2′R) configuration; the (2S,2′S) diastereomeric adduct 7 then results by nucleophilic attack of chloride at C-2′ under ring opening.
    Notes: Die 1-Acryloylprolinester (S)-3 werden durch N-Acylierung der Prolinester (S)-1 mit Acryloylchlorid (2) in guten Ausbeuten hergestellt; sie addieren Benzolsulfenylchlorid (6) bei -95°C in Dichlormethan mit hoher Diastereoselektivität zu 1-[2-Chlor-3-(phenylthio)propionyl]prolinestern (2S,2′R/2S,2′S)-7, die mittels MPLC getrennt werden. Die Diastereoselektivität der Addition hängt vom Konformerenverhältnis 3′/3″ der Edukte (S)-3 ab. Der Beweis der Konfiguration an C-2′ der als Hauptprodukte anfallenden Diastereomeren (2S,2′S)-7 wird durch eine unabhängige Synthese erbracht. Die Diastereoselektivität der Addition von 6 an (S)-3 wird über eine Komplexbildung des Phenylsulfenylkations mit der Prolinestergruppe und eine sich anschließende elektrophile Reaktion zu einer Thiiranium-Zwischenstufe B mit (2S,2-R)-Konfiguration gedeutet; das (2S,2′S)-diastereomere Additionsprodukt 7 entsteht dann durch nucleophilen Angriff des Chlorids an C-2′ unter Ringöffnung.
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  • 85
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 851-855 
    ISSN: 0009-2940
    Keywords: Diphosphines ; Tungsten - tungsten quadruple bond ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Struktur von W2Cl4{μ(iPr2PCH2CH2CH2PiPr2)}2: Eine durch sperrige, chelatisierende Diphosphane überbrückte Wolfram - Wolfram-VierfachbindungDie Reduktion von WCl4 in THF durch zwei Äquivalente Na/Hg in Gegenwart des sperrigen, chelatisierenden Diphosphinopropans iPr2PCH2CH2CH2PiPr2 (dippp) liefert den violetten, zweikernigen Komplex W2Cl4(μ-dippp)2. Der Komplex besitzt eine W-W-Vierfachbindung und β-Struktur, d.h. die chelatisierenden Diphosphinopropan-Liganden verbrücken die beiden Metall-Zentren. Die 1H-NMR-spektroskopischen Daten zeigen Tieffeldverschiebungen für die dippp-Liganden, die im Einklang mit der β-Struktur stehen. Das 31P{1H}-NMR-Spektrum besteht aus einem Singulett mit 183W-Satelliten. Die Röntgen-Stukturanalyse ergibt für die β-Struktur einen Torsionswinkel P-W-W-P von 75.9° und eine W-W-Bindungslänge von 2.297(1) Å. Aus den Molekülstruktur-Daten und den 1H-NMR-Tieffeldverschiebungen kann die diamagnetische Anisotropie χ der W-W-Vierfachbindung mit - 3000 ± 300 × 10-36 m3/Molekül abgeschätzt werden. Die für den festen Zustand beobachtete Chiralität wird auch in Lösung beibehalten.
    Notes: The reduction of WCl4 in THF by two equivalents of Na/Hg in the presence of the bulky chelating diphosphine iPr2PCH2-CH2CH2PiPr2 (dippp) generates the purple, binuclear complex W2Cl4(μ-dippp)2. The quadruply-bonded molecule has a β structure, that is, the chelating diphosphine bridges the two metal centers. 1H-NMR spectral data show downfield shifts for the ligand protons consistent with the β structure. The 31P{1H}-NMR spectrum consists of a singlet with 183W satellites. The X-ray crystal structure has a twist angle (P-W-W-P torsion angle) of 75.9°, and the W-W bond length is 2.297(1) Å. Using the solidstate data and the observed downfield shifts in the 1H-NMR spectrum, the diamagnetic anisotropy χ has been estimated as - 3000 ± 300 × 10-36 m3/molecule. The chiral structure observed in the solid phase is retained in solution.
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 861-864 
    ISSN: 0009-2940
    Keywords: Aminoiminophosphanes ; 1,3,2λ5,4-Thiazaphosphaboretidines ; 1,2,4,3,5-Trithiadiborolanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Characterization of 1, 3, 2λ5, 4-ThiazaphosphaboretidinesThe reaction of 1,2,4,3,5-trithiadiborolanes with silylated aminoiminophosphanes leads to the 1,3,2λ5,4-thiazaphosphaboretidines 1a-i. The formation of 1h, i is accompanied by an exchange of the substituents bonded to the N atoms. 1H-, 11B-, 13C-, 29Si-, 31P-NMR, and mass spectra are discussed.
    Notes: Die Umsetzung von 1,2,4,3,5-Trithiadiborolanen mit silylierten Aminoiminophosphanen führt zu den 1,3,2λ5,4-Thiazaphosphaboretidinen 1a-i. Die Bildung von 1h, i wird von einem Austausch der N-ständigen Substituenten begleitet. 1H-, 11B-, 13C-, 29Si-, 31P-NMR- und Massenspektren werden diskutiert.
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  • 87
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 857-860 
    ISSN: 0009-2940
    Keywords: Alkenylboranes ; Alkenylstannanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Convenient Route from Alkenylboranes to AlkenylstannanesAlkenyldialkylboranes 1 with various substituents at the C=C double bond, including organometallic groups such as the trimethylstannyl or trimethylsilyl group, react in hexane solution with (diethylamino)- or (dimethylamino)trimethylstannane (2) in the presence of a catalytic amount of lithium dimethyl- or diethylamide (3) to give aminodialkylboranes 4 and alkenyltrimethylstannanes 5 in high yields with retention of the configuration at the C—C double bond. With (diethylamino)trimethylplumbane (2c) the less stable alkenes 5Pb are obtained. A mechanism is proposed, and 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-data are reported.
    Notes: Alkenyldialkylborane 1 mit verschiedenen Substituenten an der C=C-Doppelbindung, einschließlich organometallischer Gruppen wie dem Trimethylstannyl- oder dem Trimethylsilyl-Rest, reagieren in Hexan mit (Diethylamino)- oder (Dimethylamino)trimethylstannan (2) in Gegenwart einer katalytischen Menge von Lithium-diethylamid (3b) oder -dimethylamid (3a) in hoher Ausbeute unter Beibehaltung der Konfiguration an der C—C-Doppelbindung zu den entsprechenden Alkenylstannanen 5 und Aminoboranen 4. Durch Einsatz von (Diethylamino)trimethylplumban (2c) lassen sich die weniger stabilen Alkene 5Pb erhalten. Ein Mechanismus wird vorgeschlagen, und 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-Daten werden mitgeteilt.
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  • 88
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1919-1924 
    ISSN: 0009-2940
    Keywords: Hydrogen transfer ; Ziegler catalysis ; Dihydroarenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ziegler Nickel Catalysts for Hydrogen Transfer ReactionsCatalysts prepared from Ni(acac)2 and AlEt3 show high catalytic activity in the hydrogen transfer between dihydroarenes, but hardly any isomerisation and H/D scrambling is observed. The active form of the catalyst is produced only in the presence of the starting material. Kinetic experiments, especially those concerning the introduction periods and the inhibition, are indicative of a complex reaction mechanism. The first hydrogen is preferentially abstracted from the 2-position, the second with complete cis selectivity.
    Notes: Der aus Ni(acac)2 und AlEt3 dargestellte Katalysator zeigt eine hohe Aktivität beim H-Transfer zwischen Dihydroarenen, neben dem Isomerisierungen und H/D-Austausch kaum ablaufen. Die aktive Form entsteht erst in Gegenwart des Edukts. Kinetische Untersuchungen, vor allem zur Induktionsperiode und zur Hemmung, deuten auf einen komplexen Ablauf. Der Wasserstoff wird cis-selektiv abgespalten, primär bevorzugt aus der 2-Position.
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  • 89
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1925-1927 
    ISSN: 0009-2940
    Keywords: Hydrogen transfer ; Olefin isomerization ; Cobalt complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrogen Transfer Reactions, 13.  -  Catalysis of Disproportionation by (Dinitrogen)hydridotris(triphenylphosphine)cobalt(I)For both C—H activation and olefin isomerization, CoH(N2)(PPh3)3 (1) is a more powerful catalyst than the Wilkinson complex. In 1,2-dihydronaphthalene (2), a two-step cis abstraction of the hydrogen atoms is found with small regioselectivity in the first step.
    Notes: Die Aktivität des Komplexes CoH(N2)(PPh3)3 (1) liegt bei der C—H-Aktivierung deutlich höher als beim Wilkinson-Katalysator. Noch effektiver wird aber eine Olefin-Isomerisierung induziert. Die zweistufige H-Abstraktion erfolgt beim 1,2-Dihydronaphthalin (2) cis-selektiv, der Primärschritt aber kaum regioselektiv.
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  • 90
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1935-1938 
    ISSN: 0009-2940
    Keywords: as-Triazinium salt, fused ; Ring transformation ; Solvatochromy, negative ; Zwitterion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Ringtransformation von neuen kondensierten as-Triazinium-SalzenDie Reaktion des 1,2-Diaminopyridinium-Salzes 1 mit dem Furandion 2 ergab ein Pyrido-as-triazinon 3, das zum tricyclischen Furo[2,3-e]pyrido[1,2-b]-as-triazinium-Salz 5 cyclisiert wurde. Die Reaktion von 5 mit Nucleophilen führte zu unterschiedlichen Produkten: mit wäßriger Base entstand das bicyclische Triazinon 4, mit dem Methoxid-Ion und sekundären Aminen wurden die stabilen Zwitter-Ionen 7a, b erhalten, wohingegen Ammoniak und Hydrazine unter Transformation des Furanringes die neuen tricyclischen kondensierten Pyrrole 10, 11 bzw. Pyridazine 13, 14a, b ergaben.
    Notes: The 1,2-Diaminopyridinium salt 1 was treated with furandione 2 to give pyrido-as-triazinone 3, which could be cyclized to the tricyclic furo[2,3-e]pyrido[1,2,-b]-as-triazinium salt 5. Reaction of 5 with nucleophiles resulted in different types of products. Thus, aqueous base afforded bicyclic triazinone 4, methoxide ion or secondary amine led to stable zwitterions 7a, b, whereas ammonia and hydrazines resulted in ring transformation of the furan moiety, and gave new fused tricyclic pyrroles (10, 11) and pyridazines (13, 14), respectively.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1947-1953 
    ISSN: 0009-2940
    Keywords: Enol ethers ; [n](2,4)Phloroglucinophanes ; Autoxidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations of the Autoxidation and the Rearrangement of [n](2,4)PhloroglucinophanesIn the autoxidation of [n](2,4)phloroglucinophanes 3 hydroperoxides 7 are isolated in several cases as the first oxidation products; they react to the more stable monohydroxylated compounds 8 with different rates. Acylphloroglucinophanes 5, however, react with oxygen to give the dihydroxylated compounds 9. The autoxidation rate of the phloroglucinophanes 3, 5 is markedly larger than that of diethylphloroglucinols 6. In alkaline solution the hydroxy compounds 8 rearrange to the dihydroxycyclopentenones 12; the rate of rearrangement correlates with the decrease of ring strain.
    Notes: Bei der Autoxidation von [n](2,4)Pholoroglucinophanen 3 können in einigen Fällen Hydroperoxide 7 als erste Oxidationsprodukte isoliert werden, die unterschiedlich rasch in die stabileren monohydroxylierten Verbindungen 8 übergehen. Aclphloroglucinophane 5 reagieren mit Luftsauerstoff dagegen zu den zweifach hydroxylierten Verbindungen 9. Die Geschwindigkeit der Autoxidation ist bei den Phloroglucinophanen 3, 5 deutlich größer als bei den 2,4-Diethylphloroglucinen 6. Im alkalischen Medium lagern sich die Hydroxyverbindungen 8 in die Dihydroxycyclopentenone 12 um, wobei für die Geschwindigkeit der Umlagerung eine Korrelation mit der Abnahme an Ringspannung gefunden wird.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1963-1967 
    ISSN: 0009-2940
    Keywords: Allenyl azides, ring closure of ; Propargyl azides, rearrangement, base-induced ; Triazafulvenes, nucleophilic addition to ; 1,2,3-Triazoles, preparation of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Unsaturated Azides, 7.  -  Base-catalyzed Formation of Allenyl Azides from Propargyl Azides: New Syntheses for 1,2,3-TriazolesThe propargyl azides 10, 14, 17, 20, and 28 undergo a base-catalyzed (prototropic) rearrangement to short-lived allenyl azides. These intermediates rapidly cyclize to triazafulvenes, which can be trapped by nucleophiles (methanol, sodium hydroxide, ammonia) to give 1,2,3-triazoles. Starting with the precursors 9, 13, 16, 19, and 27 one-pot syntheses lead to the heterocycles 12, 15, 18, 21, and 29. Depending on the reaction conditions, compound 10 regioselectively yields 12c (75%) by prototropic rearrangement (path B) or by migration of the azide group (path A) the isomer 11c (62%).
    Notes: Die Propargylazide 10, 14, 17, 20 und 28 lagern sich basenkatalysiert (prototrop) zu kurzlebigen Allenylaziden um. Diese Zwischenstufen cyclisieren rasch zu Triazafulvenen, die mit Nucleophilen (Methanol, Natriumhydroxid, Ammoniak) als 1,2,3-Triazole abgefangen werden können. Ausgehend von den Vorläufern 9, 13, 16, 19 und 27 führen Eintopf-Synthesen zu den Heterocyclen 12, 15, 18, 21 und 29. In Abhängigkeit von den Reaktionsbedingungen liefert 10 über die prototrope Umlagerung (Weg B) regioselektiv 12c (75%) oder durch Azidwanderung (Weg A) die isomere Verbindung 11c (62%).
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2023-2025 
    ISSN: 0009-2940
    Keywords: Homoallylic alcohols ; [2,3] Sigmatropic rearrangement ; Stereoselective synthesis of alcohols ; [2,3] Wittig rearrangement ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reductive cleavages of allyl [(phenylthio)methyl] ethers (8, 11) and an allyl [(tolylsulfonyl)methyl] ether (14) with lithium naphthalenide in THF furnish homoallylic alcohols (9, 12). The steric course of these transformations (E/Z selectivity in the case of 9, syn/anti selectivity for 12) is very similar to that of analogous Wittig-Still rearrangements.
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  • 94
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2049-2054 
    ISSN: 0009-2940
    Keywords: Ligating properties ; Pentaphosphaferrocenes ; Sandwich and triple-decker complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pentaphospaferrocenes as Complex LigandsThe interaction of [Cp*Fe(P5)] (1a) with [Cr(CO)5(thf)] and [Cp(CO)2Mn(thf)], respectively, affords [Cp*Fe(P5){Cr(CO)5}2] (2) as well as [Cp*Fe(P5){Mn(CO)2Cp}n] (4a-d; n = 1-4; Cp* = η5-C5Me5). Irradiation of 1 and [CpFe(C6H6)]PF6 gives the cationic 30-VE triple-decker complexes [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5). In addition to the NMR studies 2 and 3b have been characterized by X-ray structure analyses.
    Notes: Die Umsetzung von [Cp*Fe(P5)] (1a) mit [Cr(CO)5(THF)] bzw. [Cp(CO)2Mn(THF)] ergibt [Cp*Fe(P5){Cr(CO)5}2] (2) sowie [HCp*Fe(P5){Mn(CO)2Cp}n] (4a-d; 1-4; Cp* = η5-C5Me5). Aus 1 und [CpFe(C6H6)]PF6 lassen sich photochemisch die kationischen 30-VE-Tripeldeckerkomplexe [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5) aufbauen. Zusätzlich zu den NMR-spektroskopischen Studien wurden von 2 und 3b Kristallstrukturanalysen angefertigt.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1139-1145 
    ISSN: 0009-2940
    Keywords: C-(Alkylideneamino)ketene imines ; Isocyanides, C=C coupling with aminocarbene ligands ; (2-Azaallenyl)chromium complexes ; 2-Imidazolin-5-ones ; α-Amino acids ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Syntheses via Transition Metal Complexes, 35. - (C-Amino) Ketene Imines, 2-Imidazolin-5-ones, and α-Amino Acids from Aminocarbene Chromium Complexes and IsocyanidesC-(Alkylidenamino)ketene imines 1,4-diaza-1,2,4-pentatrienes) 8 are easily accessible by C=C coupling of isocyanides R1 - NC (2, R1 = t-C4H9, c-C5H11, CH3) with the (alkylideneamino)carbene (= 2-azaallenyl-) ligand of (6). The tendency for an insertion of 2 into M=C bonds of aminocarbene complexes strongly depends on the electronic character of the aminocarbene ligand. Electron-rich aminocarbene chromium complexes like (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), show only little tendency for an insertion but mainly give cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) by substitution of CO. Electron-poor aminocarbene complexes like 6 (readily available on N-benzoylation of 1a) undergo a facile insertion of 2 into the M=C bond with smooth formation of 7. From 7 ketene imine 8 is spontaneously disengaged by a second equivalent of 2. The reaction works especially well with bulky isocyanides 2a, b. In the case of methyl isocyanide (2c) a [bis(imino)dihydropyrrol]chromium complex 15 is obtained as a minor product besides 8c. 15 results from a [4+1] cycloaddition of 2c at the ketene imine ligand of 7c. C-(Alkylideneamino)ketene imines 8 are easily accessible by our method. They prove to be very thermolabile in solution and spontaneously isomerize to give 2-imidazolin-5-ones 10 and C-amidoketene imines 11. Under the influence of wet silica gel keten imine derivatives 8 rapidly form α-amino acid amides 16 by hydrolysis with concomitant migration of a benzoyl group. Under the same conditions 11 also gives the „normal“ α-amino acid amides 17.
    Notes: C-(Alkylideneamino)ketenimine (1,4-Diaza-1,2,4-pentatriene) 8 wurden durch C=C-Kupplung von Isocyaniden R1-NC (2, R1 = t-C4H9, c-C5H11, CH3) mit dem (Alkylideneamino)carben-(= 2-Azaallenyl-)Ligand von (6) erstmals hergestellt. Die Bereitschaft zur Insertion von 2 in M=C-Bindungen von Aminocarbenkomplexen hängt stark von den elektronischen Eigenschaften der Aminocarbenliganden ab. Elektronenreiche (Aminocarben)chromkomplexe, wie z. B. (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), zeigen eine nur geringe Neigung zur Insertion von 2 und bilden bevorzugt cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) unter Substitution von CO. Elektronenarme (Aminocarben)chromkomplexe hingegen, wie z. B. 6 (durch N-Benzoylierung von 1a leicht zugänglich), zeigen ausschließlich Insertion zu 7. Aus 7 wird spontan 8 freigesetzt durch Substitution mit einem zweiten Äquivalent 2. Sperrige Isocyanide 2a, c reagieren besonders einheitlich. Mit Methylisocyanid (2c) entsteht zusätzlich zu 8c der [Bis(imino)dihydropyrrol]-chromkomplex 15 unter [4+1]-Cycloaddition von 2c am Keteniminligand von 7c. C-(Alkylidenamino)ketenimine 8 sind nach unserem Verfahren einfach zugänglich; sie isomerisieren jedoch leicht zu 2-Imidazolin-5-onen 10 und C-Amidoketeniminen 11. An feuchtem Kieselgel entstehen aus 8 rasch α-Aminosäureamide 16 durch Hydrolyse unter Wanderung eines Benzoylrestes; aus 11 unter gleichen Bedingungen zusätzlich „normale“ α-Aminosäureamide 17.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2177-2181 
    ISSN: 0009-2940
    Keywords: Benzonitriles ; Hetero Diels-Alder reactions, “inverse” ; Pyrazines, annulated ; Triazines, benzofuro- and benzothieno- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Donor-Substituted Benzoitriles as Side-Chain Dienophiles in the Intramolecular [4+2] Cycloaddition with Inverse Electron DemandExpanding the scope of the intramolecular Diels-Alder reaction of 1,2,4,5-tetrazines to include donor-substituted benzonitriles as side-chain dienophiles we describe synthetic routes to novel fused heterotricycles such as the benzofuro[3,2-e]-1,2,4-triazines 11a, b and the benzothieno[3,2-e]-1,2,4-triazines 14a, b, and 17. The doubly annulated pyrazines 22 and 23 are constructed by a subsequent second intramolecular Diels-Alder cycloaddition of the benzonitrile moiety with the fused 1,2,4-triazine system, starting from 11a and 14a.
    Notes: Unter Einschluß donorsubstituierter Benzonitrile als Seitenkettendienophile haben wir die Anwendungsbreite der intramolekularen Diels-Alder-Reaktion von 1,2,4,5-Tetrazinen erweitert und beschreiben Synthesewege zu neuen anellierten Heterotricyclen wie den Benzofuro[3,2-e]-1,2,4-triazinen 11a, b und den Benzothieno[3,2-e]-1,2,4-triazinen 14a, b sowie 17. Die doppelt anellierten Pyrazine 22 und 23 lassen sich durch eine nachfolgende zweite intramolekulare Benzonitril/1,2,4-Triazin-Diels-Alder-Cycloaddition mit 11a bzw. 14a als Edukten herstellen.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2147-2157 
    ISSN: 0009-2940
    Keywords: 1,3-Dipolar cycloadditions, intramolecular ; Nitrile oxides ; Regioselectivity ; Furanophanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Intramolecular Cycloadditions with Nitrile Oxides: Investigtions towards the Synthesis of HeterophanesThe intramolecular cycloaddition reactions of the nitrile oxides 30a-d, 35, 36, and 47, obtained in situ from the 2,5-difunctional furan hydroximoyl chlorides 12a, b, 18 and the nitro compounds 9c, d, 21, 29, are described. With 30c the expected isoxazolofuranophane of type 31 is formed in acceptable yield; the additionally formed regioisomer 32c and the dimer 34c are very minor products in this case. Whereas the highest homologue 30d gives a complex product mixture with small amounts of 31 d and the macrocycle 34d as the only identified compounds, the derivatives bearing a shorter side chain (30a, b; n = 1, 2) give rise to the exclusive reaction of the dipole with a double bond of the furan system (to give 33a, b). The same behavior is observed in the case of the electronically and sterically modified dipole systems 35/36 and 47, resp.; in spite of the much more favorable conditions for the formation of cyclophanes the cycloadditions result in the exclusive formation of the heterotricycles 41, 42 and 49. Possible preparative applications of the isomeric cycloaddition compounds are discussed.
    Notes: Die intramolekularen Cycloadditionsreaktionen der aus 2,5-difunktionellen Furan-Hydroximsäurechloriden (12a, b und 18) bzw. den Nitroverbindungen 9c, d, 21 und 29 in situ hergestellten Nitriloxide 30a-d, 35, 36 und 47 werden beschrieben. Eine Reaktion zu den angestrebten Isoxazolo-furanophanen des Typs 31 verläuft für 30c in brauchbarer Ausbeute; das Regioisomere 32c sowie das Dimere 34c treten hierbei nur in geringem Maße auf. Während das höchste Homologe 30d neben 31d und dem Makrocyclus 34d hauptsächlich Zersetzungsprodukte bildet, reagieren die Derivate mit kürzerer Seitenkette (30a, b; n = 1, 2) ausschließlich unter dipolarer Addition an eine Furandoppelbindung zu 33a, b. Für n = 1 entsprechen diesem Verhalten auch die elektronisch bzw. sterisch modifizierten Dipolsysteme 35/36 und 47, die trotz günstigerer Voraussetzungen für die Cyclophanbildung nur zu den Tricyclen 41, 42 bzw. 49 reagieren. Die präparativen Anwendungsmöglichkeiten der isomeren Cycloadditionsverbindungen als Synthesezwischenprodukte werden diskutiert.
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    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2183-2185 
    ISSN: 0009-2940
    Keywords: [4 + 2] Cycloaddition ; 3,5-Dihydroxytropone ; Singlet oxygen ; Y aromaticity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese von 3,5-DihydroxytroponWir beschreiben eine vierstufige Synthese des bisher unbekannten 3,5-Dihydroxytropons (6), die von Tropon ausgeht und eine [4 + 2]-Cycloaddition mit Singulett-Sauerstoff einschließt.
    Notes: Starting from tropone, the hitherto unknown 3,5-dihydroxytropone (6) is prepared in a four-step synthesis including a [4 + 2] cycloaddition reaction of singlet oxygen.
    Type of Medium: Electronic Resource
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