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  • General Chemistry  (13,904)
  • Animals  (2,876)
  • AERODYNAMICS
  • Geophysics
  • 2020-2024  (26)
  • 1995-1999  (11,051)
  • 1955-1959  (2,486)
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  • 1
    Unknown
    London : The Geological Society
    Keywords: Petrophysik ; Geophysics ; Petroleum - Geology ; Petroleum engineering ; Rocks
    Description / Table of Contents: P. D. Jackson, D. G. Gunn, R. C. Flint, D. Beamish, P. I. Meldrum, M. A. Lovell, P. K. Harvey, and A. Peyton: A non-contacting resistivity imaging method for characterizing whole round core while in its liner / Geological Society, London, Special Publications, 122:1-10, doi:10.1144/GSL.SP.1997.122.01.01 --- D. J. Prosser, A. Hurst, and M. R. Wilson: One-man-operable probe permeameters / Geological Society, London, Special Publications, 122:11-18, doi:10.1144/GSL.SP.1997.122.01.02 --- S. R. McDougall, A. B. Dixit, and K. S. Sorbie: Network analogues of wettability at the pore scale / Geological Society, London, Special Publications, 122:19-35, doi:10.1144/GSL.SP.1997.122.01.03 --- S. Pugliese and N. Petford: Pore-structure visualization in microdioritic enclaves / Geological Society, London, Special Publications, 122:37-46, doi:10.1144/GSL.SP.1997.122.01.04 --- Paul B. Basan, Ben D. Lowden, Peter R. Whattler, and John J. Attard: Pore-size data in petrophysics: a perspective on the measurement of pore geometry / Geological Society, London, Special Publications, 122:47-67, doi:10.1144/GSL.SP.1997.122.01.05 --- M. S. King, A. Shakeel, and N. A. Chaudhry: Acoustic wave propagation and permeability in sandstones with systems of aligned cracks / Geological Society, London, Special Publications, 122:69-85, doi:10.1144/GSL.SP.1997.122.01.06 --- Shiyu Xu, Just Doorenbos, Sue Raikes, and Roy White: A simple but powerful model for simulating elastic wave velocities in clastic Silicate rocks / Geological Society, London, Special Publications, 122:87-105, doi:10.1144/GSL.SP.1997.122.01.07 --- T. Apuani, M. S. King, C. Butenuth, and M. H. De Freitas: Measurements of the relationship between Sonic wave velocities and tensile strength in Anisotropic rock / Geological Society, London, Special Publications, 122:107-119, doi:10.1144/GSL.SP.1997.122.01.08 --- C. McCann, J. Sothcott, and S. B. Assefa: Prediction of petrophysical properties from seismic quality factor measurements / Geological Society, London, Special Publications, 122:121-130, doi:10.1144/GSL.SP.1997.122.01.09 --- Y. F. Sun and D. Goldberg: Estimation of aspect-ratio changes with pressure from seismic velocities / Geological Society, London, Special Publications, 122:131-139, doi:10.1144/GSL.SP.1997.122.01.10 --- P. K. Harvey, M. A. Lovell, J. C. Lofts, P. A. Pezard, and J. F. Bristow: Petrophysical estimation from downhole Mineralogy logs / Geological Society, London, Special Publications, 122:141-157, doi:10.1144/GSL.SP.1997.122.01.11 --- Paul F. Worthington: Petrophysical estimation of permeability as a function of scale / Geological Society, London, Special Publications, 122:159-168, doi:10.1144/GSL.SP.1997.122.01.12 --- C. A. Gonçalves, P. K. Harvey, and M. A. Lovell: Prediction of petrophysical parameter logs using a multilayer backpropagation neural network / Geological Society, London, Special Publications, 122:169-180, doi:10.1144/GSL.SP.1997.122.01.13 --- Brian P. Moss: The partitioning of petrophysical data: a review / Geological Society, London, Special Publications, 122:181-252, doi:10.1144/GSL.SP.1997.122.01.14 --- A. Revil, P. A. Pezard, and M. Darot: Electrical conductivity, spontaneous potential and ionic diffusion in porous media / Geological Society, London, Special Publications, 122:253-275, doi:10.1144/GSL.SP.1997.122.01.15 --- Brígida Ramati P. Da Rocha and Tarek M. Habashy: Fractal Geometry, porosity and complex resistivity: from rough pore interfaces to hand specimens / Geological Society, London, Special Publications, 122:277-286, doi:10.1144/GSL.SP.1997.122.01.16 --- Brígida Ramati P. Da Rocha and Tarek M. Habashy: Fractal Geometry, porosity and complex resistivity: from hand specimen to field data / Geological Society, London, Special Publications, 122:287-297, doi:10.1144/GSL.SP.1997.122.01.17 --- M. Ben Clennell: Tortuosity: a guide through the maze / Geological Society, London, Special Publications, 122:299-344, doi:10.1144/GSL.SP.1997.122.01.18 --- J. C. Lofts, J. Bedford, H. Boulton, J. A. van Doorn, and P. Jeffreys: Feature recognition and the interpretation of images acquired from horizontal wellbores / Geological Society, London, Special Publications, 122:345-365, doi:10.1144/GSL.SP.1997.122.01.19 --- D. Goldberg and Y. F. Sun: Scattering attenuation as a function of depth in the Upper Oceanic Crust / Geological Society, London, Special Publications, 122:367-375, doi:10.1144/GSL.SP.1997.122.01.20 --- N. Passas, C. Butenuth, and M. H. De Freitas: An application of the Moiré Method to a study of local strains during rock failure in tension / Geological Society, London, Special Publications, 122:377-388, doi:10.1144/GSL.SP.1997.122.01.21
    Pages: Online-Ressource (VII, 393 Seiten) , Illustrationen, Diagramme, Karten
    ISBN: 1897799810
    Language: English
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  • 2
    Publication Date: 2024-03-23
    Description: The Australian Continent: A Geophysical Synthesis is designed to provide a summary of the character of the Australian continent through the extensive information available at the continental scale, as a contribution to the understanding of Australia's lithospheric architecture and its evolution.The results build on the extensive databases assembled at Geoscience Australia, particularly for potential fields, supplemented by the full range of seismological information, mostly from The Australian National University. To aid in cross comparison of results from different disciplines, information is presented with a common projection and scales.
    Keywords: Australia ; Geophysics ; thema EDItEUR::1 Place qualifiers::1M Australasia, Oceania, Pacific Islands, Atlantic Islands::1MB Australia and New Zealand / Aotearoa ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RB Earth sciences
    Language: English
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  • 3
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    University of Calgary Press
    Publication Date: 2022-07-19
    Description: How have our interactions with animals shaped Calgary? What can we do to ensure that humans and animals in the city continue to co-exist, and even flourish together? This wide-ranging book explores the ways that animals inhabit our city, our lives and our imaginations. Essays from animal historians, wildlife specialists, artists and writers address key issues such as human-wildlife interactions, livestock in the city, and animal performers at the Calgary Stampede. Contributions from some of Calgary's iconic arts institutions, including One Yellow Rabbit Performance Theatre, Decidedly Jazz Danceworks, and the Glenbow Museum, demonstrate how animals continue to be a source of inspiration and exploration for fashion, art, dance, and theatre. The full-colour volume is beautifully illustrated throughout with archival images, wildlife photography, documentary and production stills, and original artwork. Calgary: City of Animals is published in co-operation with the Calgary Institute for the Humanities.
    Keywords: Nature ; Animals ; bic Book Industry Communication::J Society & social sciences::JF Society & culture: general::JFF Social issues & processes::JFFZ Animals & society
    Language: English
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  • 4
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    transcript Verlag | transcript Verlag
    Publication Date: 2024-03-28
    Description: Wie werden Natur und Tiere durch die Multispezies-Ethnographie inklusiv in Forschungsprojekte integriert? Katharina Ameli fokussiert die inter- und multidisziplinäre Zusammenarbeit. Aus einer Untersuchung der Schnittstellen zwischen gesellschafts- und naturwissenschaftlich orientierten Fachdisziplinen ergibt sich eine komplexe Betrachtung von Natur, Mensch und Tier. Die Einblicke in Interdependenzen unterschiedlicher Fachdisziplinen verdeutlichen den Bedarf an einer Multispezies-Ethnographie zur Analyse von MenschenTiereNaturenKulturen.
    Keywords: Natur ; Mensch ; Tiere ; Naturverständnis ; Interdisziplinarität ; Qualitative Forschung ; Kultur ; Ethnographie ; Umwelt ; Tier ; Human-animal Studies ; Umweltsoziologie ; Kulturanthropologie ; Kultursoziologie ; Kulturwissenschaft ; Nature ; Human ; Animals ; Understanding of Nature ; Interdisciplinarity ; Qualitative Research ; Culture ; Ethnography ; Environment ; Animal ; Environmental Sociology ; Cultural Anthropology ; Sociology of Culture ; Cultural Studies ; thema EDItEUR::J Society and Social Sciences::JB Society and culture: general::JBF Social and ethical issues::JBFU Animals and society ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RN The environment::RNT Social impact of environmental issues ; thema EDItEUR::J Society and Social Sciences::JH Sociology and anthropology::JHM Anthropology::JHMC Social and cultural anthropology
    Language: German
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  • 5
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    University of Calgary Press
    Publication Date: 2022-07-19
    Description: Animal Metropolis brings a Canadian perspective to the growing field of animal history, ranging across species and cities, from the beavers who engineered Stanley Park to the carthorses who shaped the city of Montreal. Some essays consider animals as spectacle: orca captivity in Vancouver, polar bear tourism in Churchill, Manitoba, fish on display in the Dominion Fisheries Museum, and the racialized memory of Jumbo the elephant in St. Thomas, Ontario. Others examine the bodily intimacies of shared urban spaces: the regulation of rabid dogs in Banff, the maternal politics of pure milk in Hamilton and the circulation of tetanus bacilli from horse to human in Toronto. Another considers the marginalization of women in Canada’s animal welfare movement. The authors collectively push forward from a historiography that features nonhuman animals as objects within human-centered inquiries to a historiography that considers the eclectic contacts, exchanges, and cohabitation of human and nonhuman animals. With contributions by: Kristoffer Archibald, Jason Colby, George Colpitts, Joanna Dean, Carla Hustak, Darcy Ingram, Sean Kheraj, William Knight, Sherry Olson, Rachel Poliquin, and Christabelle Sethna
    Keywords: Animals ; Anthropology ; Environmental Science ; History ; bic Book Industry Communication::J Society & social sciences::JH Sociology & anthropology::JHM Anthropology ; bic Book Industry Communication::H Humanities::HB History ; bic Book Industry Communication::K Economics, finance, business & management::KC Economics::KCN Environmental economics ; bic Book Industry Communication::J Society & social sciences::JF Society & culture: general::JFF Social issues & processes::JFFZ Animals & society
    Language: English
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  • 6
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    Springer Nature
    Publication Date: 2024-04-07
    Description: This open access peer-reviewed volume was inspired by the UNESCO UNITWIN Network for Underwater Archaeology International Workshop held at Flinders University, Adelaide, Australia in November 2016. Content is based on, but not limited to, the work presented at the workshop which was dedicated to 3D recording and interpretation for maritime archaeology. The volume consists of contributions from leading international experts as well as up-and-coming early career researchers from around the globe. The content of the book includes recording and analysis of maritime archaeology through emerging technologies, including both practical and theoretical contributions. Topics include photogrammetric recording, laser scanning, marine geophysical 3D survey techniques, virtual reality, 3D modelling and reconstruction, data integration and Geographic Information Systems. The principal incentive for this publication is the ongoing rapid shift in the methodologies of maritime archaeology within recent years and a marked increase in the use of 3D and digital approaches. This convergence of digital technologies such as underwater photography and photogrammetry, 3D sonar, 3D virtual reality, and 3D printing has highlighted a pressing need for these new methodologies to be considered together, both in terms of defining the state-of-the-art and for consideration of future directions. As a scholarly publication, the audience for the book includes students and researchers, as well as professionals working in various aspects of archaeology, heritage management, education, museums, and public policy. It will be of special interest to those working in the field of coastal cultural resource management and underwater archaeology but will also be of broader interest to anyone interested in archaeology and to those in other disciplines who are now engaging with 3D recording and visualization.
    Keywords: Geography ; Remote sensing ; Archaeology ; Coasts ; Application software ; Geophysics ; thema EDItEUR::N History and Archaeology::NH History ; thema EDItEUR::N History and Archaeology::NK Archaeology ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RG Geography::RGB Physical geography and topography::RGBP Coastlines ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RG Geography::RGW Geographical information systems, geodata and remote sensing
    Language: English
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  • 7
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Hyperspectral imagery has received considerable attention in the last decade as it provides rich spectral information and allows the analysis of objects that are unidentifiable by traditional imaging techniques. It has a wide range of applications, including remote sensing, industry sorting, food analysis, biomedical imaging, etc. However, in contrast to RGB images from which information can be intuitively extracted, hyperspectral data is only useful with proper processing and analysis. This book covers theoretical advances of hyperspectral image processing and applications of hyperspectral processing, including unmixing, classification, super-resolution, and quality estimation with classical and deep learning methods.
    Keywords: Geophysics ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics
    Language: English
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  • 8
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    University Press of Colorado | University Press of Colorado
    Publication Date: 2024-04-02
    Description: Animals and Inequality in the Ancient World explores the current trends in the social archaeology of human-animal relationships, focusing on the ways in which animals are used to structure, create, support, and even deconstruct social inequalities. The authors provide a global range of case studies from both New and Old World archaeology—royal Aztec dog burial, the monumental horse tombs of Central Asia, and the ceremonial macaw cages of ancient Mexico among them. They explore the complex relationships between people and animals in social, economic, political, and ritual contexts, incorporating animal remains from archaeological sites with artifacts, texts, and iconography to develop their interpretations. Animals and Inequality in the Ancient World presents new data and interpretations that reveal the role of animals, their products, and their symbolism in structuring social inequalities in the ancient world. The volume will be of interest to archaeologists, especially zooarchaeologists, and classical scholars of pre-modern civilizations and societies.  Contributors: Alejandra Aguirre Molina, Benjamin S. Arbuckle, Levent Atici, Douglas V. Campana, Roderick Campbell, Ximena Chá­vez Balderas, Pam J. Crabtree, Susan D. deFrance, Kitty F. Emery, Abigail Holeman, H. Edwin Jackson, Leonardo López Lujá­n, Michael MacKinnon, Arkadiusz Marciniak, Sue Ann McCarty, Neil L. Norman, Gilberto Perez, Bernardo Rodriguez, William A. Saturno, Ashley E. Sharpe, Nawa Sugiyama, Charlotte K. Sunseri, Naomi Sykes, Fabiola Torres, Raul Valadez, Norma Valentin Maldonado, Adam S. Watson, Joshua Wright, Belem Zuniga-Arelleno
    Keywords: History ; Ancient ; Social Science ; Archaeology ; Nature ; Animals ; thema EDItEUR::N History and Archaeology::NH History::NHC Ancient history ; thema EDItEUR::N History and Archaeology::NK Archaeology ; thema EDItEUR::W Lifestyle, Hobbies and Leisure::WN Nature and the natural world: general interest::WNC Wildlife: general interest
    Language: English
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  • 9
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    Archaeopress Publishing Ltd
    Publication Date: 2024-04-04
    Description: Non-Intrusive Methodologies for Large Area Urban Research brings together contributions from a conference held in 2021 in association with the ERC-funded ‘Rome Transformed’ research project. The papers address a major challenge in archaeology. Non-intrusive research in pursuit of a deeper understanding of urban areas can be both richly informative and cost-effective. Multiple successes in the field have led to an impressive array of innovative methodologies, methodologies that are frequently combined for still greater insight and impact. Geophysical surveys, the use of UAVs, the study of exposed historic structures and the exhaustive examination of archival records can all play a vital role, and the development of these data capture methodologies is of the utmost importance for the future of research. As well as advances in data capture methodologies, however, the papers also present case studies in the management of the big data generated and in the integration of different methodologies. A further strength of this collection lies in the range of site types considered. While many projects have historically pursued non-intrusive research in areas relatively clear of modern buildings, a growing number of research initiatives, such as ‘Rome Transformed’ are seeking to advance them in areas which remain densely occupied. Accordingly the material presented here will also be of interest to non-archaeologists working in such diverse fields as civil engineering, urban planning and physical geography.
    Keywords: Social Science ; Archaeology ; Science ; Physics ; Geophysics ; Computers ; Data Science ; Data Analytics ; thema EDItEUR::N History and Archaeology::NK Archaeology ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics ; thema EDItEUR::U Computing and Information Technology::UN Databases::UNF Data mining
    Language: English
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  • 10
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book “Geophysics and Ocean Waves Studies” presents the collected chapters in two sections named “Geophysics” and “Ocean Waves Studies”. The first section, “Geophysics”, provides a thorough overview of using different geophysical methods including gravity, self-potential, and EM in exploration. Moreover, it shows the significance of rock physics properties and enhanced oil recovery phases during oil reservoir production. The second section, “Ocean Waves Studies”, is intended to provide the reader with a strong description of the latest developments in the physical and numerical description of wind-generated and long waves, including some new features discovered in the last few years. The section is organized with the aim to introduce the reader from offshore to nearshore phenomena including a description of wave dissipation and large-scale phenomena (i.e., storm surges and landslide-induced tsunamis). This book shall be of great interest to students, scientists, geologists, geophysicists, and the investment community.
    Keywords: Geophysics ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics
    Language: English
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  • 11
    Publication Date: 2024-04-05
    Description: Neurodegenerative diseases are the most frequent cause of dementia, representing a burden for public health systems (especially in middle and middle-high income countries). Although most research on this issue is concentrated in first-world centers, growing efforts in South America are affording important breakthroughs. This emerging agenda poses new challenges for the region but also new opportunities for the field. This book aims to integrate the community of experts across the globe and the region, and to establish new challenges and developments for future investigation. We present research focused on neurodegenerative research in South America. We introduce studies assessing the interplay among genetic, neural, and behavioral dimensions of these diseases, as well as articles on vulnerability factors, comparisons of findings from various countries, and works promoting multicenter and collaborative networking. More generally, our book covers a broad scope of human-research approaches (behavioral assessment, neuroimaging, electromagnetic techniques, brain connectivity, peripheral measures), animal methodologies (genetics, epigenetics, proteomics, metabolomics, other molecular biology tools), species (all human and non-human animals, sporadic, and genetic versions), and article types (original research, review, and opinion papers). Through this wide-ranging proposal, we hope to introduce a fresh approach to the challenges and opportunities of research on neurodegeneration in South America.
    Keywords: RC321-571 ; Q1-390 ; South America ; Multicenter research ; Neurodegenerative Diseases ; Neurosciences ; Public Health ; Animals ; Clinical Protocols ; Research ; Human Experimentation ; Dementia ; thema EDItEUR::P Mathematics and Science::PS Biology, life sciences::PSA Life sciences: general issues::PSAN Neurosciences
    Language: English
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  • 12
    Publication Date: 2024-04-04
    Description: This eBook is a collection of articles from a Frontiers Research Topic. Frontiers Research Topics are very popular trademarks of the Frontiers Journals Series: they are collections of at least ten articles, all centered on a particular subject. With their unique mix of varied contributions from Original Research to Review Articles, Frontiers Research Topics unify the most influential researchers, the latest key findings and historical advances in a hot research area! Find out more on how to host your own Frontiers Research Topic or contribute to one as an author by contacting the Frontiers Editorial Office: frontiersin.org/about/contact
    Keywords: drugs ; Behavior ; Memory tasks ; pre-clinical ; clinical ; Humans ; Animals ; thema EDItEUR::P Mathematics and Science::PD Science: general issues ; thema EDItEUR::M Medicine and Nursing::MK Medical specialties, branches of medicine::MKG Pharmacology
    Language: English
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  • 13
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    Berghahn Books | Berghahn Books
    Publication Date: 2023-02-02
    Description: Employing methodological perspectives from the fields of political geography, environmental studies, anthropology, and their cognate disciplines, this volume explores alternative logics of sentient landscapes as racist, xenophobic, and right-wing. While the field of sentient landscapes has gained critical attention, the literature rarely seems to question the intentionality of sentient landscapes, which are often romanticized as pure, good, and just, and perceived as protectors of those who are powerless, indigenous, and colonized. The book takes a new stance on sentient landscapes with the intention of dispelling the denial of “coevalness” represented by their scholarly romanticization.
    Keywords: Social Science ; Sociology ; Rural ; Nature ; Animals ; Social Science ; Anthropology ; Cultural & Social ; bic Book Industry Communication::J Society & social sciences::JF Society & culture: general::JFS Social groups::JFSF Rural communities ; bic Book Industry Communication::W Lifestyle, sport & leisure::WN Natural history::WNC Wildlife: general interest ; bic Book Industry Communication::J Society & social sciences::JH Sociology & anthropology::JHM Anthropology::JHMC Social & cultural anthropology, ethnography
    Language: English
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  • 14
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book Radioisotopes - Applications in Physical Sciences is divided into three sections namely: Radioisotopes and Some Physical Aspects, Radioisotopes in Environment and Radioisotopes in Power System Space Applications. Section I contains nine chapters on radioisotopes and production and their various applications in some physical and chemical processes. In Section II, ten chapters on the applications of radioisotopes in environment have been added. The interesting articles related to soil, water, environmental dosimetry/tracer and composition analyzer etc. are worth reading. Section III has three chapters on the use of radioisotopes in power systems which generate electrical power by converting heat released from the nuclear decay of radioactive isotopes. The system has to be flown in space for space exploration and radioisotopes can be a good alternative for heat-to-electrical energy conversion. The reader will very much benefit from the chapters presented in this section.
    Keywords: Geophysics ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics
    Language: English
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  • 15
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    Springer Nature | Springer
    Publication Date: 2024-04-05
    Description: This open access book explores the interactions between water and earthquakes, including recent concerns about induced seismicity. It further highlights that a better understanding of the response of the water system to disturbances such as earthquakes is needed to safeguard water resources, to shield underground waste repositories, and to mitigate groundwater contamination. Although the effects of earthquakes on streams and groundwater have been reported for thousands of years, this field has only blossomed into an active area of research in the last twenty years after quantitative and continuous documentation of field data became available. This volume gathers the important advances that have been made in the field over the past decade, which to date have been scattered in the form of research articles in various scientific journals.
    Keywords: Geophysics/Geodesy ; Hydrology/Water Resources ; Hydrogeology ; Natural Hazards ; Solid Earth Sciences ; Water ; Earth Sciences ; Groundwater Response ; water-induced seismicity ; Liquefaction ; Mud Volcanoes ; Stream discharge ; Hydrologic Precursors ; Hydrologic changes after earthquakes ; Induced seismicity ; Open Access ; Geophysics ; Hydrology & the hydrosphere ; Natural disasters ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RB Earth sciences::RBK Hydrology and the hydrosphere ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RN The environment::RNR Natural disasters
    Language: English
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  • 16
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The importance of Geographic Information Systems (GIS) can hardly be overemphasized in today’s academic and professional arena. More professionals and academics have been using GIS than ever – urban & regional planners, civil engineers, geographers, spatial economists, sociologists, environmental scientists, criminal justice professionals, political scientists, and alike. As such, it is extremely important to understand the theories and applications of GIS in our teaching, professional work, and research. “The Application of Geographic Information Systems” presents research findings that explain GIS’s applications in different subfields of social sciences. With several case studies conducted in different parts of the world, the book blends together the theories of GIS and their practical implementations in different conditions. It deals with GIS’s application in the broad spectrum of geospatial analysis and modeling, water resources analysis, land use analysis, infrastructure network analysis like transportation and water distribution network, and such. The book is expected to be a useful source of knowledge to the users of GIS who envision its applications in their teaching and research. This easy-to-understand book is surely not the end in itself but a little contribution to toward our understanding of the rich and wonderful subject of GIS.
    Keywords: Geophysics ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics
    Language: English
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  • 17
    Publication Date: 2022-01-31
    Description: Recent advances in environmental magnetism offer the opportunity to link the magnetic signature of marine and continental rocks to the paleoenvironmental and paleoclimatic settings that controlled their formation or deposition, as well as to post-depositional events, such as diagenesis, that can alter their primary signature. This Research Topic assembles studies that used state of the art rock magnetic techniques to unravel the causes and effects of catastrophic geological events, including tsunami, meteorite impacts, Archean oxygenation event, geomagnetic reversals, and global climate changes linked to large volcanic eruptions.
    Keywords: GB3-5030 ; Q1-390 ; rock magnetism ; Geology ; paleomagnetism ; Geophysics ; extreme events
    Language: English
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  • 18
    Publication Date: 2024-04-05
    Description: This open access book provides an overview of the building blocks necessary for managing, steering and guiding the establishment of a research infrastructure (RI). It offers valuable insights into RI investment, access and management at the academic, grants management, agency and policy level, and serves as a useful guide for the research community, students, and those in the private sector wishing to understand the approaches and opportunities involved in the establishment, maintenance and management of research infrastructure platforms. Presenting a holistic view of RI investment and granting cycles from a South African perspective, the book’s target audience includes those working in science diplomacy, policymaking and science grants councils (especially in Africa) as well as funders and donors.
    Keywords: Earth sciences ; Geophysics ; thema EDItEUR::P Mathematics and Science::PH Physics::PHV Applied physics::PHVG Geophysics
    Language: English
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  • 19
    Publication Date: 2023-01-10
    Description: The Cartesian-based least squares reverse time migration (LSRTM) aims to obtain a relatively high-resolution amplitude preserving imaging by calculating and solving the Hessian matrix. In addition, conjugate gradient algorithm is proved to be an efficient iterative method, which makes the traditional LSRTM feasible in practical data processing applications. Each iteration process of LSRTM includes two main parts; The first part is the forward simulation of wavefield, and the second part is the back propagation of wavefield. However, the calculation of these two parts takes a lot of time, and oversampling effects will occur in the calculation process. The thesis develops a smooth understanding of the LSRTM scheme in pseudodepth domain and gives information about this type of wavefield extrapolation method to achieve amplitude-preserved image with low computational costs in terms of memory and time. The underground media faced by seismic exploration usually include low velocity bodies, high steep structures and pore fracture units. When simulating the seismic wavefield in these media, in order to ensure the simulation accuracy and computational stability by finite difference methods, the grid spacing needs to be very small, which leads to the oversampling problem of the traditional finite difference forward simulation method in Cartesian coordinate system. In order to overcome this problem, the pseudo depth domain algorithm is applied to the least-squares reverse time migration to improve its computational efficiency. The problem of stabilizing this Pseudodepth wavefield arises from the introduction of the mapping function and velocity and also the vertical axis operator that converts the finite difference solution partially from time into frequency domains. Stability and convergence analysis suggests that the spatial derivatives of Riemannian axis should be approximated by a mixed Fourier pseudo-spectral and ordinary finite-difference schemes methods using a special Gaussian-like impulse function to generate the vector-matrix of the complex source term within the finite-difference operator, in addition to the mapping velocity, which is a differential form of the initial input velocity model, manifestly controls the CFL conditions of the associated Riemannian-finite difference operator. Numerical and synthetic examples indicated that this approach is more stable and efficient in extrapolating a smooth Riemannian wavefield while maintaining Claerbout’s principle for locating subsurface reflectors also choosing an appropriate sampling rate for the new vertical axis is related inversely by the maximum frequency of the impulse wavelet and directly with minimum velocity value in the given model. The LSRTM wavefield extrapolation usually uses the two-dimensional constant density acoustic wave equation, by considering the change of velocity field distribution, and converts it to the corresponding pseudodepth domain, so as to solve the oversampling problem in the true depth domain. For each point in the Cartesian coordinate system, there is a corresponding point in the pseudo depth domain. Therefore, we can interpolate and remodel the reconstructed finite difference modelled wavefield in the new coordinate system through the Cartesian-to-pseudodepth mapping function. Regardless of the applied finite difference algorithm and boundary conditions, wavefield extrapolation in pseudodepth domain can ensure high accuracy and efficiency. Through the test of synthetic and actual data, compared with the traditional LSRTM results, pseudodepth domain LSRTM shows great potentiality in amplitude preserving imaging. On the other hand, pseudodepth domain LSRTM has great advantages in computational efficiency and ensures computational accuracy.
    Description: Masters
    Description: 基于笛卡尔的最小二乘逆时偏移(LSRTM)旨在通过计算和求解Hessian矩阵获得相对高分辨率和保幅的成像。此外,共轭梯度算法被证明是一种有效的迭代方法,这使得传统的LSRTM在实际数据处理应用中是可行的。LSRTM的每个迭代过程包括两个主要部分;第一部分是波场的正演模拟,第二部分是波场的反向传播。然而,这两部分的计算需要花费大量时间,并且在计算过程中会出现过采样效应。本论文对伪深度域LSRTM方法进行了研究,给出了该方法波场外推的信息,获取了保幅的图像,并且该方法有较低的内存和时间成本。 地震勘探面临的地下介质通常包括低速体、高陡构造和孔隙裂隙单元。在模拟这些介质中的地震波场时,为了保证有限差分法的模拟精度和计算稳定性,需要非常小的网格间距,这导致了传统的笛卡尔坐标系有限差分正演模拟方法的过采样问题。为了克服这一问题,将伪深度域算法应用于LSRTM,以提高其计算效率。伪深度域波场稳定是因为引入了映射函数和速度,还有垂直轴算子,并将有限差分解从时间域转换为频率域。稳定性和收敛性分析表明,除了映射速度之外,黎曼轴的空间导数还应该通过傅里叶伪谱方法来近似,该方法使用一种特殊的类高斯脉冲函数来生成有限差分算子内复数震源项的向量矩阵,它是初始输入速度模型的微分形式,控制相关黎曼有限差分算子的CFL条件。合成数据的例子表明,这种方法在推导平滑的黎曼波场时更加稳定和高效,同时保持了Claerbout地下反射体的定位原则,也为新纵轴选择了合适的采样率,该采样率与脉冲小波的最大频率成反比,与给定模型中的最小速度值直接相关。 LSRTM波场外推法采用二维常密度声波方程,通过考虑速度场分布的变化,将其转换为相应的伪深度域,从而解决真深度域的过采样问题。对于笛卡尔坐标系中的每个点,伪深度域中都有一个对应点。因此,我们可以通过笛卡尔到伪深度映射函数,在新坐标系下对重建的有限差分模拟波场进行插值和重塑。无论采用何种有限差分算法和边界条件,伪深度域的波场外推都能保证较高的精度和效率。通过对合成数据和实际数据的测试,与传统的LSRTM结果相比,伪深度域LSRTM在保幅成像方面显示出巨大的潜力。另一方面,伪深度域LSRTM在计算效率和计算精度方面也有很大优势。
    Keywords: Geophysics ; Seismic Waves Propagationa and Imaging
    Repository Name: AquaDocs
    Type: Thesis/Dissertation
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  • 20
    Publication Date: 2023-06-14
    Description: Complex geology in glacial terrain makes groundwater exploration challenging for water supply companies. Abrupt lateral changes of geological conditions, for example, raise the risk of unsuccessful exploration drilling. At some locations, local water supply companies experience a large number of dry wells, raising the need for better exploration approaches. The use of geophysical techniques enables the detection and characterization of subsurface structures in terms of aquifers and aquitards. We present two examples in which seismic and resistivity methods are combined for subsurface characterization. A thrust structure is detected in the Varde study area in Denmark and a channel structure is mapped in the Hamburg-Sülldorf study area in Germany. The different imaging characteristics of seismic P‑ and S‑waves are demonstrated. The combination of seismic and resistivity methods enables delineating groundwater-bearing and groundwater-barrier layers down to a depth of 150 m.
    Description: Interreg North Sea Region Programme
    Description: Leibniz-Institut für Angewandte Geophysik (3464)
    Keywords: ddc:622.15 ; Seismic reflection ; Electrical resistivity ; P‑waves ; S‑waves ; Geophysics ; Reflexionsseismik ; Widerstandsverfahren ; P‑Wellen ; S‑Wellen ; Geophysik
    Language: English
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  • 21
    Publication Date: 2023-08-09
    Description: Sedimentäre Strukturen können die Fließ- und Stofftransportpfade in feinkörnigen Talfüllungen stark beeinflussen. Diese Strukturen müssen gezielt auf ihre Ausdehnung und Eigenschaften untersucht werden, um Verweilzeiten, Fließpfade und das Abbaupotenzial eingetragener Schadstoffe zu bestimmen. In der quartären Talfüllung der Ammeraue bei Tübingen wurden beispielhaft Torflagen und eine Kiesrinne untersucht, um ihre Einflüsse auf die regionale Hydrogeologie und Hydrochemie zu bewerten. Dafür wurden geophysikalische und hydrogeologische Erkundungsmethoden ausgewählt und kombiniert. Mit geoelektrischen Oberflächenmessungen konnte die Ausdehnung der betrachteten Strukturen erkundet werden. Unterschiedliche Direct-Push-Sondierungen, darunter eine In-situ-Bestimmung der Sedimentfarbe, und bohrlochgeophysikalische Messungen erfassten ihre Geometrie und interne Heterogenität. Die hydraulischen und biogeochemischen Eigenschaften der Sedimente und des Grundwassers wurden anschließend durch gezielte Probennahmen und hydraulische Tests an repräsentativen Ansatzpunkten bestimmt. Die dargestellte Methodenkombination zur Abgrenzung relevanter Teilgebiete mit anschließender hochauflösender Untersuchung lässt sich auch auf die Untersuchung großflächiger Täler übertragen.
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: Eberhard Karls Universität Tübingen (1020)
    Description: Eberhard Karls Universität Tübingen (1020)
    Keywords: ddc:551.49 ; Geophysik ; Standortuntersuchung ; Auengebiet ; Direct-Push ; Sedimentäre Strukturen ; Geophysics ; Site characterization ; Floodplain ; Direct-push ; Sedimentary features
    Language: German
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  • 22
    Publication Date: 2024-02-26
    Description: Identifcation of ontogenetic age classes plays an important role in the felds of zoology, palaeontology and archaeology, where accurate age classifcations of (sub)fossil remains are a crucial component for the reconstruction \nof past life. Textural ageing\xe2\x80\x94the identifcation of age-related bone surface textures\xe2\x80\x94provides a size-independent \nmethod for age assessment of vertebrate material. However, most of the work so far is limited to qualitative results. \nWhile qualitative approaches provide helpful insights on textural ageing patterns, they are heavily subject to observer \nbias and fall short of quantitative data relevant for detailed statistical analyses and cross-comparisons. Here, we present a pilot study on the application of 3D surface digital microscopy to quantify bone surface textures on the long \nbones of the grey heron (Ardea cinerea) and the Canada goose (Branta canadensis) using internationally verifed \nroughness parameters. Using a standardised measuring protocol, computed roughness values show a strong correlation with qualitative descriptions of textural patterns. Overall, higher roughness values correspond to increased numbers of grooves and pits and vice versa. Most of the roughness parameters allowed distinguishing between diferent \nontogenetic classes and closely followed the typical sigmoidal animal growth curve. Our results show that bone \ntexture quantifcation is a feasible approach to identifying ontogenetic age classes.
    Keywords: General Physics and Astronomy ; General Environmental Science ; General Biochemistry ; Genetics and Molecular Biology ; General Materials Science ; General Chemistry ; Roughness ; Surfaces ; Taphonomy ; Topography ; Bone ; Ontogeny ; Digital microscopy
    Repository Name: National Museum of Natural History, Netherlands
    Type: info:eu-repo/semantics/article
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  • 23
    Publication Date: 2024-01-15
    Description: Geothermal heat flow in the polar regions plays a crucial role in understanding ice-sheet dynamics and predictions of sea level rise. Continental-scale indirect estimates often have a low spatial resolution and yield largest discrepancies in West Antarctica. Here we analyse geophysical data to estimate geothermal heat flow in the Amundsen Sea Sector of West Antarctica. With Curie depth analysis based on a new magnetic anomaly grid compilation, we reveal variations in lithospheric thermal gradients. We show that the rapidly retreating Thwaites and Pope glaciers in particular are underlain by areas of largely elevated geothermal heat flow, which relates to the tectonic and magmatic history of the West Antarctic Rift System in this region. Our results imply that the behavior of this vulnerable sector of the West Antarctic Ice Sheet is strongly coupled to the dynamics of the underlying lithosphere.
    Description: The Amundsen Sea sector, Antarctica, is underlain by shallow Curie depths – where the magnetic properties of rocks change – according to airborne magnetic data. This suggests high geothermal heat flow in this region of the West Antarctic Rift System.
    Description: Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (Alfred-Wegener- Institute, Helmholtz Centre for Polar and Marine Research) https://doi.org/10.13039/501100003207
    Description: European Space Agency (ESA) https://doi.org/10.13039/501100000844
    Description: Deutsche Forschungsgemeinschaft (German Research Foundation) https://doi.org/10.13039/501100001659
    Description: https://doi.org/10.1594/PANGAEA.932452
    Keywords: ddc:551.1 ; Cryospheric science ; Geomagnetism ; Geophysics ; West Antarctica ; Amundsen Sea sector
    Language: English
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  • 24
    Electronic Resource
    Electronic Resource
    Springer
    Cellular and molecular life sciences 51 (1995), S. 703-709 
    ISSN: 1420-9071
    Keywords: Geophysics ; geology ; natural radioactivity ; radiometry ; mining ; uranium ores ; radon ; disposal of radioactive waste
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Almost simultaneously with Roentgen rays, natural radioactivity was discovered. Its investigation led to important fundamentals of the geosciences: petrophysics, terrestrial heat flow, isotope geology, and absolute geological chronology. In applied geophysics and geology, exploration of radioactive ores and of tectonic faults, and radiometric well loggings, are used. Production of radioactive water and mining for uranium ores are discussed, including their development (especially in the Saxon ore mountains) and the consequences on health (radon in underground air and houses). Disposal of radioactive waste is touched on briefly.
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 41 (1995), S. 238-246 
    ISSN: 1432-1432
    Keywords: Cellular slime molds ; Animals ; Fungi ; Plantae ; Maximum-likelihood method ; Evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The phylogenetic position of Dictyostelium inferred from 18S rRNA data contradicts that from protein data. Protein trees always show the close affinity of Dictyostelium with animals, fungi, and plants, whereas in 18S rRNA trees the branching of Dictyostelium is placed at a position before the massive radiation of protist groups including the divergence of the three kingdoms. To settle this controversial issue and to determine the correct position of Dictyostelium, we inferred the phylogenetic relationship among Dictyostelium and the three kingdoms Animalia, Fungi, and Plantae by a maximum-likelihood method using 19 different protein data sets. It was shown at the significance level of 1 SE that the branching of Dictyostelium antedates the divergence of Animalia and Fungi, and Plantae is an outgroup of the Animalia-Fungi-Dictyostelium clade.
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  • 26
    Electronic Resource
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    Springer
    Journal of molecular evolution 42 (1996), S. 183-193 
    ISSN: 1432-1432
    Keywords: Small-subunit ribosomal RNA ; Phylogeny ; Animals ; Fungi ; Plants ; Alveolates ; Heterokonts ; Stramenopiles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The evolutionary relationships of four eukaryotic kingdoms—Animalia, Plantae, Fungi, and Protista—remain unclear. In particular, statistical support for the closeness of animals to fungi rather than to plants is lacking, and a preferred branching order of these and other eukaryotic lineages is still controversial even though molecular sequences from diverse eukaryotic taxa have been analyzed. We report a statistical analysis of 214 sequences of nuclear small-subunit ribosomal RNA (srRNA) gene undertaken to clarify these evolutionary relationships. We have considered the variability of substitution rates and the nonindependence of nucleotide substitution across sites in the srRNA gene in testing alternative hypotheses regarding the branching patterns of eukaryote phylogeny. We find that the rates of evolution among sites in the srRNA sequences vary substantially and are approximately gamma distributed with size and shape parameter equal to 0.76. Our results suggest that (1) the animals and true fungi are indeed closer to each other than to any other “crown” group in the eukaryote tree, (2) red algae are the closest relatives of animals, true fungi, and green plants, and (3) the heterokonts and alveolates probably evolved prior to the divergence of red algae and animal-fungus-green-plant lineages. Furthermore, our analyses indicate that the branching order of the eukaryotic lineages that diverged prior to the evolution of alveolates may be generally difficult to resolve with the srRNA sequence data.
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  • 27
    Electronic Resource
    Electronic Resource
    Springer
    Machine vision and applications 8 (1995), S. 187-193 
    ISSN: 1432-1769
    Keywords: Tracking ; Segmentation ; Pigs ; Animals ; Computer vision
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract An algorithm was developed for the segmentation and tracking of piglets and tested on a 200-image sequence of 10 piglets moving on a straw background. The image-capture rate was 1 image/140 ms. The segmentation method was a combination of image differencing with respect to a median background and a Laplacian operator. The features tracked were blob edges in the segmented image. During tracking, the piglets were modelled as ellipses initialised on the blobs. Each piglet was tracked by searching for blob edges in an elliptical window about the piglet's position, which was predicted from its previous two positions.
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  • 28
    Electronic Resource
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    Springer
    Astrophysics and space science 230 (1995), S. 439-456 
    ISSN: 1572-946X
    Keywords: Geophysics ; geomagnetic field
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Geomagnetic field research carried out at the Hermanus Magnetic Observatory over the past decade is reviewed. An important aspect of this research has been the study of geomagnetic field variations, with particular emphasis on ULF geomagnetic pulsations. Features of geomagnetic pulsations which are unique to low latitude locations have been investigated, such as the cavity mode nature of low latitude Pi 2 pulsations and the role played by ionosphericO + ions in the field line resonances responsible for Pc 3 pulsations. A theoretical model has been developed which is able to account for the observed relationships between geomagnetic pulsations and oscillations in the frequency of HF radio waves traversing ionospheric paths. Other facets of the research have been geomagnetic field modelling, aimed at improving the accuracy and resolution of regional geomagnetic field models, and the development of improved geomagnetic activity indices.
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  • 29
    ISSN: 1610-2924
    Keywords: Geophysics ; Numerical modelling ; Visualization ; Language ; Convection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract It was known that deep within numbers and binary data from simulations of geophysical convective flows resided various patterns. Two models of convective fluid flows were being considered. One was a model of two-dimensional (768 × 256) air convection with finite Prandtl number of one and Rayleigh number of 108−1010, and another was a model of three-dimensional (up to 120 × 120 × 90) mantle convection with infinite Prandtl number and Rayleigh number of 106−108. Clearly, phenomena existed which superceded each individual dimensionless computer model to provide a piece of information regarding actual fluid flows. The problem was how to find, prove, and communicate these patterns and phenomena for convection simulations with gigabytes of data. In a search for such an analytical and communicative tool, the alternative of visualization was considered. The need for visualization was recognized and discussed. Then, utilizing both two- and three-dimensional models of high Rayleigh number convection, basic techniques of style and content were developed. Applications of the visualization techniques were designed utilizing IBM’s Data Explorer in order to create communicative images and movies, and after the applications, the problems of data storage and transfer became apparent. Throughout the process though, it became clear how important the language of vision actually could be in the geophysics community. In a field in which words such as plumes and internal waves have in ways replaced mathematics as the basic language for science, there is a need for another resource, another language-the visualization of convective fluid flows.
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  • 30
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    Journal of agricultural and environmental ethics 10 (1997), S. 249-267 
    ISSN: 1573-322X
    Keywords: Animals ; Asia ; consciousness ; Australia ; Hong Kong ; India ; Israel ; Japan ; New Zealand ; The Philippines ; Russia ; Singapore ; Thailand
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Philosophy
    Notes: Abstract The interactions between humans, animals and the environment have shaped human values and ethics, not only the genes that we are made of. The animal rights movement challenges human beings to reconsider interactions between humans and other animals, and maybe connected to the environmental movement that begs us to recognize the fact that there are symbiotic relationships between humans and all other organisms. The first part of this paper looks at types of bioethics, the implications of autonomy and the value of being alive. Then the level of consciousness of these relationships are explored in survey results from Asia and the Pacific, especially in the 1993 International Bioethics Survey conducted in Australia, Hong Kong, India, Israel, Japan, New Zealand, The Philippines, Russia, Singapore and Thailand. Very few mentioned animal consciousness in the survey, but there were more biocentric comments in Australia and Japan; and more comments with the idea of harmony including humans in Thailand. Comparisons between questions and surveys will also be made, in an attempt to describe what people imagine animal consciousness to be, and whether this relates to human ethics of the relationships.
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  • 31
    ISSN: 1434-193X
    Keywords: Photocycloaddition ; Ring opening ; Oxetanes ; 1,2-Diols ; Alkyldealkoxylation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring opening of 3-isopropyl-2-phenyl-3-oxetanol (2a) by various nucleophiles has been studied. In the presence of BF3 as a Lewis acid, a clean reaction at the less substituted C-4 position was observed and the corresponding 1,2-diols 6-11 and 21-23 were isolated in diastereomerically pure form (47-97% yield). Alkyl-, aryl-, alkynyl- and alkenyllithium compounds proved to be suitable carbon nucleophiles. Deprotonated thiols were used as sulfur nucleophiles. An alkoxide derived from benzyl alcohol and an amide derived from benzylamine reacted less readily under these conditions, yielding the 1,2,3-trifunctional compounds 24 (42% yield) and 26 (54% yield). Other 2-phenyl-3-oxetanols such as 2b and 2c can also be employed as electrophiles, whereas 2-anisyl derivatives preferentially undergo rearrangement reactions, as exemplified by the conversion of oxetane 16 to the hydroxy ketone 17 (84% yield). The superior behaviour of 3-oxetanols as compared to their silyl derivatives in reactions with nucleophiles became evident from the reaction of 3-silyloxyoxetane 1a with alkyllithium reagents. A β elimination occurred upon treatment with nBuLi, which, after pericyclic ring opening and addition of nBuLi, yielded the allylic alcohol 20.
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  • 32
    ISSN: 1434-193X
    Keywords: Azoalkanes ; DBO ; Fluorescence quenching ; Exciplexes ; Hydrogen transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fluorescence of the DBO derivatives 1-3 is efficiently quenched by olefins and arenes, exciplex formation and hydrogen transfer operate as quenching mechanisms. The electron-accepting ester groups in the azoalkanes 1-3 promote significantly more effective quenching compared to the parent DBO. Steric hindrance accounts for the differences in the quenching efficiencies, but electronic effects dominate
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  • 33
    ISSN: 1434-193X
    Keywords: Mannich bases ; γ-Amino alcohols ; Grob fragmentation ; (Z)-Alkenes ; Oxetanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quaternized γ-amino alcohols 5 derived from ternary iminium salts 2 are stereospecifically converted into both unsaturated aldehydes/ketones 6 with a (Z)-C—C double bond in a Grob-type fragmentation and highly functionalized oxetanes 7 by intramolecular substitution.
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  • 34
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2201-2207 
    ISSN: 1434-193X
    Keywords: Antibiotics ; Asymmetric synthesis ; β-Lactams ; Michael additions ; Multicomponent reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithium dialkylcuprates react either in a sequential one-pot or in a domino “three-component” fashion with chiral Michael acceptors, like Oppolzer's N-enoyl-2,10-camphorsultams 7 and 11 or ‘Evans’ N-enoyl-4-phenyl-1,3-oxazolidin-2-ones 8 and 13, and N-(methoxycarbonylmethylidene)(4-methoxyphenyl)amine 9 to afford the corresponding cis-3-alkyl-4-methoxycarbonyl-1-(4-methoxyphenyl)azetidin-2-ones 10, 14-15 in overall yields of 40-67% and enantiomeric excesses of 91-99%.
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  • 35
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2229-2235 
    ISSN: 1434-193X
    Keywords: 3-Nitro-ω-benzylideneacetophenone ; Carbanions ; Michael addition ; Intramolecular vicarious nucleophilic substitution of hydrogen ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Nitro-ω-benzylideneacetophenone (1) reacts with carbanions containing leaving groups to give addition products to the electrophilic side chain. As a result of conjugated addition and subsequent intramolecular vicarious nucleophilic substitution of hydrogen (VNS) in the nitroaromatic ring of 1 in the position para to the nitro group, 4-cyano-7-nitro-3-phenyl-1,2,3,4-tetrahydronaphthalen-1-one and 4-cyano-7-nitro-3-phenylnaphth-1-ol are obtained. Smooth intramolecular VNS in the position para to the nitro group was observed for 4-chloro-1-(3-nitrophenyl)-3-phenyl-4-(p-tosyl)butanol.
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  • 36
    ISSN: 1434-193X
    Keywords: Conformation analysis ; Electrochemistry ; Nitrogen heterocycles ; Dimerization ; Mechanism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In aqueous media the one-electron reduction of the title compounds on a mercury pool generally gives rise to three dimers, which are distinguishable by HPL chromatography. From spectroscopic analyses it has been possible to propose a structure for these conformers and their stability has been studied. Two conformers are unstable, yielding the third conformer. A mechanism is proposed for this transformation.
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  • 37
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 837-846 
    ISSN: 1434-193X
    Keywords: AZT ; cycloSal-pro-nucleotide ; Prodrugs ; Nucleotide delivery ; HIV chemotherapy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of our cycloSaligenyl- (cycloSal) pronucleotide concept to the approved anti-HIV dideoxynucleoside 3′-azido-3′-deoxythymidine AZT (1) is reported. This pro-nucleotide concept has been designed to deliver the corresponding 3′-azido-3′-deoxythymidine monophosphate AZTMP (2) by selective chemical hydrolysis from the lipophilic precursors cycloSal-AZTMP 4a-h. All derivatives 4a-h were synthesized using differently substituted salicyl alcohols 7a-h as starting materials. In hydrolysis studies, compounds 4 decomposed selectively releasing AZTMP (2) and the salicyl alcohols 7 following the designed tandem reaction. Furthermore, due to the electronic properties introduced by substituents, the half-lives of the triesters 4 could be ajusted over a wide range. Phosphotriesters 4 exhibited considerable biological activity in HIV-1 and HIV-2 infected wild-type human T-lymphocyte (CEM/O) cells, whereas, contrary to our expectations, nearly all activity was lost in HIV-2 infected thymidine-kinase-deficient CEM cells.
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  • 38
    ISSN: 1434-193X
    Keywords: N-Alkylation ; Diketopiperazine building block ; Peptidomimetics ; RGD analogues ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As a new scaffold for peptidomimetic synthesis, a highly constrained bifunctional diketopiperazine, 4, has been prepared by smooth N-alkylation with tert-butyl bromoacetate. As a first application, we describe herein the synthesis of new peptidomimetics of the Arg-Gly-Asp (RGD) sequence. The product 30, which shows a selective platelet-aggregation inhibiting activity, can be used as a lead for the preparation of more potent products.
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  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 871-876 
    ISSN: 1434-193X
    Keywords: Dioxirane ; Homolysis, induced ; Aminoxyl ; Oxidation ; Spin-trapping ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the reactions of dimethyldioxirane (1a) and methyl(trifluoromethyl)dioxirane (1b) with 2,2,6,6-tetramethylpiperidinyl-1-oxyl (2) (TEMPO) in acetone, the corresponding methoxyamine 1-methoxy-2,2,6,6-tetramethylpiperidine (5) is produced in ≥98% yield, both in air and under N2, and in the absence or presence of a hydrocarbon (adamantane). Kinetic experiments show that aminoxyl 2 triggers the radical decomposition of the dioxirane, in addition to scavenging methyl radicals derived therefrom. The reactions of an aminoxyl less prone to oxidation, namely 1,2-dihydro-2-methyl-2-phenyl-3H-indol-3-one-1-oxyl (4), with dioxiranes 1a and 1b in acetone have also been studied. In these cases, not only is the corresponding methoxyamine 8a produced (yield 12-16%), but quinoneimine-N-oxides 10 (yield 12-21%) and 11 (yield 18-19%) are also formed. Furthermore, significant amounts (8-14%) of the amine 9 (the product of deoxygenation of 4) can be isolated. These observations provide useful information concerning the free-radical mechanism that follows the initial attack by the aminoxyl at the dioxirane.
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  • 40
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2373-2377 
    ISSN: 1434-193X
    Keywords: Charge-transfer fluorescence ; Fluorogenic probe ; Fluorescence labelling ; Maleimide group ; Solvatochromism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural modification of the highly fluorescent donor-bridge-acceptor molecule “Fluoroprobe” (FP) is shown to extend the excitation window to longer wavelengths. The resulting “Fluorotrope” (FT) shows appreciable absorption in the 350-420-nm range, so that visible (blue) light can be used for excitation. Further functionalization with a maleimide group results in the novel fluorogenic reagent MaleimidoFluorotrope (MFT) which yields fluorescent adducts with amines, thiols and other reactive groups that add to the double bond of the maleimide. The fluorescence wavelength of these adducts is extremely sensitive to the polarity and mobility of the medium.
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  • 41
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2379-2387 
    ISSN: 1434-193X
    Keywords: β-Peptides ; Polylithiation of peptides ; Li-enolates of peptides ; Back-bone alkylation of β-peptides ; Diastereoselective alkylation of β-peptide enolates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of N-Boc-protected β-tripeptide derivatives with or without N-methyl groups and with free or Me-ester-protected C terminus has been prepared (8-14, 16, 17). As with α-peptides (→ A), the β-peptide derivatives can be polylithiated (→ B, C). No epimerization of stereogenic centers and no β elimination (exception 17 → 24) is observed upon treatment with bases as strong as tBuLi. The C terminal ester Li-enolate moiety of tetralithio β-tripeptides (cf. C) can be selectively alkylated with methyl, benzyl and allyl halides, and with tert-butyl bromoacetate in yields ranging from 35-80% (8 → 18, 14 → 20-23).
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  • 42
    ISSN: 1434-193X
    Keywords: Natural products ; Steroids ; Chenodeoxycholic acid ; Brassinosteroid analogues ; Biological activity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and spectroscopic characterization of two new bioactive analogues of brassinosteroids with a 24-hydroxylated cholanic side chain, an A/B ring cis-junction and oxygenated functions in C-7 is described.
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  • 43
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2409-2416 
    ISSN: 1434-193X
    Keywords: Sulfur heterocycles ; Rearrangements ; Reductions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of 1,2-benzodithiino[5,4,3-cde][1,2]benzodithiin-2,7-diamine (1) and dithio-bridged benzidine 2 have been achieved. The starting material for the synthesis of 1 was 1,3-diiodo-5-nitrobenzene (15) which was transformed by conventional means into 1,2-bis[3,5-bis(ethylthio)phenyl]diazane (19). The benzidine rearrangement of 19 in the presence of HBF4 at -30 °C yielded 4,4′-diamino-2,2′,6,6′-tetraethylthiobiphenyl (20) in 50 % yield. Treatment of 20 with sodium in ammonia and work-up in the presence of air yielded 1. The latter compound could be reduced with LiAlH4 to the tetrathiol 20a. The starting material for the preparation of 2 was 3-chloro-1-iodo-5-nitrobenzene (23), a side product of the preparation of 15. It was transformed analogously to the preparation of 1 into 1,2-bis(3-ethylthiophenyl)diazane (28). The benzidine rearrangement of 28 in presence of HBF4 at -30 °C afforded 4,4′-diamino-2,2′-bis(ethylthio)biphenyl (29) in 49 % yield. Treatment of 29 with sodium in ammonia and work-up under aerobic conditions yielded 2. Quantitative reduction of 2 to the thiol 29a could be achieved with LiAlH4. The reversible electrochemical reduction of 1 on unmodified glassy carbon electrodes leads to a product to which the structure of 3 was assigned.
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  • 44
    ISSN: 1434-193X
    Keywords: N-Heterocycles ; Porphyrins ; Radical cations ; N-Dealkylation ; Stereoelectronic effects ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Evidence for a stereoelectronic inhibition of deprotonation of the radical cation of N-benzylpiperidine is presented. This stereoelectronic effect, which is due to the cyclic structure of the precursor, provides a tool to differentiate hydrogen-atom- versus electron-transfer routes in the biomimetic oxidative N-dealkylation of tertiary amines: the electron-transfer route appears to be the operating mechanism.
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  • 45
    ISSN: 1434-193X
    Keywords: Colchicine ; 10-Ethylthiocolchicide, diene properties of ; π-Facial diastereoselectivity ; Consecutive [4+2],[3+2] cycloadditions ; Atropisomerism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cycloaddition reactions of the facially dissymmetric diene moiety of (-)-(M,7S)-colchicine (5) and (-)-(M,7S)-10-ethylthiocolchicide (9) to various alkynes have been studied. With 5 and the dienophilic benzyne (3), dimethyl acetylenedicarboxylate (DMAD) (4) and cyclooctyne (6) as starting materials all cycloadditions could be realized with high regioselectivity at the 8,12-positions of the alkaloid. The approach of the dienophiles preferentially occurred toward the syn π-face of the diene. In contrast to the cycloaddition mode of 5 the ethylthiocolchicide 9 surprisingly reacted in a different manner. With benzyne as starting material a novel [3+2] cycloaddition of the thioenol ether moiety of 9 towards the dipolarophilic benzyne is supposed, affording the unexpected colchicide 10 after [1,5]H shift of the primarily formed cycloadduct followed by cleavage of the C-S linkage. With DMAD (4) and cyclooctyne (6) the reaction course is more complex. In a consecutive [4+2]/[3+2] cycloaddition (or vice versa) followed by a thermally induced cycloreversion of a not identified intermediate DMAD (4) gives rise to the polycyclic thiophene derivative 13 and the novel allocolchicinoid 14. In a similar way cyclooctyne (6) yielded three products, the thiophene-annulated homobarrelenones 18 and 19 and the tetracyclic allocolchicinoid 21. The structures of the novel colchicine derivatives were assigned on the basis of spectral data, those of the cycloadducts 1 and 19 were verified by X-ray crystallography. For the unprecedented formation of the various allocolchicinoids by consecutive [4+2]/[3+2] cycloadditions plausible reaction pathways are suggested, as far as possible. In addition the inhibitory effects on the tubulin polymerization reaction in vitro of 10, 14, and 21 are reported.
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  • 46
    ISSN: 1434-193X
    Keywords: Paclitaxel (Taxol®) ; Paclitaxel CD-ring ; High-pressure Diels-Alder reactions ; Furan cycloadditions ; Ether cleavage in 7-oxabicyclo[2.2.1]heptanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high-pressure promoted Diels-Alder reactions between several furans and citraconic anhydride have been studied and the cycloadducts obtained have been explored in new straightforward routes to the CD-ring fragment of paclitaxel. The reaction between furan and citraconic anhydride afforded the exo cycloadduct diastereoselectively, whereas a variety of 2-substituted furans afforded approximate 1:1 mixtures of exo regioisomers. Separation of both regioisomers was accomplished after either diastereoselective esterification or regioselective reduction of the anhydride function. Ether cleavage of the bicyclic compounds by either high-pressure promoted ether cleavage or Boord elimination afforded several potential CD-ring precursors which can be used in the total synthesis of paclitaxel analogues.
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  • 47
    ISSN: 1434-193X
    Keywords: Camphoracetyl chloride ; Lactols, fused ; Lactones, fused ; Pseudoacid chlorides ; Reagents, stereoselective ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: endo-Fused lactone 3 was obtained in high yield from the camphoracetic acid 2 with thionyl chloride and a subsequent reduction of intermediate 5 with tributyltin hydride. The structure of 5 was elaborated and some aspects of the mechanism of its formation and reactivity were investigated. Lactone 3 serves as key intermediate for lactol 1 which is a useful reagent in racemate resolution and asymmetric synthesis.
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  • 48
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    Liebigs Annalen 1998 (1998), S. 2609-2615 
    ISSN: 1434-193X
    Keywords: Supramolecular chemistry ; Domino reactions ; Bipyridines ; 1,x-Cyclohexanediones ; Mannich bases ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A one-pot reaction using 1,x-cyclohexanediones, a Mannich base (or its hydrochloride), and ammonium acetate delivers novel pyridines or 3,3′-bridged bipyridine compounds 8, 16, 18, 20, and 22. This strategy offers a great flexibility in the design of new building blocks, e.g. in supramolecular chemistry and underlines the efficiency of domino reactions.
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  • 49
    Electronic Resource
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    Liebigs Annalen 1998 (1998), S. 2603-2607 
    ISSN: 1434-193X
    Keywords: Fluoro analogs of vitamin A ; Horner-Wittig reaction ; Fluoroisoprenoid building blocks ; Stereoselectivity ; Hydrolysis of chlorofluorocyclopropanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An improved method for the preparation of ethyl 2-fluoro-3-methyl-2-butenoate (3) is described. The two stereoisomers [(E)-4 and (Z)-4] obtained after γ-bromination can be separated and can be individually converted into the corresponding diethyl phosphonates. The PO-ylides generated by α-deprotonation of the latter lose their stereochemical integrity by rapid torsional equilibration of the ester tail. Thus, Horner-Wittig reactions accomplished with benzaldehyde and (Z)- or (E)-(β-ionylidene)-acetaldehyde lead inevitably to stereorandomization at the terminal, ethoxycarbonyl-bearing double bond affording (E)- and (Z)-isomers in 50:50 to 15:85 ratios, depending on the reaction conditions. The new double bond, however, is formed with perfect trans-selectivity.
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  • 50
    ISSN: 1434-193X
    Keywords: Alkaloids ; Total synthesis/Pumiliotoxin ; PTX-C ; PTX isomers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for the synthesis of pumiliotoxin C (1a) and related stereoisomeric compounds 1c-1f. Starting from (+)- or (-)-3-methylcyclohexanone (6a,b), the oxo esters 7a and 7b were prepared. Condensation with (+)- or (-)-3-aminohexanol (8a,b) gave the stereoisomeric 3-aminoacrylates 9a, 9b and 9c. The hydroxy group of the amino-acrylates was transformed into bromide using the tosylate method. Cyclization of the bromides led to unsaturated quinoline ring systems. Finally, decarboxylation and catalytic hydrogenation gave the different cis- and trans-fused stereoisomeric alkaloids of the pumiliotoxin C type. The structures were verified by X-ray analysis.
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  • 51
    ISSN: 1434-193X
    Keywords: Lawesson's reagent ; Thiolation of cyclic ketones ; Anchimeric effect ; cis-Bicyclo[3.3.0]octane-3,7-diones ; 9-Thiatricyclo[3.3.1.03,7]nonane ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple and efficient approach to the 9-thiatricyclo[3.3.1.03,7]nonane ring system (5) has been found by treating cis-bicyclo[3.3.0]octane-3,7-diones (1) with Lawesson's reagent or phosphorus pentasulfide. When dione 1 is treated with Lawesson's reagent tetramethyl 3(4aH)oxo-1,4-dihydrophenanthro[9,10-a]pentalene-1,2,4,4a-tetracarboxylate (6) is obtained as a by-product as shown by X-ray structural analysis.
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  • 52
    ISSN: 1434-193X
    Keywords: Pyrazolidin-3-ones ; Optical activity ; Asymmetric synthesis ; Ring transformation ; Hydrazines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiopure α-alkylidenelactones 7 were prepared by a Wittig reaction from α-bromolactones 4 and chiral aldehydes 6. Compounds 7 react with hydrazines 9 by stereoselective Michael-like addition and ring-chain transformation affording optically active 4-(ω-hydroxyalkyl)pyrazolidin-3-ones 11.
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  • 53
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    Liebigs Annalen 1998 (1998), S. 2673-2676 
    ISSN: 1434-193X
    Keywords: Aromatic aldehydes ; Pinacol coupling ; Radical reactions ; Reagent control ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel concept for conductingtransition-metal-catalyzed radical reactions that allows highly diastereoselective titanocene-catalyzed pinacol couplings is described.
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  • 54
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    Liebigs Annalen 1998 (1998), S. 2677-2682 
    ISSN: 1434-193X
    Keywords: Terpenoid lactones ; Antifeedants ; Limonene ; Claisen rearrangement ; Iodolactonization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four enantiomeric pairs of spirolactones were obtained in a four step synthesis from (+) and (-) limonene. The Claisen rearrangement and iodolactonization were the key steps of the syntheses presented. The structures of products were confirmed by X-ray crystallography of 11, 18b, and 19.
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  • 55
    ISSN: 1434-193X
    Keywords: Phosphole ; Phosphanorbornadiene ; Stille cross-coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of alkynylstannanes with 1-phenyl-3,4-dimethylphosphole at 150 °C affords the corresponding 2-stannyl-1-phosphanorbornadienes (2a, b), in fair yield. Oxidation under mild conditions affords the corresponding phosphane oxides (3a, b), whereas more drastic conditions (H2O2, 15% in toluene at 80 °C) induce the oxidative cleavage of the P-CH2 bond of the bridge to give a bicyclic phosphinate such as 4. Treatement of 4 by iodine leads to a tin → iodine exchange. The X-ray crystal structure analysis of the resulting 1-phospha-2-oxabicyclo[2.2.2]octa-5,7-diene 1-oxide confirms the functionalisation at the α-position and the relief of ring strain taking place upon insertion of oxygen into the P-CH2 bond of the norbornadiene. The 2-stannyl-1-phosphanorbornadiene 1-oxides (3a, b) readily undergo tin → iodine exchange. The resulting 2-iodo derivatives (6a, b) can be cross-coupled with 2-furyl-, 2-thienyl-, 2-pyrrolyl-, phenylethynyl-, and vinyl-tributylstannanes to give the corresponding 2-functional 1-phosphanorbornadiene 1-oxides in excellent yields (80-95%)
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  • 56
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Density functional calculations ; Cycloadditions ; Dihydropyrans ; Enantioselective oxidations ; Sulfur heterocycles ; Sulfoxides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 4-benzylidene-3-oxo[1,3]oxathiolan-5-ones 13-15, which were derived from the 3-oxo[1,3]oxathiolan-5-ones 9-11 by Knoevenagel condensation with the aldehydes 12, cyclize in an intramolecular hetero Diels-Alder reaction with high yield and excellent endo/exo as well as induced diastereoselectivity to give the hetero Diels-Alder adducts 16-18. The preferred formation of the Knoevenagel products 13-15 with a (Z) configuration was predicted with DFT calculations (B3LYP-6-311+G*) using the model systems 28 and 29. In addition B3LYP-6-31G*/sB3LYP/3-21G(*) calculations on transition structures for the hetero Diels-Alder reaction of 29 and 30 allowed a good correlation with the experimental results, which show that an endo attack of the dienophile syn to the S-O group in 13-15 leads to the main products.
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  • 57
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    Liebigs Annalen 1998 (1998), S. 2759-2767 
    ISSN: 1434-193X
    Keywords: Phosphorus phthalocyanines ; Triazatetrabenzcorroles ; Dihydroxyphosphorus(V) phthalocyanine hydroxides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The previously reported reaction of phthalocyanines [H2(pc)] with PBr3, which was claimed to give a phosphorus(III) phthalocyanine “(PcPIII)”, has been reinvestigated in detail with both unsubstituted and alkyl-substituted phthalocyanines, 1-4. The products exhibit unusual electronic and mass spectra compared to normal phthalocyanines and have been identified as oxophosphorus(V) triazatetrabenzcorroles 5-8. The corresponding dihydroxyphosphorus(V) phthalocyanine hydroxides 9-12 have also been synthesized for the first time by insertion of phosphorus(V) into phthalocyanines and have been characterized in detail. The different reactivities of PBr3 and POX3 (X = Cl, Br) toward phthalocyanines are discussed.
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  • 58
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    Liebigs Annalen 1998 (1998), S. 2769-2773 
    ISSN: 1434-193X
    Keywords: Rubicenes ; Cyclization ; Polycyclic aromatic hydrocarbons ; Arenes ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of novel disubstituted rubicenes 1a-k is described. Starting from 1,5-dichloroanthraquinone and aryllithium reagents 3, the diol adducts 4 are reduced and the resulting diarylanthracenes 5 are cyclized to afford the title compounds in fair to good overall yield.
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  • 59
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    Liebigs Annalen 1999 (1999), S. 57-60 
    ISSN: 1434-193X
    Keywords: Benzyne ; Dehydroanthracene ; Matrix isolation ; Photochemistry ; Bergman reaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -9,10-Didehydroanthracene (1) is an interesting derivative of p-benzyne that has been subject of several studies. In contrast to an earlier report, the photochemical decarbonylation of 9,10-dicarbonyl-9,10-dihydroanthracene (2) does not lead to 1 but rather to the ring-opened ene-diyne 4. The key intermediate for this reaction is keto carbene 7 which is formed by monodecarbonylation of 2. Carbene 7 is labile towards visible-light irradiation and easily looses the second CO molecule to give 4. Carbene 7 and diyne 4 are characterized by IR and UV/Vis spectra, the IR spectra are compared to calculations at the B3LYP/6-31G(d,p) level of theory.
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  • 60
    ISSN: 1434-193X
    Keywords: Nucleophilic addition ; Solvent effect ; Reversal of diastereoselectivity ; Temperature effect ; Imines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Commonly observed, but rarely explored, is the possibility of modifying the diastereomeric excess (de%) by means of temperature. A complete reversal in the diastereofacial selectivity could be obtained whenever the diastereoisomers concerned are differentially favored by enthalpy and entropy. The enthalpic or entropic dominance of a diastereoisomer depends greatly on the reaction solvent used.
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  • 61
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    Liebigs Annalen 1999 (1999), S. 73-81 
    ISSN: 1434-193X
    Keywords: Donor-acceptor systems ; Cage compounds ; Stelladione ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A number of condensations could be carried out using tricyclo[3.3.0.03,7]octane-2-one (stellanone, 4) and tricyclo[3.3.0.03,7]octane-2,6-dione (2,6-stelladione, 5) as starting materials. The components for condensations were 2-trimethylsilyl-1,3-dithiane (6), 1,1-bis(trimethylsilyl)-1H-cyclopropa[b]naphthalene (7), its 3,6-dimethoxy-substituted analogue 8, fluorene (12), xanthene (13), diethyl malonate (14), and malononitrile (15). The condensation reactions with 5 yielded mono- and disubstituted products, among them were the donor-acceptor-substituted 2,6-stellanes 33-35. The structures of 18 (prepared from stellanone and fluorene), 19, 24, 27, 31 and 32 (synthesized by condensation of 2,6-stelladione and 2-trimethylsilyl-1,3-dithiane and malononitrile, respectively) were determined by X-ray crystallography.
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  • 62
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    Liebigs Annalen 1999 (1999), S. 87-90 
    ISSN: 1434-193X
    Keywords: Water ; α-Nitrocycloalkanones ; ω-Nitro acids ; Surfactant ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The reaction of various α-nitrocycloalkanones 1 with aqueous 0.05 M NaOH, at 80 °C, in the presence of cetyltrimethylammonium chloride (CTACl) as a cationic surfactant, produces ω-nitro acids 2 in good yields. Reduction of the latter with HCOONH4/Pd-C, in methanol, at 80 °C affords ω-amino acids 3. The synthesis of methyl 9-oxodecanoate (8) is also reported.
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  • 63
    ISSN: 1434-193X
    Keywords: O-Alkylation ; Ambident nucleophile ; Thiazolethione ; Thiohydroxamic acid ; Phase-transfer reaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -O-Alkylation of cyclic thiohydroxamic acids 1 and 3-5 has been studied with a view to developing an efficient method for the synthesis of N-(alkoxy)pyridine-2(1H)-thiones and N-(alkoxy)thiazole-2(3H)-thiones. Four issues have been addressed and the following conclusions can be drawn: (i) Thiones 1 and 5 exist as O-H acids in the solid state. (ii) According to NMR investigations (1H, 13C), the thione structures should be largely retained in CDCl3, [D6]DMSO, and CD3OD solutions of acids 1, 3-5, as is also the case for pyridinethione salts 2a-h. (iii) O-Alkylation of pyridinethione salts occurs in competition with S-alkylation. Selective O-alkylation is however possible, if thiohydroxamate salts with large countercations, such as M = NBu4, are treated with hard alkylating reagents in polar aprotic media. (iv) As tetrabutylammonium thiohydroxamates, such as 2f, are highly useful in the synthesis of cyclic thiohydroxamic acid O-esters, we have developed an efficient protocol for the preparation of N-(alkoxy)pyridine-2(1H)-thiones directly from acid 1 using phase-transfer conditions (alkyl halide or sulfonic acid ester, CH3CN, K2CO3, Bu4NHSO4). This method has proved particularly successful for the synthesis of N-(alkoxy)thiazole-2(3H)-thiones 11, 20-28, which were obtained in yields of up to 87%.
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  • 64
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    Liebigs Annalen 1999 (1999), S. 129-134 
    ISSN: 1434-193X
    Keywords: Tetrahydro-2-vinylquinoxaline ; Cyclization ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Reaction of (Z)-1,2-bis(methoxycarbonyloxy)but-2-ene (2) with various N,N-bis(arylsulfonyl)-o-phenylenediamines 1 was catalyzed by a palladium complex associated with chiral ligands to give optically active 1,4-bis(arylsulfonyl)-1,2,3,4-tetrahydro-2-vinylquinoxalines 3 with up to 62% ee. The use of (S)-MeOBIPHEP as the chiral ligand and N,N-bis(p-tolylsulfonyl)-o-phenylenediamine (1i) as the nucleophile led to the highest ee at 25 °C, regardless of the solvent used. The enantioselectivity of the cyclization is strongly affected by the nature of the substituents at the nitrogen atom.
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  • 65
    ISSN: 1434-193X
    Keywords: Fluorine ; Lactones ; Annulation ; Ketene ; Sulfoxides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Enantiomerically pure α,α-dichloro β-fluoroalkyl γ-p-tolylthio γ-butyrolactones trans-6a-c have been obtained with excellent stereocontrol (〉 98:2) and enantiomeric purity (〉 98:2) by sulfoxide-directed lactonization (Marino's annu-lation reaction) of β-fluoroalkyl vinyl sulfoxides (R)-(E)-5a-c with dichloroketene. Highly chemoselective dechlorination and desulfurization reactions performed on trans-6c efficiently provided the β-chlorodifluoromethyl γ-butyrolactone (S)-8c, the absolute stereochemistry of which was determined by X-ray diffraction analysis of its γ-p-tolylthio precursor (2R,3S)-7c.
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  • 66
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    Liebigs Annalen 1999 (1999), S. 141-143 
    ISSN: 1434-193X
    Keywords: Nitrosobenzene ; 4-Methoxy-N-methyleneaniline ; 1,3,5-Tris(4-methoxyphenyl)-1,3,5-triazinane ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A 1:1 adduct produced in the reaction of nitrosobenzene (2) with 1,3,5-tris(4-methoxyphenyl)-1,3,5-triazinane (3) has been shown by X-ray diffraction structure analysis to be the N′-(4-methoxyphenyl)-N-phenyl-N-oxyformamidinium species 5.
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  • 67
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    Liebigs Annalen 1999 (1999), S. 155-161 
    ISSN: 1434-193X
    Keywords: Alkylation ; Oxazolines ; anti-α-Alkyl α-hydroxy β-amino acids ; Lithium dianion ; Penicillin G acylase ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -As part of an ongoing project concerning the synthesis of enantiomerically pure α-hydroxy β-amino acids, we have now developed a general strategy allowing the synthesis of anti-α-alkyl α-hydroxy β-amino acids. Our procedure involves the intermediate formation of trans-oxazolines, which are alkylated at C-5 with good to high diastereoselectivity and then hydrolysed under mildly acidic conditions, affording in quantitative yield the corresponding hydroxy amides. The starting (R)-3-amino-3-phenylpropanoic acid and (S)-3-aminobutanoic acid were obtained in enantiomerically pure form by selective enzymatic hydrolysis of the corresponding phenylacetylamides with penicillin G acylase.
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  • 68
    ISSN: 1434-193X
    Keywords: Palladium catalysis ; Homogeneous catalysis ; Anilines ; Alkylation ; Oxazolidinones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Palladium-catalyzed reaction of acidic anilines with (Z)-2-butene-1,4-diyl dicarbonate affords N-aryl-4-vinyloxazolidin-2-ones. The success of the reaction depends on the acidity of the aniline and requires in situ conversion of the dicarbonate into carbamate carbonate by nucleophilic attack of the aniline conjugate base followed by palladium-catalyzed intramolecular cyclization.
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  • 69
    ISSN: 1434-193X
    Keywords: Density functional calculations ; Vinylcyclopropane-cyclopentene rearrangement ; [1,3]-Sigmatropic shift ; Biradical-like transition structure ; Substituent effects ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The effect of donor substitution by the hydroxy group and of acceptor substitution by the cyano group on the activation energies of the vinylcyclopropane-cyclopentene rearrangement was calculated by the spin-restricted RB3LYP/6-31G* method for reactant structures and by the spin-unrestricted UB3LYP/6-31G* method for transition structures. The activation energies of the rearrangement of hydroxy- and cyano-substituted vinylcyclopropanes are very similar for substitution in the same position. In agreement with earlier findings the substituent effects on the activation energies are closely connected with the radical stabilizing properties of the substituents. As indicated by singlet/triplet splitting energies, the transition structures are essentially biradicaloid. In spite of spin pairing in the transition structure the substituent effects on bond lengths and on stabilization energies are very similar to those of the free radicals corresponding to the two radical substructures. Thus, the transition structures may be considered, in good approximation, as structures consisting of two weakly interacting radicals.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/98349_s.pdf or from the author.
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  • 70
    ISSN: 1434-193X
    Keywords: Cyclopropanes ; Rearrangements ; Cyanohydrins ; Schiff bases ; Small ring systems ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The direct cyclization of 2-amino-4-chloro-3,3-dimethylbutanenitrile with potassium tert-butoxide in THF afforded 1-amino-2,2-dimethylcyclopropane-1-carbonitrile and a dimerization product. Various new cis- and trans-1-(tert-butylamino)-2-benzyl-2-methylcyclopropane-carbonitriles and© the corresponding cyclopropanecarboxamides have been synthesized, with focus on the isolation of the pure stereoisomeric cyclopropanecarboxamides. The relative configuration of the stereoisomers was established by X-ray crystallographic analysis of one of the model compounds. A new route to the latter functionalized cyclopropanes was developed by reaction of 1-methoxycyclopropylamines with potassium cyanide. Some remarkable rearrangements of 1-aminocyclopropane-1-carbonitriles into azetidine and oxazine derivatives via Favorskii-derived intermediates are reported. Various aspects of the chemistry of geminally functionalized cyclopropanes are discussed.
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  • 71
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    Liebigs Annalen 1999 (1999), S. 267-275 
    ISSN: 1434-193X
    Keywords: Vinylallenes ; Organocuprates ; Substitution ; Stereoselective synthesis ; Copper catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Enyne acetates 2, 4, 6, and 8, as well as enyne oxiranes 10, with different substitution patterns react with organocuprates regioselectively under 1,5-(SN2′′)-substitution to provide vinylallenes 11 and 12. With lithium dimethylcuprate, reduced vinylallenes originating from a (formal) transfer of a hydride ion to the substrate are formed in some cases. The products are usually obtained as mixtures of (E/Z)isomers; however, pure (E)-vinylallenes are formed occasionally. The 1,5-substitutions can also be carried out with catalytic amounts of copper reagents. The reaction of chiral enyne acetate (S)-2a with tBu2CuLi · LiCN proceeds enantioselectively, so that this transformation constitutes a new case of remote stereocontrol.
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  • 72
    ISSN: 1434-193X
    Keywords: Nitrogen heterocycles ; Open-chain analogue of Reissert compound ; Hydrofluoroborate salts ; α,β-Ethylenic esters ; 1,3-Dipolar cycloaddition ; Azomethine ylide ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The reaction of the hydrofluoroborate salt of an open-chain analogue of a Reissert compound with some α,β-ethylenic esters does not give a [4 + 2] cycloadduct, as previously described in the case of ethyl acrylate. The reaction starts with a 1,3-dipolar cycloaddition of a münchnone imine 5c, d. The [3 + 2] cycloadducts 13 evolve via a rearrangement-condensation sequence to give a substituted 2-pyridone derivative 18 or 19. The proposed mechanism has been verified by the isolation and structural X-ray analysis of some compounds of the reaction sequence.
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  • 73
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    Liebigs Annalen 1999 (1999), S. 335-360 
    ISSN: 1434-193X
    Keywords: 2-tert-Butylhydropyrimidinones ; 3-Aminocarboxylic acid derivatives ; Cyclic imino esters ; Lithium enaminates ; Alkylations ; β-Amino acids ; Asymmetric synthesis ; Kinetic resolution ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Racemic and enantiopure 2-tert-butyltetrahydropyrimidinones (from pivalaldehyde and 3-aminocarboxylic acids) are converted to Alloc-, Boc-, and Z-protected cyclic imino esters (7-10, Schemes 2-4). These are deprotonated to Li enaminates (K, L). Reactions with electrophiles (prim., sec. alkyl, allyl, benzyl, propargyl halides, aldehydes, imines, enoates) give good yields and are highly diastereoselective (products 11-42, Schemes 5-10). A two-step cleavage (removal of protecting group and hydrolysis) under very mild conditions converts the heterocyclic products to α-branched β-amino acid methyl esters (43-61, Schemes 11-13). The structure of the products is determined by NMR spectroscopy (Figure 1), by chemical correlation (Scheme 14), and by X-ray analysis (Figure 2, 3, 7, Table 1). A structure of the Li enaminates is proposed (Figure 4). Mechanistic models are derived for the reactions occurring with formation of two stereogenic centers with relative topicity like (Figures 5, 6).
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  • 74
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    Liebigs Annalen 1999 (1999), S. 373-378 
    ISSN: 1434-193X
    Keywords: Alkaloids ; Cross-coupling ; N-Heterocycles ; Palladium ; Synthesis design ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Thermal or acetyl chloride induced cyclization of bromoenamide 10 affords the pentacyclic derivative 12 with high yield and regioselectivity. From this common synthetic intermediate, palladium-catalyzed reactions allow the total synthesis of indolopyridine alkaloids 1-6.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/98332_s.pdf or from the author.
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  • 75
    ISSN: 1434-193X
    Keywords: Reverse-turn mimics ; γ-Turns ; β-Turns ; β-Hairpins ; NMR spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The solid-phase synthesis and characterization of a series of peptides (3-9), containing reverse-turn mimetic bicyclic lactams (1a, 1b), was reported in the preceding paper. The bicyclic lactams (1a, 1b) possess high structural similarity to the two central residues of a β-turn. The conformational preferences of the constrained peptides have been investigated by NMR spectroscopy and IR spectroscopy. Our experimental results have been complemented by computer modelling studies and show that the constrained peptides (3-9) form an inverse γ-turn or a type-II′ β-turn through intramolecular hydrogen bonding, depending on the nature of the reverse-turn mimic. In N-acetylated tetrapeptide mimics incorporating the two different bicyclic lactams (a series and b series), H5 is available for either a γ-turn (7-membered ring with the carbonyl group of the bicyclic lactam) or a β-turn (10-membered ring with the carbonyl group of residue 2), as shown in Figures 7 and 9. The a series incorporating the (5,7)-bicyclic lactam predominantly induces the γ-turn conformation, while the b series incorporating the (5,6)-bicyclic lactam can promote either a γ-turn or a β-turn conformation, with the β-turn usually being preferred and with varying degrees of β-hairpin formation.
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  • 76
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    Liebigs Annalen 1999 (1999), S. 409-417 
    ISSN: 1434-193X
    Keywords: Deprotonation ; Oxiranyloxazolines ; Oxazolinyloxiranyllithium compounds ; Oxazolidines ; Acyloxiranes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Deprotonation of oxazolinyloxiranes 1a, 1h, and 1k with sBuLi/TMEDA at -100 °C in Et2O furnishes oxazolinyloxiranyllithium compounds[1]1b, 1i, and 1l which are stable at low temperature and can be trapped with electrophiles to give substituted oxiranes 1c-1g and 1j. The reaction of 1b with aldehydes produced diastereomers syn (2a-d) and anti (3a-d). Oxiranyllithium 1i from trans-1-(4,4-dimethyl-2-oxazolinyl)-2-p-tolylepoxyethane (1h) was found to be configurationally stable while oxiranyllithium 1l, generated from the cis isomer 1k, was not. Oxazolinylepoxides 1d, 1j, and 1m could be deblocked to acyloxiranes 5a-e through oxazolidines 4a-e.
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  • 77
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    Liebigs Annalen 1999 (1999), S. 419-430 
    ISSN: 1434-193X
    Keywords: Electrochemistry ; Electrosynthesis ; Nitrosobenzenes ; Nitrogen heterocycles ; 1-Aminoindoles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -An electrochemical methodology offering efficient access to N-alkyl- and N-aryl-substituted 1-aminoindoles has been developed. N-Substituted 2-(ortho-nitrosophenyl)ethylamines, electrogenerated in a “redox” flow cell, undergo intramolecular cyclization to hydrocinnoline-type intermediates. Under slightly basic conditions, these undergo spontaneous ring-contraction to produce the N-substituted heterocycles in good yields. The reactions have been studied in slightly acidic and slightly basic aqueous alcoholic media.
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  • 78
    ISSN: 1434-193X
    Keywords: Aminoacylsilanes ; Amino aldehydes ; Amino alcohols ; Allylation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A practical route is described for the synthesis of enantiopure β- and γ-amino alcohols with two stereocenters, starting from homochiral α- (1 and 5) and β- (13 and 16) -aminoacylsilanes, and involving stereoselective addition of allylmetal compounds and subsequent stereospecific protiodesilylation of the adducts. The degree of diastereoselectivity achieved in the nucleophilic addition step depends on both the nitrogen-protecting group and the reagents used. Diastereomeric excess (de) values equal to or higher than 98% were obtained in the TiCl4-promoted allylation of the N-Pht-aminoacylsilanes 1 and 13 and of the N-Ts-aminoacylsilane 5 with allyltrimethylsilane. Lower de values were obtained in the Sc(OTf)3-catalyzed allylation of 5 with tetraallyltin and in the additions of both allyltrimethylsilane and tetraallyltin to the N-Ts-β-aminoacylsilane 16. Protiodesilylation of the adducts, leading to the β- and γ-amino alcohols, was accomplished with TBAF, except in the case of the adducts obtained from 5. For these, a preliminary removal of the tosyl group was necessary, which was accomplished with simultaneous desilylation by treatment with Na in liquid ammonia.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/98342_s.pdf or from the author.
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  • 79
    ISSN: 1434-193X
    Keywords: meta Photocycloaddition ; Photochemistry ; Steric hindrance ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Irradiation of a series of 5-(2-methoxyphenyl)pent-1-enes substituted with a hydroxy or trimethylsilyloxy group at the α-, β-, or γ-position of the side-chain yields in all cases meta photocycloadducts, in which the configuration at the substituted carbon atom is mainly endo. This indicates that the diastereoselectivity originates from minimization of steric interactions between the side-chain substituent and the ortho-methoxy group at the arene unit. Hydrogen bonding does not seem to be involved. The introduction of the side-chain substituents also influences the regioselectivity of the addition: The linear to angular adduct ratios are significantly increased compared to the case of the parent compound.
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  • 80
    ISSN: 1434-193X
    Keywords: 5-Aza-7-deaza-2′-deoxyguanosine ; Oligonucleotides ; Parallel DNA ; Protonated base pairs ; Tm values ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Oligonucleotides containing 5-aza-7-deaza-2′-deoxyguanosine (1) were synthesized. Solid-phase synthesis was performed with the phosphonate 15 or the phosphoramidite 5. The amino-unprotected phosphonate 4 was also employed. Hybridization studies of oligonucleotides containing 1 resulted in new base pairs leading to duplexes with parallel (ps) or antiparallel (aps) chain orientation. Among those with parallel chains a stable “purine-purine” base pair was observed between 5-aza-7-deazaguanine and guanine or 7-deazaguanine. Antiparallel stranded duplexes are formed when 5-aza-7-deazaguanine pairs with cytosine. This base pair has only two hydrogen bonds under neutral conditions but is stabilized by a third one in acidic medium. A new base pair is also detected between the base of 1 and isoguanine (neutral medium).
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  • 81
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    Liebigs Annalen 1999 (1999), S. 523-523 
    ISSN: 1434-193X
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -By mistake wrong concentrations were given in the footnote of Table 1 and in the Discussion. Instead of c0 = 1.2 M read c0 = 0.12 M if 2-naphthalenethiol was used as hydrogen donor and instead of c0 = 1.8 M read c0 = 0.18 M if Bu3SnH was used to trap photoproducts. In Table 2 relative rate constants of radical 2d refer to radical 2e and vice versa as correctly stated in the Discussion. In the Experimental Section (Iodocyclization) read 2.25 g (8.86 mmol) of iodine instead of 2.25 g (1.10 mmol) of iodine.
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  • 82
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    Liebigs Annalen 1999 (1999), S. 527-538 
    ISSN: 1434-193X
    Keywords: Tris(pentafluorophenyl)borane ; Diarylborinic acid ; Arylboronic acid ; Chiral arylboron catalyst ; Lewis acid ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Arylboron compounds, ArnB(OH)3-n (n = 1-3), bearing electron-withdrawing aromatic groups such as triarylboranes, diarylborinic acids, and arylboronic acids represent a new class of air-stable and water-tolerant Lewis acid or Brønsted acid catalysts in organic synthesis. In particular, while tris(pentafluorophenyl)borane has primarily been used as a co-catalyst in metallocene-mediated olefin polymerization, its potential as a Lewis acid catalyst for organic transformation is now much more extensive. Diarylborinic acids and arylboronic acids have shown themselves to be powerful tools in the design of chiral boron catalysts. This article provides a comprehensive summary of the organic transformations catalyzed by arylboron compounds as acids.
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  • 83
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    Liebigs Annalen 1999 (1999), S. 573-577 
    ISSN: 1434-193X
    Keywords: Structure elucidation ; Constitutional analysis ; Natural products ; HMBC ; Computational chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The computer program COCON is introduced as a tool for the comprehensive structure elucidation of unknown organic compounds. In particular, structural proposals made on the basis of the molecular formula and of 2D-NMR experiments can be analyzed for the existence of alternative constitutions being in agreement with the same data set. The computational speed grounds on the evaluation of ambiguous long-range connectivity information during the process of structure generation. The data set experimentally obtained for the marine natural product oroidin (1) was selected, because proton-poor compounds usually cause uncertainties in NMR-based structure determinations. The calculation results encourage to move from the experience-based analysis of NMR chemical shifts or of MS fragmentations to the automated evaluation of routinely available connectivity information.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/98241_s.pdf or from the author.
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  • 84
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    Liebigs Annalen 1999 (1999), S. 587-595 
    ISSN: 1434-193X
    Keywords: Phosphaalkenes ; Heterodiphospholes ; Cycloadditions ; Phosphaalkyne cyclooligomers ; Phosphorus-carbon cage compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The first synthesis of a 1,2,4-oxadiphosphole 6 has been achieved by vacuum thermolysis of mesitylphosphaalkene 5. The novel heterocycle 6 exhibits an enormous potential for cycloaddition reactions, which predominantly proceed selectively at low temperatures. Compound 6 undergoes addition with two equivalents of phosphaalkynes 10 by a [4+2] cycloaddition/homo Diels-Alder reaction sequence to form novel oxatetraphosphadeltacyclenes 12 and 13. Tetrachloro-o-benzoquinone (14) undergoes a selective [4+1] cycloaddition with 12 and 13 leading to the spirocyclic products 15 and 16 containing λ5-phosphorus atoms. Treatment of the oxadiphosphole 6 with dimethyl acetylenedicarboxylate (17) provides the first access to a 1,2-oxaphosphole 18, which is formed after an initial [4+2] cycloaddition followed by a retro Diels-Alder reaction. An unexpected reaction of 6 is observed with tri-tert-butylazete (20) furnishing a new polycyclic system (→ 21).
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  • 85
    ISSN: 1434-193X
    Keywords: 1β-Methylcarbapenems ; Palladium ; Ruthenium ; Catalysis ; Cyclizations ; Stereoselective hydrogenation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -An efficient diastereoselective multi-step synthesis of bicyclic 1β-methylcarbapenem antibiotic precursors has been developed, starting from the commercially available 4-acetoxyazetidin-2-one 4. Chiral ruthenium catalysts are used in the hydrogenation step to control the β-stereochemistry at the 1-position, and a π-allylpalladium ring-closure strategy is used to form the functionalized carbapenem skeleton.
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  • 86
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    Liebigs Annalen 1999 (1999), S. 643-651 
    ISSN: 1434-193X
    Keywords: Oligomers ; Synthesis design ; Substituent effects ; Luminescence ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Synthetic strategies towards appropriate symmetric and unsymmetric functionalization of the naphthalene ring are presented. By means of Knoevenagel and Wittig condensation reactions new fluorescent, differently functionalized oligo(2,6-naphthylenevinylene)s have been synthesized, the presence of terminal aldehyde or bromine substitution opening the way to the incorporation of the fluorescent trimers in a variety of polymeric materials. The effect of substituting the phenylene ring by the more bulky dialkoxynaphthalene system in arylenevinylene-type materials is studied from the structural point of view and the possibility to tune the emission color and the electron affinity through the introduction of naphthylenevinylene and cyano-substituted naphthylenevinylene units is also investigated.
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  • 87
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    Liebigs Annalen 1999 (1999), S. 661-664 
    ISSN: 1434-193X
    Keywords: Aziridines ; N-Heterocycles ; Fatty acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The first successful preparation of the aziridines methyl cis-9,10;cis-12,13-diepiminooctadecanoate (3) derived from linoleic acid, and methyl cis-9,10;cis-12,13;cis-15,16-triepiminooctadecanoate (6) derived from linolenic acid, is reported. Remarkably, the bis- and trisaziridine were obtained in a reaction sequence that consists of only two steps, using technically pure methyl esters of epoxidized sunflower and linseed oil. The conversion of methyl 9,10;12,13-diepoxyoctadecanoate (1), with sodium azide and ammonium chloride in ethanol in the presence of water, yielded the new diazidodihydroxy compound methyl 9(10),12(13)-diazido-10(9),13(12)-dihydroxyoctadecanoate (2) in the first step. 2 was obtained as a regioisomeric mixture. The reaction of 2 with triphenylphosphane led to the bisaziridine 3. The analogous conversion of methyl 9,10;12,13;15,16-triepoxyoctadecanoate (4), via the new triazidotrihydroxy compound methyl 9(10),12(13),15(16)-triazido-10(9),13(12),16(15)-trihydroxyoctadecanoate (5), afforded trisaziridine 6.
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  • 88
    ISSN: 1434-193X
    Keywords: Cavitands ; Nuclear waste ; Actinide/lanthanide separation ; Solvent extraction ; Sulfur atoms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Cavitands with phosphane sulfide moieties 4 and 8a,b were prepared in good yields from their phosphane oxide analogues, as more stable alternatives for the dithiophosphinic acids used at present. The cavitands 7a and 7b with flexible butoxyphosphane oxide ligating sites are more efficient than cavitand 3 having rigid methylphosphane oxide groups as was studied with EuIII picrate extractions. Due to the absence of an ionic functionality in the phosphane sulfides 4 and 8a,b AmIII and EuIII are not extracted, not even in the presence of synergents (e.g. TBP, TOPO, HDNNS). Cavitand 10 with phosphinic acid groups efficiently extracts EuIII in 1:1 or 2:1 complexes, depending on the metal-to-ligand concentration ratio (extraction constants Kex1 = 3.9·10-5M2 and Kex2 = 1.9·102M, respectively). Furthermore, in the case of 10 EuIII is preferentially extracted over AmIII with a separation factor SEu/Am up to 5.
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  • 89
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 691-696 
    ISSN: 1434-193X
    Keywords: Carbohydrates ; 4-Thiofuranosides ; Nucleosides ; Reaction mechanisms ; NOE measurements ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -1-O-Acetyl-2,3,5-tri-O-benzyl-4-thio-L-arabino-furanose (9) has been prepared from D-xylose via the 1,4-dithio-L-arabino-furanoside 8. The crucial step of the reaction, i.e. the intramolecular cyclization of the open-chain dithioacetal 5, has been achieved in a yield of 90% by applying tetrabutylammonium iodide as promoter. Reaction of 9 with bis(trimethylsilyl)uracil or -thymine led to the benzyl derivatives 12 and 13 from which the deprotected 4′-thionucleoside analogues 14 and 15 have been prepared by debenzylation with boron tribromide.
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  • 90
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 737-750 
    ISSN: 1434-193X
    Keywords: Baeyer-Villiger oxidation ; Ketones ; Monopersulfate ; Peracids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -In the present review, we report the discovery of the formation of esters and lactones by oxidation of ketones with a peroxide derivative, namely the Baeyer-Villiger reaction. This reaction was first reported by Adolf von Baeyer and Victor Villiger a century ago in 1899, just one year after the oxidant they used (KHSO5) has been described. Furthermore, Baeyer and Villiger established the composition of this new inorganic peroxide and showed that its instability was the reason of a controversy between several European chemists between 1878 and 1893. For the first 50 years the mechanism of the Baeyer-Villiger reaction was a matter of debate. A side product, 1,2,4,5-tetraoxocyclohexane, was ruled out as an intermediate in the ester formation by Dilthey. Criegee postulated a nucleophilic attack of the oxidant on the carbonyl group. This mechanism was confirmed by von E. Doering by a labeling experiment with [18O]benzophenone. The rearrangement step occurs with retention of the stereochemistry at the migrating center. The competitive migration and the rate-determining step are also discussed in this review.
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  • 91
    ISSN: 1434-193X
    Keywords: Transglycosylation ; Glycosidases ; Thermus thermophilus ; Carbohydrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The aim of this paper is to test the ability of a β-glycosidase from Thermus thermophilus to catalyse transglycosylation reactions in the presence of nitrophenyl glycosides as donors and other monosaccharides as acceptors. Our results show that this enzyme is able to induce such reactions either with nitrophenylgalactosides, -glucosides and -fucosides. With the two former donors, the autocondensation of the donor, which thus acts also as an acceptor, is faster than the transglycosylation with other acceptors. Furthermore, as the regioselectivity of the reactions is mainly of the β-[1→3] type, good yields are obtained for the synthesis of 2-nitrophenyl-β-D-galactopyranosyl-[1→3]-β-D-galactopyranoside and 2-nitrophenyl-β-D-glucopyranosyl-[1→3]-β-D-glucopyranoside. Conversely, in the presence of p-nitrophenylfucoside, the autocondensation is very limited, and with methyl-α-D-galactoside as an acceptor, the regioselectivity is mainly of the β-[1→6]-type resulting in the synthesis of methyl-β-D-fucopyranosyl-[1→6]-α-D-galactopyranoside.
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  • 92
    ISSN: 1434-193X
    Keywords: Monoynes ; Polyynes ; Alkali metals ; Liquid NH3 ; Hexamethylphosphoric triamide ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Efficient procedures have been developed for the stereospecific reduction by alkali metals of disubstituted acetylenes with long carbon chains. Acetylenes containing two or more (isolated) triple bonds are reduced considerably more easily than are monoynes.
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  • 93
    ISSN: 1434-193X
    Keywords: Aminophenols /Asymmetric synthesis ; C-C coupling ; Reductions ; Conformation analysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Enantiopure o-hydroxybenzylamines 2a-i were synthesized by diastereoselective reduction of the 2-imidoylphenols (R)-1a-i. Conformational analysis enabled the assignment of the absolute configurations of compounds 2a-i. The accessible o-hydroxybenzylamine (R,R)-2h serves as an effective catalyst precursor for highly enantioselective addition of diethylzinc to aliphatic and aromatic aldehydes. This pathway represents a practical and operationally very simple methodology for the enantioselective synthesis of both the enantiomers of secondary alcohols 7a-f.
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  • 94
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 837-846 
    ISSN: 1434-193X
    Keywords: Friedel-Crafts reaction ; Hydroxyalkylation ; Aromatics ; Epoxides ; Zeolites ; Clays ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Solid acids, such as zeolites and clays, catalyse the intramolecular hydroxyalkylation (cyclialkylation) of several arylalkyl epoxides in moderate to excellent conversions and selectivities. The use of solid acids in these cyclialkylations provides a cleaner, better alternative to conventional Lewis and Brønsted acids, enabling a more facile workup of reaction mixtures and, in several cases, better selectivities.
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  • 95
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 861-868 
    ISSN: 1434-193X
    Keywords: Red phosphorus ; Phosphane PH3 ; Phosphorylations ; Ultrasound irradiation ; Redox chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The reactivity of red phosphorus towards aldehydes was investigated under basic and acidic media. It was demonstrated that the real phosphorylating agent involved in the reaction was phosphane (PH3) in basic media, and hypophosphorous acid (H3PO2) in acidic media. A convenient one-pot synthesis of (α-hydroxyalkyl)phosphinic acids from red phosphorus and aldehydes in basic media was realized under sonication. The same reaction under acidic media in the presence of hydriodic acid led to the corresponding phosphonic acids. The (α-hydroxyalkyl)phosphinic acids were readily prepared under sonication from hypophosphorous acid and aldehydes in the presence of catalytic amounts of hydrochloric acid. The mechanism of the addition reaction of PH3 to benzaldehyde was elucidated and shows the complexity of the reaction as a function of the experimental conditions.
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  • 96
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 909-915 
    ISSN: 1434-193X
    Keywords: Erythrina alkaloids ; Nitrogen heterocycles ; Nitro aldol reaction ; Michael addition ; Pummerer reaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A successful new strategy for the synthesis of erythrinanes is reported. (Nitromethyl)arene derivative 16 was condensed with aldehyde 17 to give nitro aldol 19. After removal of the hydroxy group, the subunits 26a,b, containing the erythrinane rings A and D, were formed by intramolecular Michael addition. Reduction of the nitro function, followed by cyclization of the resulting amino group with the appended acetate group afforded the bicyclic lactams 29a,b, bearing an angular aryl group. Two-carbon elongation at the nitrogen atoms of 29a and 29b by means of hetero Michael addition of methyl phenyl sulfoxide, followed by Pummerer-type cyclization, gave cis- and trans-11-phenylthioerythrinan-8-ones 35a and 35b, respectively. Reductive desulfurization at C-11 furnished the desired erythrinan-8-ones 39a and 39b in 8 steps from 16.
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  • 97
    ISSN: 1434-193X
    Keywords: Crystal engineering ; Diynes ; Photochemistry ; Solid-state chemistry ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The 1,6-bis(2,5-dimethoxyphenyl)hexa-2,4-diynes 4a-c were obtained from the corresponding 2,5-dimethoxybenzenes 1 by bromination followed by a copper-catalyzed Grignard reaction with 3-bromoprop-1-yne. Catalyzed coupling of the resulting 3-(2,5-dimethoxyphenyl)prop-1-ynes 3 under Hay conditions gave the hexa-2,4-diynes 4a-c in good yields. The molecular structures of the diynes 4a and 4b were determined by X-ray diffraction analysis. In each crystal structure, an unusual 1,6-synperiplanar conformation of the hexa-2,4-diyne unit is observed, with the 1,6-diphenyl substituents arranged in a coplanar orientation. According to the crystal structure data obtained, irradiation of diynes 4a and 4b afforded the deeply-colored, highly-ordered polymers 5a and 5b under topochemical control. Oxidation of 4a and 4b with cerium(IV) ammonium nitrate gave the corresponding 1,6-bis(2,5-dimethoxyphenyl)hexa-2,4-diyne-1,6-diones 6a and 6b.
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  • 98
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 931-936 
    ISSN: 1434-193X
    Keywords: Nucleosides ; Phosphonates ; Nucleophilic additions ; C-C coupling ; Reduction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Acyclic carba-nucleoside phosphonates, modelled on natural deoxyribonucleotides have been prepared starting from DNA nucleobases and tert-butyl acrylate. The products obtained from a Michael-type reaction were elongated to β-oxo esters that were first reduced to β-hydroxy esters and then transformed into protected β-hydroxy aldehydes. Wittig-Horner-Emmons reaction with the anion of tetraisopropyl methylenebisphosphonate gave, after deprotection, the desired 4-hydroxy-6-purinyl- or -6-pyrimidinyl-1-hexenylphosphonic acids. A dimer, potential precursor of acyclic polynucleotides (APN), homomorphous with DNA, was also prepared.
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  • 99
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 955-958 
    ISSN: 1434-193X
    Keywords: Tetraethylammonium peroxydicarbonate ; Tetraethylammonium carbonate ; N-alkylated pyrroles ; Electrochemistry ; Electrogenerated bases ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Electrochemically generated tetraethylammonium peroxydicarbonate (TEAPC) and tetraethylammonium carbonate (TEAC) react under very mild conditions with pyrroles affording, after addition of a suitable alkylating agent, the corresponding N-alkylated pyrroles in high yields. C-Alkylated pyrroles have not been isolated in any case reported.
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  • 100
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 979-980 
    ISSN: 1434-193X
    Keywords: Ketones ; Myxobacterium ; Pheromones ; Stigmatellaaurantiaca ; Stigmolone ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The racemic myxobacterial pheromone (±)-1 (stigmolone), which induces the formation of the fruiting body of Stigmatellaaurantiaca, was synthesized from methyl isobutyl ketone (2) in 48% overall yield in four steps
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