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  • General Chemistry  (77,717)
  • Erdgas
  • Erdölgeologie
  • petrology
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  • 1
    facet.materialart.
    Unknown
    Nomos Verlagsgesellschaft mbH & Co. KG
    Publication Date: 2023-08-07
    Description: Despite the cessation of coal mining in 2018, the Ruhr area continues to be of considerable importance for the German energy supply. The study uses statistical data to discuss the development since the mid-19th century. The focus is on the historical energy turns triggered by coal, electricity supply, oil and natural gas and the associated processes of change. Another focus, also with topical relevance, is on the nearly one hundred years of experience in the hydrogen economy as the basis of the chemical industry. Thus, for the first time, it offers a synthesis of the diverse energy-economic relationships within the region.
    Description: Published
    Description: Trotz der Einstellung des Steinkohlenbergbaus 2018 besitzt das Ruhrgebiet weiterhin eine erhebliche Bedeutung für die deutsche Energieversorgung. Die Studie diskutiert anhand statistischer Daten die Entwicklung seit Mitte des 19. Jahrhunderts. Im Vordergrund stehen die durch Kohle, Elektrizitätsversorgung, Erdöl und Erdgas ausgelösten historischen Energiewenden und die damit verbundenen Wandlungsprozesse. Ein weiterer Schwerpunkt liegt, ebenfalls mit aktuellem Bezug, auf den annähernd hundertjährigen Erfahrungen im Bereich der Wasserstoffwirtschaft als Grundlage der chemischen Industrie. Damit bietet es erstmals eine Synthese der vielfältigen energiewirtschaftlichen Beziehungen innerhalb der Region.
    Keywords: 19th century ; 19. Jahrhundert ; chemische Industrie ; chemical industry ; Deutschland ; coal ; coal mining ; Elektrizitätsversorgung ; electricity supply ; Energieregion ; energy industry ; Energieversorgung ; Energiewende ; energy region ; Energiewirtschaft ; energy supply ; energy transition ; Erdgas ; Germany ; Erdöl ; hydrogen economy ; Kohle ; natural gas ; Ruhrgebiet ; petroleum ; Statistik ; Ruhr area ; Steinkohlenbergbau ; statistics ; Synthese ; Wandlungsprozesse ; synthesis ; transformation processes ; Wasserstoffwirtschaft ; KZC ; KNB ; 3JJ ; 1DFG ; 3JH ; 3JM
    Language: German
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  • 2
    facet.materialart.
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    MDPI - Multidisciplinary Digital Publishing Institute
    Publication Date: 2024-03-27
    Description: Dating and geochemical analyses of detrital minerals (mainly zircons) combined with traditional methods, such as heavy minerals and sandstone modes, are a powerful tool in paleogeographic and paleotectonic research and industrial applications.
    Keywords: detrital zircon U-Pb geochronology ; bulk geochemistry ; provenance ; tectonic setting ; West Bogeda Shan ; U-Pb geochronology ; detrital zircon ; source-to-sink ; provenance analysis ; mixing model ; sediment budgeting ; east China seas ; Pennsylvanian ; Sino-Korean Block ; detrital zircons ; U–Pb ages ; subduction zones ; U–Pb dating ; sandstone petrography ; peripheral bulge ; tectonics ; zircon U-Pb ages ; muscovite 40Ar/39Ar ages ; sediment provenance ; Yangtze River ; detrital-zircon age spectrum ; Ereendavaa terrane ; Mongol-Okhotsk orogenic belt ; opening of the Mongol-Okhotsk ocean ; northeastern Mongolia ; Lu-Hf isotopes ; early Miocene ; Yinggehai-Song Hong Basin ; South China Sea ; stratigraphic thicknesses ; net sand to gross thickness ratio ; conglomerate percentage ; heavy mineral analysis ; detrital zircon U‒Pb geochronology ; Intermontane basin ; Mongolia ; laser ablation U-Pb dating ; Hafnium isotope-ratio ; terrane definition ; paleotectonic reconstruction ; Western Andes ; Miocene ; Silante Formation ; Ecuador ; compositional heterogeneity ; major element ; nonmarine basin ; gejiu basalts ; zircon U–Pb dating ; geochemistry ; Sr–Nd–Pb isotope ; petrogenesis ; Cameroon ; Meiganga ; gold placer ; trace element ; geochronology ; Archean-Proterozoic origins ; zircon crystal morphology ; zircon textures ; zircon trace elements ; alteration of zircon ; REE in zircon ; rare metal granites ; Li-F granites ; Western Hercynian Meseta ; Permian basin ; Tiddas Souk Es-Sebt des ait ikko volcanic basin ; U–Pb geochronology ; mineralogy ; petrology ; n/a ; thema EDItEUR::G Reference, Information and Interdisciplinary subjects::GP Research and information: general
    Language: English
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  • 3
    Publication Date: 2023-01-27
    Description: The architecture of the magma storage system underneath Fogo Volcano (Cape Verde Archipelago) is characterised using novel fluid inclusion results from fifteen basanites, spanning the last 120 thousand years of volcanic activity, and encompassing a major flank collapse event at ~73 ka. Fluid inclusions, hosted in olivine and clinopyroxene, are made of pure CO2, and based on their textural characteristics, are distinguished in early (Type I) and late (Type II) stage. Inclusions homogenize to a liquid phase in the 2.8 to 30.8 ◦C temperature range. Densities values, recalculated assuming an original 10% H2O content at the time of trapping, range from 543 to 952 kg⋅m3, and correspond to entrapment or re-equilibration pressure ranges of 500–595 MPa, 700–740 MPa, and 245–610 MPa respectively for pre-collapse, early post-collapse, and Holocene/historical eruptions. These entrapment pressures are interpreted as reflecting the existence of two main magma accumulation zones at ~25 km and ~ 13–21 km depth, and a zone of fluid inclusion re-equilibration at 9–12 km depth. There is evidence of a complex temporal evolution of the magma system. Historical eruptions, and especially the three most recent ones (occurred in 1951, 1995 and 2014–25), bring fluid inclusion evidence for transient, pre-eruptive shallow (9–17 km depth) magma ponding. Early post-collapse (60 ka) volcanics, in contrast, document fast magma transport from ~25 km, and suggest a reconfiguration of the magma system after the Monte Amarelo collapse event.
    Description: Published
    Description: 107730
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: JCR Journal
    Keywords: Oceanic island volcanism ; Magma ascent path ; 04.08. Volcanology ; petrology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
    Publication Date: 2024-01-26
    Description: Recent Icelandic rifting events have illuminated the roles of centralized crustal magma reservoirs and lateral magma transport1-4, important characteristics of mid-ocean ridge magmatism1,5. A consequence of such shallow crustal processing of magmas4,5 is the overprinting of signatures that trace the origin, evolution and transport of melts in the uppermost mantle and lowermost crust6,7. Here we present unique insights into processes occurring in this zone from integrated petrologic and geochemical studies of the 2021 Fagradalsfjall eruption on the Reykjanes Peninsula in Iceland. Geochemical analyses of basalts erupted during the first 50 days of the eruption, combined with associated gas emissions, reveal direct sourcing from a near-Moho magma storage zone. Geochemical proxies, which signify different mantle compositions and melting conditions, changed at a rate unparalleled for individual basaltic eruptions globally. Initially, the erupted lava was dominated by melts sourced from the shallowest mantle but over the following three weeks became increasingly dominated by magmas generated at a greater depth. This exceptionally rapid trend in erupted compositions provides an unprecedented temporal record of magma mixing that filters the mantle signal, consistent with processing in near-Moho melt lenses containing 107-108 m3 of basaltic magma. Exposing previously inaccessible parts of this key magma processing zone to near-real-time investigations provides new insights into the timescales and operational mode of basaltic magma systems.
    Description: The NordSIMS ion microprobe facility acknowledges support by the Swedish Research Council (grant no. 2017-00671), the Swedish Museum of Natural History and the University of Iceland; this is NordSIMS publication no. 713. The involvement of S.A.H. was partly in relation to H2020 project EUROVOLC, funded by the European Commission (grant no. 731070). This work was supported by the Icelandic Research Fund, grant no. 228933-051. A.A. ackowledges funding from Italian Ministero Istruzione Università e Ricerca (Miur), grant PRIN2017-2017LMNLAW
    Description: Published
    Description: 529–534
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Keywords: Fagradalsfjall ; Icelandic rifting ; geochemistry ; petrology ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
    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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  • 6
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    Unknown
    Cambridge University Press
    Publication Date: 2022-08-09
    Description: Summarizing ten years of research by the Deep Carbon Observatory, this is a comprehensive guide to carbon inside Earth - its quantities, movements, forms, origins, changes over time, and impact on planetary processes - for students and researchers in Earth and planetary sciences. Also available as Open Access on Cambridge Core.
    Keywords: geochemistry ; biogeochemistry ; petrology ; volcanology ; Earth system science ; planetary science ; bic Book Industry Communication::R Earth sciences, geography, environment, planning::RB Earth sciences::RBG Geology & the lithosphere::RBGK Geochemistry ; bic Book Industry Communication::R Earth sciences, geography, environment, planning::RB Earth sciences::RBG Geology & the lithosphere::RBGG Petrology ; bic Book Industry Communication::W Lifestyle, sport & leisure::WN Natural history::WNR Rocks, minerals & fossils ; bic Book Industry Communication::P Mathematics & science::PG Astronomy, space & time::PGS Solar system: the Sun & planets ; bic Book Industry Communication::R Earth sciences, geography, environment, planning::RN The environment::RNC Applied ecology
    Language: English
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  • 7
    Publication Date: 2024-03-30
    Description: Barely known in public is the life of long-distance commute workers who extract the „blue and black gold” for the export to Europe. They are travelling people who work and live rotationally for a few weeks at the extraction sites before they go back again to their families in the southern regions. This ethnography takes the reader from the Volga Region to the Arcitc “Russian Gas Capital” Novy Urengoy and provides critically insights into the Russian petroleum industry.
    Description: Nahezu unbekannt sind der Öffentlichkeit die Lebensweisen jener ArbeiterInnen, die das „schwarze und blaue Gold“ für den Export nach Europa fördern. Sie sind fahrende und fliegende Menschen, die zyklisch für Wochen oder Monate in den Fördergebieten leben und arbeiten, um wieder für eine Weile zu ihren Familien heimzukehren. Die Ethnographie führt von der Wolgaregion in die subarktische „russische Gashauptstadt“ Novy Urengoy und gibt einen kritischen Einblick in die russische Petroleumindustrie.
    Keywords: Crude oil ; natural gas ; Russia ; Siberia ; Arctic ; long-distance commuting (LDC) ; fly-in/fly-out (FIFO) ; mobility ; normality ; multi-locality ; Erdöl ; Erdgas ; Russland ; Sibirien ; Arktis ; Fernpendleln ; Mobilität ; Normalität ; Multilokalität ; Gazprom ; Novy Urengoy ; thema EDItEUR::K Economics, Finance, Business and Management::KC Economics
    Language: English , German , Russian
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  • 8
    Publication Date: 2024-04-05
    Description: Diese Arbeit befasst sich mit der Wasserdampfreformierung von Methan, Ethan, Propan, Butan und Alkanmischungen an einem mit Rhodium beladenen Wabenkatalysator, der Entwicklung eines mehrstufigen Reaktionsmechanismus dazu und dessen Validierung unter Verwendung numerischer Modelle. Simulationen mit dem Mechanismus erlauben, Einblicke in das molekulare Geschehen im Reaktor zu nehmen und Vorhersagen für ähnliche Reaktionssysteme abzugeben. Auch die Katalysatordeaktivierung wird untersucht.
    Keywords: QD1-999 ; Erdgas ; Wasserdampfreformierung ; numerische Simulation ; Rhodiumkatalysator ; Reaktionsmechanismus ; thema EDItEUR::P Mathematics and Science::PN Chemistry
    Language: German
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  • 9
    facet.materialart.
    Unknown
    MDPI - Multidisciplinary Digital Publishing Institute
    Publication Date: 2024-03-27
    Description: During the last decade, software developments in Scanning Electron Microscopy (SEM) provoked a notable increase of applications to the study of solid matter. The mineral liberation analysis (MLA) of processed metal ores was an important drive for innovations that led to QEMSCAN, MLA and other software platforms. These combine the assessment of the backscattered electron (BSE) image to the directed steering of the electron beam for energy dispersive spectroscopy (EDS) to automated mineralogy. However, despite a wide distribution of SEM instruments in material research and industry, the potential of SEM automated mineralogy is still under-utilised. The characterisation of primary ores, and the optimisation of comminution, flotation, mineral concentration and metallurgical processes in the mining industry by generating quantified data, is still the major application field of SEM automated mineralogy. However, there is interesting potential beyond these classical fields of geometallurgy and metal ore fingerprinting. Slags, pottery and artefacts can be studied in an archeological context for the recognition of provenance and trade pathways; soil, and solid particles of all kinds, are objects in forensic science. SEM automated mineralogy allows new insight in the fields of process chemistry and recycling technology.
    Keywords: Zr-REE-Nb deposits ; alkaline rocks ; automated mineralogy ; Khalzan Buregtei ; automated scanning electron microscopy ; QEMSCAN® ; trace minerals ; gold ; REE minerals ; REE carbonatite ore ; comminution ; multi-stage flotation ; EDX spectra ; MLA ; mineral processing ; iron ore ; Kiruna ; Raman spectroscopy ; magnetite ; hematite ; scanning electron microscopy (SEM) ; automated quantitative analysis (AQM) ; spectrum quantification ; signal deconvolution ; fault gouge ; 200-nm resolution ; grain size distribution ; Ikkattup nunaa ; mineral maps ; submicrometer ; automated quantitative mineralogy (AQM) ; scanning electron microscopy ; ZEISS Mineralogic ; Fiskenæsset complex ; Feret angle ; element concentration map ; visualization ; mineral association ; bulk composition ; grain size ; waste of electrical and electronic equipment ; X-ray computed tomography ; mineral liberation analysis ; indicator minerals ; heavy mineral concentrates ; till sampling ; VMS ; Izok Lake ; sewage sludge ashes (SSA) ; phosphate ; recycling ; recovery ; SEM-automated mineralogy ; mineral liberation analysis (MLA) ; scanning electron microscope ; raw materials ; resource technology ; granular material ; petrology ; n/a ; thema EDItEUR::G Reference, Information and Interdisciplinary subjects::GP Research and information: general
    Language: English
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  • 10
    Publication Date: 2021-07-20
    Description: Raw material characterization in Paleolithic archaeology has widened our knowledge of Middle Paleolithic societies. Procurement of raw material, specifically flint, has allowed the tracing of the mobility of both stones and people, as well as selective processes to obtain specific types or even extraction activities. The analysis of quartzite has also developed in recent years, providing an opportunity to better understand prehistoric societies. This study characterizes the procurement strategies implemented by Middle Paleolithic people in the mountainous region of the Picos de Europa. To this end, we present a comprehensive characterization of potential catchment areas: massive outcrops, conglomerates, and river deposits. The exploitation of quartzite at the sites of El Habario and El Arteu allows us to understand the territorial management of this mountainous area through the combination of selective processes and mobility mechanisms in lower and middle altitudes. These perspectives enable us to view the mountainous region not as a barrier but as an environmental mosaic managed by Middle Paleolithic groups. This study shows strategies that bring together direct and embedded procurement based on both intensive and extensive searches. These discourses are more closely related to the daily life of people than those only considering the mobility of people and objects.
    Description: A comprehensive geoarchaeological research project based on the integration of a geographic information system, field survey, stereomicroscopy, and thin‐section petrography, is presented to characterize potential procurement areas of quartzite. The application of this methodology in the Deva, Cares, and Güeña valleys and in three different geological contexts; massive outcrops, conglomerates, and secondary deposits, suggest potential acquisition processes of lithic resources. The analysis of the quartzite assemblages of El Habario and El Arteu unveils complex management of terrain based on a mobility mechanism that connects middle altitude plateaus with open and lower river valleys, as well as intensive and extensive procurement mechanisms of raw material.
    Description: Education Department of the Government of the Basque Country
    Description: The Spanish Ministry of Science Project
    Description: The Consolidated Research Group in Prehistory of the Basque Country University
    Keywords: 552.4 ; Cantabrian Region ; field survey ; Middle Paleolithic ; petrology ; quartzite ; raw material procurement
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  • 11
    Publication Date: 2021-01-27
    Description: The Holocene volcanism at El Hierro consists of basaltic monogenetic volcanic fields associated with o the three rift systems present in this island. In this work we report preliminary petrological and geochemical data of Holocene lava flows belonging to the WNW-striking rift. Sampling was focused in three zones: Orchilla, Verodal-Sabinosa, and Tanganasoga. Petrography of the studied lavas shows that they are homogeneous. All samples are porphyritic with macrocrysts of clinopyroxene and olivine immersed in a groundmass formed by microcrysts of plagioclase, Fe-Ti oxides and clinopyroxene. Clinopyroxenes are diopsides, olivines have forsterite contents ranging from 74 to 84 % and anorthite in plagioclase varies from 66 to 76% (labradorite). Whole-rock geochemical results evidence that all magmas are basic in composition, ranging from picrobasalts to phonotephrites. Major, trace elements and isotope support fractional crystallization as the main process of magma evolution. However, petrography and chemistry of clinopyroxene cores agree with a xenocrystic nature of some of them. We suggest that these clinopyroxene cores crystallized from a genetically related magma and subsequently were entrapped or cannibalized by the basic rising magmas.
    Description: Published
    Description: 35-38
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: N/A or not JCR
    Keywords: El Hierro, Holocene ; volcanism ; petrology ; geochemistry
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 12
    Publication Date: 2020-05-05
    Description: The reconstruction of the pre-eruptive storage conditions as well as syn-eruptive magma ascent dynamics of past eruptions is of fundamental importance to decipher the relationship between surface-monitored signals and the sub-volcanic processes in order to learn more about the eruptive behaviour of active volcanoes. The Pomici di Base Plinian eruption is the first (22 ka) and largest (〉 4.4 km3 ) event of the SommaVesuvius volcanic complex. Here we present the preliminary results of a geochemical, isotopic, two-dimensional and three-dimensional textural study performed on volcanic products emitted during the Plinian phase of this eruptive event with the aim to reconstruct in more details the magmatic evolution of this large caldera-forming eruption. Particularly, it was fed by chemically and thermally zoned magmas extracted from a crystal mush zone in a magma chamber with top at ~4.5 km depth. During this eruption, crustal (limestone) contamination and subsequent CO2 emissions as well as changes in degassing mechanisms mainly controlled the eruptive dynamics.
    Description: Published
    Description: 23-40
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Keywords: Somma-Vesuvius, Plinian eruptions, magma storage and ascent. ; petrology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 13
    Publication Date: 2022-08-26
    Description: Abstract
    Description: This data collection provides digital access to data and publications of the KTB (German Continental Deep Drilling Program) project. KTB was a very detailed, long-term Earth science investigation on the structure, dynamics and formation of the Central European crust in Northeastern Bavaria, Germany (Harms, Kück 2016). With geophysical sounding and ultra-deep drilling it elucidated a crustal block at the border of a micro-continental collision zones amalgamated during the Caledonian and Variscan orogenies. Major research themes were: i) the nature of geophysical structures and phenomena, ii) the crustal stress field and the brittle-ductile transition, iii) the thermal structure of the crust, iv) crustal fluids and transport processes, and v) structure and evolution of the central European Variscan basement. KTB started in 1982 with pre-site selection studies and scientific objective definition followed in 1985 by site selection studies including shallow boreholes. From 1987 to 1990 a pilot borehole of 4000 m depth was drilled and fluid tests and borehole studies were conducted. In 1990 started drilling of a so-called superdeep main borehole of 9101 m depth that was reached in 1994. Again, the final drilling phase was concluded with large-scale fluid and seismic experiments. The rocks drilled comprise metamorphic series of mafic volcanic, volcano-clastics as well as minor gabbroic to ultramafic rocks that are intercalated with leucocratic meta-sedimentary gneisses. They represent most likely a deeply subducted accretionary wedge mélange with a complex P-T-t history. The undisturbed bottom hole temperature is ~265°C. Among the outstanding results are the following: (1) A continuous profile of the complete stress tensor was obtained. (2) Several lines of evidence indicate that KTB reached the present-day brittle-ductile transition. (3) The drilled crustal segment is distinguished by large amounts of free fluids down to mid-crustal levels. (4) The role of post-orogenic brittle deformation had been grossly underestimated. (5) Steep-angle seismic reflection surveys depict the deformation pattern of the upper crust. (6) High-resolution seismic images of the crust can be obtained with a newly developed technique of true-amplitude prestack depth migration. (7) The electrical behavior of the crust is determined by secondary graphite (+/-sulfides) in shear zones. (after Emmermann und Lauterjung (1997)
    Description: Other
    Description: The data are ordered according to disciplines, wells and working groups and currently available via the original KTB site (https://data.icdp-online.org/sites/ktb/welcome.html). The DOI-referenced data publication of KTB data is in progress. Scientific disciplines: Borehole Measurements Geology, Petrology, Tectonics - Microscopy - Lithological description of cores - Lithological description of cuttings - Tectonic elements Geochemistry - Gas analysis - XRF, XRD analysis - Infrared Spectrometry - IC, ICP-AES Petrophysics - Density - Porosity - Electrical resistivity - Natural gamma-ray activity - Inner surface - Permeability - Relaxation - Magnetic susceptibility - Ultrasonic seismics - Thermal conductivity Rock Mechanics - Compressive strength - Tensile strength Technical drilling parameter Fluid/Hydraulic experiments Hydrofrac/Seismic experiments
    Keywords: German Continental Deep Drilling Program ; KTB ; Bavaria ; Windischeschenbach ; field laboratory ; downhole logging unit ; geology ; petrology ; tectonics ; geochemistry ; petrophysics ; rock mechanics ; borehole measurements ; drilling engineering ; final experiments ; hydrolaulic tests ; presite surveys ; dekorp iso89 ; EARTH SCIENCE 〉 SOLID EARTH 〉 EARTH GASES/LIQUIDS ; EARTH SCIENCE 〉 SOLID EARTH 〉 GEOCHEMISTRY ; EARTH SCIENCE 〉 SOLID EARTH 〉 GEOMAGNETISM ; EARTH SCIENCE 〉 SOLID EARTH 〉 ROCKS/MINERALS/CRYSTALS ; EARTH SCIENCE 〉 SOLID EARTH 〉 TECTONICS ; In Situ/Laboratory Instruments 〉 Corers
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  • 14
    Publication Date: 2019-03-26
    Description: The eruptions of December 2015 and May 2016 at Voragine crater were among the most explosive recorded during the last two decades at Mt. Etna volcano. Here we present data coming from geophysics (infrasound, LP, VLP, volcanic tremor, VT earthquakes, and ground deformations) and petrology (textural and microanalytical data on plagioclase and olivine crystals) to investigate the preeruptive magma storage and transfer dynamics leading to these exceptional explosive eruptions. Integration of all the avail- able data has led us to constrain chemically, physically, and kinetically the environments where magmas were stored before the eruption, and how they have interacted during the transfer en-route to the surface. Although the evolution and behavior of volcanic phenomena at the surface was rather similar, some differ- ences in storage and transfer dynamics were observed for 2015 and 2016 eruptions. Specifically, the 2015 eruptions have been fed by magmas stored at shallow levels that were pushed upward as a response of magma injections from deeper environments, whereas evidence of chemical interaction between shallow and deep magmatic environments becomes more prominent during the 2016 eruptions. Main findings evidence the activation of magmatic environments deeper than those generally observed for other recent Etnean eruptions, with involvement of deep basic magmas that were brought to shallow crustal levels in very short time scales (~1 month). The fast transfer from the deepest levels of the plumbing system of basic, undegassed magmas might be viewed as the crucial triggering factor leading to development of exceptionally violent volcanic phenomena even with only basic magma involved.
    Description: Programma Nazionale Ricerche . Grant Number: PNRA14_00011 University of Catania FIR 2014 . Grant Numbers: 2F119B , PRA 2016‐18 , 22722132120
    Description: Published
    Description: 471–495
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Keywords: Etna ; geophysics ; petrology ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 15
    Publication Date: 2018-09-20
    Description: The relationships between trachytes and peralkaline rhyolites (i.e. pantellerites and comendites), which occur in many continental rift systems, oceanic islands and continental intraplate settings, is unclear. To fill this gap, we have performed phase equilibrium experiments on two representative metaluminous trachytes from Pantelleria to determine both their pre-eruptive equilibration conditions (pressure, temperature, H2O content and redox state) and liquid lines of descent. Experiments were performed in the temperature range 750–950 C, pressure 0 5–1 5 kbar and fluid saturation conditions with XH2O [¼H2O/(H2OþCO2)] ranging between zero and unity. Redox conditions were fixed below the nickel–nickel oxide buffer (NNO). The results show that at 950 C and melt water contents (H2Omelt) close to saturation, trachytes are at liquidus conditions at all pressures. Clinopyroxene is the liquidus phase, being followed by iron-rich olivine and alkali feldspar. Comparison of experimental and natural phases (abundances and compositions) yields the following pre-eruptive conditions: P¼160 5 kbar, T¼925625 C, H2Omelt¼261wt %, and fO2 between NNO– 0 5 and NNO– 2. A decrease in temperature from 950 C to 750 C, as well as of H2Omelt, promotes a massive crystallization of alkali feldspar to over 80 wt %. Iron-bearing minerals show gradual iron enrichment when T and fO2 decrease, trending towards the compositions of the phenocrysts of natural pantellerites. Despite the metaluminous character of the bulk-rock compositions, residual glasses obtained after 80 wt % crystallization evolve toward comenditic compositions, owing to profuse alkali feldspar crystallization, which decreases the Al2O3 of the melt, leading to a consequent increase in the peralkalinity index [PI¼molar (Na2OþK2O)/Al2O3]. This is the first experimental demonstration that peralkaline felsic derivatives can be produced by low-pressure fractional crystallization of metaluminous mafic magmas. Our results show that the pantelleritic magmas of basalt–trachyte–rhyolite igneous suites require at least 95 wt % of parental basalt crystallization, consistent with trace element evidence. Redox conditions, through their effect on Fe–Ti oxide stabilities, control the final iron content of the evolving melt.
    Description: Published
    Description: 559- 588
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: JCR Journal
    Keywords: peralkaline silicic magmatism ; Pantelleria ; Green Tuff ; petrology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 16
    Keywords: Crude oil ; natural gas ; Russia ; Siberia ; Arctic ; long-distance commuting (LDC) ; fly-in/fly-out (FIFO) ; mobility ; normality ; multi-locality ; Erdöl ; Erdgas ; Russland ; Sibirien ; Arktis ; Fernpendleln ; Mobilität ; Normalität ; Multilokalität
    Description / Table of Contents: Nahezu unbekannt sind der Öffentlichkeit die Lebensweisen jener ArbeiterInnen, die das „schwarze und blaue Gold“ für den Export nach Europa fördern. Sie sind fahrende und fliegende Menschen, die zyklisch für Wochen oder Monate in den Fördergebieten leben und arbeiten, um wieder für eine Weile zu ihren Familien heimzukehren. Das Buch führt kurzweilig von der Wolgaregion in das subarktische Sibirien. Die Autorin begleitet fernpendelnde Menschen über Tausende von Kilometern. Sie erzählt vom Leben in der sogenannten „Russischen Erdgashauptstadt“ Novy Urengoy, das sich zwischen Erinnerungen an die Sowjetunion und staatsnahen sowie neoliberalen Wirtschaftspraktiken abspielt. Diese faszinierende Ethnographie gibt einen kritischen Einblick in die russische Petroleumindustrie.
    Pages: Online-Ressource (206 Seiten)
    ISBN: 9783205796947
    Language: German
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  • 17
    Publication Date: 2022-06-09
    Description: Merapi volcano (Indonesia) is one of the most active and hazardous volcanoes in the world. It is known for frequent small to moderate eruptions, pyroclastic flows produced by lava dome collapse, and the large population settled on and around the flanks of the volcano that is at risk. Its usual behavior for the last decades abruptly changed in late October and early November 2010, when the volcano produced its largest and most explosive eruptions in more than a century, displacing at least a third of a million people, and claiming nearly 400 lives. Despite the challenges involved in forecasting this ‘hundred year eruption’, we show that the magnitude of precursory signals (seismicity, ground deformation, gas emissions) was proportional to the large size and intensity of the eruption. In addition and for the first time, near-real-time satellite radar imagery played an equal role with seismic, geodetic, and gas observations in monitoring eruptive activity during a major volcanic crisis. The Indonesian Center of Volcanology and Geological Hazard Mitigation (CVGHM) issued timely forecasts of the magnitude of the eruption phases, saving 10,000–20,000 lives. In addition to reporting on aspects of the crisis management, we report the first synthesis of scientific observations of the eruption. Our monitoring and petrologic data show that the 2010 eruption was fed by rapid ascent of magma from depths ranging from 5 to 30km. Magma reached the surface with variable gas content resulting in alternating explosive and rapid effusive eruptions, and released a total of ~0.44Tg of SO2. The eruptive behavior seems also related to the seismicity along a tectonic fault more than 40km from the volcano, highlighting both the complex stress pattern of the Merapi region of Java and the role of magmatic pressurization in activating regional faults. We suggest a dynamic triggering of the main explosions on 3 and 4 November by the passing seismic waves generated by regional earthquakes on these days.
    Description: Published
    Description: 121–135
    Description: 5V. Sorveglianza vulcanica ed emergenze
    Description: JCR Journal
    Description: restricted
    Keywords: Merapi ; SAR change detection ; eruption monitoring ; petrology ; satellite monitoring ; volcano tremors ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 18
    Unknown
    Rijeka : InTech
    Keywords: petrology ; geology ; geophysics
    Description / Table of Contents: Petrology, New Perspectives and Applications is designed for advanced graduate courses and professionals in petrology. The book includes eight chapters that are focused on the recent advances and application of modern petrologic and geochemical methods for the understanding of igneous, metamorphic and even sedimentary rocks. Research studies contained in this volume provide an overview of application of modern petrologic techniques to rocks of diverse origins. They reflect a wide variety of settings (from South America to the Far East, and from Africa to Central Asia) as well as ages ranging from late Precambrian to late Cenozoic, with several on Mesozoic/Cenozoic volcanism.
    Pages: Online-Ressource (224 Seiten)
    ISBN: 9789533078007
    Language: English
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  • 19
    Publication Date: 2017-04-04
    Description: Three lava flows (hereafter, flows A, B, and C) from Salina Island (Italy) consist of basaltic andesitic enclaves dispersed in a dacitic matrix. Enclaves represent 8–12 vol.% of the erupted magma. The number of enclaves and the surface covered by the enclaves at each outcrop do not vary significantly with the distance from the vent in the flows A and B. These feature reflect the dynamics of magma mingling within the reservoir and not the kinematics of the lava flow. In the flow C, these parameters vary irregularly. The statistical entropy S(t) of the enclaves, which is a measure of their spatial distribution (dispersion), is estimated in outcrops located at different distance from the vent. The Kolmogorov–Sinai entropy rate k, which describes the variations of S(t) with time, is also determined. In the lava flow A, S(t) increases linearly with time t for 0btb0.4; k is 0.04. For tN0.5, S(t) attains its maximum value and maintains constant with increasing t. In the lava flow B, S(t) linearly increases with t, and k is 0.01. In the lava flow C, there is not correlation between S(t) and t. The comparison between the results from the analysis of the Porri enclaves and those from numerical experiments on the variation of S(t) in chaotic advective mixing systems and from previous experimental models on magma mixing, allow us to draw some conclusions on dynamics of the basaltic andesite– dacite mingling in the magma chamber. Fully chaotic magma mingling systems show three evolution stages. An initial stage, which is unknown because of the disruption of the initial configuration of the interacting magmas, a second stage characterized by a linear increase of the statistical entropy with time, and a third stage, in which the uniformity of the system is reached, and the entropy does not vary with increasing time. A system in which the uniformity is never attained, is characterized by irregular variations of S(t) with time. In the flows A and B, the relations between S(t) and t are consistent with those of a fully chaotic dynamics possibly associated to convection. The basaltic andesite was uniformly distributed in the dacitic host due to the occurrence of convective movements driven by the injection of the basaltic andesite within the dacitic chamber. The mingling system recorded by the lava flow A evolved with a higher rate with respect to that of the flow B. This suggests that chaotic advection (stirring and folding) is more efficient in the magmatic system A than in B. On the contrary, the mingling system C is characterized by a non-uniform distribution of the basaltic andesite within dacite. This reflects the occurrence of a dynamics in which stirring and folding processes do not operate efficiently and are unable to uniformly distribute the dispersed phase within the continuous one. The decrease of k from A to B, and the lack of a measurable k in C, along with the observation that A and B were emitted before C, indicate that the efficiency of advective movements within the Porri magma chamber declined with decreasing time. Mingled magmas characterized by a homogeneous spatial distribution of enclaves or an initially inhomogeneous distribution evolving towards a homogeneous one are indicative of efficient advection processes that may favor magma mixing. Mingled magmas characterized by an inhomogeneous distribution of enclaves suggest low dynamical interaction between the two end-members. Magma mixing is not allowed.
    Description: Published
    Description: 128–140
    Description: JCR Journal
    Description: reserved
    Keywords: volcanology ; petrology ; magma mingling ; enclaves ; lava flows ; entropy ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 20
    facet.materialart.
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    In:  Scripta Geologica (0375-7587) vol.131 (2006) p.1
    Publication Date: 2007-01-09
    Description: As one of the most valuable gemstones, emeralds are known to occur in several countries of the world, such as Colombia, Zambia, Brazil, Pakistan, Afghanistan, Russia, Madagascar and Zimbabwe. The emerald deposits at Sandawana, Zimbabwe, are described, the emeralds from this deposit characterised and a model of emerald formation presented; this is compared with existing models. The emeralds from Sandawana, Zimbabwe, show relatively constant physical properties, with high refractive indices and specific gravities. They are characterized by laths and fibres of amphibole, both actinolite and cummingtonite. Other common inclusions are albite and apatite. Rare, opaque and chromium-rich inclusions constitute a new variety of ilmenorutile. Compared to emeralds from most other localities, fl uid inclusions are rare and small. Sandawana emeralds have very high contents of chromium, sodium, magnesium, lithium and caesium. They can be readily separated from emeralds from most other localities by using traditional gem testing techniques, on the basis of a combination of physical properties, inclusions and chemistry. In cases of possible doubt, such as in comparison with emeralds from Rajasthan (India), the use of oxygen isotopes is helpful. Sandawana emeralds occur at the contact between greenstones of the Mweza Greenstone Belt (MGB) and pegmatite intrusions. Rare-element granitic pegmatites intruded the MGB just prior to and/or during a main deformation event at 2.6 Ga, at the southern border of the Zimbabwe craton. Subsequently, a late-stage Na-rich ‘solution-melt’ containing F, P, Li, Be and Cr was injected along shear zones, causing albitisation of the pegmatite and phlogopitization in the greenstone wall-rock. Coeval ductile deformation is indicated by boudinage, pinch-and-swell and folding of pegmatites, by differentiated layering in associated amphibole-phlogopite schist and by the presence of (micro)shear zones. The synkinematic growth of not only phlogopite, but also emerald, fl uorapatite, holmquistite and chromian ilmenorutile, indicates enrichment of Na, K, Li, Be, F, P, Rb, Cs, Ta and Nb in the emerald-bearing shear zone. This suggests that emerald formation is closely related to syntectonic K-Na metasomatism. In this process, microcline, oligoclase, quartz (from the pegmatite) and chlorite (from the greenstones) were consumed, in favour of albite (in the pegmatite), phlogopite, some new actinolite and cummingtonite, holmquistite, fl uorapatite and emerald (at the contact and in the greenstone). Mass balance calculations indicate that a Na- and F-rich hydrous fl uid must have been involved in the alterations that ultimately caused emerald formation. The presence of small, isolated, highly saline brine inclusions in emerald supports this result. Formation of gem-quality emerald occurred in relatively low-pressure domains, such as ‘traps’ under folded pegmatite or pinch areas near pegmatites with pinch-and-swell or boudin structures. Apatite-phlogopite thermometry gives T = 560-650°C, interpreted as the temperature range at which emerald was formed. These temperatures imply contact metamorphic rather than regional metamorphic conditions. From the general conditions of primary consolidation of rare element pegmatites, and from the inferred crystallisation path of the similar Bikita pegmatite, a corresponding pressure of around 2.5-3 kbar appears plausible at Sandawana. Because of the intimate spatial and temporal relationship with magmatic activity, the pegmatitic/hydrothermal nature of the involved fl uid, and the near magmatic temperatures of phlogopite and apatite formation, a magmatic source for the Na-rich fl uids is very likely. It means that intrusion of the pegmatites, and subsequent albitisation and metasomatism during deformation, have been part of a continuous process in a restricted period of time. The Sandawana data lead to a new model of emerald formation, as a product of contact metasomatism at the border of ultramafic rocks and rare-element pegmatites during a deformation event, involving late stage magmatic/hydrothermal activity channelled by shearing. Hence, Sandawana emeralds were formed in the Late Archaean, around 2.6 Ga, at the border of a major Late Archaean suture zone. As a consequence, they are by far the oldest, compared to other commercially available emeralds. 40Ar/39Ar dates, varying from 1900 to 2400 Ma, are interpreted as Archaean ages that became partially to completely reset during a Proterozoic thermal overprint. The Sandawana model for emerald genesis does not fit into any of the genetic classification schemes proposed in the literature, and shows that no single theory can be applied to all schist-type deposits. Emeralds of gem quality can be formed in very different geological settings, as long as basic conditions are fulfilled. In this respect, the following factors are essential: availability of beryllium and chromium (± vanadium); means of transport to bring the elements together, that is, fl uids of magmatic, hydrothermal, metamorphic or a combined origin; conditions in which emerald may form as a stable mineral, with temperatures generally from 600° down to 300°C; and sufficient space to grow transparent and well-formed crystals.
    Keywords: Emerald ; Sandawana ; Zimbabwe ; gemmology ; petrology ; geothermometry ; geochronology ; 38.30
    Repository Name: National Museum of Natural History, Netherlands
    Type: Article / Letter to the editor
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  • 21
    facet.materialart.
    Unknown
    In:  Scripta Geologica vol. 131, pp. 1-212
    Publication Date: 2024-01-12
    Description: As one of the most valuable gemstones, emeralds are known to occur in several countries of the world, such as Colombia, Zambia, Brazil, Pakistan, Afghanistan, Russia, Madagascar and Zimbabwe. The emerald deposits at Sandawana, Zimbabwe, are described, the emeralds from this deposit characterised and a model of emerald formation presented; this is compared with existing models. \nThe emeralds from Sandawana, Zimbabwe, show relatively constant physical properties, with high refractive indices and specific gravities. They are characterized by laths and fibres of amphibole, both actinolite and cummingtonite. Other common inclusions are albite and apatite. Rare, opaque and chromium-rich inclusions constitute a new variety of ilmenorutile. Compared to emeralds from most other localities, fl uid inclusions are rare and small. Sandawana emeralds have very high contents of chromium, sodium, magnesium, lithium and caesium. They can be readily separated from emeralds from most other localities by using traditional gem testing techniques, on the basis of a combination of physical properties, inclusions and chemistry. In cases of possible doubt, such as in comparison with emeralds from Rajasthan (India), the use of oxygen isotopes is helpful.\nSandawana emeralds occur at the contact between greenstones of the Mweza Greenstone Belt (MGB) and pegmatite intrusions. Rare-element granitic pegmatites intruded the MGB just prior to and/or during a main deformation event at 2.6 Ga, at the southern border of the Zimbabwe craton. Subsequently, a late-stage Na-rich \xe2\x80\x98solution-melt\xe2\x80\x99 containing F, P, Li, Be and Cr was injected along shear zones, causing albitisation of the pegmatite and phlogopitization in the greenstone wall-rock. Coeval ductile deformation is indicated by boudinage, pinch-and-swell and folding of pegmatites, by differentiated layering in associated amphibole-phlogopite schist and by the presence of (micro)shear zones. The synkinematic growth of not only phlogopite, but also emerald, fl uorapatite, holmquistite and chromian ilmenorutile, indicates enrichment of Na, K, Li, Be, F, P, Rb, Cs, Ta and Nb in the emerald-bearing shear zone. This suggests that emerald formation is closely related to syntectonic K-Na metasomatism. In this process, microcline, oligoclase, quartz (from the pegmatite) and chlorite (from the greenstones) were consumed, in favour of albite (in the pegmatite), phlogopite, some new actinolite and cummingtonite, holmquistite, fl uorapatite and emerald (at the contact and in the greenstone). Mass balance calculations indicate that a Na- and F-rich hydrous fl uid must have been involved in the alterations that ultimately caused emerald formation. The presence of small, isolated, highly saline brine inclusions in emerald supports this result. Formation of gem-quality emerald occurred in relatively low-pressure domains, such as \xe2\x80\x98traps\xe2\x80\x99 under folded pegmatite or pinch areas near pegmatites with pinch-and-swell or boudin structures.\nApatite-phlogopite thermometry gives T = 560-650\xc2\xb0C, interpreted as the temperature range at which emerald was formed. These temperatures imply contact metamorphic rather than regional metamorphic conditions. From the general conditions of primary consolidation of rare element pegmatites, and from the inferred crystallisation path of the similar Bikita pegmatite, a corresponding pressure of around 2.5-3 kbar appears plausible at Sandawana. Because of the intimate spatial and temporal relationship with\nmagmatic activity, the pegmatitic/hydrothermal nature of the involved fl uid, and the near magmatic temperatures of phlogopite and apatite formation, a magmatic source for the Na-rich fl uids is very likely. It means that intrusion of the pegmatites, and subsequent albitisation and metasomatism during deformation, have been part of a continuous process in a restricted period of time.\nThe Sandawana data lead to a new model of emerald formation, as a product of contact metasomatism at the border of ultramafic rocks and rare-element pegmatites during a deformation event, involving late stage magmatic/hydrothermal activity channelled by shearing. Hence, Sandawana emeralds were formed in the Late Archaean, around 2.6 Ga, at the border of a major Late Archaean suture zone. As a consequence, they are by far the oldest, compared to other commercially available emeralds.\n40Ar/39Ar dates, varying from 1900 to 2400 Ma, are interpreted as Archaean ages that became partially to completely reset during a Proterozoic thermal overprint. \nThe Sandawana model for emerald genesis does not fit into any of the genetic classification schemes proposed in the literature, and shows that no single theory can be applied to all schist-type deposits. Emeralds of gem quality can be formed in very different geological settings, as long as basic conditions are fulfilled. In this respect, the following factors are essential: availability of beryllium and chromium (\xc2\xb1 vanadium); means of transport to bring the elements together, that is, fl uids of magmatic, hydrothermal,\nmetamorphic or a combined origin; conditions in which emerald may form as a stable mineral, with temperatures generally from 600\xc2\xb0 down to 300\xc2\xb0C; and sufficient space to grow transparent and well-formed crystals.
    Keywords: Emerald ; Sandawana ; Zimbabwe ; gemmology ; petrology ; geothermometry ; geochronology
    Repository Name: National Museum of Natural History, Netherlands
    Type: info:eu-repo/semantics/article
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  • 22
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    In:  Geophys. Res. Lett., L'wiw, Inst. f. Theoret. Geodäsie, vol. 32, no. 13, pp. 383-388, pp. L13312, (ISSN: 1340-4202)
    Publication Date: 2005
    Keywords: Geochemistry ; Mineralogy ; Fluids ; Subduction zone ; Plate tectonics ; presure ; temperature ; 410 ; discontinuity ; GRL ; 1025 ; Geochemistry: ; Composition ; of ; the ; mantle ; 3630 ; Mineralogy ; and ; Petrology: ; Experimental ; mineralogy ; and ; petrology ; 3924 ; Mineral ; Physics: ; High-pressure ; behavior
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  • 23
    facet.materialart.
    Unknown
    In:  Scripta Geologica. Special Issue vol. 4, pp. 200-215
    Publication Date: 2024-01-12
    Description: Petrological collections result from sampling for academic research, for aesthetic or commercial reasons, and to document natural diversity. Selection criteria for reducing and enhancing collections include adequate documentation, potential for future use, information density, time and money invested in specimens, and spatial and financial constraints. Application of these criteria to the voluminous (c. 300,000 samples) rock collections of the University of Amsterdam, led to partial acquisition by the Nationaal Natuurhistorisch Museum in Leiden (Naturalis) late in 2002. Selected items included: (i) historical collections; (ii) material from former overseas domains; (iii) material from poorly accessible areas; (iv) material useful for research at the museum itself; (v) non-voluminous items with high information density (thin sections) or subjected to laboratory treatment (rock powders, mineral separates); and (vi) all samples quoted in academic dissertations.\nPromotion and advertising of the newly acquired collections is expected to lead to a second life for these important academic specimens. Application of similar criteria to other museum collections will lead to partial de-accessioning, thus creating space for future acquisitions in the framework where Naturalis is increasingly regarded as the Dutch national repository of geological collections. Researchers from partner institutions will be stimulated to (de-)select their collections at the end of a project, to avoid the much higher costs of later selection by museum staff.
    Keywords: geology ; petrology ; collections ; selection ; de-selection ; de-accessioning
    Repository Name: National Museum of Natural History, Netherlands
    Type: info:eu-repo/semantics/article
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  • 24
    facet.materialart.
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    In:  J. Geophys. Res., New York, Scientific American, vol. 108, no. B3, pp. ECV 7-1 - ECV 7-13, pp. 2171, (ISSN: 1340-4202)
    Publication Date: 2003
    Keywords: Borehole geophys. ; Volcanology ; 0915 ; Exploration ; Geophysics: ; Downhole ; methods ; 0910 ; Exploration ; Geophysics: ; Data ; processing ; Volcanology, ; geochemistry, ; and ; petrology ; 5102 ; Physical ; Properties ; of ; Rocks: ; Acoustic ; properties ; JGR
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  • 25
    facet.materialart.
    Unknown
    In:  Physics Today, London, Institution of Mining and Metallurgy, vol. 55, no. 4, pp. 48-53, pp. 1869, (ISBN: 0-12-018847-3)
    Publication Date: 2002
    Description: Petroleum engineers use a variety of physical techniques to find and exploit petroleum reservoirs in increasingly remote and complicated geological environments.
    Keywords: Applied geophysics ; Borehole geophys. ; NMR ; MWD ; Seismics (controlled source seismology) ; neutron ; gamma ; ray ; spectroscopy ; petrology ; Physical properties of rocks ; Review article
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  • 26
    facet.materialart.
    Unknown
    In:  Tectonics, Regensburg, Inst. Electrical & Electronics Engineers, vol. 21, no. 6, pp. 6-1 to 6-19, pp. 1056, (ISBN: 0534351875, 2nd edition)
    Publication Date: 2002
    Keywords: Tectonics ; Subduction zone ; Rheology ; pTt-path ; 3210 ; Mathematical ; Geophysics: ; Modeling ; 3660 ; Mineralogy, ; Petrology, ; and ; Mineral ; Physics: ; Metamorphic ; petrology ; 8150 ; Tectonophysics: ; Plate ; boundary--general ; (3040) ; 8045 ; Structural ; Geology: ; Role ; of ; fluids ; 5120 ; Physical ; Properties ; of ; Rocks: ; Plasticity, ; diffusion, ; and ; creep ; Stoeckhert ; Stockhert ; Structural geology ; Mineralogy ; Physical properties of rocks
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  • 27
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    In:  Eos, Trans., Am. Geophys. Un., London, Army Corps of Engineers, Woodward-Clyde Consultants, vol. 82, no. 6, pp. 65, 68-69, pp. 1062, (ISBN: 0-12-018847-3)
    Publication Date: 2001
    Keywords: Volcanology ; Mineralogy ; petrology ; Adaktite ; Subduction zone ; MORB
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  • 28
    ISSN: 1573-0581
    Keywords: Structure ; morphology ; petrology ; peridotite-basalt
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The St. Paul F.Z. is a large structural domain made up of multiple transform faults interrupted by several Intra-Transform Ridge (ITR) spreading segments. Two regions were studied in details by submersible: (1) The ITR short (〈20 km in length) segment near 0° 37′N–25° 27′W and 1° N–27° 42′W and (2) The St. Peter and St. Paul's Rocks (SPPR) massif located at 29° 25′W (¡3700 m depth). (1) The short ITR segments consist of a magma starved rift valley with recent volcanic activities at 4700 m depth. A geological profile made along the rift valley wall showed localized volcanics (basalts and dykes) which are believed to overlay and intrude the ultramafics. The geological setting and the high ultramafic/volcanic ratio suggest an extremely low magmatic supply and crustal-mantle uplift during lithospheric stretching and denudation. (2) The St. Peter and St. Paul's Rocks (SPPR) massif consists of a sigmoidal ridge within the active transform zone. The SPPR is divided into two different geological domains called the North and the South Ridges. The North Ridge consists of strongly tectonized fault scarps composed of banded and mylonitized peridotite, sporadic gabbros (3900–2500 m) and metabasalts (2700–1700 m). The South Ridge is less tectonized with undeformed, serpentinized spinel lherzolite (2000–1400 m) and basalts. Extensional motion and denudation accompanied by diapirism affected the South Ridge within a transform domain. Instead, the North Ridge was formed during an important strike-slip and faulting motion resulting in the uplifted portion of the St. Paul F.Z. transverse ridge. There is a regional compositional variation of the volcanics where E-MORBs and alkali basalts are produced on the SPPR massif and are comparable to the adjacent northern segments of the Mid-Atlantic Ridge. On the other hand, N and T- MORBs collected from the eastern part of the St. Paul F.Z. (25° 27′ W IRT) are similar to the volcanics from the southern segments of the MAR. The peridotites exposed in these provinces (SPPR and ITR) are similar in their REE and trace element distribution. Different degrees (3–15%) of partial melting of a mixed composite mantle consisting of spinel and amphibole bearing lherzolite veined with 5–40% clinopyroxenite gave rise to the observed MORBs and alkali basalts.
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  • 29
    ISSN: 1434-193X
    Keywords: Triplet recombination ; Electron transfer ; Radical ions ; Photochemistry ; Terpenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The triphenypyrylium tetrafluoroborate (TPT)-sensitized reactions of several terpene donor molecules, including sabinene (1), α-phellandrene (4), α-terpinene (5) and γ-terpinene (6) give rise to significantly different products than reactions induced by other electron-transfer sensitizers, such as 1,4-dicyanobenzene (DCB). The divergent reactions require decidedly different key intermediates; the products obtained with TPT can be explained by dissociative recombination of the intermediate radical-radical cation pair in the triplet state, generating donor-derived biradicals.
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  • 30
    ISSN: 1434-193X
    Keywords: Azides ; Cleavage reactions ; Cycloadditions ; Nitrogen heterocycles ; Polycycles ; Ring expansion ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---2-Alkyl-1-methylquinazolinium hexafluorophosphates 9 are deprotonated by sodium or potassium hydride to afford solutions of 2-alkylidenedihydroquinazolines 10, which were investigated by NMR spectroscopy. Trapping with methanesulfonyl azide (5a) of 10 in situ or subsequent treatment with trifluoromethanesulfonyl azide (5b) gives mixtures of colourless (15) and intensely yellow N-sulfonylimino-1,4-benzodiazepines 16 along with products due to cleavage of the exocyclic double bond of 10, viz. 11 and 13. The ethylidene compound 10b yields the bicyclic products 18 and 19, apparently by complex sequences of reactions that are triggered by removal of the acidic proton at C-2 of 16b and 16f. The structures of the products are based on spectroscopic evidence and X-ray diffraction analyses performed on 15b, 16d, 16e, and 19.
    Additional Material: 6 Ill.
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  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1589-1593 
    ISSN: 1434-193X
    Keywords: Azaallenium ions ; Azaallylium ions ; Iminium ion ; Kinetics ; Linear Free Energy Relationships ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The rate constants for the reactions of the 2-azaallenium ion 1b+, the 2-azaallylium ion 2a+ and the iminium ion 3+ with different nucleophiles were determined by 1H NMR spectroscopy. By correlation with the Linear Free Enthalpy Relationship (LFER) lg k20°C = s (E + N), developed by Mayr and Patz, the electrophilicity parameters E(1b+) = -3.7, E(2a+) ≍ -16 and E(3+) = -10.43 were obtained. They show that the relative reactivities of these ions are approximately 1012:1:106. Quantum chemical calculations (ab initio, DFT) of the methyl anion affinities for the ions 1b+,2a+ and3+ are in agreement with the experimental E values. The X-ray structure of 3+·CF3SO3- is reported for the first time; it shows no strong interaction between the cation and the anion.
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  • 32
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1595-1601 
    ISSN: 1434-193X
    Keywords: Oxazoline N-oxide ; Cycloadditions ; Cycloadditions ; Lactams ; Thienamycin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---[3+2] Cycloaddition between a camphor-derived oxazoline N-oxide 9 and the γ,δ-unsaturated enamino ester 11 afforded the single adduct 6. A stereoselective reduction of the enamino ester side chain allowed the control of the absolute configuration of the two additional asymmetric centres. Nitrogen protection and oxidative hydrolysis of the resulting product 13, followed by further functional group manipulations, led to the β-lactam derivative 1, a known precursor of the β-methylthienamycin derivative2a.
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  • 33
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1603-1607 
    ISSN: 1434-193X
    Keywords: Boron ; Cyclotrimerizations ; Nitrogen heterocycles ; Macrocycles ; Subphthalocyanines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The regioselective preparation of ortho-substituted subphthalocyanides was achieved employing 3-substituted phthalonitrile derivatives as starting materials. A mechanistic proposal has been outlined.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99525_s.pdf or from the author.
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  • 34
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1609-1615 
    ISSN: 1434-193X
    Keywords: Terpenoids ; Natural products ; Total synthesis ; Cyclizations ; Rearrangements ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A new route for the synthesis of 2,7- and 7-functionalized labdanes starts from (R)-carvone (1). 11-Nordrim-7-en-9-one (15) is an appropriate starting material for the total synthesis of hispanone (21), a biologically active furolabdane isolated from the Mediterranean medicinal plant Ballota saxatilis.
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  • 35
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1623-1626 
    ISSN: 1434-193X
    Keywords: Iridoid glucoside ; (8S)-Kingiside ; (8S)-Loganin ; (8S)-7-Ketologanin ; Asymmetric synthesis ; Natural products ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The tetraacetyl derivative 8 of the naturally occurring kingiside (8a) was prepared from aucubin (1). Intermediates in the synthesis were (8S)-tetraacetyl loganin (6) and (8S)-tetraacetyl-7-ketologanin (7), whose free (8R)-epimers occur in many different plants (Caprifoliaceae, Loganiaceae). The 13C NMR spectrum allows the structure to be unequivocally identified.
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  • 36
    ISSN: 1434-193X
    Keywords: Tetrakis(dimethylamino)naphthalenes ; Basicity ; Hydrogen bonds ; Cyclicvoltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---For comparison to the recently described 2,3,6,7-tetrakis(dimethylamino)naphthalene (1) the three isomers 2,3, and 4 were synthesized. The basicities of this group of isomers are strongly dependent upon the different mutual orientations of the pairs of dimethylamino substituents: only the isomers 3 and, partially, 4, both with dimethylamino groups in adjacent peri-positions of the naphthalene, are strong “proton sponges”. For the isomers 1 and 2 with the same number and kind of twofold dimethylamino substituents in neighbouring ortho-positions, however, no significant basicity increase is observed. To explain this difference between the two groups of isomers it is suggested that in the ortho-pairs of 1 and 2 the C-N bonds diverge considerably, leading to an increased N···N distance and consequently to less stable [N···H···N]+ hydrogen bonds in contrast to the parallel C-N bonds in the peri-substituted isomers 3 and 4. X-ray crystal structure analyses of the bases and of some of the salts derived therefrom were solved and are discussed. Cyclic voltammetry indicates that 1 to 4 are strong electron donors, reacting easily to radical cations or dications which with suitable acids have been obtained as salts.
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  • 37
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1677-1683 
    ISSN: 1434-193X
    Keywords: Radicals ; Cyclizations ; Pyridinethione ; Tetrahydrofurans ; Asymmetric synthesis ; Thiazolethione ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The trisubstituted functionalized tetrahydrofurans 10, 11, 16, 18, and 19 were photochemically prepared from 2,3-syn- and 2,3-anti-configuredN-(3-benzoyloxy-5-hexen-2-oxy)thiazole-2(3H)-thione anti-6, pyridinethiones 7, anti-8, and BrCCl3. The formation of tetrahydrofurans was achieved by an efficient and highly regioselective alkoxyl radical cyclization (5-exo-trig). The 2,3-anti substituted intermediates 9 and 12 cyclize stereoselectively whereas a 2,3-syn-configured O-radical affords both possible diastereomeric addition products in equal amounts. The cyclized tetrahydrofuryl methyl radicals were trapped with the bromine atom donor BrCCl3 to afford the bromomethyl-substituted cyclic ethers 10, 11, 18, and 19 in excellent yields. The utility of this reaction was stressed by conversion of one of the newly prepared tetrahydrofurans in a two-step synthesis into (+)-allo-muscarine (+)-20.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99590_s.pdf or from the author.
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  • 38
    ISSN: 1434-193X
    Keywords: Thioketones ; Thiocarbonyl ylides ; Cycloadditions ; Cycloreversions ; Sulfur heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reactions of diaryl thioketones with diazomethane at room temperature afford 4,4,5,5-tetraaryl-1,3-dithiolanes; the scope of this surprising 2:1 interaction has been studied for decades (Schönberg Reaction). The clue to the mechanism was our observation that the stoichiometry is 1:1 at -78 °C, and 2,5-dihydro-2,2-diaryl-1,3,4-thiadiazoles are formed as primary [2+3] cycloadducts. They lose N2 at -45 °C in first-order reactions generating diaryl thioketone S-methylides which can be intercepted by thioketones (→1,3-dithiolanes), multiple CC bonds, or acids HX. In the absence of trapping reagents, the elusive intermediates either dimerize furnishing 2,2,3,3-tetraaryl-1,4-dithianes or give rise to 2,2-diarylthiiranes by electrocyclization. Beyond thiobenzophenone and diazomethane, our main model reaction, the studies involve fluorene-9-thione, 4,4-dimethoxy- and 4,4-dichlorothiobenzophenone. The ring of 2,5-dihydro-2,2-diphenyl-1,3,4-thiadiazole (8) is opened by LDA at -78 °C and derivatives of anion 12 are obtained. - In summa: The Schönberg reaction consists of two 1,3-dipolar cycloadditions, linked by a 1,3-dipolar cycloreversion.
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  • 39
    ISSN: 1434-193X
    Keywords: Conjugation ; Boron ; Sensors ; Cyclic voltammetry ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---New electropolymerizable aromatic compounds (i.e. pyrrole, thiophene, aniline) bearing boronic acid and ester substituents have been synthesized and their electrochemical behavior has been investigated. Functionalized polythiophene and polypyrrole films could be anodically generated in acetonitrile, whereas the polyaniline derivative was electroformed in an acidic aqueous solution. The electrochemical responses of some of these materials were changed when fluoride ions were added to the electrolytic solutions. The strongest modifications, caused by binding of fluoride by the immobilized boron, were observed for the polypyrrole derivative in hydroorganic media.
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  • 40
    ISSN: 1434-193X
    Keywords: Heterocycles ; Zinc ; Palladium ; Catalysts ; Sulfur ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3-(phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.
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  • 41
    ISSN: 1434-193X
    Keywords: Self-assembly ; Vapor-pressure osmometry ; Resorcin[4]arenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Resorcin[4]arene tetracarboxylic acids 5,6 (A) and resorcin[4]arene tetrapyridines 2,3 (P) self-assemble in chloroform solution to form stable heterotopic AP dimers. Data from NMR titration and dilution experiments, as well as from vapor-pressure osmometry (VPO), indicate that the AP dimer is formed with an association constant greater than 107 M-1. Solid-solution extraction experiments are indicative of the formation of a 2:1 trimer (A2P), while self-associated homotopic species (A2 and A3) can be detected by NMR and VPO. Analysis of the heterotopic noncovalent assembly process over a range of compositions shows that these other species are much less stable than the AP heterodimer, which is the exclusive species at an A/P concentration ratio of 1:1 (〉 99.7% of the total at 10 mM).
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  • 42
    ISSN: 1434-193X
    Keywords: Sulfoxides ; β-Amino sulfones ; Mannich type reaction ; Lithium perchlorate ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding β-(dialkylamino) sulfoxides and β-(dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use.
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  • 43
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    Liebigs Annalen 2000 (2000), S. 1741-1744 
    ISSN: 1434-193X
    Keywords: Bridged pyranose derivatives ; Ring enlargement ; Carbenes ; Glycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Addition of dichlorocarbene to the glycal (±±)-2 followed by cyclopropyl-allyl rearrangement leads to the chloro-2H-pyran (±±)-4. Oxidation of (±±)-4 and reduction of the obtained hydroxypyranone (±±)-5 gave the methyl pyranoside (±±)-6. The relative configuration of (±±)-6 was established by X-ray structural analysis of the corresponding acetate (±±)-7. The synthesis of the optically active starting materials (+)-2 and (-)-2 is also reported.
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  • 44
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    Liebigs Annalen 2000 (2000), S. 1745-1758 
    ISSN: 1434-193X
    Keywords: CMP-Neu5Ac analogues ; Enzyme inhibitors ; Substrate analogues ; Transition state analogues ; Transferases ; Carbohydrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Quinic acid was transformed into phosphitamides 16, 25, and 36, which could be readily linked to 5′-O-unprotected cytidine derivative 17. Ensuing oxidation of the obtained phosphite triesters with tBuO2H and hydrogenolytic de-O-benzylation furnished the corresponding phosphate diesters 18, 26, and 38. Base catalyzed removal of acetyl protecting groups, and methyl ester hydrolysis furnished CMP-Neu5Ac analogues 1d, 1e, and 2. Quinic acid was also transformed into 1,2-unsaturated diallyl α-hydroxymethyl-phosphate derivatives (R)- and (S)-46, which on reaction with cytidine phosphitamide 47 afforded the phosphite triesters. Subsequent oxidation with tBuO2H and then treatment with NEt3 gave phosphate diester derivatives (R)- and (S)-48. Deallylation, acetyl group removal, and methyl ester hydrolysis furnished (R)- and (S)-3, respectively. Treatment of (R)- and (S)-48 with DBU as a base led to acetic acid elimination, thus yielding, after de-O-allylation, acetyl group cleavage, and ester hydrolysis, diene derivative (E)-4. Donor substrate analogues 1d and 1e exhibited good α(2-6)-sialyltransferase inhibition (Ki: 2.0·10-4 and 2.0·10-5 M). However, transition state analogues (R)-, and particularly (S)-3 showed excellent inhibition properties (Ki: 1.6·10-6 and 2.7·10-7 M).
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  • 45
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    Liebigs Annalen 2000 (2000), S. 1759-1765 
    ISSN: 1434-193X
    Keywords: Cyclitols ; Aminocyclitols ; Glycosidase inhibitors ; α-Mannosidase inhibitors ; Deoxygenation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Three deoxy derivatives 2-4 of the α-mannosidase inhibitor mannostatin A (1) were synthesized, and their inhibition of Jack bean α-mannosidase was evaluated in order to elucidate the roles of each of the three hydroxyl groups of the inhibitor. The 1- and 2-deoxy derivatives 2 and 3 retained some inhibitory activity, although reduced by a factor of about 100 relative to the parent, whereas it was completely lost with the 3-deoxy derivative 4. Structure and activity relationships are discussed in the light of these findings.
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  • 46
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    Liebigs Annalen 2000 (2000), S. 1767-1772 
    ISSN: 1434-193X
    Keywords: Circular dichroism ; Conformation analysis ; s-Triazines ; Chiral auxiliaries ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---CD data of the optically pure 2-[(R)-1-(9-anthryl)ethylamino]-4-chloro-6-[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2[(R)-1-(9-anthryl)ethylamino]-4,6-bis[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2,4-bis[(R)-1-(9-anthryl)ethylamino]-6-chloro-1,3,5-triazine are presented. The analysis of the CD spectra by means of the nonempirical DeVoe approach has afforded the complete conformational characterisation of the three s-triazine derivatives, allowing us to establish how the conformation of these derivatives depends on the nature of the substituent 1-arylethylamino groups.
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  • 47
    ISSN: 1434-193X
    Keywords: Cycloadditions ; Carbenes ; Nitrones ; Nitrilimines ; Pyrazolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of tert-butylalkynyl chromium Fischer carbene complex 1 with nitrones 2 affords β-enamino-ketoaldehydes 4 by the light-promoted rearrangement of the corresponding [3+2] cycloadduct carbene complexes 3. On the other hand, [3+2] cycloaddition of chiral nonracemic Fischer alkenyl carbene complexes 19 with nitrilimines 10 yields enantiomerically pure Δ2-pyrazolines with high regio- and diastereoselectivity.
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  • 48
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Zinc ; Transition structures ; QM/MM computations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Trimethylsilyl substitutions of the fenchyl alcohols [(1R,2R,4S)-exo-(2-Ar)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, Ar = 2-methoxyphenyl (1) and Ar = 2-(dimethylaminomethyl)phenyl (2)] yield the chiral ligands 3 [Ar = 2-methoxy-3-(trimethylsilyl)phenyl] and 4 [Ar = 2-(dimethylaminomethyl)3-(trimethylsilyl)phenyl]. Increased reactivities and enantioselectivities in diethylzinc additions to benzaldehyde are obtained from 3 (63% ee R) and 4 (93% ee S), relative to 1 (26% ee S) and 2 (73% ee S). X-ray crystal structures of 3 and of its methylzinc complex 3-Zn reveal out-of-plane bending of the methoxy groups as major geometrical consequences of the trimethylsilyl substitutions. Analyses of QM/MM ONIOM μ-O transition-structure models for 1, 2, 3, and 4 show that trimethylsilyl-induced distortions of methoxy and of dimethylaminomethyl groups explain the observed increased enantioselectivities.
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  • 49
    ISSN: 1434-193X
    Keywords: Palladium ; exo-π-Allylpalladium complexes ; Allylic alkylation ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The palladium(0)-catalyzed alkylation of 2,3-bis(acetoxymethyl)bicyclo[2.2.1]hepta-2,5-diene 1 with malonate-type enolates as nucleophiles is investigated. A monoalkylated product is formed first, and undergoes (depending on the nucleophile used) a second intramolecular reaction leading to spirocyclopropane-annulated bicyclo[2.2.1]heptene derivatives 5. The formation of endo spirobicyclic cyclopropanes adducts as major isomer is rationalized by assuming formation of an intermediate exo-(π-allyl)palladium complex.
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  • 50
    ISSN: 1434-193X
    Keywords: Ketones ; Reductions ; Micelles ; Cobalt ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Operationally simple and environmentally benign procedures have been developed to selectively reduce different α,β-unsaturated ketones, 4,4-dimethylcyclohex-2-ene-1-one (1), isophorone (2), benzylideneacetone (3), chalcone (4) by NaBH4 or by the system NaBH4 + CoCl2. Alternative reaction media to the extensively used MeOH have been explored, and new procedures take advantage of the acceleration and chemoselectivity induced by water or by aqueous micellar solutions. It was possible to selectively and quantitatively afford pure products of 1,2 and of 1,4 reduction as well as the totally reduced compounds (yield and selectivity 〉 90%) by simple changes in the experimental conditions.
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  • 51
    ISSN: 1434-193X
    Keywords: C-Glycosides ; Conformation analysis ; Molecular dynamics ; Selectins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The conformational behavior of the C-glycosyl analogue of sialyl-α-(2→3)-galactose, synthesized as a glycosidase inhibitor, has been studied using a combination of NMR spectroscopy (J and NOE data) and molecular dynamics calculations. The obtained results show that the population distribution of conformers with respect to the orientation about the pseudo-glycosidic linkages is mainly controlled by steric interactions. This is in contrast to findings made for O-glycosides. In these natural compounds, the conformational behavior about the glycosidic linkage Φ is mainly governed by the exo-anomeric effect.
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  • 52
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    Liebigs Annalen 2000 (2000), S. 1815-1820 
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Palladium-catalysed couplings ; Palladacycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Chiral C2-symmetric N-benzylazetidines have been conveniently prepared from optically pure anti-1,3-diols without loss of enantiomeric purity. N-Debenzylation led to the corresponding N-unsubstituted azetidines, which were then subjected to palladium-catalysed coupling reactions with aryl bromides to afford chiral N-arylazetidines. (R,R)-N-Benzyl-2,4-dimethylazetidine has been employed in the synthesis of a new cyclopalladated complex, which can be used, for instance, as a chiral recognition agent for phosphorus ligands.
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  • 53
    ISSN: 1434-193X
    Keywords: Cyclizations ; Spiro compounds ; Nucleosides ; Isomerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Syntheses of the spiro nucleosides 2′-deoxyhydantocidin 3a and its 1′-epimer 3b are described. The newly developed route involves a Horner-Wadsworth-Emmons condensation of the phosphonate 16 with the erythrose derivative 15 affording a mixture of six isomers which was fully assigned by NMR spectroscopy. The mixture was directly converted into the final compounds in an efficient base-catalyzed cyclization reaction. A base-catalyzed interconversion between the two isomers was observed.
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  • 54
    ISSN: 1434-193X
    Keywords: Benzodiazepines ; Heterocycles ; Azeto[1,2-a]-1,5-benzodiazepines ; Cyclizations ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of o-phenylenediamine (4) with one, two or three equivalents of p-substituted 3-dimethylaminopropiophenone hydrochlorides 5a-e was studied. 4-Aryl-2,3-dihydro-1H-1,5-benzodiazepine derivatives 6a-e were obtained in good yields, along with the 1:2-adducts 7c-e and the unexpected 1:3-adducts rac-8c-e. The type of adduct formed is determined by the molar ratio of the reactants 4 and 5 and by the nature of the substituent in the para position of the propiophenone 5.
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  • 55
    ISSN: 1434-193X
    Keywords: Cup-shaped PAHs ; Host-guest compounds ; Host-guest chemistry ; Cyclizations ; Semiempirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Cyclotrimerisation of benzo-polycyclic bromostannylalkenes 8a-d with Cu(NO3)2·3H2O in THF affords benzotri(benzonorbornadienes) 3a-d as a mixture of the syn and anti isomers. The ratio of syn to anti is close to the 1:3 statistical value in most cases (i.e. in cyclotrimers 3a,b,d), but highly in favour of the anti isomer in 3c, where steric hindrance by the methoxy groups plays an important role in the stereochemistry of the cyclotrimerisation. The substrates for the cyclotrimerisation, i.e. the bromostannyl alkenes 8a-d, were prepared from bromoalkenes 7a-d by treatment with base (LDA) and quenching with trimethyltin chloride. In turn, bromoalkenes 7a-d were prepared from alkenes 5a-d by radical bromination-elimination. The reaction conditions used were designed to minimise Wagner-Meerwein rearrangements that would lead to unwanted bromo isomers. The cup-shaped syn cyclotrimers 3a-d exhibit high electron density within the cavity as determined by AM1 semiempirical calculations of their electrostatic potential surfaces and are valuable substrates for supramolecular chemistry. As an example, it is shown that fullerene C60 is drawn into solution in acetonitrile by complexation with both the syn and anti trimer of benzonorbornadiene 3a.
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  • 56
    ISSN: 1434-193X
    Keywords: Carbene complexes ; Enamines ; Metallatrienes ; Cyclopentadienes ; Dihydropyrroles ; spiro-Tetrahydropyrroles ; Iminium carbonylmetalates ; Dimetallapolyenes ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reactions of the [(1-alkynyl)carbene]tungsten complex (CO)5W=C(OEt)C≡CPh (1) with 1-aminocyclohexenes 2a-c and 7a-c afford different types of products depending on the amino substituents and the reaction conditions. (4-Aminocyclobutenyl)carbene complexes B have been shown to be generated in the first reaction step through a [2+2] cycloaddition. These are key intermediates and afford cross-conjugated tungstatrienes E, (conjugated) 1-tungsta-1,3,5-hexatrienes G, or (non-conjugated) 1-tungsta-1,3,6-heptatrienes F by following competing reaction pathways. Cross-conjugated 1-tungstatrienes 3 have been isolated in 52-74% yield by performing the reactions of 1-aminobenzocyclohexenes 2a-c with compound 1 in pentane. In dichloromethane instead of pentane, (conjugated) 1-tungsta-1,3,5-hexatrienes 4 are obtained, which subse-quently undergo fragmentation to give cyclopentadienes 6 (by π-cyclization) and dihydropyrroles (by α-cyclization) in a molar ratio dependent on the nature of the amino substituents. (Non-conjugated) 1-tungsta-1,3,6-heptatrienes 10 are generated upon reaction of 1-aminocyclohexenes 7a-c with compounds 1, which are transformed into cyclopentadienes 12 via conjugated 1-tungsta-1,3,5-hexatrienes 9 as intermediates. Reactions of 1-tungsta-1,3,6-heptatrienes 10 with the (1-alkynyl)carbene complex 1 afford dinuclear compounds 14, which subsequently yield indenes 15 (by two successive π-cyclization steps) and spiro-tetrahydropyrroles 16 (by both a π-cyclization and an α-cyclization step), depending on the steric bulk of the amino substituent.
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  • 57
    ISSN: 1434-193X
    Keywords: Allyl alcohols ; Organocerium reagents ; Alkenes ; Addition reactions ; Cerium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Alkylcerium reagents add to the multiple bonds of allyl and propargyl alcohols in good yields and under mild conditions. The double bond can be reduced with lithium aluminum hydride in the presence of cerium trichloride. The regiochemistry of the attack depends on electronic factors.
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  • 58
    ISSN: 1434-193X
    Keywords: Amidines ; Chiral bases ; N-Acyliminium ions ; Enantioselective catalysis ; Chiral pool ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of four enantiopure hydroxyamidines is described. One amidine was obtained from (S)-pyroglutamic acid. Its key step involved the addition of phenylmagnesium bromide to the corresponding ester, affording the tertiary alcohol without detectable racemization. The second amidine was obtained by coupling of an (S)-malic acid derived N-acyliminium ion with β-naphthol. The other amidines were obtained from an (S)-serine-derived imide which was reduced to two diastereomeric lactams that were eventually transformed into the corresponding amidines.
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  • 59
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    Liebigs Annalen 2000 (2000), S. 155-163 
    ISSN: 1434-193X
    Keywords: Macrocycles ; Cyclizations ; Strained compounds ; Ketophosphonate ; Iodoalkyne ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two strategies have been explored to build the highly strained eleven-membered ring 2, a potential precursor for the biosynthetic key intermediate of the protoilludane family: an intramolecular Horner-Wadsworth-Emmons olefination and an intramolecular Nozaki-Hiyama-Kishi type-ring closure.
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  • 60
    ISSN: 1434-193X
    Keywords: Neutral anion receptor ; Hydrogen bonds ; Urea moieties ; Donor-acceptor systems ; Macrocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of macrocyclic and acyclic cleft-like anion receptors in which four hydrogen bond donating urea moieties are present in a preorganized fashion is described. NMR spectroscopy shows the complex formation with H2PO4- and Cl -. Cleft-like receptors bind H2PO4- in a 2:1 guest-host stoichiometry (Ka = 107M-2) in DMSO, whereas Cl - is bound in a 1:1 stoichiometry (Ka = 103M-1). The macrocyclic receptors form a 1:1 complex with H2PO4- (Ka = 103M-1 in DMSO) with a 100-fold selectivity for H2PO4- over Cl -.
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  • 61
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    Liebigs Annalen 2000 (2000), S. 193-198 
    ISSN: 1434-193X
    Keywords: Nucleophilic substitutions ; Azulenes ; Hydroxylation ; Amination ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Hydroxylation of azulenes with tert-butylhydroperoxide proceeds efficiently at the 6-position when the former contain electron-withdrawing substituents in the five-membered ring. Similarly, VNS amination of azulenes proceeds with 4-amino-1,2,4-triazole; its anion, being an active nucleophile, also reacts with unsubstituted azulene. A variety of transformations of 6-hydroxyazulenes, such as substitution of the corresponding sulfonates with nitrogen, oxygen, sulfur, carbon nucleophiles and halogens, and the Claisen rearrangement of allylic ethers, is reported.
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  • 62
    ISSN: 1434-193X
    Keywords: Heterocycles ; Carbohydrates ; Imidazolidines ; Oxazolidines ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Prochiral 1,3-dihydroxyacetone forms racemic oxazolidine- and oxazoline-type spiro[4.4]nonanes upon reactions with potassium (thio)cyanate and cyanamide. In contrast, 1,3-diaminoacetone yields only the corresponding spiro-bisimidazolidinethione under similar conditions together with monocyclic by-products, but the spiro-bisimidazolidinone is accessible by reaction of 1,3-dichloroacetone with urea. The resolution of the racemic spiro-bisoxazolidinethione 2a was achieved by using brucine as the resolving agent.
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  • 63
    ISSN: 1434-193X
    Keywords: Homogeneous catalysis ; Palladium ; Acetoxylation ; Acryloxylation ; Addition reactions ; Cyclooctadiene ; Cyclooct-4-enone ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Palladium-catalyzed acryloxylation of several cycloalkenes in the presence of the Pd(OAc)2/p-benzoquinone/MnO2 catalytic system is reported. This oxidation reaction yields allylic acrylates as the sole products through the intermediacy of an η3-allyl complex. However, with 1,5-cyclooctadiene (3), cyclooct-4-enone (4) is the major reaction product. Its formation results from oxidation, which is also observed in the palladium-catalyzed acetoxylation of 3. It has been shown that this is the result of a 1,2-trans addition (acryloxy-palladation), followed by a β-hydride elimination, which yields an enol acrylate or acetate. A second Markovnikov-oriented 1,2-trans-acryloxy-palladation on the latter yields a palladium complex, rearrangement of which gives 4.
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  • 64
    ISSN: 1434-193X
    Keywords: Amino acids ; coupling ; N-Substituted amide ; Cyclizations ; Cyclic dipeptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A short synthesis of new, functionalized seven-membered ring cyclic dipeptides is described. After the coupling of N-protected β-amino acids to N-substituted α-amino tert-butyl esters, the protective groups of the terminal functions were removed and the cyclization took place diastereoselectively in the presence of the coupling agent BOP. Amide substitution was found to be effective in promoting the cyclization of linear dipeptides.
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  • 65
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    Liebigs Annalen 2000 (2000), S. 275-280 
    ISSN: 1434-193X
    Keywords: Radical reactions ; Substituent effects ; Nitrogen heterocycles ; Dihydropyridines ; Pyrrolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A set of allene-tethered benzoyloximes (5) has been treated with nBu3SnH. Depending on their substitution pattern, a wide range of compounds has been obtained. If the stannyl radical adds on the allene, the C-centred radical thus formed undergoes either a 5-exo ring closure to give the cyclopentene derivatives 7 or a 6-endo ring closure onto the N atom to give the dihydropyridines 8. If the stannyl radical adds on the benzoyl moiety, an iminyl radical is formed which leads to the 3H-pyrroles 9 and the alkylidene-pyrrolines 10. Steric effects as well as polar effects are the factors governing the reaction course.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99373_s.pdf or from the author.
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  • 66
    ISSN: 1434-193X
    Keywords: Antibiotics ; Configuration determination ; Heterocycles ; Hongoquercin A ; Terpenoids ; Total synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---(±)-Hongoquercin A (1), the racemate of an antibacterial fungal metabolite, has been synthesized starting from geranylacetone (2) and ethyl orsellinate (ethyl 2,4-dihydroxy-6-methylbenzoate, 5). The structure (±)-1 has been confirmed by X-ray analysis of its ethyl ester (±)-10. Synthesis of the naturally occurring (+)-hongoquercin A from (-)-sclareol (11) established its configuration as depicted in 1.
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  • 67
    ISSN: 1434-193X
    Keywords: Carbohydrates ; Amino sugars ; Protecting groups ; Glycosylations ; Trichloroacetimidates ; Oligosaccharides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The N-DMM-Protected lactosamine derivative 2 was readily transformed into the corresponding glycosyl donor 4 and into acceptor 5. A TMSOTf-catalyzed glycosidation afforded the derived tetrasaccharide 6 which led to glycosyl donor 9. Reaction of 9 with lactose derivative 10 as acceptor gave the desired hexasaccharide 11. Cleavage of all protective groups and N-acetylation afforded the target molecule 1b (lacto-N-neohexaose). Glycosylation of acceptor 10 with donor 4 furnished tetrasaccharide 16 which, employing standard procedures, gave acceptor 18. Glycosylation of 18 with donor 9 furnished, under standard conditions, octasaccharide 19. Cleavage of all protective groups and N-acetylation afforded the target molecule 1c (lacto-N-neooctaose). Both 1b and 1c were obtained in good overall yields.
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  • 68
    ISSN: 1434-193X
    Keywords: Sharpless asymmetric dihydroxylation ; Asimilobin ; Tetrahydrofuran ring ; Wittig reactions ; Annonaceous acetogenins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The most efficient method for the synthesis of the trans/threo/trans-bis(tetrahydrofuran) (THF) ring unit was established, and the first total synthesis of (-)-asimilobin and its diastereomer was then accomplished in twelve and fourteen steps, respectively, from trans-1,5,9-decatriene, by a convergent route with a Wittig reaction as the key step. By virtue of these synthetic results, the absolute configuration of the bis(THF) unit in naturally occurring asimilobin should be corrected.
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  • 69
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    Liebigs Annalen 2000 (2000), S. 381-385 
    ISSN: 1434-193X
    Keywords: Enynes ; Macrocycles ; Coordination chemistry ; Crown compounds ; Radicals ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The complex molecular structure and interesting activation mechanisms of naturally occurring enediynes have inspired the synthesis of a variety of simpler model systems to mimic their properties. While in most model compounds nucleophilic attack, isomerization or bioreduction are used to activate the unsaturated system for diradical cyclization, some attempts have been made to employ metal-ion coordination for this purpose. Significant enhancement of the thermal reactivity has been achieved by metal-ion induced conformational and electronic changes of suitably substituted enediynes, such as 1, 5, 6, 17 and 18. Enediyne activation by stoichiometric or catalytic formation of vinylidene complexes, such as 22, from terminal alkynes has also been investigated. This paper summarizes recent results pursuing the activation of enediyne diradical cyclization by metal ions.
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  • 70
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    Liebigs Annalen 2000 (2000), S. 419-423 
    ISSN: 1434-193X
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The first enantioselective synthesis of enantiomerically pure (-)-wine lactone, (-)-1a, a fragrance constituent of various white wines, and its epimer (+)-1b, was carried out. The key steps are allylic substitution of (±)-2-cyclohexen-1-yl acetate (2) with dimethylmalonate using palladium complexes of phosphanyldihydrooxazol L1 or of the phosphanylcarboxylic acid L2 as catalyst, subsequent decarboxylation, iodolactonization and elimination, furnishing enantiomerically pure bicyclic lactone (+)-7 in 47% overall yield. The diastereoselective introduction of methyl groups by SN2′-type substitution with an organocopper compound and by enolate alkylation gave lactone (-)-1a in 43% overall yield from (+)-7.
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  • 71
    ISSN: 1434-193X
    Keywords: Aplykurodins ; Marine steroids ; C-C coupling ; Cyclic peroxides ; Lactonization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---An approach to the synthesis of aplykurodins, ichthyotoxic marine lactones, is presented. The carbon framework was derived from vitamin D3 by conversion of the readily accessible allyl alcohol 13 to the protected Grundmann's hydroxy ketone 22 and subsequent introduction of the C2 side chain through a Pd0-promoted coupling. Highly stereoselective hetero Diels-Alder reaction with O21 produced the key intermediate peroxide 25. Functional group transformations, coupled with a series of chemo- and stereoselective reactions, finally resulted in the synthesis of the unnatural analogue 17,18-dihydro-3,9-di-epi-aplykurodinone B (6).
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  • 72
    ISSN: 1434-193X
    Keywords: Zeolites ; Radical ions ; Ring opening ; Electron transfer ; Oxidations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Incorporation of trans-1,2-diphenylcyclopropane (1) and its 3,3-D2-isotopomer into the channels of a redox-active pentasil zeolite (Na-ZSM-5) resulted in the formation of exo,exo-1,3-diphenylallyl radical (2•) and its 2-D1 isotopomer, respectively. This conversion requires oxidation, ring opening, and deprotonation, in an unspecified sequence. The allyl radical 2• is also formed upon incorporation of trans-1,3-diphenylpropene (3). A comparison with the solution photochemistry, in the presence or absence of added base, shows the conversion of 1 into 2• to be a zeolite-specific reaction. Incorporation of arylcyclopropanes 9 (R = H, OCH3) into ZSM-5 generated trans-propenylbenzene radical cations 10•+ (R = H, OCH3); the 2,2-D2 isotopomer of 9 (R = OCH3) gave rise to three different isotopomers of 10•+ (R = OCH3).
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  • 73
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    Liebigs Annalen 2000 (2000), S. 485-490 
    ISSN: 1434-193X
    Keywords: Calixarenes ; Tripodal cryptand ; Extraction abilities ; Cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The tripodal calixcryptands have been one of the scarcely explored fields in calixarene chemistry due to the difficulties in their preparation. The strategy presented in this paper shows that novel tripodal calixcryptands can be conveniently prepared by directly treacing p-tert-butylcalix[n]arenes (n = 4, 6) with a multi-functional polypode reagent, e.g. 1,1,1-tris(tosyloxyethoxyethoxymethyl)propane or tetrakis(tosyloxyethoxyethoxymethyl)methane, under selected conditions. The first example of 1,2,4-tripodal calix[6]cryptands has been prepared. Novel calix[6]crown and doublecalix[4]arenes were co-prepared. The extraction abilities of these novel calixcryptands toward several alkali metal ions, ammonium and alkylammonium ions are presented.
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  • 74
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    Liebigs Annalen 2000 (2000), S. 521-525 
    ISSN: 1434-193X
    Keywords: Allyl aryl sulfones ; Nitroarenes ; Condensation reaction ; Lewis acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Allyl aryl sulfones 2 react with aryl nitrocompounds 1 in a DBU/MgCl2 system giving the 4-arylsulfonyl quinolines 3. Some mechanistic aspects of the reaction are discussed. Application of this reaction to the formal total synthesis of the natural product (-)Eupolauramine is described.
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  • 75
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    Liebigs Annalen 2000 (2000), S. 527-538 
    ISSN: 1434-193X
    Keywords: Furans ; Pyrans ; Dihydropyran-2-ylidenes ; Ring closure ; Addition reaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---On treatment with base the pentynones 8a-f undergo anionic addition reactions of the resulting enolate species to the alkyne moiety and afford the 2,5-disubstituted furans 10a-f in yields ranging from 10-91%. The proposed mechanism involves the 2-methylene-dihydrofurans 11 as intermediates which tautomerize to yield the observed products. In the case of the α-picolyl derivative 8g both possible enolates 12 and 13 are formed which are subsequently transformed to the products 10g and 14g, respectively. Starting with the hexynones 9a-e an analogous reaction takes place with the formation of the pyran derivatives 15 and 16 in comparable yields. Under the same reaction conditions the n-butyl ketone 9f gives rise to two isomeric compounds, namely the 4H-pyran 16f and the cyclohexenone 17. This result is explained by assuming initial formation of two isomeric enolates which react either by O- or C-attack on the carbon-carbon triple bond.
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  • 76
    ISSN: 1434-193X
    Keywords: Alkylations ; Deaminated AdoHcy ; Decarboxylated AdoHcy ; Mitsunobu reaction ; Nucleosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---5′-Acetylthio-5′-deoxy-2′,3′-O-isopropylideneadenosine (8) was directly prepared from commercially available 2′,3′-O-isopropylideneadenosine (7) and thioacetic acid under Mitsunobu conditions in almost quantitative yield. In situ cleavage of the acetylthio function of 8 followed by coupling with different alkyl bromides proceeded with high yields. Deprotection of the obtained 5′-thionucleosides yielded the S-adenosyl-L-homocysteine analogues decarboxylated AdoHcy (11), deaminated AdoHcy (14) and 5′-[3-(cyano)propylthio]-5′-deoxyadenosine (16) in good overall yields. Direct deprotection of the thionucleoside 8 delivered 5′-thio-5′-deoxyadenosine (18) in excellent yield. In addition, binding constants of these AdoHcy analogues and the DNA methyltransferase M·HhaI were determined in a fluorescence assay.
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  • 77
    ISSN: 1434-193X
    Keywords: Amino ketones ; Homogeneous catalysis ; Aziridination ; Copper ; Enols ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A series of acyclic and cyclic enol derivatives 1 has been transformed into the corresponding α-amino-functionalized ketones 2 by means of enantioselective catalytic aziridination with chiral Cu complexes, prepared in situ from [Cu(MeCN)4]PF6 and the optically active ligands 3, by using (N-tosylimino)iodobenzene (PhINTs) as a nitrogen source. The best enantioselectivities (ee values of up to 52%) have been achieved for the electronically deactivated enol acetate 1aδ, but the incorporation of steric bulk and the substitution pattern at the enol double bond do not improve the ee values. The cyclic substrates react considerably less readily (only up to 45% conversion) compared to their acyclic counterparts (complete consumption). A transition structure is suggested for the asymmetric Cu-catalyzed aziridination of the enol acetate 1aδ in the presence of the chiral ligand 3b that could account for the sense of the (R)-configured product 2a.
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  • 78
    ISSN: 1434-193X
    Keywords: Porphyrins ; Chiral auxiliaries ; Macrocycles ; Pyrethroids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Esters, N,N-disubstituted amides, and a N-acylurea derived from the enantiopure industrial intermediate (1R)-cis-hemicaronaldehydic acid (or biocartol) are convenient synthons for the preparation of a series of chiroporphyrins by condensation with pyrrole. These chiral meso-tetracyclopropylporphyrins are obtained exclusively as the D2-symmetric α,β,α,β atropisomer, generally in low to moderate yields (2-20%), and in the urea case in excellent yield (60%). Hydrolysis of the urea substituents affords a chiroporphyrin with mono-N-substituted amide groups. 1H-NMR spectroscopy indicates that the ester, amide, and urea stereogenic groups sit on the porphyrin close to the metal binding site and restrict substrate or ligand access along a C2-symmetric groove. This structural feature of chiroporphyrins and of their metal complexes is of high potential interest in asymmetric catalysis and chiral recognition.
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  • 79
    ISSN: 1434-193X
    Keywords: Cyclophanes ; Molecular recognition ; Molecular shuttles ; Rotaxanes ; Template-directed synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two dumbbell-shaped compounds (8 and 11), each composed of two polyether chains intercepted by a 1,4-dioxybenzene recognition site, terminated by tetraarylmethane-based stoppers, and emanating from a central 9,10- or a 2,6-dioxyanthracene unit, have been synthesized. Two [2]rotaxanes (9 · 4 PF6 and 12 · 4 PF6) have been prepared by interlocking these dumbbell-shaped compounds (8 and 11) with a bipyridinium-based tetracationic cyclophane (15 · 4 PF6) - namely, cyclobis(paraquat-p-phenylene). A [3]rotaxane (10 · 8 PF6) incorporating two cyclophane components (15 · 4 PF6) was also obtained when the 9,10-dioxyanthracene-containing dumbbell-shaped compound (8) incorporating two 1,4-dioxybenzene recognition sites was employed. The 1H-NMR spectroscopic investigation of the [2]rotaxanes (9 · 4 PF6 and 12 · 4PF6) revealed that the cyclophane component encircles one of the two 1,4-dioxybenzene recognition sites in the 9,10-dioxyanthracene-containing [2]rotaxane (9 · 4 PF6) and the 2,6-dioxyanthracene unit in the other [2]rotaxane (12 · 4 PF6). These structures have been confirmed by UV/Vis and electrochemical experiments. Comparison with the spectroscopic properties of simple model compounds shows the presence of electronic interactions which lead to (i) the occurrence of very efficient energy transfer processes in the dumbbell-shaped components and (ii) perturbations in the absorption spectra with appearance of two charge-transfer absorption bands and complete luminescence quenching in the [2]rotaxanes. For the 2,6-dioxyanthracene-containing [2]rotaxane (12 · 4 PF6), it has been demonstrated that the cyclophane can be displaced from the dioxyanthracene to the 1,4-dioxybenzene station upon electrochemical oxidation.
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  • 80
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    Liebigs Annalen 2000 (2000), S. 627-631 
    ISSN: 1434-193X
    Keywords: Complex nucleoside ; Antibiotics ; Radicals ; Zn-Cu couple ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Homosinefungin 5, which can be considered as an analogue of S-adenosylmethionine (SAM) and of S-adenosylhomocysteine (SAH), has been synthesized by means of a sequence in which the key step was the addition of a radical, produced by the simple treatment of an iodide precursor with a zinc-copper couple, to suitably activated olefins.
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  • 81
    ISSN: 1434-193X
    Keywords: Amide linkage ; Phosphodiester ; Hammerhead ribozyme ; Oligonucleotides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A nucleoside dimer in which the natural phosphodiester bond is replaced by an isosteric amide linkage has been prepared. This dimer analogue was subsequently incorporated chemically at the cleavage position of a hammerhead ribozyme substrate. Although the resulting substrate analogue exhibited a high affinity for the ribozyme as shown by gel retardation assays, the amide bond proved to be fully resistant to cleavage under standard conditions of ribozyme cleavage activity.
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  • 82
    ISSN: 1434-193X
    Keywords: Solid-phase synthesis ; Wang resin ; Hetero Diels-Alder reactions ; Dihydropyrans ; Reductive reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The OH groups of Wang resin were esterified with benzylidenepyruvic acid (1) to give the immobilized 1-oxabutadiene 2. The latter reacted with vinyl ethers 3a-h (dienophiles) in the presence of Eu(fod)3, and the resulting adducts 4a-h underwent reductive cleavage with LiAlH4 to afford the dihydropyrans 5a-h in high (62 to 100%) overall yields. A similar sequence carried out under conventional homogeneous liquid phase conditions led to significantly lower yields. The endo/exo selectivity of the cycloaddition reaction was the same in both cases.
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  • 83
    ISSN: 1434-193X
    Keywords: Cationic amphiphiles ; Transfection ; Pyridinium salts ; Vesicles ; Lipoplex ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Pyridinium amphiphiles have found practical use for the delivery of DNA into cells. Starting from 4-methylpyridine, a general synthesis has been devised for the production of pyridinium amphiphiles which allows variation in both the hydrophobic part and in the headgroup area of the compounds. By means of differential scanning microcalorimetry, zeta potential, particle size measurements and cryo electron microscopy, some characteristics of the pyridinium amphiphile/DNA complexes have been determined.
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  • 84
    ISSN: 1434-193X
    Keywords: Pauson-Khand reaction ; Cyclopentenones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---1-Methyl-norbornene ester 9 and 1-methyl-2,3-diazabicyclo[2.2.1]heptene ester 10 were employed in intermolecular Pauson-Khand reactions with various terminal alkynes 11a-f to give the dimethyl 1-methyltricyclo[5.2.1.05,9]dec-7-en-6-one 2,3-dicarboxylates 12 and 13, and diethyl 2,3-diaza-1-methyltricyclo[5.2.1.05,9]dec-7-en-6-one 2,3-dicarboxylates 14 and 15, respectively. Whereas the co-cyclization of norbornene 9 with alkynes 11 bearing small substituents R resulted in the preferred formation of 12 (12:13 ≤ 85:15), regioisomer 13 was obtained as the major product when sterically bulky alkynes were employed (12:13 ≥ 6:94). For 2-methyl-3-butyn-2-ol 11e a strong temperature dependency of the regioselectivity was found. The ratio of regioisomers (12e:13e) changed from 95:5 at -25 °C to 12:88 at 120 °C in toluene. In contrast, reactions with 2,3-diazanorbornene 10 showed only moderate regioselectivities in favour of 14 (14:15 ≤ 69:31), regardless of the temperature and the size of R. The observed regioselectivities support a mechanism for the Pauson-Khand reaction in which the apical rather than the basal anti oriented carbon monoxide ligand of cobalt alkyne complex 1 is replaced by the alkene.
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  • 85
    ISSN: 1434-193X
    Keywords: Reverse-turn mimics ; γ-Turns ; β-Turns ; β-Hairpins ; Peptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Conformational analysis of N-acetylated hexapeptide mimics incorporating a bicyclic lactam (1-4) was carried out by a combination of 1H-NMR spectroscopy, IR spectroscopy, and computer modeling. The nature of the bicyclic lactam determines the turn motifs and the folding patterns of these constrained peptides. The (5,6)-bicyclic lactam derivatives 1 and 2, characterized by a type-II' β-turn (C=O3···H6-N), are very compact intramolecularly H-bonded structures. The (5,7)-bicyclic lactam derivative 3, characterized by an inverse γ-turn (C=O4···H6-N), is a quite flexible “tweezer-like” structure.
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  • 86
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 707-711 
    ISSN: 1434-193X
    Keywords: Radical reactions ; Photolysis ; X-ray scattering ; Rearrangements ; Semiempirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The previously reported tandem cyclisation of N-aryl α-(2-cyanophenyl)sulfanyl imidoyl radicals affords one quinoxaline derivative arising from exclusive 1,6-cyclisation of the final iminyl radical onto the N-aryl ring. When the imidoyl radicals are generated by addition of photolytically generated (2-cyanophenyl)sulfanyl radicals to isocyanides, the reaction also gives small amounts of a by-product that is formed by an analogous route and whose X-ray crystallographic data are reported here. The formation of this product entails a rare ortho-selective photo-Fries rearrangement of the starting disulfide, followed by addition to the isocyanide and regioselective 1,5-cyclisation of the resulting imidoyl onto only one of the two available radical acceptors, i.e. the cyano group and the sulfide moiety. Semiempirical MNDO-d calculations were performed in order to throw some light on the factors affecting these competitive cyclisations.
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  • 87
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 713-721 
    ISSN: 1434-193X
    Keywords: Reductive alkylation ; Acenaphthylenes ; Carbanions ; Polycycles ; Single-electron transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reaction of the 5-hydroacenaphthylene anion with benzyl halides proceeds at carbon atom 1 as well as at carbon atom 2a, in the latter case creating a quaternary centre. The hardness-softness of the electrophiles was shown to play only a minor role in determining the regioselectivity of the reaction of the hydroanion with several benzyl and alkyl halides: the leaving group hardly affects the ratio of 1- and 2a-substituted products. This indicates that the alkylation might proceed by an electron transfer (SET) instead of an SN2 mechanism. Further evidence for SET was obtained by the use of free radical and electron scavengers. The substitution products 1-benzylacenaphthene and 2a-benzyl-2a,5-dihydroacenaphthylene could be isolated and purified.
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  • 88
    ISSN: 1434-193X
    Keywords: Isotopic labeling ; Isotopic labeling ; Isotopic labeling ; Deuterium ; Carbon-13 ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Three selectively labeled propynes were prepared either with deuterium or carbon-13 at position 3 and doubly labeled with carbon-13 at positions 1 and 2 by an alkylation reaction from the corresponding labeled or unlabeled monolithio acetylides and dimethylsulfates. Their lithiation with nBuLi gave the corresponding propynyllithium derivatives which reacted with dimethyl squarate to afford the corresponding propargylic alcohols. These were thermolysed in p-xylene to furnish [5-D3-methyl]-, [5-13C-methyl]-, and [5,6-13C2-2,5-cyclohexadienyl]ubiquinone. The farnesyl side chain was introduced onto the labeled quinones with farnesyl trimethyltin under BF3 catalysis to provide [5-D3-methyl]-, [5-13C-methyl]-, and [5,6-13C2-2,5-cyclohexadienyl]ubiquinone 3 (6c, 6b, 6a, respectively).
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  • 89
    ISSN: 1434-193X
    Keywords: Tetrathiafulvalenes ; Charge transfer ; UV/Vis spectroscopy ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---4-[2-tetrathiafulvalenyl-ethenyl]pyridine (1) has been prepared from a Wittig reaction between formyltetrathiafulvalene and 4-picolyltriphenylphosphonium chloride hydrochloride. Conversion of the pyridine moiety of 1 by reaction with methyl iodide leads to 4-[2-tetrathiafulvalenyl-ethenyl]-1-methylpyridinium iodide (2a). Neutralization of 1 with a large excess of L-tartaric acid affords 4-[2-tetrathiafulvalenyl-ethenyl]-1-methylpyridinium hydrogen tartrate (3). These TTF-π-spacer-acceptor compounds have been characterized by elemental analysis, and IR and 1H NMR spectroscopy. The crystal structure of 2a has been determined by X-ray diffraction. The cation is essentially planar. Examination of the bond lengths in 2a, UV/Vis spectra and CV data, and calculations indicate that an intramolecular charge transfer occurs in the studied compounds, although it is rather limited, and larger in 2a and 3 than in 1.
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  • 90
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 807-811 
    ISSN: 1434-193X
    Keywords: Proline analogues ; Asymmetric synthesis ; Schöllkopf's method ; Silicon ; Amino acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The asymmetric synthesis of a new proline surrogate, incorporating the dimethylsilyl group at position 4 of proline using Schöllkopf's bis-lactim ether method, is described.
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  • 91
    ISSN: 1434-193X
    Keywords: Bisdiazenes ; Homoconjugation ; Photochemistry ; Heterocycles ; Diazenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Rigid N=N/N=N (diazene/diazene) systems (F) consisting of more or less alkylated DBH and DBO chromophoric units (1, 2, X-ray structures), with very short π,π distances [d = 2.849 (1a, av.), 2.822 Å (2)] and almost perfect syn-periplanar π,π alignments [ω = 168.6 (1a), 174.2° (2)] as well as the more flexible, less “proximate” metathesis isomers (3a,c, 27a,c, d 〉4.6 Å, ω = 90-100°) have been synthesized. Homoconjugate π,π interaction (in 1, 2, not in 3, 27) is deduced from UV spectroscopic measurements [π → π* maxima at 239 (234) nm (sh, 260)], while PE analyses furnished only small interaction parameters (1a: 〈0.3 eV). The potential of the novel syn-periplanar N=N/N=N motif in 1 and 2 for the synthesis of somewhat exotic polyheterocycles has been explored by calculation (B3LYP) as well as experimentally: i.a. kinetically stabilized, all-cis-peralkylated tetrazolidines (38, 44) and perhydro-1,2,4,5-tetrazines (41, 47) have become accessible (i.a. via novel azomethine/diazene and azomethine/azomethine cycloadditions). In 1a with its unreactive DBO chromophoric subunits, in the “buttressed” derivatives 1b-d, as well as in the DBH/DBO combination 2, and likewise in more ‘distant’ 27 (differently from the analogous C=C/C=C and N=N/C=C systems), irrespective of the excitation conditions employed (light of λ ≥≥ 280, 254 nm, low temperature matrix irradiation, acetone sensitization) no [2+2]photocycloaddition was observed. Instead exclusively N2-elimination took place. It is argued that unproductive N=N/N=N photocycloaddition would have become observable through metathesis isomerization of the respective tetrazetidines.
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  • 92
    ISSN: 1434-193X
    Keywords: Photochemistry ; Heterocycles ; Diazenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Of two very proximate syn-periplanar bisdiazenes (1,2) mono-, di-, tri- and tetra-N-oxides were prepared, representing six combinations of the individual N=N/N=NO/ON=NO chromophores. According to DFT calculations (B3LYP/6-31G*), [2+2]photocycloaddition to the respective oxidized tetrazetidines is significantly to moderately endothermic. The metathesis isomerization of the oxidized tetrazetidines is generally highly exothermic and kinetically increasingly favorable with increasing oxidation state. In practice, four out of the six bichromophoric combinations undergo selectively, in competition with N2 elimination from a DBH unit (13) still partially, metathesis isomerization upon π → π* excitation (monochromatic 254 nm light). In the case of the syn-N=NO/N=NO combinations (5/6, 14), the photoaddition is thermally reversed. For a ON=NO/N=N combination (30), internal electron transfer is responsible for a complex reaction pattern. The preparative value of the metathesis reactions, though, is limited: The metathesis-derived bis[diazene mono(di)oxides] undergo relatively fast secondary photoreactions, while the tri(tetra)oxides undergo rapid thermal transformations. For the N=N/N=NO systems (12), of three potential pathways for its metathesis isomerization, the one that takes place via σ-symmetric intermediates (63, 64) is excluded by virtue of the retention of optical purity in the photometathesis of a highly enriched enantiomer [(-)-12]. Matrix irradiation experiments (12 K, IR control) with 12 result in the appearance of a kinetically highly labile transient. Supported by DFT calculations it is concluded that in the metathesis reactions, the respective tetrazetidine oxides (increasingly destabilized by interactions between oxygen lone pairs and NNσ* orbitals) function as vibrationally excited transients. That thermal reversion of these transients might be a general, nonproductive competition, is suggested by the experimental verification of a “reversed photometathesis” (51 → 15) and by the generally low rates in product formation upon irradiation. The question remains to be answered why in structurally analogous molecular skeletons, [2+2]photocycloaddition occurs in the C=C/N=N and variously oxidized N=N/N=N, and not, however, in the parent N=N/N=N combinations.
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  • 93
    ISSN: 1434-193X
    Keywords: Amphiphiles ; Ketone ; Glycosides ; Electron transfer ; Chiral resolution ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Electroreducible amphiphilic aromatic ketones derived from D-glucose and D-glucofuranurono-6,3-lactone (D-glucurone) have been synthesized by Schmidt condensation and reaction of the unprotected lactone with the appropriate substrates, respectively. The macroscale electrolyses of the glucose derivatives, performed in an aprotic solvent (DMF), yield the pinacols possessing two glycosidic side chains. Under the same conditions of electrolysis with the D-glucurone derivative, the glyosidic carbon-oxygen bond is cleaved. The use of a redox mediator (couple anthracene-•/anthracene) has demonstrated that a glucosidic bond can be reduced by a homogeneous electron transfer. In the presence of a proton donor the expected D-glucuronic pinacol is obtained. The radical-radical coupling involves the formation of two chiral centers. The diastereo- and the enantioselectivity of the reaction have been studied by 1H- and 2H-NMR spectroscopy, respectively.
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  • 94
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    Liebigs Annalen 2000 (2000), S. 837-840 
    ISSN: 1434-193X
    Keywords: Chiral auxiliaries ; Analytical methods ; Through-space interactions ; Lactic acid ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The enantiomeric purity of a chiral compound is determined by NMR spectroscopic analysis of the diastereomers formed with a chiral derivatizing agent. Fluorinated O-aryllactic acids (FAC) 1 are efficient chiral reporters, whose spectacular remote anisotropic effects allow an easy identification and measurement of diastereomers. The remote effects are attributed to the particular design of FAC esters relative to other CDAs.
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  • 95
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 849-855 
    ISSN: 1434-193X
    Keywords: Marine alkaloids ; Heterocycles ; Natural products ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Ascididemine (9H-quino[4,3,2-de][1,10]phenanthrolin-9-one) (1) and an isomer (9H-quino[4,3,2-de][1,7]phenanthrolin-9-one) (4) have been synthesized starting from 1,4-dimethoxyacridone (7). The acridone was converted into 1,4-dimethoxy-9-ethynylacridine (11) by a triflate coupling. The ethynylacridine was converted in one-pot into 3H-6-methoxypyrido[2,3,4-kl]acridine (15) by reaction with sodium diformylamide; the mechanism of this key transformation is discussed. Conversion into 6H-4-bromopyrido[2,3,4-kl]acridin-6-one (19) and 6H-pyrido[2,3,4-kl]acridin-6-one (17), followed by reaction of each of these under high pressure conditions with acrolein N,N-dimethylhydrazone, gave ascididemine and its isomer, respectively.
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  • 96
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 861-866 
    ISSN: 1434-193X
    Keywords: DNA ; Dihydroxyacetone monophosphate ; Aldolase ; Carbon-13 ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A synthesis of [3′,4′-13C2]thymidine (1) is described in which [13C2]acetic acid (2) is converted into the nucleoside in twelve steps with 9% overall yield. D-2-Deoxyribose-5-phosphate aldolase (DERA, EC 4.1.2.4) and triosephosphate isomerase (TPI, EC 5.3.1.1) are used for the stereocontrolled formation of D-[3,4-13C2]-2-deoxyribose-5-phosphate (8) from [2,3-13C2]dihydroxyacetone monophosphate (DHAP, 7) and acetaldehyde in 80% yield. The route permits the introduction of isotopically enriched carbon atoms at any position or combination of positions in the furanose ring and the product can be coupled with any of the four naturally occurring base moieties.
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  • 97
    ISSN: 1434-193X
    Keywords: Benzothiazole carbene ; Palladium complex ; Homogeneous catalysis ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The first diiodo palladium complex with nucleophilic benzothiazole carbenes as ligands has been synthesized and characterized. The complex, which is extraordinarily stable towards heat, oxygen, and moisture, has been found to show good catalytic activity in the Heck coupling reaction.
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  • 98
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Addition reactions ; Sulfones ; Alkylations ; Amines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The aza-Michael addition of enantiopure 1-aminopyrrolidines to (E)-alkenyl sulfones in the presence of a catalytic amount of ytterbium trifluoromethanesulfonate [Yb(OTf)3] yields β-hydrazino sulfones in moderate to good yields and with diastereoselectivities of up to ≥ 98%. The latter undergo reductive N-N bond cleavage with BH3 · THF and, after N-protection with Boc2O or benzyl bromide, afford N-protected β-amino sulfones with moderate to high enantiomeric excesses (ee = 42 to ≥96%) without racemization. Subsequent α-alkylation of the N,N-dibenzyl protected β-amino sulfones with various electrophiles yields α-alkyl-β-amino sulfones in excellent yields (88-97%) with high diastereomeric (de ≥96 to ≥98%) and enantiomeric purity (ee = 94 to ≥96%). The absolute configuration of the new stereogenic centre was determined by X-ray structural analysis and confirmed by NMR spectroscopy (NOE experiments). Possible reaction mechanisms for the conjugate addition and α-alkylation are presented.
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  • 99
    ISSN: 1434-193X
    Keywords: Dinitrothiophene ; Ring-opening ; Dinitrobutadienes ; Pyrrolidines ; Pyrroles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reactions between 1,4-diaryl-2,3-dinitro-1,3-butadienes 1a-d and primary alkylamines gave high yields of N-alkyl-2,5-diaryl-3-alkylamino-4-nitropyrrolidines 2 as pure all-trans diastereomers via an unusually favoured 5-endo-trig ring closure. The stereochemistry of compounds 2 has been attributed through an X-ray crystal structure analysis of the acetyl derivative 5 of 2ai. Amine elimination from 2 gave the N-alkyl-2,5-diaryl-3-nitro-3-pyrrolines 3 which could be easily aromatized to the corresponding pyrroles 4.
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  • 100
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    Liebigs Annalen 2000 (2000), S. 921-928 
    ISSN: 1434-193X
    Keywords: Gas-phase chemistry ; Phenoxy radicals ; Dioxins ; Phenoxyphenols ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Phenols are demonstrated precursors of “dioxins” - polychlorinated dibenzo-p-dioxins (DDs) and dibenzofurans (DFs) - in thermal processes, especially incineration. Heterogeneous catalysis, depending on conditions, can play an important role, but mere gas-phase combination of phenolic entities to ultimately DD and/or DF is always possible. The present paper addresses the fundamental role of phenol itself. Phenol has long been known to give DF upon pyrolysis and in similar thermal reactions. In the liquid phase under oxidative conditions it yields five condensation products (A-E); this clearly occurs through the dimerization of two phenoxy (PhO) radicals, followed by enolisation/rearomatisation. Our study shows that in the gas phase, at the lower T end, such dimers are also formed, but still with very little DF. That DF, indeed, is almost the only condensation product at elevated temperatures is substantiated by thermochemical-kinetic analysis (favouring the pathway of ortho-C/ortho-C combination of two PhO radicals), as well as by results obtained with two plausible intermediates, viz. 2,2′-dihydroxybiphenyl (A) and 2-phenoxyphenol (C). Mechanisms for the requisite enolisation and dehydration steps leading to DF are discussed.
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