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  • Inorganic Chemistry  (3.415)
  • 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
  • Carbon cycle
  • Numerical modeling
  • Wiley-Blackwell  (3.423)
  • American Geophysical Union  (35)
  • Birkhauser  (1)
  • American Institute of Physics (AIP)
  • 2010-2014  (44)
  • 1985-1989  (3.415)
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  • 1
    Publikationsdatum: 2017-04-04
    Beschreibung: From December 2005 to January 2006, an anomalous degassing episode was observed at Mount Etna, well-correlated with an increase in volcanic tremor, and in the almost complete absence of eruptive activity. In the same period, more than 10,000 very long period (VLP) events were detected. Through moment tensor inversion analyses of the VLP pulses, we obtained quantitative estimates of the volumetric variations associated with these events. This allowed a quantitative investigation of the relationship between VLP seismic activity, volcanic tremor, and gas emission rate at Mount Etna. We found a statistically significant positive correlation between SO2 gas flux and volcanic tremor, suggesting that tremor amplitude can be used as a first-order proxy for the background degassing activity of the volcano. VLP volumetric changes and SO2 gas flux are correlated only for the last part of our observations, following a slight change in the VLP source depth. We calculate that the gas associated with VLP signal genesis contributed less than 5% of the total gas emission. The existence of a linear correlation between VLP and degassing activities indicates a general relationship between these two processes. The effectiveness of such coupling appears to depend upon the particular location of the VLP source, suggesting that conduit geometry might play a significant role in the VLP-generating process. These results are the first report on Mount Etna of a quantitative relationship between the amounts of gas emissions directly estimated through instrumental flux measurements and the quantities of gas mass inferred in the VLP source inversion.
    Beschreibung: Published
    Beschreibung: 4910-4921
    Beschreibung: 2V. Dinamiche di unrest e scenari pre-eruttivi
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Very Long Period seismicity ; UV scanners network ; Etna Volcano ; volcano monitoring ; 04. Solid Earth::04.02. Exploration geophysics::04.02.06. Seismic methods ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 2
    Publikationsdatum: 2021-11-25
    Beschreibung: Here we inverted the GPS data to infer the coseismic slip of the Tohoku-Oki earthquake and the time-dependent afterslip distribution in the 4 months following the main shock. The Tohoku-Oki earthquake showed an unexpected magnitude and a characteristic depth-dependent differentiation of seismic energy radiation. In this context the estimation and comparison of the distribution of the fault portions that slip coseismically and post-seismically contribute to a better understanding of the variation of frictional characteristics of the plate interface. The inferred coseismic slip extends in a relatively compact region located updip from the hypocentre and reaches its highest value (about 60 m) near the trench. Afterslip occurs mostly outside the coseismic rupture and is distributed in two main modal centres. It reaches its largest values in an area located downdip of the coseismic slip and extends to a depth of 80 km. In the depth range between 30 and 50 km afterslip overlaps the portion of the fault that experienced historical moderate earthquakes, high-frequency seismic radiation and thrust-type aftershocks. The behaviour of this area can be explained by a rheologically heterogeneous region made of a ductile fault matrix interspersed with compact brittle asperities. On the contrary, the region beneath 50–60 km depth is probably characterized by a fully velocity strengthening behaviour. Southern afterslip, located off-Chiba Prefecture, is probably related to the Mw 7.9 Ibaraki-Oki aftershock. The northward extension of the afterslip stops at a latitude of about 40◦ N, just south of the off-Aomori region. This may be related to three large events occurred in this area during the last century and the consequent strong coupling or complete depletion of the accumulated strain that characterize this region.
    Beschreibung: Published
    Beschreibung: 580-596
    Beschreibung: 2T. Tettonica attiva
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Satellite geodesy; Seismic cycle; Earthquake source observations; Subduction zone processes ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.04. Plate boundaries, motion, and tectonics ; 04. Solid Earth::04.07. Tectonophysics::04.07.06. Subduction related processes
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 3
    Publikationsdatum: 2017-04-04
    Beschreibung: We used the SBAS DInSAR analysis technique to estimate the interseismic deformation along the western part of the Doruneh fault system (DFS), northeastern Iran. We processed 90 ENVISAT images from four different frames from ascending and descending orbits. Three of the ground velocity maps show a significant interseismic signal. Using a simple dislocation approach we model 2-D velocity profiles concerning three InSAR data set relative to the western part of the DFS, obtaining a good fit to the observations. The resulting model indicates that a slip rate of ∼5mmyr−1 accumulates on the fault below 10 km depth, and that in its western sector the Doruneh fault is not purely strike-slip (left-lateral) as in its central part, but shows a significant thrust component. Based on published geological observations, and assuming that all interseismic deformation is recovered with a single event, we can estimate a characteristic recurrence interval between 630 and 1400 yr.
    Beschreibung: Published
    Beschreibung: 622-628
    Beschreibung: 1.10. TTC - Telerilevamento
    Beschreibung: 3.2. Tettonica attiva
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Image processing; Satellite geodesy; Seismic cycle; Radar interferometry; Seismicity and tectonics; Continental tectonics: strike-slip and transform. ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.03. Geodesy::04.03.06. Measurements and monitoring ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 4
    Publikationsdatum: 2017-04-04
    Beschreibung: The peculiar source characteristics of long-period seismic events (time persistency of the source, low-frequency peaks in the source spectrum, absence of high-frequency radiation) prevent the formation of a definite high-frequency coda in the seismograms. In contrast, this is well formed in volcano–tectonic quakes. For this reason, the widely used duration magnitude scale that is based on the proportionality between the energy and the coda duration cannot be used for long-period estimation. In observatory practice, the long-period magnitude is sometimes estimated using the same duration magnitude scale, leading to confusing results. In this report, we show a new method to estimate the magnitude of long-period events that generally occur for volcanoes, with some application examples from data for Mt Etna (Italy), Colima Volcano (Mexico) and Campi Flegrei (Italy).
    Beschreibung: Published
    Beschreibung: 911-919
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Earthquake source observations; ; Volcano monitoring ; Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 5
    Publikationsdatum: 2017-04-04
    Beschreibung: For decades, many authors have attempted to define the location, geometry and kinematics of the causative fault for the 1908 December 28, M 7.1 earthquake that struck the Messina Straits between Sicily and Calabria (southern Italy). The coseismic displacement caused a predominant downwarping of the Straits and small land uplift away from it, which were documented by levelling surveys performed 1 yr before and immediately after the earthquake. Most of the source models based on inversion of levelling data suggested that the earthquake was caused by a low angle, east-dipping blind normal fault, whose upper projection intersects the Earth surface on the Sicilian (west) side of the Messina Straits.An alternative interpretation holds that the causative fault is one of the high-angle, west-dipping faults located in southern Calabria, on the eastern side of the Straits, and may in large part coincide with the mapped Armo Fault. Here, we critically review the levelling data with the aim of defining both their usefulness and limits in modelling the seismogenic fault. We demonstrate that the levelling data alone are not capable of discriminating between the two oppositely dipping fault models, and thus their role as a keystone for modellers is untenable. However, new morphotectonic and geodetic data indicate that the Armo Fault has very recent activity and is accumulating strain. The surface observations, together with appraisal ofmacroseismic intensity distribution, available seismic tomography and marine geophysical evidence, lends credit to the hypothesis that the Armo and possibly the S. Eufemia faults are part of a major crustal structure that slipped during the 1908 earthquake.
    Beschreibung: Published
    Beschreibung: 1025-1041
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Earthquake source ; Messina Straits ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics ; 05. General::05.01. Computational geophysics::05.01.03. Inverse methods ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 6
    Publikationsdatum: 2022-05-24
    Beschreibung: The broad availability of geodetic measurements for the Mw 6.3 April 6th 2009 L’Aquila earthquake allowed an unprecedented description of the co- and post-seismic ground deformations, leading to the definition of the Paganica fault geometry and kinematics. Through DInSAR, we found, in a wide area of 20 kilometres on the Paganica hangingwall, a further displacement up to 7 cm, which might have occurred in the earthquake proximity. In this study, we explore the possibility of the co-, post- and pre-seismic alternative scenarios. Although our data are not sufficient to undoubtedly prove that this signal occurred before the main event, this seems to be the most likely hypothesis based on tectonics constraints and image acquisition times. The nature of this deformation remains unclear, but we speculate that deep fluids played a role. These results can drive ad hoc requirements for future space-based missions and design of the GPS network.
    Beschreibung: Published
    Beschreibung: 343–351
    Beschreibung: 1.10. TTC - Telerilevamento
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): InSAR ; L'Aquila earthquake ; GPS ; Anomalous signature ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 7
    facet.materialart.
    Unbekannt
    American Geophysical Union
    Publikationsdatum: 2017-04-03
    Beschreibung: The weakening mechanisms occurring during an earthquake failure are of prominent importance in determining the resulting energy release and the seismic waves excitation. In this paper we consider the fully dynamic response of a seismogenic structure where lubrication processes take place. In particular, we numerically model the spontaneous propagation of a 3-D rupture in a fault zone where the frictional resistance is controlled by the properties of a low viscosity slurry, formed by gouge particles and fluids. This model allows for the description of the fault motion in the extreme case of vanishing effective normal stress, by considering a viscous fault response and therefore without the need to invoke, in the framework of Coulomb friction, the generation of the tensile mode of fracture. We explore the effects of the parameters controlling the resulting governing law for such a lubricated fault; the viscosity of the slurry, the roughness of the fault surfaces and the thickness of the slurry film. Our results indicate that lubricated faults produce a nearly complete stress drop (i.e., a very low residual friction coefficient; mu ~ 0.01), a high fracture energy density (E_G ~ few 10s of MJ/m^2) and significant slip velocities (vpeak ~ few 10s of m/s). The resulting values of the equivalent characteristic slip-weakening distance (d_0_eq = 0.1–0.8 m, depending on the adopted parameters) are compatible with the seismological inferences. Moreover, in the framework of our model we found that supershear ruptures are highly favored. In the case of enlarging gap height we can have the healing of slip or even the inhibition of the rupture. Quantitative comparisons with different weakening mechanisms previously proposed in the literature, such as the exponential weakening and the frictional melting, are also discussed.
    Beschreibung: Published
    Beschreibung: B05304
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): governing models ; theoretical seismology ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 8
    Publikationsdatum: 2020-03-16
    Beschreibung: Post-seismic relaxation is known to occur after large or moderate earthquakes, on time scales ranging from days to years or even decades. In general, long-term deformation following seismic events has been detected by means of standard geodetic measurements, although seismic instruments are only used to estimate short timescale transient processes. Albeit inertial seismic sensors are also sensitive to rotation around their sensitive axes, the recording of very slow inclination of the ground surface at their standard output channels is practically impossible, because of their design characteristics. However, modern force-balance, broad- band seismometers provide the possibility to detect and measure slow surface inclination, through the analysis of the mass position signal. This output channel represents the integral of the broad-band velocity and is generally considered only for state-of-health diagnostics. In fact, the analysis of mass position data recorded at the time of the 2009 April 6, L’Aquila (MW = 6.3) earthquake, by a closely located STS-2 seismometer, evidenced the occurrence of a very low frequency signal, starting right at the time of the seismic event. This waveform is only visible on the horizontal components and is not related to the usual drift coupled with the temperature changes. This analysis suggests that the observed signal is to be ascribed to slowly developing ground inclination at the station site, caused by post-seismic relaxation following the main shock. The observed tilt reached 1.7 × 10−5 rad in about 2 months. This estimate is in very good agreement with the geodetic observations, giving comparable tilt magnitude and direction at the same site. This study represents the first seismic analysis ever for the mass position signal, suggesting useful applications for usually neglected data.
    Beschreibung: Published
    Beschreibung: 1717-1724
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Seismic cycle ; Earthquake source observations ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 9
    Publikationsdatum: 2017-04-04
    Beschreibung: One hundred twenty-nine long-period (LP) events, divided into two families of similar events, were recorded by the 50 stations deployed on Mount Etna in the second half of June 2008. During this period lava was flowing from a lateral fracture after a summit Strombolian eruption. In order to understand the mechanisms of these events, we perform moment tensor inversions. Inversions are initially kept unconstrained to estimate the most likely mechanism. Numerical tests show that unconstrained inversion leads to reliable moment tensor solutions because of the close proximity of numerous stations to the source positions. However, single forces cannot be accurately determined as they are very sensitive to uncertainties in the velocity model. Constrained inversions for a crack, a pipe or an explosion then allow us to accurately determine the structural orientations of the source mechanisms. Both numerical tests and LP event inversions emphasise the importance of using stations located as close as possible to the source. Inversions for both families show mechanisms with a strong volumetric component. These events are most likely generated by cracks striking SW–NE for both families and dipping 70° SE (family 1) and 50° NW (family 2). For family 1 events, the crack geometry is nearly orthogonal to the dikelike structure along which events are located, while for family 2 the location gave two pipelike bodies that belong to the same plane as the crack mechanism. The orientations of the cracks are consistent with local tectonics, which shows a SW–NE weakness direction. The LP events appear to be a response to the lava fountain occurring on 10 May 2008 as opposed to the flank lava flow.
    Beschreibung: Published
    Beschreibung: B01304
    Beschreibung: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): Etna Volcano ; long-period events ; source mechanism ; location ; plumbing systems ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 10
    Publikationsdatum: 2017-04-04
    Beschreibung: Near-fault strong-ground motions (0.1–10 Hz) recorded during the Mw 6.3 2009 L’Aquila earthquake exhibit great spatial variability. Modeling the observed seismograms allows linking distinct features of the observed wavefield to particular source and propagation effects and provides insights on strong motion complexity from this moderate magnitude event. We utilize a hybrid integral-composite approach based on a k-square kinematic rupture model, combining low-frequency coherent and high-frequency incoherent source radiation and providing omega-squared source spectral decay. Several source model features, proven to be stable by means of an uncertainty analysis in the preceding low-frequency (〈0.2 Hz) multiple finite-extent source inversion (Paper 1), were constrained. Synthetic Green’s functions are calculated in a 1D-layered crustal model including 1D soil profiles to account for site-specific response (where available). The results show that although the local site effects improve the modeling, the spatial broadband ground-motion variability is to large extent controlled by the rupture kinematics. The modeling thus confirms and further constraints the source model features, including the position and slip amount of the two main asperities, the largest asperity time delay and the rupture velocity distribution on the fault. Furthermore, we demonstrate that the crossover frequency dividing the coherent and incoherent wavefield, often considered independent on the station position, has to be variable in order to adequately reproduce both near and far station recordings. This suggests that the incoherency of the radiated wavefield is controlled by the wave-propagation phenomena and/or the initial updip rupture propagation was very smooth (coherent) up to relatively high frequencies (〉2 Hz)
    Beschreibung: Published
    Beschreibung: B0438
    Beschreibung: 4.1. Metodologie sismologiche per l'ingegneria sismica
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): broad band modeling, source complexity, aquila earthquake ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 11
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 116 (2011): C12020, doi:10.1029/2011JC006998.
    Beschreibung: A three dimensional model of Arctic Ocean circulation and mixing, with a horizontal resolution of 18 km, is overlain by a biogeochemical model resolving the physical, chemical and biological transport and transformations of phosphorus, alkalinity, oxygen and carbon, including the air-sea exchange of dissolved gases and the riverine delivery of dissolved organic carbon. The model qualitatively captures the observed regional and seasonal trends in surface ocean PO4, dissolved inorganic carbon, total alkalinity, and pCO2. Integrated annually, over the basin, the model suggests a net annual uptake of 59 Tg C a−1, within the range of published estimates based on the extrapolation of local observations (20–199 Tg C a−1). This flux is attributable to the cooling (increasing solubility) of waters moving into the basin, mainly from the subpolar North Atlantic. The air-sea flux is regulated seasonally and regionally by sea-ice cover, which modulates both air-sea gas transfer and the photosynthetic production of organic matter, and by the delivery of riverine dissolved organic carbon (RDOC), which drive the regional contrasts in pCO2 between Eurasian and North American coastal waters. Integrated over the basin, the delivery and remineralization of RDOC reduces the net oceanic CO2 uptake by ~10%.
    Beschreibung: This study has been carried out as part of ECCO2 and SASS (Synthesis of the Arctic System Science) projects funded by NASA and NSF, respectively. MM and MJF are grateful for support from the National Science Foundation (ARC-0531119 and ARC-0806229) for financial support. MM also acknowledges NASA for providing computer time, the use of the computing facilities at NAS center and also the Scripps post-doctoral program for further financial support that helped to complete the manuscript. RMK also acknowledges NOAA for support (NA08OAR4310820 and NA08OAR4320752).
    Beschreibung: 2012-06-15
    Schlagwort(e): Air-sea gas exchange ; Biogeochemical cycles ; Land-ocean coupling ; Numerical modeling ; Ocean carbon cycle ; Polar oceans
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
    Format: application/pdf
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  • 12
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 27 (2012): PA3225, doi:10.1029/2011PA002273.
    Beschreibung: The midpoint of the Last Termination occurred 4,000 years earlier in the deep Atlantic than the deep Pacific according to a pair of benthic foraminiferal δ18O records, seemingly implying an internal circulation shift because the lag is much longer than the deep radiocarbon age. Here a scenario where the lag is instead caused by regional surface boundary condition changes, delays due to oceanic transit timescales, and the interplay between temperature and seawater δ18O (δ18Ow) is quantified with a tracer transport model of the modern-day ocean circulation. Using an inverse method with individual Green functions for 2,806 surface sources, a time history of surface temperature and δ18Ow is reconstructed for the last 30,000 years that is consistent with the foraminiferal oxygen-isotope data, Mg/Ca-derived deep temperature, and glacial pore water records. Thus, in the case that the ocean circulation was relatively unchanged between glacial and modern times, the interbasin lag could be explained by the relatively late local glacial maximum around Antarctica where surface δ18Ow continues to rise even after the North Atlantic δ18Ow falls. The arrival of the signal of the Termination is delayed at the Pacific core site due to the destructive interference of the still-rising Antarctic signal and the falling North Atlantic signal. This scenario is only possible because the ocean is not a single conveyor belt where all waters at the Pacific core site previously passed the Atlantic core site, but instead the Pacific core site is bathed more prominently by waters with a direct Antarctic source.
    Beschreibung: G.G. is supported by NSF grant OIA-1124880 and the WHOI Arctic Research Initiative.
    Beschreibung: 2013-03-06
    Schlagwort(e): Deglaciation ; Foraminiferal data ; Inverse methods ; Numerical modeling ; Oxygen-18 ; Tracers
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
    Format: application/pdf
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  • 13
    facet.materialart.
    Unbekannt
    American Geophysical Union
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 39 (2012): L19703, doi:10.1029/2012GL052883.
    Beschreibung: Carbon cycling studies focusing on transport and transformation of terrigenous carbon sources toward marine sedimentary sinks necessitate separation of particulate organic carbon (OC) derived from many different sources and integrated by river systems. Much progress has been made on isolating and characterizing young biologically-formed OC that is still chemically intact, however quantification and characterization of old, refractory rock-bound OC has remained troublesome. Quantification of both endmembers of riverine OC is important to constrain exchanges linking biologic and geologic carbon cycles and regulating atmospheric CO2 and O2. Here, we constrain petrogenic OC proportions in suspended sediment from the headwaters of the Ganges River in Nepal through direct measurement using ramped pyrolysis radiocarbon analysis. The unique results apportion the biospheric and petrogenic fractions of bulk particulate OC and characterize biospheric OC residence time. Compared to the same treatment of POC from the lower Mississippi-Atchafalaya River system, contrast in age spectra of the Ganges tributary samples illustrates the difference between small mountainous river systems and large integrative ones in terms of the global carbon cycle.
    Beschreibung: This work was partially supported by U.S. National Science Foundation (NSF) Cooperative Agreement OCE-228996 to NOSAMS and NSF grants OCE-0851015 & OCE-0928582 to VG.
    Beschreibung: 2013-04-03
    Schlagwort(e): Ganges ; Himalaya ; Mississippi ; POC ; Carbon cycle ; Radiocarbon
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
    Format: application/pdf
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  • 14
    Publikationsdatum: 2024-05-09
    Beschreibung: In this paper, we propose a new model of the crustal structure and seismotectonics for central Sicily (southern Italy) through the analysis of the depth distribution and kinematics of the instrumental seismicity, occurring during the period from 1983 to 2010, and its comparison with individual geological structures that may be active in the area. The analysed data set consists of 392 earthquakes with local magnitudes ranging from 1.0 to 4.7. We defined a new, detailed 1-D velocity model to relocate the earthquakes that occurred in central Sicily, and we calculated a Moho depth of 37 km and a mean VP/VS ratio of 1.73. The relocated seismic events are clustered mainly in the area north of Caltanissetta (e.g. Mainland Sicily) and in the northeastern sector (Madonie Mountains) of the study area; only minor and greatly dispersed seismicity is located in the western sector, near Belice, and along the southern coast, between Gela and Sciacca. The relocated hypocentral distribution depicts a bimodal pattern: 50 per cent of the events occur within the upper crust at depths less than ~16 km, 40 per cent of the events occur within the middle and depth crust, at depths between 16 and 32 km, and the remaining 10 per cent occur at subcrustal depths. The energy release pattern shows a similar depth distribution. On the basis of the kinematic analysis of 38 newly computed focal plane solutions, two major geographically distinct seismotectonic domains are distinguished: the Madonie Mountain domain, with prevalent extensional and extensional-oblique kinematics associated with upper crust Late Pliocene–Quaternary faulting, and the Mainland Sicily domain, with prevalent compressional and compressional-oblique kinematics associated with thrust faulting, at mid to deep crust depth, along the north-dipping Sicilian Basal Thrust (SBT). The stress inversion of the Mainland Sicily focal solutions integrated with neighbouring mechanisms available in the literature highlights a regional homogeneous compressional tensor, with a subhorizontal NNW–SSE-striking σ1 axis. In addition, on the basis of geodetic data, the Mainland Sicily domain may be attributed to the SSE-ward thrusting of the Mainland Sicily block along the SBT plane. Seismogenic shearing along the SBT at mid-crustal depths was responsible for the unexpected Belice 1968 earthquake (Mw 6.1), with evident implications in terms of hazard assessment.
    Beschreibung: Published
    Beschreibung: 1237-2252
    Beschreibung: 1.1. TTC - Monitoraggio sismico del territorio nazionale
    Beschreibung: 3.2. Tettonica attiva
    Beschreibung: 3.3. Geodinamica e struttura dell'interno della Terra
    Beschreibung: 5.2. TTC - Banche dati di sismologia strumentale
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Seismicity and tectonics ; Continental tectonics: compressional ; Dynamics: seismotectonics ; Crustal structure ; Europe ; 04. Solid Earth::04.06. Seismology::04.06.99. General or miscellaneous ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.04. Plate boundaries, motion, and tectonics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 15
    Publikationsdatum: 2017-04-04
    Beschreibung: Intermediate-focus seismicity (50〈H〈100km) related to the underplating zone of the South Shetland plate have been recorded at a small aperture seismic array set up in Deception Island, Antarctica.
    Beschreibung: Published
    Beschreibung: 531-534
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): Deep earthquakes ; Antarctica ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 16
    Publikationsdatum: 2017-04-04
    Beschreibung: The 2009 April 6, Mw= 6.3 L’Aquila earthquake occurred within a complex system of NW–SE trending normal faults in the Abruzzi Central Apennines (Italy). We analyse the coseismic deformation as measured by 〉70 global positioning system (GPS) stations, both from continuous and survey-mode networks, providing unprecedented details for a moderate normal faulting earthquake in Italy from GPS measurements. We use rectangular, uniform-slip, dislocations embedded in an elastic, homogeneous and isotropic half-space and a constrained, non-linear optimization algorithm, to solve for the best-fitting rectangular dislocation geometry and coseismic-slip distribution. We use a bootstrap approach to investigate uncertainties in the model parameters and define confidence bounds for all the inverted parameters. The rupture occurred on a N129°E striking and 50° southwestward dipping normal fault, in agreement with geological observations of surface breaks along the Paganica fault. Our distributed slip model exhibits a zone of relatively higher slip (〉60 cm) between ∼1.5 and ∼11 km depth, along a roughly downdip, NW–SE elongated patch, confined within the fault plane inverted assuming uniform-slip. The highest slip, of the order of ∼1 m, occurred on a ∼16 km2 area located at ∼5 km depth, SE of the mainshock epicentre. The analysis of model resolution suggests that slip at depth below ∼5 km can be resolved only at a spatial scale larger than 2 km, so a finer discretization of different asperities within the main patch of coseismic-slip is not allowed by GPS data. We compute the coseismic Coulomb stress changes in the crustal volume affected by the major aftershocks, and compare the results obtained from the uniform-slip and the heterogeneous-slip models. We find that most of the large aftershocks occurred in areas of Coulomb stress increase of 0.2–13 bar and that a deepening of the slip distribution down to a depth greater than 6 km in the SE part of the fault plane, in agreement with the inverted slip model, can explain the deepest, April 7, Mw 5.3 aftershock.
    Beschreibung: Published
    Beschreibung: 473-489
    Beschreibung: 1.9. Rete GPS nazionale
    Beschreibung: 3.2. Tettonica attiva
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): Satellite geodesy ; Space geodetic surveys ; Earthquake ground motions ; Earthquake source observations ; Earthquake interaction, forecasting, and prediction ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution ; 04. Solid Earth::04.06. Seismology::04.06.02. Earthquake interactions and probability ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 17
    Publikationsdatum: 2017-04-04
    Beschreibung: 129 Long Period (LP) events, divided in two families were recorded by 50 stations deployed on Mount Etna within an eruptive context in the second half of June 2008. In order to understand the mechanisms of these events, we perform moment tensor inversion. Numerical tests show that unconstrained inversion leads to reliable moment tensor solutions because of the close proximity of numerous stations to the source positions. However, single forces cannot be accurately determined as they are very sensitive to uncertainities in the velocity model. These tests emphasize the importance of using stations located as close as possible to the source in the inversion of LP events. Inversion of LP signals is initially unconstrained, in order to estimate the most likely mechanism. Constrained inversions then allow us to accurately determine the structural orientations of the mechanisms. Inversions for both families show mechanisms with strong volumetric components. These events are generated by cracks striking SW-NE for both families and dipping 70± SE (fam. 1) and 50± NW (fam. 2). The geometries of the cracks are different from the structures obtained by the location of these events. The orientation of the cracks is consistent with the local tectonic context on Mount Etna. The LP events seem to be a response to the lava fountain occuring on the 10th of May, 2008.
    Beschreibung: In press
    Beschreibung: (38)
    Beschreibung: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): Long-Period events ; earthquake source mechanism ; Etna Volcano ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 18
    Publikationsdatum: 2017-04-04
    Beschreibung: We (re)analyzed the source of the 26 December 2004 Sumatra-Andaman earthquake and tsunami through a nonlinear joint inversion of an inhomogeneous data set made up of tide gauges, satellite altimetry, and far-field GPS recordings. The purpose is twofold: (1) the retrieval of the main kinematics rupture parameters (slip, rake, and rupture velocity) and (2) the inference of the rigidity of the source zone. We independently estimate the slip from tsunami data and the seismic moment from geodetic data to derive the rigidity. Our results confirm that the source of the 2004 Sumatra-Andaman earthquake has a complex geometry, constituted by three main slip patches, with slip peaking at ~30 m in the southern part of the source. The rake direction rotates counterclockwise at the northern part of the source, according to the direction of convergence along the trench. The rupture velocity is higher in the deeper than in the shallower part of the source, consistent with the expected increase of rigidity with depth. It is also lower in the northern part, consistent with known variations of the incoming plate properties and shear velocity. Our model features a rigidity (20–30 GPa) that is lower than the preliminary reference Earth model (PREM) average for the seismogenic volume. The source rigidity is one of the factors controlling the tsunami genesis: for a given seismic moment, the lower the rigidity, the higher the induced seafloor displacement. The general consistence between our source model and previous studies supports the effectiveness of our approach to the joint inversion of geodetic and tsunami data for the rigidity estimation.
    Beschreibung: Published
    Beschreibung: B02304
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): Source process ; Sumatra ; Tsunami ; Joint Inversion ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 19
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 38 (2011): L09804, doi:10.1029/2011GL047238.
    Beschreibung: Atmospheric mixing ratios of CO2 are strongly seasonal in the Arctic due to mid-latitude transport. Here we analyze the seasonal influence of moist synoptic storms by diagnosing CO2 transport from a global model on moist isentropes (to represent parcel trajectories through stormtracks) and parsing transport into eddy and mean components. During winter when northern plants respire, warm moist air, high in CO2, is swept poleward into the polar vortex, while cold dry air, low in CO2, that had been transported into the polar vortex earlier in the year is swept equatorward. Eddies reduce seasonality in mid-latitudes by ∼50% of NEE (∼100% of fossil fuel) while amplifying seasonality at high latitudes. Transport along stormtracks is correlated with rising, moist, cloudy air, which systematically hides this CO2 transport from satellites. We recommend that (1) regional inversions carefully account for meridional transport and (2) inversion models represent moist and frontal processes with high fidelity.
    Beschreibung: This research is supported by the National Aeronautics and Space Administration contracts NNX08AT77G, NNX06AC75G, and NNX08AM56G.
    Schlagwort(e): Atmospheric transport ; Carbon cycle ; Inversion ; Isentropic coordinates ; Synoptic weather ; Tracer modeling
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 20
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 25 (2011): GB3018, doi:10.1029/2010GB003813.
    Beschreibung: Studies indicate that, historically, terrestrial ecosystems of the northern high-latitude region may have been responsible for up to 60% of the global net land-based sink for atmospheric CO2. However, these regions have recently experienced remarkable modification of the major driving forces of the carbon cycle, including surface air temperature warming that is significantly greater than the global average and associated increases in the frequency and severity of disturbances. Whether Arctic tundra and boreal forest ecosystems will continue to sequester atmospheric CO2 in the face of these dramatic changes is unknown. Here we show the results of model simulations that estimate a 41 Tg C yr−1 sink in the boreal land regions from 1997 to 2006, which represents a 73% reduction in the strength of the sink estimated for previous decades in the late 20th century. Our results suggest that CO2 uptake by the region in previous decades may not be as strong as previously estimated. The recent decline in sink strength is the combined result of (1) weakening sinks due to warming-induced increases in soil organic matter decomposition and (2) strengthening sources from pyrogenic CO2 emissions as a result of the substantial area of boreal forest burned in wildfires across the region in recent years. Such changes create positive feedbacks to the climate system that accelerate global warming, putting further pressure on emission reductions to achieve atmospheric stabilization targets.
    Beschreibung: This study was supported through grants provided as part of the Arctic System Science Program (NSF OPP‐ 0531047), the North American Carbon Program (NASA NNG05GD25G), and the Bonanza Creek Long‐Term Ecological Program (funded jointly by NSF grant DEB‐0423442 and USDA Forest Service, Pacific Northwest Research Station grant PNW01‐JV11261952‐231).
    Schlagwort(e): Carbon cycle ; High-latitude ecosystems ; Modeling
    Repository-Name: Woods Hole Open Access Server
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  • 21
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 25 (2011): GB3022, doi:10.1029/2010GB003892.
    Beschreibung: The North Atlantic Ocean accounts for about 25% of the global oceanic anthropogenic carbon sink. This basin experiences significant interannual variability primarily driven by the North Atlantic Oscillation (NAO). A suite of biogeochemical model simulations is used to analyze the impact of interannual variability on the uptake and storage of contemporary and anthropogenic carbon (Canthro) in the North Atlantic Ocean. Greater winter mixing during positive NAO years results in increased mode water formation and subsequent increases in subtropical and subpolar Canthro inventories. Our analysis suggests that changes in mode water Canthro inventories are primarily due to changes in water mass volumes driven by variations in water mass transformation rates rather than local air-sea CO2 exchange. This suggests that a significant portion of anthropogenic carbon found in the ocean interior may be derived from surface waters advected into water formation regions rather than from local gas exchange. Therefore, changes in climate modes, such as the NAO, may alter the residence time of anthropogenic carbon in the ocean by altering the rate of water mass transformation. In addition, interannual variability in Canthro storage increases the difficulty of Canthro detection and attribution through hydrographic observations, which are limited by sparse sampling of subsurface waters in time and space.
    Beschreibung: We would like to acknowledge funding from the NOAA Climate Program under the Office of Climate Observations and Global Carbon Cycle Program (NOAA‐NA07OAR4310098), NSF (OCE‐0623034), NCAR, the WHOI Ocean Climate Institute, a National Defense Science and Engineering Graduate Fellowship and an Environmental Protection Agency STAR graduate fellowship. NCAR is sponsored by the National Science Foundation.
    Schlagwort(e): North Atlantic Oscillation ; Anthropogenic carbon ; Carbon cycle ; Climate change ; Global climate model ; Mode waters
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 22
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    American Geophysical Union
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 38 (2011): L13405, doi:10.1029/2011GL047630.
    Beschreibung: Wave-influenced deltas, with large-scale arcuate shapes and demarcated beach ridge complexes, often display an asymmetrical form about their river channel. Here, we use a numerical model to demonstrate that the angles from which waves approach a delta can have a first-order influence upon its plan-view morphologic evolution and sedimentary architecture. The directional spread of incoming waves plays a dominant role over fluvial sediment discharge in controlling the width of an active delta lobe, which in turn affects the characteristic rates of delta progradation. Oblique wave approach (and a consequent net alongshore sediment transport) can lead to the development of morphologic asymmetry about the river in a delta's plan-view form. This plan-form asymmetry can include the development of discrete breaks in shoreline orientation and the appearance of self-organized features arising from shoreline instability along the downdrift delta flank, such as spits and migrating shoreline sand waves—features observed on natural deltas. Somewhat surprisingly, waves approaching preferentially from one direction tend to increase sediment deposition updrift of the river. This ‘morphodynamic groin effect’ occurs when the delta's plan-form aspect ratio is sufficiently large such that the orientation of the shoreline on the downdrift flank is rotated past the angle of maximum alongshore sediment transport, resulting in preferential redirection of fluvial sediment updrift of the river mouth.
    Beschreibung: This research was supported by NSF grants EAR‐0952146 and OCE‐0623766, the Exxon‐Mobil Upstream Research Company, and the WHOI‐USGS postdoctoral fellowship.
    Schlagwort(e): Depositional asymmetry ; Large-scale coastal evolution ; Numerical modeling ; Plan-view delta evolution
    Repository-Name: Woods Hole Open Access Server
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  • 23
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 116 (2011): C11019, doi:10.1029/2010JC006509.
    Beschreibung: The advance and retreat of sea ice produces seasonal convection and stratification, dampens surface waves and creates a separation between the ocean and atmosphere. These are all phenomena that can affect the air-sea gas transfer velocity (k660), and therefore it is not straightforward to determine how sea ice cover modulates air-sea flux. In this study we use field estimates k660 to examine how sea ice affects the net gas flux between the ocean and atmosphere. An inventory of salinity, 3He, and CFC-11 in the mixed layer is used to infer k660 during the drift of Ice Station Weddell in 1992. The average of k660 is 0.11 m d−1 across nearly 100% ice cover. In comparison, the only prior field estimates of k660 are disproportionately larger, with average values of 2.4 m d−1 across 90% sea ice cover, and 3.2 m d−1 across approximately 70% sea ice cover. We use these values to formulate two scenarios for the modulation of k660 by the fraction of sea ice cover in a 1-D transport model for the Southern Ocean seasonal ice zone. Results show the net CO2 flux through sea ice cover represents 14–46% of the net annual air-sea flux, depending on the relationship between sea ice cover and k660. The model also indicates that as much as 68% of net annual CO2 flux in the sea ice zone occurs in the springtime marginal ice zone, which demonstrates the need for accurate parameterizations of gas flux and primary productivity under partially ice-covered conditions.
    Beschreibung: Support for this work was provided by the Climate Center at the Lamont‐Doherty Earth Observatory, an NSF IGERT Fellowship and a NOAA Climate and Global Change Postdoctoral Fellowship to BL, and NSF grant OPP 01‐25523/ANT 04‐40825 (PS).
    Beschreibung: 2012-05-15
    Schlagwort(e): CO2 ; Southern Ocean ; Carbon cycle ; Gas exchange ; Sea ice
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 24
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 116 (2011): C10036, doi:10.1029/2011JC007035.
    Beschreibung: Inner-shelf circulation is governed by the interaction between tides, baroclinic forcing, winds, waves, and frictional losses; the mean circulation ultimately governs exchange between the coast and ocean. In some cases, oscillatory tidal currents interact with bathymetric features to generate a tidally rectified flow. Recent observational and modeling efforts in an overlapping domain centered on the Martha's Vineyard Coastal Observatory (MVCO) provided an opportunity to investigate the spatial and temporal complexity of circulation on the inner shelf. ADCP and surface radar observations revealed a mean circulation pattern that was highly variable in the alongshore and cross-shore directions. Nested modeling incrementally improved representation of the mean circulation as grid resolution increased and indicated tidal rectification as the generation mechanism of a counter-clockwise gyre near the MVCO. The loss of model skill with decreasing resolution is attributed to insufficient representation of the bathymetric gradients (Δh/h), which is important for representing nonlinear interactions between currents and bathymetry. The modeled momentum balance was characterized by large spatial variability of the pressure gradient and horizontal advection terms over short distances, suggesting that observed inner-shelf momentum balances may be confounded. Given the available observational and modeling data, this work defines the spatially variable mean circulation and its formation mechanism—tidal rectification—and illustrates the importance of model resolution for resolving circulation and constituent exchange near the coast. The results of this study have implications for future observational and modeling studies near the MVCO and other inner-shelf locations with alongshore bathymetric variability.
    Beschreibung: Funding was provided through the Office of Naval Research Ripples DRI, U.S. Geological Survey Coastal and Marine Geology Program, and National Science Foundation.
    Schlagwort(e): Coastal and nearshore circulation ; Grid resolution ; Nesting ; Numerical modeling ; Tidal rectification
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  • 25
    Publikationsdatum: 2017-04-04
    Beschreibung: We (re)analyzed the source of the 26 December 2004 Sumatra-Andaman earthquake and tsunami through a nonlinear joint inversion of an in-homogeneous dataset made up of tide-gages, satellite altimetry, and far-field GPS recordings. The purpose is two-fold: (1) the retrieval of the main kinematics rupture parameters (slip, rake, rupture velocity); (2) the inference of the rigidity of the source zone. We independently estimate the slip from tsunami data and the seismic moment from geodetic data, so to derive the rigidity. Our results confirm that the source of the 2004 Sumatra-Andaman earthquake has a complex geometry, constituted by three main slip patches, with slip peaking at ~30 meters in the Southern part of the source. The rake direction rotates counter-clockwise at North, according to the direction of convergence along the trench. The rupture velocity is higher in the deeper than in the shallower part of the source, consistently with the expected increase of rigidity with depth. It is also lower in the Northern part, consistently with known variations of the incoming plate properties and shear velocity. Our model features a rigidity (20-30 GPa), that is lower than PREM average for the seismogenic volume [Dziewonski and Anderson, 1981]. The source rigidity is one of the factors controlling the tsunamigenesis: for a given seismic moment, the lower the rigidity, the higher the induced seafloor displacement. The general consistence between our source model and previous studies supports the effectiveness of our approach to the joint inversion of geodetic and tsunami data for the rigidity estimation.
    Beschreibung: In press
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): Source process ; Sumatra ; Tsunami ; joint inversion ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 26
    Publikationsdatum: 2017-04-04
    Beschreibung: In a recent work on the problem of sliding surfaces under the presence of frictional melt (applying in particular to earthquake fault dynamics), we derived from first principles an expression for the steady state friction compatible with experimental observations. Building on the expressions of heat and mass balance obtained in the above study for this particular case of Stefan problem (phase transition with a migrating boundary) we propose here an extension providing the full time-dependent solution (including the weakening transient after pervasive melting has started, the effect of eventual steps in velocity and the final decelerating phase). A system of coupled equations is derived and solved numerically. The resulting transient friction and wear evolution yield a satisfactory fit (1) with experiments performed under variable sliding velocities (0.9-2 m/s) and different normal stresses (0.5-20 MPa) for various rock types and (2) with estimates of slip weakening obtained from observations on ancient seismogenic faults that host pseudotachylite (solidified melt). The model allows to extrapolate the experimentally observed frictional behavior to large normal stresses representative of the seismogenic Earth crust (up to 200 MPa), high slip rates (up to 9 m/s) and cases where melt extrusion is negligible. Though weakening distance and peak stress vary widely, the net breakdown energy appears to be essentially independent of either slip velocity and normal stress. In addition, the response to earthquake-like slip can be simulated, showing a rapid friction recovery when slip rate drops. We discuss the properties of energy dissipation, transient duration, velocity weakening, restrengthening in the decelerating final slip phase and the implications for earthquake source dynamics.
    Beschreibung: S.N. and G.D.T. were supported by a European Research Council Starting Grant Project (acronym USEMS) and by a Progetti di Eccellenza Fondazione Cassa di Risparmio di Padova e Rovigo. We are grateful to Nick Beeler (and to an anonymous referee) for their constructive reviews and their help to improve the clarity of the manuscript.
    Beschreibung: Published
    Beschreibung: B10301
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): Friction ; Melt ; Earthquake dynamics ; fault mechanics ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 27
    Publikationsdatum: 2017-04-04
    Beschreibung: The amount of energy radiated from an earthquake can be measured using recent methods based on earthquake coda signals and spectral ratios. Such methods are not altered by either site or directivity effects, with the advantage of a greatly improved accuracy. Several studies of earthquake sequences based on the above measurements showed evidence of a breakdown in self-similarity in the moment to energy relation. Radiated energy can be also used as a gauge to estimate the average dynamic stress drop on the fault. Here we compute the dynamic stress drop, infer the co-seismic friction and estimate the co-seismic heating resulting from the frictional work during events from different main shock-aftershock earthquake sequences. We relate the dynamic friction to the maximum temperature rise estimated on the faults for each earthquake. Our results are strongly indicative that a thermally triggered dynamic frictional weakening is present, responsible for the breakdown in self-similarity. These observations from seismic data are compatible with recent laboratory evidence of thermal weakening in rock friction under seismic slip-rates, associated to various physical processes such as melting, decarbonation or dehydration.
    Beschreibung: Kevin Mayeda was supported under Weston Geophysical subcontract No. GC19762NGD and AFRL contract No. FA8718-06-C-0024. Work by L. Malagnini was performed under the auspices of the Dipartimento della Protezione Civile, under contract S3 – INGV-DPC (2007-2009), project: “Valutazione rapida dei parametri e degli effetti dei forti terremoti in Italia e nel Mediterraneo”.
    Beschreibung: Published
    Beschreibung: B06319
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): earthquake radiation ; coda ; friction ; self-similarity ; dynamic weakening ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 28
    Publikationsdatum: 2012-02-03
    Beschreibung: An edited version of this paper was published by AGU. Copyright (2010) American Geophysical Union.
    Beschreibung: An eleven‐month deployment of 25 ocean bottom seismometers provides an unprecedented opportunity to study low‐magnitude local earthquakes in the complex transpressive plate boundary setting of the Gulf of Cadiz, known for the 1755 Lisbon earthquake and tsunami. 36 relocated earthquakes (ML 2.2 to 4.8) concentrate at 40– 60 km depth, near the base of the seismogenic layer in ∼140 Ma old oceanic mantle lithosphere, and roughly align along two perpendicular, NNE‐SSW and WNWESE striking structures. First motion focal mechanisms indicate compressive stress for the cluster close to the northern Horseshoe fault termination which trends perpendicular to plate convergence. Focal mechanisms for the second cluster near the southern termination of the Horseshoe fault indicate a strike‐slip regime, providing evidence for present‐day activity of a dextral shear zone proposed to represent the Eurasia‐Africa plate contact. We hypothesize that regional tectonics is characterized by slip partitioning.
    Beschreibung: Published
    Beschreibung: L18309
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: 3.2. Tettonica attiva
    Beschreibung: 3.3. Geodinamica e struttura dell'interno della Terra
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): oceanic lithospheric mantle ; focal mechanisms ; stress tensor inversion ; Gulf of Cadiz ; ocean bottom seismometer ; 1755 Lisbon earthquake ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.10. Instruments and techniques ; 04. Solid Earth::04.07. Tectonophysics::04.07.04. Plate boundaries, motion, and tectonics ; 04. Solid Earth::04.07. Tectonophysics::04.07.05. Stress
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 29
    Publikationsdatum: 2017-04-04
    Beschreibung: We have simulated several scenarios of dynamic rupture propagation for the 1994 Northridge, California, earthquake, using a three-dimensional finite-difference method. The simulations use a rate- and slip-weakening friction law, starting from a range of initial conditions of stress and frictional parameters. A critical balance between initial conditions and friction parameters must be met in order to obtain a moment as well as a final slip distribution in agreement with kinematic slip inversion results. We find that the rupture process is strongly controlled by the average stress and connectivity of high-stress patches on the fault. In particular, a strong connectivity of the high-stress patches is required in order to promote the rupture propagation from the initial nucleation to the remaining part of the fault. Moreover, we find that a small amount of rate-weakening is needed in order to obtain a level of inhomogeneity in the final slip, similar to that obtained in the kinematic inversion results. However, when the amount of rate-weakening is increased, the overall moment drops dramatically unless the average prestress is raised to unrealistic levels. A velocity-weakening parameter on the order of 10 cm per second is found to be adequate for an average prestress of about a hundred bars. The presence of the free surface and of the uppermost low-impedance layers in the model are found to have negligible influence on the rupture dynamics itself, because the top of the fault is at a depth of several kilometers. The 0.1–0.5 Hz radiated waves from the dynamic simulation provides a good fit to strong motion data at sites NWH and SSA. Underprediction of the recorded peak amplitude at JFP is likely due to omission of near-surface low velocity and 3-D basin effects in the simulations.
    Beschreibung: Published
    Beschreibung: 2029-2046
    Beschreibung: 3.1. Fisica dei terremoti
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): stress drop ; slip pulses ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 30
    Publikationsdatum: 2017-04-04
    Beschreibung: An edited version of this paper was published by AGU. Copyright (2010) American Geophysical Union.
    Beschreibung: Tectonic tremor has been recorded at many subduction zones, including the Nankai, Cascadia, Mexican, and Alaskan subduction zones. This study, the first to use small aperture seismic arrays to track tremor, deployed three small aperture seismic arrays along the Cascadia subduction zone during a tremor and slow slip episode in July 2004. The tremor was active during virtually all (up to 99%) minutes of the analyzed tremor episode using 5 min sample windows. Individual wave phases were tracked across the arrays and used to derive slowness vectors. These were compared with slowness vectors computed from a standard layered Earth model to derive tremor locations. Locations were stable within a volume roughly 250 km2 in epicenter and 20 km in depth for hours to days before moving to a new volume. The migration between volumes was not smooth, and the movement of the sources within the volume followed no specific pattern. Overall migration speeds along the strike of the subduction zone were between 5 and 15 km/d; smaller scale migration speeds between volumes reached speeds up to 2 km/min. Uncertainties in the best locations were 5 km in epicenter and 10 km in depth. For this data set and processing methodology, tremor does not locate predominately on the primary subduction interface. Our favored model for the generation of tectonic tremor signals is that the tremor is triggered by stress and fluid pressure changes caused by slow slip and is composed, at least in part, of low‐frequency earthquakes broadly distributed in location
    Beschreibung: Published
    Beschreibung: B00A24
    Beschreibung: 3.2. Tettonica attiva
    Beschreibung: 3.3. Geodinamica e struttura dell'interno della Terra
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): tremor migration ; Cascadia 2004 ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis ; 04. Solid Earth::04.07. Tectonophysics::04.07.04. Plate boundaries, motion, and tectonics
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  • 31
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 23 (2009): GB4028, doi:10.1029/2009GB003519.
    Beschreibung: Nitrogen cycle dynamics have the capacity to attenuate the magnitude of global terrestrial carbon sinks and sources driven by CO2 fertilization and changes in climate. In this study, two versions of the terrestrial carbon and nitrogen cycle components of the Integrated Science Assessment Model (ISAM) are used to evaluate how variation in nitrogen availability influences terrestrial carbon sinks and sources in response to changes over the 20th century in global environmental factors including atmospheric CO2 concentration, nitrogen inputs, temperature, precipitation and land use. The two versions of ISAM vary in their treatment of nitrogen availability: ISAM-NC has a terrestrial carbon cycle model coupled to a fully dynamic nitrogen cycle while ISAM-C has an identical carbon cycle model but nitrogen availability is always in sufficient supply. Overall, the two versions of the model estimate approximately the same amount of global mean carbon uptake over the 20th century. However, comparisons of results of ISAM-NC relative to ISAM-C reveal that nitrogen dynamics: (1) reduced the 1990s carbon sink associated with increasing atmospheric CO2 by 0.53 PgC yr−1 (1 Pg = 1015g), (2) reduced the 1990s carbon source associated with changes in temperature and precipitation of 0.34 PgC yr−1 in the 1990s, (3) an enhanced sink associated with nitrogen inputs by 0.26 PgC yr−1, and (4) enhanced the 1990s carbon source associated with changes in land use by 0.08 PgC yr−1 in the 1990s. These effects of nitrogen limitation influenced the spatial distribution of the estimated exchange of CO2 with greater sink activity in high latitudes associated with climate effects and a smaller sink of CO2 in the southeastern United States caused by N limitation associated with both CO2 fertilization and forest regrowth. These results indicate that the dynamics of nitrogen availability are important to consider in assessing the spatial distribution and temporal dynamics of terrestrial carbon sources and sinks.
    Beschreibung: We also acknowledge the financial support of the National Aeronautics and Space Administration Land Cover and Land Use Change Program (NNX08AK75G).
    Schlagwort(e): Nitrogen cycle ; Carbon cycle ; ISAM
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  • 32
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 9 (2008): Q08O10, doi:10.1029/2008GC001965.
    Beschreibung: We use 2-D numerical models to explore the thermal and mechanical effects of magma intrusion on fault initiation and growth at slow and intermediate spreading ridges. Magma intrusion is simulated by widening a vertical column of model elements located within the lithosphere at a rate equal to a fraction, M, of the total spreading rate (i.e., M = 1 for fully magmatic spreading). Heat is added in proportion to the rate of intrusion to simulate the thermal effects of magma crystallization and the injection of hot magma into the crust. We examine a range of intrusion rates and axial thermal structures by varying M, spreading rate, and the efficiency of crustal cooling by conduction and hydrothermal circulation. Fault development proceeds in a sequential manner, with deformation focused on a single active normal fault whose location alternates between the two sides of the ridge axis. Fault spacing and heave are primarily sensitive to M and secondarily sensitive to axial lithosphere thickness and the rate that the lithosphere thickens with distance from the axis. Contrary to what is often cited in the literature, but consistent with prior results of mechanical modeling, we find that thicker axial lithosphere tends to reduce fault spacing and heave. In addition, fault spacing and heave are predicted to increase with decreasing rates of off-axis lithospheric thickening. The combination of low M, particularly when M approaches 0.5, as well as a reduced rate of off-axis lithospheric thickening produces long-lived, large-offset faults, similar to oceanic core complexes. Such long-lived faults produce a highly asymmetric axial thermal structure, with thinner lithosphere on the side with the active fault. This across-axis variation in thermal structure may tend to stabilize the active fault for longer periods of time and could concentrate hydrothermal circulation in the footwall of oceanic core complexes.
    Beschreibung: Funding for this research was provided by NSF grants OCE-0327018 (M.D.B.), OCE-0548672 (M.D.B.), OCE- 0327051 (G.I.), and OCE-03-51234 (G.I.).
    Schlagwort(e): Mid-ocean ridges ; Faulting ; Magmatism ; Numerical modeling
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  • 33
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 21 (2007): GB3007, doi:10.1029/2006GB002857.
    Beschreibung: Results are presented of export production, dissolved organic matter (DOM) and dissolved oxygen simulated by 12 global ocean models participating in the second phase of the Ocean Carbon-cycle Model Intercomparison Project. A common, simple biogeochemical model is utilized in different coarse-resolution ocean circulation models. The model mean (±1σ) downward flux of organic matter across 75 m depth is 17 ± 6 Pg C yr−1. Model means of globally averaged particle export, the fraction of total export in dissolved form, surface semilabile dissolved organic carbon (DOC), and seasonal net outgassing (SNO) of oxygen are in good agreement with observation-based estimates, but particle export and surface DOC are too high in the tropics. There is a high sensitivity of the results to circulation, as evidenced by (1) the correlation of surface DOC and export with circulation metrics, including chlorofluorocarbon inventory and deep-ocean radiocarbon, (2) very large intermodel differences in Southern Ocean export, and (3) greater export production, fraction of export as DOM, and SNO in models with explicit mixed layer physics. However, deep-ocean oxygen, which varies widely among the models, is poorly correlated with other model indices. Cross-model means of several biogeochemical metrics show better agreement with observation-based estimates when restricted to those models that best simulate deep-ocean radiocarbon. Overall, the results emphasize the importance of physical processes in marine biogeochemical modeling and suggest that the development of circulation models can be accelerated by evaluating them with marine biogeochemical metrics.
    Beschreibung: R. G. N. and J. L. S. acknowledge the support of NASA grants NAG5-6451 and NAG5-6591, respectively, as part of the JGOFS Synthesis and Modeling Program. G. K. P. and F. J. acknowledge support by the Swiss National Science Foundation. European contributions were supported by the EU GOSAC Project (ENV4-CT97- 0495).
    Schlagwort(e): Export production ; Numerical modeling ; Ocean circulation
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  • 34
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 21 (2007): GB2026, doi:10.1029/2006GB002900.
    Beschreibung: We investigate the interannual variability in the flux of CO2 between the atmosphere and the Southern Ocean on the basis of hindcast simulations with a coupled physical-biogeochemical-ecological model with particular emphasis on the role of the Southern Annular Mode (SAM). The simulations are run under either pre-industrial or historical CO2 concentrations, permitting us to separately investigate natural, anthropogenic, and contemporary CO2 flux variability. We find large interannual variability (±0.19 PgC yr−1) in the contemporary air-sea CO2 flux from the Southern Ocean (〈35°S). Forty-three percent of the contemporary air-sea CO2 flux variance is coherent with SAM, mostly driven by variations in the flux of natural CO2, for which SAM explains 48%. Positive phases of the SAM are associated with anomalous outgassing of natural CO2 at a rate of 0.1 PgC yr−1 per standard deviation of the SAM. In contrast, we find an anomalous uptake of anthropogenic CO2 at a rate of 0.01 PgC yr−1 during positive phases of the SAM. This uptake of anthropogenic CO2 only slightly mitigates the outgassing of natural CO2, so that a positive SAM is associated with anomalous outgassing in contemporaneous times. The primary cause of the natural CO2 outgassing is anomalously high oceanic partial pressures of CO2 caused by elevated dissolved inorganic carbon (DIC) concentrations. These anomalies in DIC are primarily a result of the circulation changes associated with the southward shift and strengthening of the zonal winds during positive phases of the SAM. The secular, positive trend in the SAM has led to a reduction in the rate of increase of the uptake of CO2 by the Southern Ocean over the past 50 years.
    Beschreibung: This work was supported by NASA headquarters under the Earth System Science Fellowship Grant NNG05GP78H to N. S. L. and grants NAG5-12528 and NNG04GH53G to N. G. Both S. C. D. and I. D. L. were supported by NSF/ONR NOPP (N000140210370) and NASA (NNG05GG30G).
    Schlagwort(e): Southern Ocean ; Carbon cycle ; Southern Annular Mode
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  • 35
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 112 (2007): F03016, doi:10.1029/2006JF000666.
    Beschreibung: We employ a numerical model to study the development of sorted bed forms under a variety of hydrodynamic and sedimentary conditions. Results indicate that increased variability in wave height decreases the growth rate of the features and can potentially give rise to complicated, a priori unpredictable, behavior. This happens because the system responds to a change in wave characteristics by attempting to self-organize into a patterned seabed of different geometry and spacing. The new wavelength might not have enough time to emerge before a new change in wave characteristics occurs, leading to less regular seabed configurations. The new seabed configuration is also highly dependent on the preexisting morphology, which further limits the possibility of predicting future behavior. For the same reasons, variability in the mean current magnitude and direction slows down the growth of features and causes patterns to develop that differ from classical sorted bed forms. Spatial variability in grain size distribution and different types of net sediment aggradation/degradation can also result in the development of sorted bed forms characterized by a less regular shape. Numerical simulations qualitatively agree with observed geometry (spacing and height) of sorted bed forms. Also in agreement with observations is that at shallower depths, sorted bed forms are more likely to be affected by changes in the forcing conditions, which might also explain why, in shallow waters, sorted bed forms are described as ephemeral features. Finally, simulations indicate that the different sorted bed form shapes and patterns observed in the field might not necessarily be related to diverse physical mechanisms. Instead, variations in sorted bed form characteristics may result from variations in local hydrodynamic and/or sedimentary conditions.
    Beschreibung: G.C., M.O.G., and T.M.H. acknowledge funding from the (New Zealand) Foundation for Research, Science and Technology (contract C01X0401). The National Science Foundation (OCE0452178) supported A.B.M.
    Schlagwort(e): Self-organization ; Sorted bed forms ; Numerical modeling
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  • 36
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 112 (2007): C04S15, doi:10.1029/2006JC003728.
    Beschreibung: The summer circulations and hydrographic fields of the Kara Sea are reconstructed for mean, positive and negative Arctic Oscillation regimes employing a variational data assimilation technique which provides the best fit of reconstructed fields to climatological data and satisfies dynamical and kinematic constraints of a quasi-stationary primitive equation ocean circulation model. The reconstructed circulations agree well with the measurements and are characterized by inflow of 0.63, 0.8, 0.51 Sv through Kara Gate and 1.18, 1.1, 1.12 Sv between Novaya Zemlya and Franz Josef Land, for mean climatologic conditions, positive and negative AO indexes, respectively. The major regions of water outflow for these regimes are the St. Anna Trough (1.17, 1.21, 1.34 Sv) and Vilkitsky/Shokalsky Straits (0.52, 0.7, 0.51 Sv). The optimized velocity pattern for the mean climatological summer reveals a strong anticyclonic circulation in the central part of the Kara Sea (Region of Fresh Water Inflow, ROFI zone) and is confirmed by ADCP surveys and laboratory modeling. This circulation is well pronounced for both high and low AO phases, but in the positive AO phase it is shifted approximately 200 km west relatively to its climatological center. During the negative AO phase the ROFI locaion is close to its climatological position. The results of the variational data assimilation approach were compared with the simulated data from the Hamburg Shelf Ocean Model (HAMSOM) and Naval Postgraduate School 18 km resolution (NPS-18) model to validate these models.
    Beschreibung: This research is supported by the Frontier Research System for Global Change, through JAMSTEC, Japan, and by the National Science Foundation Office of Polar Programs (under cooperative agreements OPP-0002239 and OPP-0327664 with the International Arctic Research Center, University of Alaska Fairbanks). The development of the data assimilation system, utilized in this study, was also supported by NSF grant OCE-0118200.
    Schlagwort(e): Kara Sea ; Variational approach ; Numerical modeling
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  • 37
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2010. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 115 (2010): C11015, doi:10.1029/2010JC006152.
    Beschreibung: The concentration of inert gases and their isotopes in the deep ocean are useful as tracers of air-sea gas exchange during deepwater formation. ΔKr/Ar, ΔN2/Ar, and δ40Ar were measured in deep profiles of samples collected in the northwest Pacific, subtropical North Pacific and tropical Atlantic oceans. For the ocean below 2000 m, we determined a mean ΔKr/Ar composition of −0.96% ± 0.16%, a mean ΔN2/Ar of 1.29% ± 0.21% relative to equilibrium saturation, and for δ40Ar a value of 1.188‰ ± 0.055‰ relative to air. These data are used to constrain high-latitude ventilation processes in the framework of three-box and seven-box ocean models. For the three-box model tracer data, we constrain the appropriate surface area of the high-latitude region in both models to be 3.6% (+2.5%, −1.7%) of ocean surface area and the bubble air injection rate to be 22.7 (+8.8, −7.3) mol air m−2 yr−1. Results for the seven-box model were similar, with a high-latitude area of 3.3% (+2.2%, −1.3%). Our results provide geochemical support for suggestions that the effective area of high-latitude ventilation is much smaller than the region of elevated preformed nutrients and demonstrate that noble gases strongly constrain the ocean solubility pump. Reducing high-latitude surface area weakens the CO2 solubility pump in the box models and limits communication between the atmosphere and deep ocean. These tracers should be useful constraints on high-latitude ventilation and the strength of the solubility pump in more complex ocean general circulation models.
    Beschreibung: Funding was provided by NSF‐OCE‐0647979.
    Schlagwort(e): Noble gases ; Ventilation ; Carbon cycle ; Solubility pump ; Gas exchange
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  • 38
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): F01006, doi:10.1029/2007JF000885.
    Schlagwort(e): Coastline evolution ; Morphodynamic instabilities ; Numerical modeling
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  • 39
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 111 (2006): F04011, doi:10.1029/2005JF000422.
    Beschreibung: Contrary to traditional findings, the deepwater angle of wave approach strongly affects plan view coastal evolution, giving rise to an antidiffusional “high wave angle” instability for sufficiently oblique deepwater waves (with angles between wave crests and the shoreline trend larger than the value that maximizes alongshore sediment transport, ∼45°). A one-contour-line numerical model shows that a predominance of high-angle waves can cause a shoreline to self-organize into regular, quasiperiodic shapes similar to those found along many natural coasts at scales ranging from kilometers to hundreds of kilometers. The numerical model has been updated from a previous version to include a formulation for the widening of an overly thin barrier by the process of barrier overwash, which is assumed to maintain a minimum barrier width. Systematic analysis shows that the wave climate determines the form of coastal response. For nearly symmetric wave climates (small net alongshore sediment transport), cuspate coasts develop that exhibit increasing relative cross-shore amplitude and pointier tips as the proportion of high-angle waves is increased. For asymmetrical wave climates, shoreline features migrate in the downdrift direction, either as subtle alongshore sand waves or as offshore-extending “flying spits,” depending on the proportion of high-angle waves. Numerical analyses further show that the rate that the alongshore scale of model features increases through merging follows a diffusional temporal scale over several orders of magnitude, a rate that is insensitive to the proportion of high-angle waves. The proportion of high-angle waves determines the offshore versus alongshore aspect ratio of self-organized shoreline undulations.
    Beschreibung: This research was funded by the Andrew W. Mellon Foundation and NSF grants DEB-05-07987 and EAR-04-44792.
    Schlagwort(e): Coastline evolution ; Morphodynamic instabilities ; Numerical modeling
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  • 40
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): C07040, doi:10.1029/2007JC004602.
    Beschreibung: A coupled physical/biological modeling system was used to hindcast a massive Alexandrium fundyense bloom that occurred in the western Gulf of Maine in 2005 and to investigate the relative importance of factors governing the bloom's initiation and development. The coupled system consists of a state-of-the-art, free-surface primitive equation Regional Ocean Modeling System (ROMS) tailored for the Gulf of Maine (GOM) using a multinested configuration, and a population dynamics model for A. fundyense. The system was forced by realistic momentum and buoyancy fluxes, tides, river runoff, observed A. fundyense benthic cyst abundance, and climatological nutrient fields. Extensive comparisons were made between simulated (both physical and biological) fields and in situ observations, revealing that the hindcast model is capable of reproducing the temporal evolution and spatial distribution of the 2005 bloom. Sensitivity experiments were then performed to distinguish the roles of three major factors hypothesized to contribute to the bloom: (1) the high abundance of cysts in western GOM sediments; (2) strong ‘northeaster' storms with prevailing downwelling-favorable winds; and (3) a large amount of fresh water input due to abundant rainfall and heavy snowmelt. Model results suggest the following. (1) The high abundance of cysts in western GOM was the primary factor of the 2005 bloom. (2) Wind-forcing was an important regulator, as episodic bursts of northeast winds caused onshore advection of offshore populations. These downwelling favorable winds accelerated the alongshore flow, resulting in transport of high cell concentrations into Massachusetts Bay. A large regional bloom would still have happened, however, even with normal or typical winds for that period. (3) Anomalously high river runoff in 2005 resulted in stronger buoyant plumes/currents, which facilitated the transport of cell population to the western GOM. While affecting nearshore cell abundance in Massachusetts Bay, the buoyant plumes were confined near to the coast, and had limited impact on the gulf-wide bloom distribution.
    Beschreibung: Research support was provided through the Woods Hole Center for Oceans and Human Health, National Science Foundation (NSF) grant OCE-0430723 and National Institute of Environmental Health Science (NIEHS) grant 1-P50-ES012742-01, ECOHAB program through NSF grant OCE-9808173 and NOAA grant NA96OP0099, and GOMTOX program through NOAA grant NA06NOS4780245.
    Schlagwort(e): Gulf of Maine ; Harmful algal bloom ; Numerical modeling
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  • 41
    Publikationsdatum: 2022-05-26
    Beschreibung: Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 111 (2006): C08002, doi:10.1029/2005JC003254.
    Beschreibung: A high-resolution hybrid data assimilative (DA) modeling system is used to study barotropic tides and tidal dynamics on the southeast New England shelf. In situ observations include tidal harmonics of 5 major tidal constituents [M2, S2, N2, O1, and K1] analyzed from coastal sea level and bottom pressure gauges. The DA system consists of both forward and inverse models. The former is the three-dimensional, finite difference, nonlinear Regional Ocean Modeling System (ROMS). The latter is a three-dimensional linearized, frequency domain, finite element model TRUXTON. The DA system assimilates in situ observations via the inversion for the barotropic tidal open boundary conditions (OBCs). Model skill is evaluated by comparing the misfits between the observed and modeled tidal harmonics. The assimilation scheme is found effective and efficient in correcting the tidal OBCs, which in turn improve ROMS tidal solutions. Up to 50% decreases of model/data misfits are achieved after inverse data assimilation. Co-amplitude and co-phase maps and tidal current ellipses for each of 5 tidal constituents are generated, revealing complex tidal variability in this transition region between the tidally amplified Gulf of Maine in the northeast and the tidally much less energetic Middle Atlantic Bight in the southwest. Detailed examinations on the residual circulation, energetics, and momentum balances of the M2 tide reveal the key roles of the unique bottom bathymetry of Nantucket Shoals and the complex coastal geometry in affecting the regional tidal dynamics.
    Beschreibung: This work was supported by WHOI Coastal Ocean Institute Research Award. J.W. acknowledges support of the Office of Naval Research.
    Schlagwort(e): Continental shelf ; Barotropic tides ; Numerical modeling ; Data assimilation
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  • 42
    Publikationsdatum: 2022-05-26
    Beschreibung: Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): C07032, doi:10.1029/2007JC004598.
    Beschreibung: This paper examines the sensitivity of atmospheric pCO2 to changes in ocean biology that result in drawdown of nutrients at the ocean surface. We show that the global inventory of preformed nutrients is the key determinant of atmospheric pCO2 and the oceanic carbon storage due to the soft-tissue pump (OCS soft ). We develop a new theory showing that under conditions of perfect equilibrium between atmosphere and ocean, atmospheric pCO2 can be written as a sum of exponential functions of OCS soft . The theory also demonstrates how the sensitivity of atmospheric pCO2 to changes in the soft-tissue pump depends on the preformed nutrient inventory and on surface buffer chemistry. We validate our theory against simulations of nutrient depletion in a suite of realistic general circulation models (GCMs). The decrease in atmospheric pCO2 following surface nutrient depletion depends on the oceanic circulation in the models. Increasing deep ocean ventilation by increasing vertical mixing or Southern Ocean winds increases the atmospheric pCO2 sensitivity to surface nutrient forcing. Conversely, stratifying the Southern Ocean decreases the atmospheric CO2 sensitivity to surface nutrient depletion. Surface CO2 disequilibrium due to the slow gas exchange with the atmosphere acts to make atmospheric pCO2 more sensitive to nutrient depletion in high-ventilation models and less sensitive to nutrient depletion in low-ventilation models. Our findings have potentially important implications for both past and future climates.
    Beschreibung: While at MIT, I.M. was supported by the NOAA Postdoctoral Program in Climate and Global Change, administered by the University Corporation for Atmospheric Research.
    Schlagwort(e): Carbon cycle ; Preformed nutrient ; Nutrient depletion
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  • 43
    Publikationsdatum: 2022-05-26
    Beschreibung: Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 20 (2006): GB2002, doi:10.1029/2005GB002530.
    Beschreibung: Regional air-sea fluxes of anthropogenic CO2 are estimated using a Green's function inversion method that combines data-based estimates of anthropogenic CO2 in the ocean with information about ocean transport and mixing from a suite of Ocean General Circulation Models (OGCMs). In order to quantify the uncertainty associated with the estimated fluxes owing to modeled transport and errors in the data, we employ 10 OGCMs and three scenarios representing biases in the data-based anthropogenic CO2 estimates. On the basis of the prescribed anthropogenic CO2 storage, we find a global uptake of 2.2 ± 0.25 Pg C yr−1, scaled to 1995. This error estimate represents the standard deviation of the models weighted by a CFC-based model skill score, which reduces the error range and emphasizes those models that have been shown to reproduce observed tracer concentrations most accurately. The greatest anthropogenic CO2 uptake occurs in the Southern Ocean and in the tropics. The flux estimates imply vigorous northward transport in the Southern Hemisphere, northward cross-equatorial transport, and equatorward transport at high northern latitudes. Compared with forward simulations, we find substantially more uptake in the Southern Ocean, less uptake in the Pacific Ocean, and less global uptake. The large-scale spatial pattern of the estimated flux is generally insensitive to possible biases in the data and the models employed. However, the global uptake scales approximately linearly with changes in the global anthropogenic CO2 inventory. Considerable uncertainties remain in some regions, particularly the Southern Ocean.
    Beschreibung: This research was financially supported by the National Aeronautics and Space Administration under grant NAG5- 12528. N. G. also acknowledges support by the National Science Foundation (OCE-0137274). Climate and Environmental Physics, Bern acknowledges support by the European Union through the Integrated Project CarboOcean and the Swiss National Science Foundation.
    Schlagwort(e): Anthropogenic CO2 ; Carbon cycle ; Inverse modeling
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 44
    Publikationsdatum: 2022-05-26
    Beschreibung: Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 22 (2008): GB3025, doi:10.1029/2007GB003082.
    Beschreibung: Interannually varying net carbon exchange fluxes from the TransCom 3 Level 2 Atmospheric Inversion Intercomparison Experiment are presented for the 1980 to 2005 time period. The fluxes represent the model mean, net carbon exchange for 11 land and 11 ocean regions after subtraction of fossil fuel CO2 emissions. Both aggregated regional totals and the individual regional estimates are accompanied by a model uncertainty and model spread. We find that interannual variability is larger on the land than the ocean, with total land exchange correlated to the timing of both El Niño/Southern Oscillation (ENSO) as well as the eruption of Mt. Pinatubo. The post-Pinatubo negative flux anomaly is evident across much of the tropical and northern extratropical land regions. In the oceans, the tropics tend to exhibit the greatest level of interannual variability, while on land, the interannual variability is slightly greater in the tropics and northern extratropics. The interannual variation in carbon flux estimates aggregated by land and ocean across latitudinal bands remains consistent across eight different CO2 observing networks. The interannual variation in carbon flux estimates for individual flux regions remains mostly consistent across the individual observing networks. At all scales, there is considerable consistency in the interannual variations among the 13 participating model groups. Finally, consistent with other studies using different techniques, we find a considerable positive net carbon flux anomaly in the tropical land during the period of the large ENSO in 1997/1998 which is evident in the Tropical Asia, Temperate Asia, Northern African, and Southern Africa land regions. Negative anomalies are estimated for the East Pacific Ocean and South Pacific Ocean regions. Earlier ENSO events of the 1980s are most evident in southern land positive flux anomalies.
    Schlagwort(e): Carbon cycle ; Atmospheric inversion ; Interannual variability
    Repository-Name: Woods Hole Open Access Server
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  • 45
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 19-24 
    ISSN: 0009-2940
    Schlagwort(e): Bis(diorganoboryl)chalcogenides ; Pyrazaboles ; Pyrazoles ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Neuartige Substituierte B2ElVIN2 HeterocyclenDie Bis(diorganoboryl)chalkogenide (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], und (R2B)2Se [R2 = 1,5-C8H14 (7)] reagieren mit Pyrazol (Pz) und dessen Derivaten 3-Methylpyrazol (3-MePz) und Indazol (benzo-Pz) in hohen Ausbeuten (65-92%) zu stabilen 1:1-Additionsverbindungen [z. B. 2 (El = O), 4 (El = O), 6 (El = S), 8 (El = Se)]. 1H-, 13C-, 11B-NMR-Spektren und Röntgenstrukturanalysen (von 2 und 6) zeigen eine Grundstruktur mit einem zentralen B2ElN2-Heterocyclus (El = O, S, Se). Die Reaktion von 2 mit R2BH und die Thermolyse von 4 führen zu den dimeren 1-Pyrazolylboranen 9a bzw. 9b.
    Notizen: The bis(diorganoboryl) chalcogenides (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], and (R2B)2Se [R2 = 1,5-C8H14 (7)] react with pyrazole (Pz) and its derivatives 3-methylpyrazole (3-MePz) and indazole (benzo-Pz) to form in high yields (65-92%) stable 1:1 adducts [e.g. 2 (El = O), 4 (El = O), 6 (El = S) and 8 (El = Se)]. 1H-, 13C-, 11B-NMR spectra and X-ray analyses (of 2 and 6) show a basic structure with a central B2ElN2 (El = O, S, Se) heterocycle. The reaction of 2 with R2BH and the thermolysis of 4 give the dimeric 1-pyrazolylboranes 9a and 9b, respectively.
    Zusätzliches Material: 3 Ill.
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  • 46
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 31-36 
    ISSN: 0009-2940
    Schlagwort(e): Mercury - mercury contacts ; Naphthalenediylmercury compounds ; Organomercury compounds ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Extremely Short Mercury-Mercury Contacts in peri-Dimercurated Naphthalene Compounds1-Naphthylmercury chloride (1) and 1,8-naphthalenediylbis(mercury chloride) (2) were prepared from the corresponding naphthyllithium precursors and HgCl2 in ca. 80% yield. In an alternative route, 2 can be obtained from 1,8-naphthalenediyldiboric acid anhydride and HgCl2 in 85% yield. The structure of 2·DMSO has been determined by X-ray diffraction methods. The lattice contains discrete adducts in which the two mercury atoms are bridged by the DMSO oxygen atom. The HgCl moieties are bent away from each other through distortions of the naphthalene framework and of the C—Hg—Cl axes, which results in a Hg ‥ Hg distance of 3.102(1) Å. - Symmetrization of 2, induced by treatment with NaI in aqueous ethanol, affords bis(μ-1,8-naphthalenediyl)dimercury (3). In the X-ray structure determination of this compound the shortest „non-bonding“ Hg·Hg contact reported in the literature has been detected: Hg1··Hg2 = 2.797(1) Å. The molecule also shows distortions in the naphthalene framework and in the C—Hg—C axes [C—Hg—C = 173.3(5)°].
    Notizen: 1-Naphthylquecksilberchlorid (1) und 1,8-Naphthalindiylbis-(quecksilberchlorid) (2) werden aus den zugehörigen Naphthyllithium-Verbindungen und HgCl2 mit ca. 80% Ausbeute erhalten. Alternativ kann 2 auch aus 1,8-Naphthalindiyldiborsäureanhydrid und HgCl2 gewonnen werden (Ausbeute 85%). Von 2·DMSO wurde die Kristallstruktur bestimmt. Es liegen diskrete Addukte vor, in denen die beiden Hg-Atome durch das O-Atom des DMSO überbrückt werden. Die HgCl-Einheiten sind durch Verzerrungen im Naphthalingerüst, durch Winkelung der Achsen C—Hg—Cl und durch deren Auslenkung aus der Naphthalinebene voneinander weggebogen, so daß ein Hg·· Hg-Kontakt von 3.102(1) Å resultiert. - 2 symmetrisiert sich bei der Einwirkung von NaI in wäßrigem Ethanol unter Bildung von Bis(μ-1,8-naphthalindiyl)diquecksilber (3). Bei der Strukturanalyse dieser im Kristall zentrosymmetrischen Verbindung wurde der bisher kürzeste „nichtbindende“ Hg··Hg-Kontakt von 2.797(1) Å gefunden. Auch in 3 sind die C—Hg—C-Achsen abgewinkelt [C—Hg—C = 173.3(5)°], und das Naphthalingerüst ist verzerrt.
    Zusätzliches Material: 6 Ill.
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  • 47
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 59-61 
    ISSN: 0009-2940
    Schlagwort(e): N-Butyl-N′-dansylthiourea ; Complexing agent, fluorescent ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: N-Butyl-N′-dansylthiourea as Fluorescent Broad-Band Complexing AgentN-Butyl-N′-dansylthiourea (2) [dansyl = 5-(dimethylamino)-1-naphthylsulfonyl] is obtained by the reaction of dansylamide (1) with butyl isothiocyanate. The compound is a stable, fluorescent complex agent for a broad spectrum of metal ions. The UV spectra and fluorescence of the ligand and some metal complexes are discussed. The fluorescence of the dansyl group is strongly affected by metal ions.
    Zusätzliches Material: 3 Ill.
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  • 48
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 83-94 
    ISSN: 0009-2940
    Schlagwort(e): Enaminecarbaldehydes ; Enamino ketones ; hetero Diels-Alder reaction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese und Struktur von Enaminecarbaldehyden und Enamino KetonenDie Synthese der Enamincarbaldehyde 1a-s und 17a-c sowie der Enamino-Ketone 2a-k und deren N-Acyl-Derivate 19a-k und 21-t mit Elektronenacceptor-Substituenten an C-2 bzw an der CO-Gruppe wird beschrieben. Kondensation von 2-Formyl-3-oxopropansäure-methylester (13) mit Ammoniak und den Aminen 14b-s ergab die Enamincarbaldehyde 1a bzw. 1b-s in einer Ausbeute von 72-93%. Die Enamincarbaldehyde 17 konnten durch Formylierung von 15 mit dem gemischten Ameisensäureessigsäureanhydrid erhalten werden. Die Synthese der Enamino-Ketone 2a-k erfolgte mit einer Ausbeute von 61-97% durch Kondensation von Ammoniak und Aminen mit den Enolethern 24a-f, die durch Umsetzung reaktiver Acylchloride 23 mit Ethylvinyl-ether dargestellt wurden. Die für hetero-Diels-Alder-Reaktionen benötigten N-Acyl-Derivate 19a-k und 21-t wurden durch Acylierung des Enamincarbaldehyds 1a und der Enamino-Ketone 2a-k gebildet.
    Notizen: The synthesis of enaminecarbaldehydes 1a-s and 17a-c as well as enamino ketones 2a-k, and their N-acyl derivatives 19a-k and 21-t with electron accepting substituents at C-2 and at the CO group, respectively, is described. Condensation of methyl 2-formyl-3-oxopropanoate (13) with ammonia and the amines 14b-s gave the enaminecarbaldehydes 1a and 1b-s, respectively, in 72-93% yield. The enaminecarbaldehydes 17 were obtained by formylation of 15 with acetic formic anhydride. The synthesis of the enamino ketones 2a-k was accomplished in 61-97% yield by reaction of ammonia and amines with the enol ethers 24a-f, which were formed by treatment of reactive acyl chlorides 23 with ethyl vinyl ether. The enaminecarbaldehyde 1a as well as the enamino ketones 2a-k could be acylated to give 19a-k and 2l-t, respectively, which can be used in the hetero Diels-Alder reaction.
    Zusätzliches Material: 1 Ill.
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  • 49
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 119-122 
    ISSN: 0009-2940
    Schlagwort(e): Bis(phosphonium) salts ; Pyridylphosphonium salts, tri-n-butyl- and triphenyl- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Chemistry of Triphenyl-(or Tri-n-butyl-)pyridylphosphonium salts, 2. - 2,4-Pyridinediylbis(phosphonium) Salts2,4-Pyridinediylbis(phosphonium) salts 1 react with nucleophiles to give 4-substituted products 6-8. Under radical reaction conditions the 5-position in 1a is attacked to yield 9. sodium azide transforms 1a into 8. This salt is used as starting material for 11. The removal of the phosphonium groups in 1 and in the resulting products can be carried out selectively.
    Notizen: 2,4-Pyridindiylbis(phosphoniumsalze) 1 lassen sich mit nucleophilen Reaktionspartnern in die 4-substituierten Produkte 6-8 überführen. Unter radikalischen Bedingungen wird selektiv die 5-Position in 1a unter Bildung von 9 angegriffen. Nach Umsetzung mit Natriumazid entsteht zunächst das Salz 8, das als Ausgangsverbindung für 11 dient. Die Substitution der Phosphoniumgruppen aus den Edukten 1 und Produkten kann selektiv durchgeführt werden.
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  • 50
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 145-149 
    ISSN: 0009-2940
    Schlagwort(e): Cycloalkenes, 1-methyl- ; Ozonolysis ; Peroxyhemiacetals, cyclic ; Rubber, natural ; Tetrahydrofurans, 2-hydroperoxy- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Ozonolyses of 1-Methylcyclopentene, 1-Methylcyclobutene, 5-Hexen-2-one and Natural Rubber in the Presence of MethanolOzonolyses of 1-methylcyclopentene (8a) and of 1-methylcyclobutene (8b) in methanol proceeded in each case in the two possible directions. The resulting methoxyperoxides 13 and 14 afforded the corresponding peroxyhemiacetals 15 and 19 by intramolecular reactions of the OOH with the corresponding carbonyl groups. Ozonolysis of 1-methylcyclobutene (8b) additionally gave the corresponding ozonide 17b and 2-hydroperoxy-5-methoxy-2-methyl-as well as 5-hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b and 18b). The mode of formation of these hydroperoxy compounds has been elucidated by ozonolyses of 5-hexen-2-one (25) and of natural rubber (28) in the presence of methanol.
    Notizen: Ozonolysen von 1-Methylcyclopenten (8a) und von 1-Methylcyclobuten (8b) in Methanol verliefen jeweils nach beiden möglichen Spaltungsrichtungen. Die dabei gebildeten Methoxyhydroperoxide 13 und 14 ergaben durch intramolekulare Reaktionen der OOH- mit den Carbonylgruppen die entsprechenden Peroxyhalbacetale 15 bzw. 19. Bei der Ozonolyse von 1-Methylcyclobuten (8b) wurden zusätzlich das entsprechende Ozonid 17b sowie 2-Hydroperoxy-5-methoxy-2-methyl- und 5-Hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b und 18b) gebildet. Die Bildungsweise dieser Hydroperoxy-Verbindungen wurde durch Ozonolysen von 5-Hexen-2-on (25) und von Naturkautschuk (28) im Beisein von Methanol aufgeklärt.
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  • 51
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 169-174 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis of New 3-substituted PyrrolesThe synthesis of 3-alkyl- (4), 3-(ω-bromoalkyl)- (5), 3-iodo- (6), 3-formyl- (9a), 3-acetyl-1-(triisopropylsilyl)pyrrole (9b), of 2-[1-(triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(triisopropylsilyl)-3-pyrrolecarboxylic acid (8), and 7-[1-(triisopropylsilyl)-3-pyrrolyl]heptanoic acid (10) as well as the desilylation of these products to the corresponding 3-substituted pyrroles 11 is described. Intermediates in these syntheses are 1-(triisopropylsilyl)pyrrole (1), 3-bromo- (2), and 3-lithio-1-(triisopropylsilyl)pyrrole (3).
    Notizen: Die Synthese von 3-Alkyl- (4), 3-(ω-Bromalkyl)- (5), 3-Iod- (6), 3-Formyl- (9a) und 3-Acetyl-1-(triisopropylsilyl)pyrrol (9b), von 2-[1-(Triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(Triisopropylsilyl)-3-pyrrolcarbonsäure (8) und 7-[1-(Triisopropylsilyl)-3-pyrrolyl]heptansäure (10) sowie die Desilylierung dieser Produkte zu den entsprechenden 3-substituierten Pyrrolen 11 wird beschrieben. Zwischenstufen der Darstellung sind 1-(Triisopropylsilyl)pyrrol (1), 3-Brom- (2) und 3-Lithio-1-(triisopropylsilyl)pyrrol (3).
    Zusätzliches Material: 1 Ill.
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  • 52
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 53
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 223-230 
    ISSN: 0009-2940
    Schlagwort(e): Gold(I) silyl complexes ; Transition-metal silyl complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Transition-Metal Silyl Complexes, 26. - Gold(I) Silyl ComplexesComplexes of type L-Au-SiR3 with L = PR′3 or PhNC and SiR3 = Si(aryl)3, Si(SiMe3)3, or SiPh2Me are prepared by reaction of L-Au-Cl with LiSiR3. Depending on L and R, their stability decreases, in the order R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Reaction of R′3P-Au-CH3 or R′3P-Au-OAc with HSiR3 does not yield silyl complexes. However, using chlorinated silanes like HSiR2Cl, CH3/Cl or OAc/Cl exchange takes place. The Mössbauer spectrum of MePh2P-Au-SiPh3 (6) and NMR- and IR-spectroscopic investigations show that silyl groups act as strong σ donors towards the gold atom. MePh2P-Au-SiPh3 (6) and MePh2P-Au-Si(SiMe3)3 (7) have been characterized by X-ray structure analyses [Au—Si 235.4(4) and 235.6(2) pm]. The Au-Si bond in MePh2P-Au-SiPh2Tol (5) is cleaved by X2 (X = Cl, Br, I), HCl or MeI, but not by H2O or MeOH.
    Notizen: Komplexe des Typs L-Au-SiR3 mit L = PR′3 oder PhNC und SiR3 = Si(aryl)3, Si(SiMe3)3 oder SiPh2Me wurden durch Umsetzung von L-Au-Cl mit LiSiR3 dargestellt. Ihre Stabilität sinkt in Abhängigkeit von L und R in der Reihenfolge R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Umsetzung von R′3P-Au-CH3 oder R′3P-Au-OAc mit HSiR3 ergibt keine Silyl-Komplexe, bei Verwendung chlorierter Silane, HSi-R2Cl, findet lediglich CH3/Cl- bzw. OAc/Cl-Austausch statt. Das Mößbauer-Spektrum von MePh2P-Au-SiPh3 (6) sowie NMR- und IR-spektroskopische Untersuchungen zeigen, daß Silylreste als starke σ-Donor-Liganden gegenüber dem Goldatom wirken. MePh2P-Au-SiPh3 (6) und MePh2P-Au-Si(SiMe3)3 (7) wurden durch Röntgenstrukturanalysen charakterisiert [Au—Si 235.4(4) und 235.6(2) pm]. Die Au—Si-Bindung in MePh2P-Au-SiPh2 Tol (5) wird durch X2 (X = Cl, Br, I), HCl oder MeI, nicht aber durch H2O oder MeOH gespalten.
    Zusätzliches Material: 2 Ill.
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  • 54
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 245-252 
    ISSN: 0009-2940
    Schlagwort(e): Germylenes ; Germanium nitrogen compounds ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Reactions of Germylenes with Azides: Iminogermanes, Azidogermanes, Tetrazagermoles and HexaazadigermadispirododecanesGermylenes, X2Ge, stabilized by steric blocking and/or incorporation into five-membered ring systems, react with azido compounds YN3 depending on the steric requirements of the substituents X and Y to give iminogermanes, X2Ge=NY (1, 2) azidogermanes X2Ge(N3)NY2 (6-8) tetrazagermoles, X2Ge(— NY — N =)2 (10-16), and hexaazadigermadispirododecanes, [(— NR — CH2 — CH2 — NR —)Ge(μ-NY -)]2 (17, 18). NMR (1H, 13C, 14N, 15N, and 29Si), MS data, and X-ray structure analyses of the compounds 8, 9, 16, and 18 are reported.
    Notizen: Durch sterische Blockierung und/oder Einbau in fünfgliedrige Ringsysteme stabilisierte Germylene, X2Ge, reagieren mit Azidoverbindungen, YN3, in Abhängigkeit von der Raumerfüllung der Substituenten X und Y zu Iminogermanen X2 Ge=NY (1, 2), Azidogermanen, X2Ge(N3)NY2 (6′8), Tetrazagermolen, X2Ge-(-NY-N=)2 (10-16), bzw. Hexaazadigermadispirododecanen, [(—NR—CH2—CH2—NR— )Ge(μ-NY-)]2 (17, 18). NMR-(1H, 13C, 14N, 15N und 29Si), MS-Daten und Röntgenstrukturanalysen für die Verbindungen 8, 9, 16 und 18 sind angegeben.
    Zusätzliches Material: 4 Ill.
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  • 55
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 271-277 
    ISSN: 0009-2940
    Schlagwort(e): Chalcogenogermanes, (trifluoromethyl)- ; Disilaselenanes ; Germachalcogenanes, bis(trifluoromethyl)- ; Germanes, (trifluoromethyl)- ; Germatranes, (trifluoromethyl)- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: (Trifluormethyl)germanes, III. - Preparation of New (Trifluormethyl)germanium Chalcogene CompoundsStarting with the dihalogenobis(trifluoromethyl)germanes (CF3)2-GeX2 (X = Cl, or I), halogen-chalcogen exchange leads to corresponding chalcogen derivatives of the general type [(CF3)2GeE]n (6, 7) (E = O, NH, S, or Se). The resulting compounds differ in their degree of polymerisation. [(CF3)2GeO]x and the corresponding sesquioxane [(CF3)GeO1, 5]x are highly polymeric, quite in contrast to the corresponding germathianes and -selenanes. The crystal structure of [(CF3)2GeO]x (6a) was determined by X-ray single crystal diffraction. The reaction of CF3GeCl3 with triethanolamine results in the formation of 1-(trifluoromethyl)germatrane (13). Disilaselenane (10) reacts at low temperatures with chloro-(trifluoromethyl)germanes (CF3)nGeCl4-n under retention of one Si—Se bond to give (CF3)nGe(SeSiH3)4-n (11) and H3SiCl. Compounds with n = 3 and 2 could be isolated. Exchange of iodine by ECF3 takes place with iodogermanes (CF3)nGeI4-n and Hg(ECF3)2 (E = S, Se) with formation of a complete series of (trifluoromethyl)(trifluoromethylchalcogeno)germanes (CF3)nGe-(ECF3)4-n (3, 5).
    Notizen: Durch Halogen-Chalkogen-Austauschreaktionen an (CF3)2)GeX2 (X = Cl, I) wurden Bis(trifluormethyl)germachalkogenane [(CF3)2GeE]n (6, 7) E = O, NH, S, Se) von unterschiedlichem Oligomerisierungsgrad erhalten. Die Germoxane [(CF3)2GeO]x und (CF3GeO1,5)x sind im Gegensatz zu den homologen Germathianen und -selenanen polymer, wobei die Struktur von [(CF3)2GeO]x (6a) durch eine Kristallstrukturanalyse ermittelt wurde. Durch Umsetzung von CF3GeCl3 mit Triethanolamin wird 1-(Trifluormethyl)germatran (13) erhalten. Disilaselenan (10) reagiert bei tiefen Temperaturen mit den Chlor (trifluormethyl)-germanen (CF3)nGeCl4-n monofunktionell unter Erhalt einer Si—Se-Bindung zu (CF3)nGe(SeSiH3)4-n (11) und H3SiCl, von denen die Verbindungen mit n = 3 und 2 isoliert werden konnten. Reaktionen der Iodgermane (CF3)nGeI4-n(1) mit Hg(ECF3)2) (E = S, Se) führen unter Substitution des Iods gegen die ECF3-Gruppen zur vollständigen Reihe der (Trifluormethyl)(trifluormethylchalkogeno)germane (CF3)nGe(ECF3)4-n (3, 5).
    Zusätzliches Material: 3 Ill.
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  • 56
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 291-292 
    ISSN: 0009-2940
    Schlagwort(e): (Phthalocyaninato)copper complex, substituted with crown ethers ; Alkali metal extraction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A soluble (phthalocyaninato)copper(II) complex containing eight symmetrical benzo-15-crown-5 substituents, namely {2,3,9,10,16,17,23,24-octakis[[benzo-15-crown-5)-4′ -yl]oxymethyl]phthalocyaninato}copper(II) (2) from 1,2-bis{[benzo-15-crown-5)-4′-yl]oxymethyl}-4,5-dibromobenzene (1) and CuCN in quinoline or pyridine was synthesized. The crown-ether groups in 2 were shown to prefer intramolecular complexation with alkali metal ions.
    Materialart: Digitale Medien
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  • 57
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 463-466 
    ISSN: 0009-2940
    Schlagwort(e): C—C Rotation ; Sterical hindrance by SF5 groups ; Rotational barriers ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Sterical Hindrance of the C—C Rotation by two SF5 GroupsAddition of SF5Cl to SF5CH=CF2 gives products carrying two SF5 groups on one carbon atom. As a consequence, C—C single bond rotation is strongly hindered. The highest rotational barrier observed is 61.7 kJ mol-1, rotational isomers are hence detectable at room temperature.
    Notizen: Die Addition von SF5Cl an SF5CH=CF2 ergibt Produkte, die zwei SF5-Gruppen an einem Kohlenstoff tragen. In diesen kommt es zu einer starken Hinderung der Rotation um die C—C-Einfachbindung. Die höchste Rotationsbarriere wird mit 61.7 kJ mol-1 gefunden, d. h. Rotationsisomere sind bei Raumtemperatur getrennt nachweisbar.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 58
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 467-472 
    ISSN: 0009-2940
    Schlagwort(e): Tetracarbonylchromium complexes ; 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine derivatives ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis, Structure, and Reactions of 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine DerivativesThe 1,2,3,6-tetrahydro-1,2,3,6-diphosphadiborine derivatives 3a and 3b are obtained by cyclocondensation of 1,2-bis[chloro(dialkylamino)boryl]ethenes 2 and 1,2-dipotassium 1,2-di-tert-butyldiphosphanediide. As in the case of 2,5-dihydro-1H-1,2,5-phosphadiborole derivatives 1 the temperature-dependent 1H-NMR spectra of 3b exhibit a lowered barrier of inversion at phosphorus. The X-ray structure analysis of 3b shows, that the six-membered C2B2P2 ring is nonplanar and the P atoms are coordinated pyramidally. Attempts to substitute the dialkylamino groups at the boron atoms of 3a and 3b with HCl·Et2O or tBuLi lead to cleavage of the B—P bonds. Reaction between 3a or 3b and Cr(CO)3(MeCN)3 does not result in the formation of tricarbonylchromium complexes but of tetracarbonylchromium complexes 6a and 6b with pentahapto-bonded ligands 3a and 3b.
    Notizen: Die 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborin-Derivate 3a und 3b entstehen durch Cyclokondensation aus 1,2-Bis[chlor(dialkylamino)boryl]ethenen 2 und 1,2-Dikalium-1,2-di-tert-butyldiphosphandiid. Die Temperaturabhängigkeit der 1H-NMR-Spektren von 3b dokumentiert wie bei 2,5-Dihydro-1H-1,2,5-phosphadiborol-Derivaten 1 eine erniedrigte Phosphor-Inversionsbarriere. Die Röntgenstrukturanalyse von 3b zeigt, daß der C2B2P2-Sechsring im Kristall nicht eben ist und daß die P-Atome pyramidal koordiniert sind. Versuche zur Substitution der Dialkylaminogruppen an den Boratomen von 3a und 3b mit HCl·Et2O oder tBuLi führen zur Spaltung der B—P-Bindungen. Die Umsetzung von 3a bzw. 3b mit Cr(CO)3(MeCN)3 ergibt keine Tricarbonylchrom-Komplexe, sondern die Tetracarbonylchrom-Komplexe 6a bzw. 6b, in denen die Liganden 3a und 3b pentahapto gebunden sind.
    Zusätzliches Material: 7 Tab.
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  • 59
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Organic Synthesis via Transition Metal Complexes, 34. - Novel Formation of C=C Bonds by Condensation of Acid Amides with Carbene Complexes Involving an Insertion of C2 Units into M=C BondsCarben complexes LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] and acid amides RCH2CONMe2 2 undergo a novel condensation reaction in presence of POCl3/Et3N to give alkenyl aminocarbene complexes 3. The reaction involves an insertion of a C2 unit of 2 into the M=C bond of 1 to give a C=C bond. It can be achieved with open-chain and cyclic amides like N-methyl-2-pyrrolidone (8). the structures of the complexes have been determined spectroscopically. A mechanism of the reaction is suggested.
    Notizen: Carbenkomplexe LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] lassen sich mit Säureamiden RCH2CONMe2 2 und POCl3/Et3N zu Alkenyl-Aminocarben-Komplexen 3 kondensieren. Dabei wird eine C2-Einheit von 2 in die M=C-Bindung von 1 eingeschoben und eine C=C-Bindung neu geknüpft. Die Reaktion gelingt mit offenkettigen und cyclischen Amiden wie N-Methyl-2-pyrrolidon (8). Die Strukturen der Komplexe wurden spektroskopisch ermittelt und Vorschläge zur Deutung des Reaktionsablaufs gemacht.
    Zusätzliches Material: 1 Tab.
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  • 60
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 711-714 
    ISSN: 0009-2940
    Schlagwort(e): Azulenes ; 1,6-Methano[10]annulenes ; 1,2,4,5-Tetrazine ; [4 + 2] Cycloadditions, „inverse“ ; Pyridazines, annulated ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Azulene and 1,6-Methano[10]annulene as Dienophiles in the Diels-Alder Reaction with 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazineThe LUMO-diene-controlled [4 + 2] cycloadditions of azulene (2) and 1,6-methano[10]annulene (14) with the electron-deficient s-cisfixed diazadiene system of 3,6-bis(trifluoromethyl)-1,2,4,5-tetrazine (1) are described. Contrary to expectation, 1 reacts under unusually mild conditions with 2 (or its valence tautomer 3) to yield the adduct 4 which after N2 elimination rearranges to the benzo[f]phthalazine 11. The Diels-Alder reaction of 1 with 14 (or its valence tautomer 13) leads to the annulated dihydropyridazines 15 and 16, which can be dehydrogenated by silver(I) oxide to the methano-bridged aromatic cyclodecapyridazine 17 and the olefinic phthalazino[5,6-f]phthalazine 18, respectively. Besides, the methano-bridged cyclodeca[d]pyridazine 24 is prepared.
    Notizen: LUMO-Dien-kontrollierte [4 + 2]-Cycloadditionen von Azulen (2) und 1,6-Methano[10]annulen (14) an das elektronenarme, s-cis-fixierte Diazadiensystem von 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazin (1) werden beschrieben. Wider Erwarten reagiert 1 unter ungewöhnlich milden Bedingungen mit 2 (oder dessen Valenztautomerem 3) zum Addukt 4, das nach N2-Eliminierung und nachfolgender Umlagerung das Benzo[f]phthalazin 11 liefert. Die Diels-Alder-Reaktion von 1 mit 14 (oder dessen Valenztautomer 13) führt zu den beiden anellierten Dihydropyridazinen 15 und 16, die mit Silber(I)-oxid zu dem Methano-überbrückten aromatischen Cyclodecapyridazin 17 bzw. dem olefinischen Phthalazino[5,6-f]phthalazin 18 dehydriert werden können. Daneben wird das Methano-überbrückte Cyclodeca[d]pyridazin 24 dargestellt.
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  • 61
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 715-719 
    ISSN: 0009-2940
    Schlagwort(e): Alkyne ; Carbene ; Cycloisomerization ; Pyrolysis ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Über die thermische Cycloisomerisierung langkettiger Alkylacetylene in der GasphaseDie thermische Cycloisomerisierung einiger Alkylacetylene wurde in einem Laborrohrreaktor aus Quarzglas untersucht. 1-Hexin (1) wird dabei durch 1,2-H-Verschiebung und 1,5-C,H-Insertion des intermediär gebildeten Pentylidencarbens (vgl. Schema 1) in 3-Methyl-1-cyclopenten (5) umgelagert. 5-Methyl-1-hexin (2) reagiert analog; es entsteht 3,3-Dimethyl-1-cyclopenten (6). Im Gegensatz zur Bildung von in 3-Stellung methylierten Cyclopentenen aus 1-Alkinen ensteht aus 2-Hexin (3) 1-Methyl-1-cyclopenten (7). Offenbar ist die Acetylen-Vinyliden-Umlagerung nicht auf 1,2-H-Verschiebung beschränkt. Der Mechanismus der Cycloisomerisierung von Alkylacetylenen wird durch Untersuchungen mit D-markierten Alkinen bestätigt. Die Ergebnisse lassen den Schluß zu, daß die Cycloisomerisierung ohne weiteres mit dem überwiegend nach einem Radikalketten-Mechanismus verlaufenden thermischen Zerfall konkurrieren kann.
    Notizen: The thermal cycloisomerization of some alkylacetylenes was investigated in a tubular quartz reactor. At 570°C 1-hexyne (1) rearranges to 3-methyl-1-cyclopentene (5) with a selectivity of about 27 by a reaction sequence including an acetylene-vinylidene rearrangement and 1,5-C,H insertion of the intermediately formed alkylidenecarbene species. 5-methyl-1-hexyne (2) behaves analogously forming 3,3-dimethyl-1-cyclopentene (6), while 2-hexyne (3) provides 1-methyl-1-cyclopentene (7) indicating that the acetylene-vinylidene rearrangement is obviously not restricted to 1,2-H shifts. The mechanism of the cycloisomerization of alkylacetylenes is investigated by means of D-labeled parent alkynes. The results show that the unimolecular cycloisomerization via alkylidenecarbenes obviously can be an important channel despite the dominance of a radical chain course.
    Zusätzliches Material: 1 Ill.
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  • 62
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 745-748 
    ISSN: 0009-2940
    Schlagwort(e): Flash Pyrolysis ; Matrix IR spectroscopy ; Photolysis ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Methoxy- und AminoisocyanatMethoxyisocyanat (1) kann durch Photolyse von Azidoameisensäure-methylester (3) oder Pyrolyse von N-Methoxycarbonyl-O-methylhydroxylamin (4) dargestellt werden. Aminoisocyanat (2) ist auf ähnliche Weise durch Photolyse von Carbamoylazid (12) und Pyrolyse von Carbazinsäure-methylester (13) oder 3,4-Diaminofurazan (14) zugänglich. Die IR-Spektren von 1 und 2, aufgenommen in einer Argon-Matrix bei 10 K, werden diskutiert.
    Notizen: Methoxyisocyanate (1) can be prepared by photolysis of methyl azidoformate (3) or pyrolysis of N-methoxycarbonyl-O-methyl-hydroxylamine (4). Aminoisocyanate (2) is similarly formed on photolysis of carbamoyl azide (12) and pyrolysis of either methyl carbazate (13) or 3,4-diaminofurazan (14). The infrared spectra of 1 and 2 in an argon matrix at 10 K have been measured, and some of their properties are discussed.
    Zusätzliches Material: 1 Ill.
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  • 63
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 749-752 
    ISSN: 0009-2940
    Schlagwort(e): Matrix isolation ; Photochemistry ; Theoretical vibrational spectra ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Infrarot-Spektren und Photochemie von Isodiazen und seinen deuterierten IsotopomerenDie Matrixisolation von Aminoisocyanat eröffnet einen neuen ergiebigen Weg zur Darstellung von Isodiazen (Aminonitren). Damit ist es möglich geworden, nicht nur sein IR-Spektrum eindeutig festzulegen und mit Hilfe von ab-initio-Rechnungen zu interpretieren, sondern auch seine Photochemie zu untersuchen.
    Notizen: The matrix isolation of aminoisocyanate opens a new efficient route for the preparation of isodiazene (aminonitrene). Its infrared spectrum can now, with the help of ab initio calculations, be interpreted, and its photochemistry can be studied.
    Zusätzliches Material: 2 Ill.
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  • 64
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 795-796 
    ISSN: 0009-2940
    Schlagwort(e): Thiochalcones ; Thienylchalcones ; Fries rearrangement ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Four new thienylchalcones (1, 4, 5, and 6) were synthesized by condensing hydroxy-nitroacetophenones with 2-thiophene and 3-thiophenecarboxaldehydes in the presence of dilute NaOH.
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  • 65
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 767-779 
    ISSN: 0009-2940
    Schlagwort(e): Molecular twisting ; cis-9,10-Dihydronaphthalenes, persubstituted ; Valence isomerizations ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Valence Isomerizations, 17. - Persubstituted cis-9,10-Dihydronaphthalenes and their Valence IsomerizationsThe tricyclic diester 10 is available from 2-butyne in a six-step synthesis with an overall yield of 10%. Thermolysis of 10 gives the bicyclic diester 11 which upon UV irradiation yields 12 as the first persubstituted cis-9,10-dihydronaphthalene. X-ray analysis of 12 shows the molecule considerably twisted along the central bond. In addition, the planes of the ester groups are at an angle of approximately 60° to the „planes“ of the six-membered rings so that conjugation of the diene systems with the carbonyl functions is virtually interrupted, an effect which is reflected by the unusual spectroscopic properties of 12. The same structural features can be found in decamethyl-cis-9,10-dihydronaphthalene (16). When heated slightly, 12 is converted to the tetracyclic valence isomer 34. On reduction of 12 with diisobutylaluminum hydride both, dihydronaphthalene dicarbinol 25 as well as its unexpected positional isomer 26, are formed depending on the reaction conditions. Etherification of the reduction products with CH2N2/Et2O—BF3 furnishes a mixture of the three isomeric bis(methoxymethyl) compounds 31, 32 and 33. They can be separated by chromatography in the cold, but revert to the mixture of the three isomers at room temperature. We consider diradical 38 to be the intermediate of this intriguing valence isomerization.
    Notizen: Der tricyclische Diester 10 ist in sechs Stufen in einer Gesamtausbeute von 10% aus 2-Butin zugänglich. Thermolyse von 10 liefert den Bicyclus 11, bei dessen UV-Bestrahlung das erste persubstituierte cis-9,10-Dihydronaphtalin 12 gebildet wird. Eine Röntgenstrukturanalyse von 12 beweist die starke Verdrillung des Moleküls um die zentrale Bindung. Die Ebenen der Ester-Gruppen stehen ungefähr in einem 60°-Winkel zu den Sechsring-„Ebenen“, so daß die Konjugation der Dien-Systeme mit den Carbonyl-Funktionen praktisch unterbrochen ist, ein Effekt, der sich in den ungewöhnlichen spektroskopischen Eigenschaften von 12 widerspiegelt. Analoge Strukturmerkmale gelten auch für das Decamethyl-cis-9,10-dihydronaphthalin (16). Bicyclus 12 wandelt sich bei leichtem Erwärmen in den valenzisomeren Tetracyclus 34 um. Reduktion von 12 mit Diisobutylaluminiumhydrid gibt je nach den Reaktionsbedingungen das Dihydronaphthalindicarbinol 25 bzw. das unerwartete Stellungsisomere 26. Veretherung der Reduktionsprodukte mit CH2N2/Et2O—BF3 liefert ein Gemisch der drei isomeren Bis(methoxymethyl)-Verbindungen 31, 32 und 33, die chromatographisch in der Kälte trennbar sind, aber schon bei Raumtemperatur wieder das Gemisch der drei Isomeren zurückbilden, wobei das Diradikal 38 als Zwischenprodukt dieser erstaunlichen Valenzisomerisierung anzunehmen ist.
    Zusätzliches Material: 2 Ill.
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  • 66
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 803-808 
    ISSN: 0009-2940
    Schlagwort(e): Bismuth organic compounds ; Fluorinated aromatic rings ; Square pyramidal bismuth ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Structures of Pentaarylbismuth CompoundsPentaarylbismuth compounds were synthesized by the known reaction Ar3BiX2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2. Whenever possible they were characterized by single-crystal X-ray structure determination. In two cases almost ideal square-pyramidal geometry was found, in a third case there were two different molecules in the unit cell, both again with square-pyramidal geometry. None of these novel bismuth pentaaryls exhibit the deep coloration and the dichroism of Bi(C6H5)5.
    Notizen: Pentaarylbismut- Verbindungen wurden durch die bekannte Reaktion BiAr3X2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2 hergestellt und, soweit möglich, durch Röntgenbeugung an Einkristallen strukturell untersucht. In zwei Fällen erwies sich die Struktur als nahezu ideal quadratisch-pyramidal, in einem dritten Fall wurden zwei unterschiedliche Moleküle im Kristall gefunden, die aber beide wiederum quadratisch-pyramidal sind. Keines der hier vorgestellten neuen Bismutpentaaryle zeigt die tiefe Färbung und den Dichroismus von Bi(C6H5)5.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 67
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 533-535 
    ISSN: 0009-2940
    Schlagwort(e): Free radicals ; Triphenylmethyl radicals ; ESR measurements ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Sterically Hindered Free Radicals, XIX. - Stable 4,4′,4″-Trisubstituted Triphenylmethyl RadicalsThe title radicals (4-R—C6H4)3C. (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, have been prepared, the latter four for the first time, and the ESR spectra have been recorded. aoH, amH, and apR are listed. The intensities of the ESR signals remain constant within the accessible range of -30 to + 100°C. Within this range these radicals are kinetically stable and do not dimerize like other trityls by, e.g., α,p-, α,o-, α,α -recombinations.
    Notizen: Die Titelradikale (4-R—C6H4)3C· (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, wurden dargestellt, davon die vier letzten erstmalig, und mittels ESR-Spektroskopie vermessen. aoH, amH und apR werden angegeben. Die ESR-Signale bleiben im gesamten zugänglichen Temperaturbereich - 30 bis + 100°C in ihrer Intensität unverändert. Daraus folgt, daß alle diese Radikale im genannten Temperaturbereich kinetisch stabil sind, also nicht wie andere Trityle zu Dimerisierungen, etwa α,p-, α,o-, α,α-, neigen.
    Zusätzliches Material: 1 Tab.
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  • 68
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 523-531 
    ISSN: 0009-2940
    Schlagwort(e): Dicyclopenta-s-indacene ; 2-Osxa[3.3.3]propellane derivatives ; Pentalene derivatives ; [3.3.3]Propellane-3,7-dione ; Weiss reaction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Novel Products in the Weiss Reaction of 1,2-Cyclopentanedione. Improved Preparation of [3.3.3]Propellane-3,7-dioneThe reaction of 1,2-cyclopentanedione (1c, 9) with the 3-oxoglutarate 4 in methanol/water in the presence of sodium bicarbonate followed by hydrolysis and decarboxylation of the product mixture affords the oxa[3.3.3]propellane ester 11c in addition to the [3.3.3]propellanedione 6c. The alkali enolates of 4 react with 9 in boiling methanol to yield the yellow, poorly soluble alkali dihydropentalenolates 12M and the [3.3.3]propellane tetraester 5c, which on hydrolysis and decarboxylation yields 53% of 6c. The dihydropentalenol 12H equilibrates with the tautomeric β-oxodiester 13, the proportion of which increases with solvent polarity. In methanol solutions, 12H and 13 add diastereoselectively forming the dicyclopenta-s-indacene tetraester syn-14, which is derived from a novel pentacyclic ring system. The configuration of syn-14 is determined by X-ray diffraction analysis. The mechanisms of formation are discussed for 11c, 12M, and syn-14.
    Notizen: Nach Umsetzung von 1,2-Cyclopentandion (1c, 9) mit dem 3-Oxoglutarsäureester 4 in Methanol/Wasser in Gegenwart von Natriumhydrogencarbonat, saurer Hydrolyse und Decarboxylierung des Produktgemischs erhält man neben dem [3.3.3]Propellandion 6c den Oxa[3.3.3]propellanester 11c. Die Alkali-Enolate von 4 reagieren mit 9 in siedendem Methanol zu den gelben, schwer löslichen Dihydropentalenolaten 12M und dem [3.3.3]Propellantetraester 5c, der nach Hydrolyse und Decarboxylierung 53% 6c ergibt. Das Dihydropentalenol 12H liegt im Gleichgewicht mit dem tautomeren β-Oxodiester 13 vor, dessen Anteil mit der Polarität des Lösungsmittels zunimmt. In Methanol addieren sich 12H und 13 diastereoselektiv und bilden den Dicyclopenta-s-indacentetraester syn-14, der sich von einem neuartigen, pentacyclischen Ringsystem ableitet. Die Konfiguration von syn-14 wird durch Röntgenstrukturbestimmung aufgeklärt. Die Mechanismen der Bildung von 11c, 12M und syn-14 werden diskutiert.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 69
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 553-559 
    ISSN: 0009-2940
    Schlagwort(e): Amino acids ; Diastereoselective addition ; 1-(Methacryloyl)proline derivatives ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Amino Acids, 15. - Diastereoselective Addition of Thiocarboxylic Acids to 1-(Methacryloyl)proline and-prolinol DerivativesThiocarboxylic acids 6 add to 1-(methacryloyl)-substituted proline and prolinol derivatives stereoselectively to give the 1-[3-(acylthio)-2-methylpropionyl]proline and -prolinol derivatives 7,7′ and 9. The less soluble (2S,2′R)-diastereomers are obtained in optical yields ≥ 98% by digestion of the crude products, the configuration of which was determined by acid hydrolysis of (2S,2′R)-7,7′ to (R)-3-mercapto-2-methylpropionic acid [(R)-8]. The stereoselectivity of the additions may be explained by a sevenmembered ring intermediate with an intramolecular H bridge, to which the S-nucleophiles add preferentially to give the compounds with the (2′R)-configuration.
    Notizen: Thiocarbonsäuren 6 addieren stereoselektiv mit hohen optischen Ausbeuten an 1-(Methacryloyl)-substituierte Prolin- und Prolinol-Derivate zu den 1-[3-(Acylthio)-2-methylpropionyl]prolin-und -prolinol-Derivaten 7,7′ und 9. Durch Digerieren der Rohprodukte mit Diethylether werden die schwerer löslichen (2S,2′R)-Diastereomeren in optischen Ausbeuten ≥98% erhalten, deren Konfiguration durch Acidolyse von (2S,2′R)-7,7′ zu (R)-3-Mercapto-2-methylpropansäure [(R)-8] bewiesen wurde. Die Stereoselektivität der Additionen wird über einen Siebenring mit intramolekularer H-Brücke als Zwischenstufe, an die Schwefelnucleophile bevorzugt unter Bildung der (2′R)-Konfiguration addieren, gedeutet.
    Zusätzliches Material: 10 Tab.
    Materialart: Digitale Medien
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  • 70
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 545-551 
    ISSN: 0009-2940
    Schlagwort(e): Amino acids ; Diastereoselective addition ; 1-Acryloylproline esters ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Amino Acids, 14. - Diastereoselective Addition of Benzenesulfenyl Chloride to 1-Acryloylproline Esters(S)-Proline esters (S)-1 react with acryloyl chloride (2) to give 1-acryloylproline esters (S)-3 in good yields. Addition of benzenesulfenyl chloride (6) to (S)-3 at -95°C in dichloromethane results in 1-[2-chloro-3-(phenylthio)propionyl]proline esters (2S,2′R/2S,2′S)-7. The diastereoselectivity of the addition depends on the conformer ratio 3′/3″ of the starting material (S)-3. The diastereomers are separated by MPLC. Configuration at C-2′ of the resulting main products (2S,2′S)-7 was proved by independent synthesis. The diastereoselectivity of the addition of 6 to (S)-3 is interpreted to result from formation of a complex of the benzenesulfenyl cation with the proline ester group and subsequent electrophilic addition to a thiiranium intermediate B with (2S,2′R) configuration; the (2S,2′S) diastereomeric adduct 7 then results by nucleophilic attack of chloride at C-2′ under ring opening.
    Notizen: Die 1-Acryloylprolinester (S)-3 werden durch N-Acylierung der Prolinester (S)-1 mit Acryloylchlorid (2) in guten Ausbeuten hergestellt; sie addieren Benzolsulfenylchlorid (6) bei -95°C in Dichlormethan mit hoher Diastereoselektivität zu 1-[2-Chlor-3-(phenylthio)propionyl]prolinestern (2S,2′R/2S,2′S)-7, die mittels MPLC getrennt werden. Die Diastereoselektivität der Addition hängt vom Konformerenverhältnis 3′/3″ der Edukte (S)-3 ab. Der Beweis der Konfiguration an C-2′ der als Hauptprodukte anfallenden Diastereomeren (2S,2′S)-7 wird durch eine unabhängige Synthese erbracht. Die Diastereoselektivität der Addition von 6 an (S)-3 wird über eine Komplexbildung des Phenylsulfenylkations mit der Prolinestergruppe und eine sich anschließende elektrophile Reaktion zu einer Thiiranium-Zwischenstufe B mit (2S,2-R)-Konfiguration gedeutet; das (2S,2′S)-diastereomere Additionsprodukt 7 entsteht dann durch nucleophilen Angriff des Chlorids an C-2′ unter Ringöffnung.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
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  • 71
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 851-855 
    ISSN: 0009-2940
    Schlagwort(e): Diphosphines ; Tungsten - tungsten quadruple bond ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese und Struktur von W2Cl4{μ(iPr2PCH2CH2CH2PiPr2)}2: Eine durch sperrige, chelatisierende Diphosphane überbrückte Wolfram - Wolfram-VierfachbindungDie Reduktion von WCl4 in THF durch zwei Äquivalente Na/Hg in Gegenwart des sperrigen, chelatisierenden Diphosphinopropans iPr2PCH2CH2CH2PiPr2 (dippp) liefert den violetten, zweikernigen Komplex W2Cl4(μ-dippp)2. Der Komplex besitzt eine W-W-Vierfachbindung und β-Struktur, d.h. die chelatisierenden Diphosphinopropan-Liganden verbrücken die beiden Metall-Zentren. Die 1H-NMR-spektroskopischen Daten zeigen Tieffeldverschiebungen für die dippp-Liganden, die im Einklang mit der β-Struktur stehen. Das 31P{1H}-NMR-Spektrum besteht aus einem Singulett mit 183W-Satelliten. Die Röntgen-Stukturanalyse ergibt für die β-Struktur einen Torsionswinkel P-W-W-P von 75.9° und eine W-W-Bindungslänge von 2.297(1) Å. Aus den Molekülstruktur-Daten und den 1H-NMR-Tieffeldverschiebungen kann die diamagnetische Anisotropie χ der W-W-Vierfachbindung mit - 3000 ± 300 × 10-36 m3/Molekül abgeschätzt werden. Die für den festen Zustand beobachtete Chiralität wird auch in Lösung beibehalten.
    Notizen: The reduction of WCl4 in THF by two equivalents of Na/Hg in the presence of the bulky chelating diphosphine iPr2PCH2-CH2CH2PiPr2 (dippp) generates the purple, binuclear complex W2Cl4(μ-dippp)2. The quadruply-bonded molecule has a β structure, that is, the chelating diphosphine bridges the two metal centers. 1H-NMR spectral data show downfield shifts for the ligand protons consistent with the β structure. The 31P{1H}-NMR spectrum consists of a singlet with 183W satellites. The X-ray crystal structure has a twist angle (P-W-W-P torsion angle) of 75.9°, and the W-W bond length is 2.297(1) Å. Using the solidstate data and the observed downfield shifts in the 1H-NMR spectrum, the diamagnetic anisotropy χ has been estimated as - 3000 ± 300 × 10-36 m3/molecule. The chiral structure observed in the solid phase is retained in solution.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 72
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 861-864 
    ISSN: 0009-2940
    Schlagwort(e): Aminoiminophosphanes ; 1,3,2λ5,4-Thiazaphosphaboretidines ; 1,2,4,3,5-Trithiadiborolanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis and Characterization of 1, 3, 2λ5, 4-ThiazaphosphaboretidinesThe reaction of 1,2,4,3,5-trithiadiborolanes with silylated aminoiminophosphanes leads to the 1,3,2λ5,4-thiazaphosphaboretidines 1a-i. The formation of 1h, i is accompanied by an exchange of the substituents bonded to the N atoms. 1H-, 11B-, 13C-, 29Si-, 31P-NMR, and mass spectra are discussed.
    Notizen: Die Umsetzung von 1,2,4,3,5-Trithiadiborolanen mit silylierten Aminoiminophosphanen führt zu den 1,3,2λ5,4-Thiazaphosphaboretidinen 1a-i. Die Bildung von 1h, i wird von einem Austausch der N-ständigen Substituenten begleitet. 1H-, 11B-, 13C-, 29Si-, 31P-NMR- und Massenspektren werden diskutiert.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 73
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 857-860 
    ISSN: 0009-2940
    Schlagwort(e): Alkenylboranes ; Alkenylstannanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: A Convenient Route from Alkenylboranes to AlkenylstannanesAlkenyldialkylboranes 1 with various substituents at the C=C double bond, including organometallic groups such as the trimethylstannyl or trimethylsilyl group, react in hexane solution with (diethylamino)- or (dimethylamino)trimethylstannane (2) in the presence of a catalytic amount of lithium dimethyl- or diethylamide (3) to give aminodialkylboranes 4 and alkenyltrimethylstannanes 5 in high yields with retention of the configuration at the C—C double bond. With (diethylamino)trimethylplumbane (2c) the less stable alkenes 5Pb are obtained. A mechanism is proposed, and 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-data are reported.
    Notizen: Alkenyldialkylborane 1 mit verschiedenen Substituenten an der C=C-Doppelbindung, einschließlich organometallischer Gruppen wie dem Trimethylstannyl- oder dem Trimethylsilyl-Rest, reagieren in Hexan mit (Diethylamino)- oder (Dimethylamino)trimethylstannan (2) in Gegenwart einer katalytischen Menge von Lithium-diethylamid (3b) oder -dimethylamid (3a) in hoher Ausbeute unter Beibehaltung der Konfiguration an der C—C-Doppelbindung zu den entsprechenden Alkenylstannanen 5 und Aminoboranen 4. Durch Einsatz von (Diethylamino)trimethylplumban (2c) lassen sich die weniger stabilen Alkene 5Pb erhalten. Ein Mechanismus wird vorgeschlagen, und 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-Daten werden mitgeteilt.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 74
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1919-1924 
    ISSN: 0009-2940
    Schlagwort(e): Hydrogen transfer ; Ziegler catalysis ; Dihydroarenes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Ziegler Nickel Catalysts for Hydrogen Transfer ReactionsCatalysts prepared from Ni(acac)2 and AlEt3 show high catalytic activity in the hydrogen transfer between dihydroarenes, but hardly any isomerisation and H/D scrambling is observed. The active form of the catalyst is produced only in the presence of the starting material. Kinetic experiments, especially those concerning the introduction periods and the inhibition, are indicative of a complex reaction mechanism. The first hydrogen is preferentially abstracted from the 2-position, the second with complete cis selectivity.
    Notizen: Der aus Ni(acac)2 und AlEt3 dargestellte Katalysator zeigt eine hohe Aktivität beim H-Transfer zwischen Dihydroarenen, neben dem Isomerisierungen und H/D-Austausch kaum ablaufen. Die aktive Form entsteht erst in Gegenwart des Edukts. Kinetische Untersuchungen, vor allem zur Induktionsperiode und zur Hemmung, deuten auf einen komplexen Ablauf. Der Wasserstoff wird cis-selektiv abgespalten, primär bevorzugt aus der 2-Position.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 75
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1925-1927 
    ISSN: 0009-2940
    Schlagwort(e): Hydrogen transfer ; Olefin isomerization ; Cobalt complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Hydrogen Transfer Reactions, 13.  -  Catalysis of Disproportionation by (Dinitrogen)hydridotris(triphenylphosphine)cobalt(I)For both C—H activation and olefin isomerization, CoH(N2)(PPh3)3 (1) is a more powerful catalyst than the Wilkinson complex. In 1,2-dihydronaphthalene (2), a two-step cis abstraction of the hydrogen atoms is found with small regioselectivity in the first step.
    Notizen: Die Aktivität des Komplexes CoH(N2)(PPh3)3 (1) liegt bei der C—H-Aktivierung deutlich höher als beim Wilkinson-Katalysator. Noch effektiver wird aber eine Olefin-Isomerisierung induziert. Die zweistufige H-Abstraktion erfolgt beim 1,2-Dihydronaphthalin (2) cis-selektiv, der Primärschritt aber kaum regioselektiv.
    Materialart: Digitale Medien
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  • 76
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1935-1938 
    ISSN: 0009-2940
    Schlagwort(e): as-Triazinium salt, fused ; Ring transformation ; Solvatochromy, negative ; Zwitterion ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese und Ringtransformation von neuen kondensierten as-Triazinium-SalzenDie Reaktion des 1,2-Diaminopyridinium-Salzes 1 mit dem Furandion 2 ergab ein Pyrido-as-triazinon 3, das zum tricyclischen Furo[2,3-e]pyrido[1,2-b]-as-triazinium-Salz 5 cyclisiert wurde. Die Reaktion von 5 mit Nucleophilen führte zu unterschiedlichen Produkten: mit wäßriger Base entstand das bicyclische Triazinon 4, mit dem Methoxid-Ion und sekundären Aminen wurden die stabilen Zwitter-Ionen 7a, b erhalten, wohingegen Ammoniak und Hydrazine unter Transformation des Furanringes die neuen tricyclischen kondensierten Pyrrole 10, 11 bzw. Pyridazine 13, 14a, b ergaben.
    Notizen: The 1,2-Diaminopyridinium salt 1 was treated with furandione 2 to give pyrido-as-triazinone 3, which could be cyclized to the tricyclic furo[2,3-e]pyrido[1,2,-b]-as-triazinium salt 5. Reaction of 5 with nucleophiles resulted in different types of products. Thus, aqueous base afforded bicyclic triazinone 4, methoxide ion or secondary amine led to stable zwitterions 7a, b, whereas ammonia and hydrazines resulted in ring transformation of the furan moiety, and gave new fused tricyclic pyrroles (10, 11) and pyridazines (13, 14), respectively.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 77
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1947-1953 
    ISSN: 0009-2940
    Schlagwort(e): Enol ethers ; [n](2,4)Phloroglucinophanes ; Autoxidation ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Investigations of the Autoxidation and the Rearrangement of [n](2,4)PhloroglucinophanesIn the autoxidation of [n](2,4)phloroglucinophanes 3 hydroperoxides 7 are isolated in several cases as the first oxidation products; they react to the more stable monohydroxylated compounds 8 with different rates. Acylphloroglucinophanes 5, however, react with oxygen to give the dihydroxylated compounds 9. The autoxidation rate of the phloroglucinophanes 3, 5 is markedly larger than that of diethylphloroglucinols 6. In alkaline solution the hydroxy compounds 8 rearrange to the dihydroxycyclopentenones 12; the rate of rearrangement correlates with the decrease of ring strain.
    Notizen: Bei der Autoxidation von [n](2,4)Pholoroglucinophanen 3 können in einigen Fällen Hydroperoxide 7 als erste Oxidationsprodukte isoliert werden, die unterschiedlich rasch in die stabileren monohydroxylierten Verbindungen 8 übergehen. Aclphloroglucinophane 5 reagieren mit Luftsauerstoff dagegen zu den zweifach hydroxylierten Verbindungen 9. Die Geschwindigkeit der Autoxidation ist bei den Phloroglucinophanen 3, 5 deutlich größer als bei den 2,4-Diethylphloroglucinen 6. Im alkalischen Medium lagern sich die Hydroxyverbindungen 8 in die Dihydroxycyclopentenone 12 um, wobei für die Geschwindigkeit der Umlagerung eine Korrelation mit der Abnahme an Ringspannung gefunden wird.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 78
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1963-1967 
    ISSN: 0009-2940
    Schlagwort(e): Allenyl azides, ring closure of ; Propargyl azides, rearrangement, base-induced ; Triazafulvenes, nucleophilic addition to ; 1,2,3-Triazoles, preparation of ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Reactions of Unsaturated Azides, 7.  -  Base-catalyzed Formation of Allenyl Azides from Propargyl Azides: New Syntheses for 1,2,3-TriazolesThe propargyl azides 10, 14, 17, 20, and 28 undergo a base-catalyzed (prototropic) rearrangement to short-lived allenyl azides. These intermediates rapidly cyclize to triazafulvenes, which can be trapped by nucleophiles (methanol, sodium hydroxide, ammonia) to give 1,2,3-triazoles. Starting with the precursors 9, 13, 16, 19, and 27 one-pot syntheses lead to the heterocycles 12, 15, 18, 21, and 29. Depending on the reaction conditions, compound 10 regioselectively yields 12c (75%) by prototropic rearrangement (path B) or by migration of the azide group (path A) the isomer 11c (62%).
    Notizen: Die Propargylazide 10, 14, 17, 20 und 28 lagern sich basenkatalysiert (prototrop) zu kurzlebigen Allenylaziden um. Diese Zwischenstufen cyclisieren rasch zu Triazafulvenen, die mit Nucleophilen (Methanol, Natriumhydroxid, Ammoniak) als 1,2,3-Triazole abgefangen werden können. Ausgehend von den Vorläufern 9, 13, 16, 19 und 27 führen Eintopf-Synthesen zu den Heterocyclen 12, 15, 18, 21 und 29. In Abhängigkeit von den Reaktionsbedingungen liefert 10 über die prototrope Umlagerung (Weg B) regioselektiv 12c (75%) oder durch Azidwanderung (Weg A) die isomere Verbindung 11c (62%).
    Materialart: Digitale Medien
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  • 79
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2023-2025 
    ISSN: 0009-2940
    Schlagwort(e): Homoallylic alcohols ; [2,3] Sigmatropic rearrangement ; Stereoselective synthesis of alcohols ; [2,3] Wittig rearrangement ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reductive cleavages of allyl [(phenylthio)methyl] ethers (8, 11) and an allyl [(tolylsulfonyl)methyl] ether (14) with lithium naphthalenide in THF furnish homoallylic alcohols (9, 12). The steric course of these transformations (E/Z selectivity in the case of 9, syn/anti selectivity for 12) is very similar to that of analogous Wittig-Still rearrangements.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 80
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 81
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2049-2054 
    ISSN: 0009-2940
    Schlagwort(e): Ligating properties ; Pentaphosphaferrocenes ; Sandwich and triple-decker complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Pentaphospaferrocenes as Complex LigandsThe interaction of [Cp*Fe(P5)] (1a) with [Cr(CO)5(thf)] and [Cp(CO)2Mn(thf)], respectively, affords [Cp*Fe(P5){Cr(CO)5}2] (2) as well as [Cp*Fe(P5){Mn(CO)2Cp}n] (4a-d; n = 1-4; Cp* = η5-C5Me5). Irradiation of 1 and [CpFe(C6H6)]PF6 gives the cationic 30-VE triple-decker complexes [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5). In addition to the NMR studies 2 and 3b have been characterized by X-ray structure analyses.
    Notizen: Die Umsetzung von [Cp*Fe(P5)] (1a) mit [Cr(CO)5(THF)] bzw. [Cp(CO)2Mn(THF)] ergibt [Cp*Fe(P5){Cr(CO)5}2] (2) sowie [HCp*Fe(P5){Mn(CO)2Cp}n] (4a-d; 1-4; Cp* = η5-C5Me5). Aus 1 und [CpFe(C6H6)]PF6 lassen sich photochemisch die kationischen 30-VE-Tripeldeckerkomplexe [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5) aufbauen. Zusätzlich zu den NMR-spektroskopischen Studien wurden von 2 und 3b Kristallstrukturanalysen angefertigt.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 82
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 83
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1139-1145 
    ISSN: 0009-2940
    Schlagwort(e): C-(Alkylideneamino)ketene imines ; Isocyanides, C=C coupling with aminocarbene ligands ; (2-Azaallenyl)chromium complexes ; 2-Imidazolin-5-ones ; α-Amino acids ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Organic Syntheses via Transition Metal Complexes, 35. - (C-Amino) Ketene Imines, 2-Imidazolin-5-ones, and α-Amino Acids from Aminocarbene Chromium Complexes and IsocyanidesC-(Alkylidenamino)ketene imines 1,4-diaza-1,2,4-pentatrienes) 8 are easily accessible by C=C coupling of isocyanides R1 - NC (2, R1 = t-C4H9, c-C5H11, CH3) with the (alkylideneamino)carbene (= 2-azaallenyl-) ligand of (6). The tendency for an insertion of 2 into M=C bonds of aminocarbene complexes strongly depends on the electronic character of the aminocarbene ligand. Electron-rich aminocarbene chromium complexes like (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), show only little tendency for an insertion but mainly give cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) by substitution of CO. Electron-poor aminocarbene complexes like 6 (readily available on N-benzoylation of 1a) undergo a facile insertion of 2 into the M=C bond with smooth formation of 7. From 7 ketene imine 8 is spontaneously disengaged by a second equivalent of 2. The reaction works especially well with bulky isocyanides 2a, b. In the case of methyl isocyanide (2c) a [bis(imino)dihydropyrrol]chromium complex 15 is obtained as a minor product besides 8c. 15 results from a [4+1] cycloaddition of 2c at the ketene imine ligand of 7c. C-(Alkylideneamino)ketene imines 8 are easily accessible by our method. They prove to be very thermolabile in solution and spontaneously isomerize to give 2-imidazolin-5-ones 10 and C-amidoketene imines 11. Under the influence of wet silica gel keten imine derivatives 8 rapidly form α-amino acid amides 16 by hydrolysis with concomitant migration of a benzoyl group. Under the same conditions 11 also gives the „normal“ α-amino acid amides 17.
    Notizen: C-(Alkylideneamino)ketenimine (1,4-Diaza-1,2,4-pentatriene) 8 wurden durch C=C-Kupplung von Isocyaniden R1-NC (2, R1 = t-C4H9, c-C5H11, CH3) mit dem (Alkylideneamino)carben-(= 2-Azaallenyl-)Ligand von (6) erstmals hergestellt. Die Bereitschaft zur Insertion von 2 in M=C-Bindungen von Aminocarbenkomplexen hängt stark von den elektronischen Eigenschaften der Aminocarbenliganden ab. Elektronenreiche (Aminocarben)chromkomplexe, wie z. B. (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), zeigen eine nur geringe Neigung zur Insertion von 2 und bilden bevorzugt cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) unter Substitution von CO. Elektronenarme (Aminocarben)chromkomplexe hingegen, wie z. B. 6 (durch N-Benzoylierung von 1a leicht zugänglich), zeigen ausschließlich Insertion zu 7. Aus 7 wird spontan 8 freigesetzt durch Substitution mit einem zweiten Äquivalent 2. Sperrige Isocyanide 2a, c reagieren besonders einheitlich. Mit Methylisocyanid (2c) entsteht zusätzlich zu 8c der [Bis(imino)dihydropyrrol]-chromkomplex 15 unter [4+1]-Cycloaddition von 2c am Keteniminligand von 7c. C-(Alkylidenamino)ketenimine 8 sind nach unserem Verfahren einfach zugänglich; sie isomerisieren jedoch leicht zu 2-Imidazolin-5-onen 10 und C-Amidoketeniminen 11. An feuchtem Kieselgel entstehen aus 8 rasch α-Aminosäureamide 16 durch Hydrolyse unter Wanderung eines Benzoylrestes; aus 11 unter gleichen Bedingungen zusätzlich „normale“ α-Aminosäureamide 17.
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  • 84
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2177-2181 
    ISSN: 0009-2940
    Schlagwort(e): Benzonitriles ; Hetero Diels-Alder reactions, “inverse” ; Pyrazines, annulated ; Triazines, benzofuro- and benzothieno- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Donor-Substituted Benzoitriles as Side-Chain Dienophiles in the Intramolecular [4+2] Cycloaddition with Inverse Electron DemandExpanding the scope of the intramolecular Diels-Alder reaction of 1,2,4,5-tetrazines to include donor-substituted benzonitriles as side-chain dienophiles we describe synthetic routes to novel fused heterotricycles such as the benzofuro[3,2-e]-1,2,4-triazines 11a, b and the benzothieno[3,2-e]-1,2,4-triazines 14a, b, and 17. The doubly annulated pyrazines 22 and 23 are constructed by a subsequent second intramolecular Diels-Alder cycloaddition of the benzonitrile moiety with the fused 1,2,4-triazine system, starting from 11a and 14a.
    Notizen: Unter Einschluß donorsubstituierter Benzonitrile als Seitenkettendienophile haben wir die Anwendungsbreite der intramolekularen Diels-Alder-Reaktion von 1,2,4,5-Tetrazinen erweitert und beschreiben Synthesewege zu neuen anellierten Heterotricyclen wie den Benzofuro[3,2-e]-1,2,4-triazinen 11a, b und den Benzothieno[3,2-e]-1,2,4-triazinen 14a, b sowie 17. Die doppelt anellierten Pyrazine 22 und 23 lassen sich durch eine nachfolgende zweite intramolekulare Benzonitril/1,2,4-Triazin-Diels-Alder-Cycloaddition mit 11a bzw. 14a als Edukten herstellen.
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  • 85
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2147-2157 
    ISSN: 0009-2940
    Schlagwort(e): 1,3-Dipolar cycloadditions, intramolecular ; Nitrile oxides ; Regioselectivity ; Furanophanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Intramolecular Cycloadditions with Nitrile Oxides: Investigtions towards the Synthesis of HeterophanesThe intramolecular cycloaddition reactions of the nitrile oxides 30a-d, 35, 36, and 47, obtained in situ from the 2,5-difunctional furan hydroximoyl chlorides 12a, b, 18 and the nitro compounds 9c, d, 21, 29, are described. With 30c the expected isoxazolofuranophane of type 31 is formed in acceptable yield; the additionally formed regioisomer 32c and the dimer 34c are very minor products in this case. Whereas the highest homologue 30d gives a complex product mixture with small amounts of 31 d and the macrocycle 34d as the only identified compounds, the derivatives bearing a shorter side chain (30a, b; n = 1, 2) give rise to the exclusive reaction of the dipole with a double bond of the furan system (to give 33a, b). The same behavior is observed in the case of the electronically and sterically modified dipole systems 35/36 and 47, resp.; in spite of the much more favorable conditions for the formation of cyclophanes the cycloadditions result in the exclusive formation of the heterotricycles 41, 42 and 49. Possible preparative applications of the isomeric cycloaddition compounds are discussed.
    Notizen: Die intramolekularen Cycloadditionsreaktionen der aus 2,5-difunktionellen Furan-Hydroximsäurechloriden (12a, b und 18) bzw. den Nitroverbindungen 9c, d, 21 und 29 in situ hergestellten Nitriloxide 30a-d, 35, 36 und 47 werden beschrieben. Eine Reaktion zu den angestrebten Isoxazolo-furanophanen des Typs 31 verläuft für 30c in brauchbarer Ausbeute; das Regioisomere 32c sowie das Dimere 34c treten hierbei nur in geringem Maße auf. Während das höchste Homologe 30d neben 31d und dem Makrocyclus 34d hauptsächlich Zersetzungsprodukte bildet, reagieren die Derivate mit kürzerer Seitenkette (30a, b; n = 1, 2) ausschließlich unter dipolarer Addition an eine Furandoppelbindung zu 33a, b. Für n = 1 entsprechen diesem Verhalten auch die elektronisch bzw. sterisch modifizierten Dipolsysteme 35/36 und 47, die trotz günstigerer Voraussetzungen für die Cyclophanbildung nur zu den Tricyclen 41, 42 bzw. 49 reagieren. Die präparativen Anwendungsmöglichkeiten der isomeren Cycloadditionsverbindungen als Synthesezwischenprodukte werden diskutiert.
    Zusätzliches Material: 3 Tab.
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  • 86
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2183-2185 
    ISSN: 0009-2940
    Schlagwort(e): [4 + 2] Cycloaddition ; 3,5-Dihydroxytropone ; Singlet oxygen ; Y aromaticity ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese von 3,5-DihydroxytroponWir beschreiben eine vierstufige Synthese des bisher unbekannten 3,5-Dihydroxytropons (6), die von Tropon ausgeht und eine [4 + 2]-Cycloaddition mit Singulett-Sauerstoff einschließt.
    Notizen: Starting from tropone, the hitherto unknown 3,5-dihydroxytropone (6) is prepared in a four-step synthesis including a [4 + 2] cycloaddition reaction of singlet oxygen.
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  • 87
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2207-2208 
    ISSN: 0009-2940
    Schlagwort(e): Allenes ; Hetero Diels-Alder reactions ; Catalysis, heterogeneous ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Some examples of cycloadditions of 1-ethoxy-1,2-propadiene with 1-oxa-1,3-dienes, catalyzed by acid-free silica gel, are reported.
    Zusätzliches Material: 1 Tab.
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  • 88
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 89
    ISSN: 0009-2940
    Schlagwort(e): Bisporphyrinates, cerium(IV) ; Lanthanoid porphyrins ; Metalloporphyrins ; Tetrapyrrole complexes, sandwich-like ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Metallkomplexe mit Tetrapyrrol-Liganden, LIV.  -  Synthese, Spektren, Struktur und Redox-Chemie von Cer(VI)-Bisporphyrinaten mit gleichen und verschiedenen Porphyrin-Ringen im Sandwich-SystemWeitere symmetrische Cer(IV)-Bisporphyrinate werden aus Cer-(III)-acetylacetonat und Tetraphenylporphyrin, Tetra-p-chlorphenylporphyrin, und Hexadecahydrotetrabenzporphyrin hergestellt. Aus dem letzteren Porphyrin entsteht auch ein Biscer(III)-Tripeldecker; ein solcher bildet sich als einziges Produkt aus Octamethylporphyrin. Aus einem Gemisch zweier verschiedener Porphyrine, nämlich Octaethylporphyrin [H2(OEP)], und Tetraphenyl-porphyrin [H2(TPP)] oder Tetra-p-chlorphenylporphyrin [H2-(TClP)] erhält man neben den symmetrischen Spezies Ce(OEP)2 und Ce(TPP)2 die unsymmetrischen („gemischten“) Doppeldecker Ce(OEP)(TPP) oder Ce(OEP)(TClP), die verschiedene Porphyrin-Ringe im Sandwich-System haben und sich trennen lassen. Die Kristallstrukturanalyse von Ce(OEP)(TPP) zeigt CeIV in quadratisch-antiprismatischer Umgebung der Pyrrol-N-Atome der Porphyrin-Ringe. Während die IR- und NMR-Spektren der unsymmetrischen Doppeldecker-Überlagerungen der Spektren, die einzelnen Ringe darstellen, zeigen ihre UV/VIS-Spektren und die cyclischen Voltammogramme, daß die zwei unterschiedlichen Porphyrin-Ringe sich wie ein gemeinsames π-Elektronensystem verhalten. Die Darstellung der π-Kation-Radikal-Salze [Ce(OEP)2]-ClO4 und [Ce(OEP)(TPP)]SbCl6 wird ebenfalls beschrieben. In letzterem scheint sich das Defektelektron bevorzugt im OEP-Ring aufzuhalten.
    Notizen: Further symmetrical cerium(IV) bisporphyrinates are prepared from cerium(III) acetylacetonate and tetraphenylporphyrin, tetra-p-chlorophenylporphyrin, and hexadecahydrotetrabenzporphyrin. In the latter case, a biscerium(III) triple-decker is also found which is the only product in the case of octamethylporphyrin. From a mixture of two different porphyrins, namely octaethylporphyrin [H2(OEP)] and either tetraphenylporphyrin [H2(TPP)] or tetra-p-chlorophenylporphyrin [H2(TClP)], besides the symmetrical species Ce(OEP)2 and Ce(TPP)2, the unsymmetrical (“mixed”) double-deckers Ce(OEP)(TPP) or Ce(OEP)(TClP) are obtained which have different porphyrin rings in the sandwich system and can be separated by chromatography. The crystal structure analysis of Ce(OEP)(TPP) shows CeIV in a square-antiprismatic geometry of the pyrrole N atoms of the porphyrin rings. While the IR and NMR spectra of the unsymmetrical double-deckers are superpositions of the spectra of the individual rings, their UV/VIS spectra and cyclic voltammograms indicate that the two porphyrin rings behave as a common π-electron system. The preparation of the π-cation radical salts [Ce(OEP)2]ClO4 and [Ce(OEP)(TPP)]SbCl6 is also described. In the latter, the defect electron seems to reside preferentially in the OEP ring.
    Zusätzliches Material: 5 Ill.
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  • 90
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2261-2264 
    ISSN: 0009-2940
    Schlagwort(e): Iron, thiocarbonyl complex ; Iron-tin bond ; NMR, 13C-, 17O-, and 119Sn ; Dynamic molecules ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Formation of Fe-Sn Bonds by the Reaction of Tris(trimethylstannyl)amine with Fe(CO)5 and Fe(CO)4CS; 13C-, 17O-, and 119Sn-NMR-Spectroscopic StudiesThe reaction between N(SnMe3)3 and Fe(CO)5 gives the known complex cis-Fe(CO)4(SnMe3)2 (1) in high yield. In the analogous reaction of Fe(CO)4CS the complex fac-Fe(CO)3(CS)(SnMe3)2 (2) is obtained together with small amounts of 1. In addition to the 13C-NMR data, the 17O- and 119Sn-NMR measurements proved particularly useful for studying the dynamic behaviour of 1 and 2.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 91
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2273-2274 
    ISSN: 0009-2940
    Schlagwort(e): Fluorine, application in organometallic chemistry ; Rhenocene(V)-trichloride ; Rhenocene(VII)-dichloride trication ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Dichlorobis(η5-cyclopentadienyl)rhenium(VII) Tris(hexafluoroantimonate): Synthesis of the First Rhenocene(VII) Dichloride CationRhenocene trichloride ([Cp2ReCl2]⊕ Cl⊖, 1) reacts with one equivalent of AgSbF6 and three equivalents of SbF5 to provide [Cp2ReCl2]3⊕[SbF6]⊖3 (2) in high yield. 2 contains the first rhenocene(VII) dichloride cation and is the first member of a 16-electron group-7 species of the type [Cp2MCl2]n⊕ [EF6]n⊖ (M = Ti, Zr, Hf: n = 0; M = V, Nb: n = 1; M = Mo, W: n = 2; M = Re: n = 3; E = As, Sb).
    Materialart: Digitale Medien
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  • 92
    ISSN: 0009-2940
    Schlagwort(e): Manganese complexes ; Thiophosphinito complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Metal-Containing Heterocycles: Preparation, Properties, Reactions, LXVII.  -  Stereochemical Impacts on the Transition of Monomeric Thiophosphinito Manganese Compounds to the Dimeric Complexes The η2-thiophosphinito manganese complexes (3d, e) and the dimeric complexes (4a-c, f) are obtained from BrMn(CO)5 (1) and the secondary phosphane sulfides R2P(S)H (2a-f) [R = Me (a), Et (b), n-Pr (c), i-Pr (d), Cy (e), Ph (f)] in the presence of the auxiliary base Et(i-Pr)2N with elimination of CO. For the kinetic stabilization of 3d, e sterically demanding substituents R at the phosphorus are suitable. The Mn—S bond in 3e is easily cleaved under CO pressure (100 bar) resulting in the formation of (5e). The reaction 3e ⇆ 5e is reversible.
    Zusätzliches Material: 1 Tab.
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  • 93
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2283-2287 
    ISSN: 0009-2940
    Schlagwort(e): Indium, trialkyl derivatives ; Dialkylchloroindium ; Alkyldichloroindium ; Alkylindium dialkylamides ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and Properties of iPr2InCl, iPrInCl2, and (iPr2InHRtBu)2The reactions of triisopropylindium (1) with half an equivalent or two equivalents of indium (III) chloride leads to iPr2InCl (2) and iPrInCl2 (3), respectively. (iPr2InNHtBu)2 (4) can be synthesized from 2 and LiNHtBu. According to NMR, IR, and RE studies, 2-4 from dimers in solution and solid state. The X-ray analysis of 4 is reported.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 94
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2311-2317 
    ISSN: 0009-2940
    Schlagwort(e): Allenes, 1,3-diamino- and 1-amino-3-thio- ; Propene iminium salts ; Propyne iminium salts ; MO calculations ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Propyne Iminium Salts: Ambifunctional reactivity reactivity towards Sulfur and Nitrogen NucleophilesPropyne iminium ions 2a-d have been studied by both ab initio (3-21G//3-21G for 2a) and MNDO calculations (2a-d). It is found that the amino group stabilizes the propargyl cation structure at the expense of the allenyl cation structure. Furthermore, the highest positive charge density is located at the amino-substituted carbon atom.  -  Reactions of 2-propyne iminium triflates 6a, b with thiols, thiolates, morpholine, lithium morpholide, and phenylhydrazine have been investigated. C-1 attack at 6, expected under kinetically controlled conditions, is observed in a few cases only. In all other cases, products resulting from C-3 attack takes place leading either to 1,3-donorsubstituted allenes (8, 10, 12) in the absence of proton sources or to their C-2-protonated forms (9, 11, 13-15) otherwise.
    Notizen: Für die Propiniminium-Ionen 2a-d werden ab-initio- (3-21G//3-21G für 2a) und MNDO-Rechnungen (2a-d) durchgeführt. Danach stabilisiert die Aminogruppe die Propargylkation- eindeutig gegenüber der Allenylkation-Struktur. Die höchste positive Ladungsdichte befindet sich am aminosubstituierten Kohlenstoffatom.  -  Umsetzungen der 2-Propiniminium-triflate 6a, b mit Thiolen, Thiolaten, Morpholin, Lithium-morpholid und Phenylhydrazin zeigen, daß nur in einigen Fällen unter kinetisch kontrollierten Bedingungen der erwartete C-1-Angriff erfolgt, ansonsten wird C-3-Angriff gefunden. Letzterer führt in Abwesenheit von Protonquellen zu 1,3-donorsubstituierten Allenen (8, 10, 12), andernfalls entstehen deren C-2-protonierte Formen (9, 11, 13-15).
    Zusätzliches Material: 3 Tab.
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  • 95
    ISSN: 0009-2940
    Schlagwort(e): Diels-Alder reactions, intramolecular ; Allenecarboxyamides, N-(hetarylmethyl)- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Cycloadditons, 17.  -  Influence of Methyl and Phenyl Groups in the Allenic ω-Position on the Thermally Induced Isomerizations of N-[2-Furanyl-(Thienyl-, Pyrrolyl-)methyl] allenecaboxamindesThe N-(2-hetarylmethyl)-1,2-alkadienecarboxamides 9a-q were synthesized by the ylide route, and their readiness to participate in the intramolecular Diels-Alder reaction was studied. Whereas the pyrrole derivatives 9p and 9q and the thiophene derivative 9o without directly bonded phenyl nuclei only decompose, the thiophene allenes 9m and 9n form the “normal” tricycles 12a and 12b by reaction of their amide phenyl nucleus (R1 = Ph). In all N-furfurylallenecarboxamides 9a-1 the furan nucleus is involved in the intramolecular Diels-Alder reaction, irrespective of the amine substituent R1. The furan nucleus reacts in all cases with the terminal allenic double bond to form the oxatricycles 10a-1 containing a six-membered lactam moiety. Reaction with the first allenic double bond (formation of 11c, d, and g) only takes place, when the reaction with the other double bond is slowed down by one or two methyl groups in the ω-position and the formation of 11 is not prevented by a methyl group in the furan 5-position.
    Notizen: Die N-(2-Heteroarylmethyl)-1,2-alkadiencarboxamide 9a-q werden auf dem Ylid-Weg synthetisiert und auf ihre Bereitschaft zur intramolekularen Diels-Alder-Reaktion untersucht. Die Pyrrolderivate 9p und 9q und das Thiophen-Derivat 9o ohne direkt gebundenen Phenylkern zeigen lediglich Zersetzung, während die Thiophen-Allene 9m und 9n durch Reaktion ihrer Amid-Phenylkerne (R1 = Ph) die „normalen“ Tricyclen 12a und 12b bilden. In allen Furfuryl-allencarboxamiden (9a-1) geht der Furankern die intramolekulare Diels-Alder-Reaktion ein, unabhängig von der Art des Aminsubstituenten R1. Der Furankern reagiert in allen Fällen mit der endständigen Doppelbindung zu den Oxatricyclen 10a-1 mit sechsgliedrigem Lactamteil. Reaktion mit der ersten allenischen Doppelbindung (s. Bildung von 11c,d und g) wird daneben nur beobachtet, wenn durch Einbau von Methyl-gruppen in die ω-Position die Reaktion mit der endständigen Doppelbindung stark verlangsamt und die Bildung von 11 nicht durch eine Methylgruppe in der Furan-5-Position verhindert wird.
    Zusätzliches Material: 3 Tab.
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  • 96
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2377-2389 
    ISSN: 0009-2940
    Schlagwort(e): EPC syntheses ; Δ4-1,3-Oxazoline, derivatives ; Simmons-Smith reaction ; Sakurai reaction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Cycloadditions to the Double Bond of Methyl (R)-2-tert-Butyl-Δs4-1,3-oxazoline-3-carboxylates1The title compounds (with or without an additional substituent, such as methyl or vinyl, in the 5-position) are allowed to react with peracids (→ dihydroxy derivatives 3), with cyclopropanation reagents (such as ICH2ZnEt, N2CHCOOEt, HCBr3, or HCCl3/NaOH → products 5-9), with tetracyanoethylene and OsO4 (see four- and five-membered rings in 19, 20), with dienophiles (maleic anhydride, see 23). The double bond of the oxazolines reacts in a highly diastereoselective manner, with the attack preferred from the face of the five-membered ring remote from the tert-butyl group. Some of the products obtained undergo or are subjected to further reactions (4, 12-18, 23, 29-33). Stereochemical and synthetic aspects of the reactions are discussed.
    Notizen: Die Titelverbindungen (mit und ohne zusätzliche Substituenten wie z. B. Methyl oder Vinyl in der 5-Stellung) werden mit Persäuren (→ Dihydroxyderivate 3), mit Cyclopropanierungsreagentien (wie z.B. ICH2ZnEt, N2CHCOOEt, HCBr3 oder HCCl3/NaOH → Produkte 5-9), mit Tetracyanethylen und OsO4 (→ Produkte 19-20) und mit Dienophilen (Maleinsäureanhydrid, siehe 23) umgesetzt. Die Doppelbindung der Oxazoline reagiert hoch diastereoselektiv, wobei der bevorzugte Angriff von der der tert-Butylgruppe abgewandten Seite erfolgt. Einige der erhaltenen Produkte werden weiter umgesetzt (siehe 4, 12-18, 23, 29-33). Stereochemische und synthetische Aspekte der Reaktionen werden diskutiert.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 97
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2397-2398 
    ISSN: 0009-2940
    Schlagwort(e): Nucleophilic ring opening ; Regioselectivity ; Ambident nucleophiles ; Aziridines ; Tryptamine ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions with Aziridines, 52.  -  branched-Chain Tryptamine Compounds from Indolyllithium and Activated AziridinesReaction of indolyllithium 1 with activated aziridines 2 in toluene provides the tryptamines 3 or 4 in good yields.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 98
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2407-2409 
    ISSN: 0009-2940
    Schlagwort(e): Organoantimony halides ; Aziridines, cycloaddition of, α-cleavage of ; Heterocumulenes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the presence of catalytic amounts of organoantimony(V) halides such as Ph4SbI, Ph4SbBr, Ph3SbBr2, and Ph3SbCl2, the cycloaddition of aziridines 1a-g with heterocumulenes (phenyl isothiocyanate, carbon disulfide, and carbon dioxide) selectively gave ring-expanded cycloadducts 3a-d, f, g, and 6e by α-cleavage of the aziridine rings.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 99
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1263-1275 
    ISSN: 0009-2940
    Schlagwort(e): Rotational barriers ; Olefins, strained ; Heat of hydrogenation ; Force-field calculation ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Rotational Barriers of Strained OlefinesFor the olefins 1-8 heats of formation have been derived from heats of hydrogenation and force-field calculations, respectively. From the kinetics of their geometrical isomerisation the corresponding values for the transition states were obtained. The rotational barriers, which vary by nearly 30 kcal/mol, can be described by a unique torsional potential (65.9 ± 0.9 kcal/mol), which is independent of the degree of substitution, if a correction is made for the steric energy contribution in the ground- and transition-states.
    Notizen: Für die Olefine 1-8 wurde durch Hydrierwärme-Messung bzw. Kraftfeld-Rechnung die Bildungsenthalpie der Grundzustände und durch kinetische Analyse der geometrischen Isomerisierung die der Übergangszustände ermittelt. Die um fast 30 kcal/mol variierenden Rotationsenthalpien lassen sich mit einer einheitlichen, vom Substitutionsgrad unabhängigen Torsionsbarriere (65.9 ± 0.9 kcal/mol) beschreiben, wenn um die sterischen Energiebeiträge der Grund- und Übergangszustand korrigiert wird.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 100
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1285-1290 
    ISSN: 0009-2940
    Schlagwort(e): 2-Cyclopropylidene-1,3-diones ; Hetero Diels-Alder reaction ; Cyclopropane derivatives ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: [4+2] Cycloaddition reactions of 2-Cyclopropylidene-1,3-diones with Electron-Rich AlkynesCyclopropylidenedimedone 3, an unstable and highly reactive intermediate, is trapped in a Hetero Diels-Alder reaction by the addition of ynamines 7a-c, f, ynether 7d, or phenylacetylene (7e). Hydrolysis of the resulting cycloadducts 8a-d, f leads to carboxylic acid derivatives 9a-d, f. The latter may be regarded as the result of a twofold nucleophilic substitution at a cyclopropane system according to their synthesis by the sequence 17 → 5 → 8 → 9. An opening of the cyclopropane ring takes place during hydrolysis of cycloadduct 8e producing 11. Analogously, 2-cyclopropylidene-1,3-diones 13A-13C can be generated by aminocyclopropylation of CH acids 18A-18C and subsequent deamination induced by an acylation reaction. Trapping of 13A-13C by ethoxyacetylene (7d) or ethyl vinyl ether (4) provides the analogous cycloadducts 14A, B and 15C.
    Notizen: Cyclopropylidendimedon 3, eine unbeständige und hochreaktive Zwischenstufe, kann durch Inamine 7a-c, f, Inether 7d oder Phenylacetylen (7e) in einer Hetero-Diels-Alder-Reaktion abgefangen werden. Die resultierenden Cycloaddukte 8a-d, f sind zu Carbonsäurederivaten 9a-d, f hydrolysierbar, die entsprechend ihrer Herstellung über die Reaktionssequenz 17 → 5 → 8 → 9 als Produkte einer zweifachen nucleophilen Substitution am Cyclopropan anzusehen sind. Das Cycloaddukt 8e läßt sich dagegen nur unter Öffnung des Dreirings zu 11 hydrolysieren. Analog können die 2-Cyclopropyliden-1,3-dione 13A-13C durch Aminocyclopropylierung von CH-Säuren 18A-18C und anschließende Desaminierung erzeugt und unter Zusatz von Ethoxyacetylen (7d) oder Ethylvinylether (4) zu den Cycloaddukten 14A, 14B und 15C abgefangen werden.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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