ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

X
feed icon rss

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • General Chemistry  (10,236)
  • Inorganic Chemistry  (8,408)
  • Seismology
  • 2020-2024  (13)
  • 2005-2009  (306)
  • 1985-1989  (9,099)
  • 1950-1954  (3,883)
  • 1935-1939  (6,335)
Collection
Keywords
Publisher
Language
Years
Year
  • 1
    facet.materialart.
    Unknown
    Frontiers in Chemistry: Rising Stars (2021)
    Frontiers Media SA
    Details
    Publication Date: 2024-04-04
    Description: The Frontiers in Chemistry Editorial Office team are delighted to present the inaugural “Frontiers in Chemistry: Rising Stars” article collection, showcasing the high-quality work of internationally recognized researchers in the early stages of their independent careers. All Rising Star researchers featured within this collection were individually nominated by the Journal’s Chief Editors in recognition of their potential to influence the future directions in their respective fields. The work presented here highlights the diversity of research performed across the entire breadth of the chemical sciences, and presents advances in theory, experiment and methodology with applications to compelling problems. This Editorial features the corresponding author(s) of each paper published within this important collection, ordered by section alphabetically, highlighting them as the great researchers of the future. The Frontiers in Chemistry Editorial Office team would like to thank each researcher who contributed their work to this collection. We would also like to personally thank our Chief Editors for their exemplary leadership of this article collection; their strong support and passion for this important, community-driven collection has ensured its success and global impact.
    Keywords: Green and Sustainable Chemistry ; Analytical Chemistry ; Theoretical and Computational Chemistry ; Polymer Chemistry ; Medicinal and Pharmaceutical Chemistry ; Organic Chemistry ; Nanoscience ; Catalysis and Photocatalysis ; Supramolecular Chemistry ; Electrochemistry ; Inorganic Chemistry ; Chemical Biology ; thema EDItEUR::P Mathematics and Science::PD Science: general issues
    Language: English
    Format: image/jpeg
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    E-BOOK
  • 2
    facet.materialart.
    Unknown
    Hamburg in der Novemberrevolution von 1918/19 (2024)
    transcript Verlag | transcript Verlag
    Details
    Publication Date: 2024-05-13
    Description: Die Novemberrevolution von 1918/19 erschütterte die Tiefenschichten der politischen und gesellschaftlichen Ordnung der Metropole Hamburg. Diese vielschichtige Transformation wird anhand ausgewählter Akteur*innen, Institutionen und Ereignisse mit Beiträgen aus der neueren Revolutions-, Konflikt- und Kriegsforschung sowie aus der Kulturwissenschaft, der Geschichts- und Sozialwissenschaft nachgezeichnet. Die Beiträger*innen des Bandes durchleuchten die Dynamiken des revolutionären Wandels im umfassenden Dispositiv der urbanen Machtverhältnisse in ihren diskursiven Formationen: im Geschlechterverhältnis, in den Klassenverhältnissen, in der Wirtschaft, im Bildungswesen, im Film, in den Utopien und Vorstellungen der Menschen der Zeit. Die Beschreibung der dynamischen Umbrüche schließt die Nachbarstadt Altona und die Region ein und verbindet somit Lokales mit Nationalem und Globalem.
    Keywords: Revolution 1918/19 ; Hamburg ; Politik ; Gesellschaft ; Norddeutschland ; Wahlen 1919 ; Film ; Weimarer Republik ; Globalgeschichte ; Deutsche Geschichte ; Bismarck ; Metropole ; Seismologie ; Kulturgeschichte ; Geschlecht ; Stadt ; Sozialgeschichte ; Europäische Geschichte ; Geschichte des 20. Jahrhunderts ; Geschichtswissenschaft ; Politics ; Society ; North Germany ; Elections 1919 ; Weimar Republic ; Global History ; German History ; Seismology ; Cultural History ; Gender ; City ; Social History ; European History ; History of the 20th Century ; History ; thema EDItEUR::N History and Archaeology::NH History::NHD European history ; thema EDItEUR::N History and Archaeology::NH History::NHT History: specific events and topics::NHTB Social and cultural history
    Language: German
    Format: image/jpeg
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    E-BOOK
  • 3
    facet.materialart.
    Unknown
    Chapter 13 Modelling Seismic Wave Propagation for Geophysical Imaging (2021)
    InTechOpen
    Details
    Publication Date: 2024-04-04
    Description: The Earth is an heterogeneous complex media from the mineral composition scale (10−6m) to the global scale ( 106m). The reconstruction of its structure is a quite challenging problem because sampling methodologies are mainly indirect as potential methods (Günther et al., 2006; Rücker et al., 2006), diffusive methods (Cognon, 1971; Druskin & Knizhnerman, 1988; Goldman & Stover, 1983; Hohmann, 1988; Kuo & Cho, 1980; Oristaglio & Hohmann, 1984) or propagation methods (Alterman & Karal, 1968; Bolt & Smith, 1976; Dablain, 1986; Kelly et al., 1976; Levander, 1988; Marfurt, 1984; Virieux, 1986). Seismic waves belong to the last category. We shall concentrate in this chapter on the forward problem which will be at the heart of any inverse problem for imaging the Earth. The forward problem is dedicated to the estimation of seismic wavefields when one knows the medium properties while the inverse problem is devoted to the estimation of medium properties from recorded seismic wavefields.
    Keywords: seismic wave ; geophysical imaging ; seismic wave ; geophysical imaging ; Boundary value problem ; Finite element method ; Free surface ; Frequency domain ; Seismology ; Time domain ; Velocity ; thema EDItEUR::P Mathematics and Science::PD Science: general issues
    Language: English
    Format: image/jpeg
    Format: image/jpeg
    Format: image/jpeg
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    E-BOOK
  • 4
    facet.materialart.
    Unknown
    Damage distribution and seismological model of the November 24, 2004, Salo' (Northern Italy) earthquake (2007)
    Details
    Publication Date: 2017-04-04
    Description: The West side of lake of Garda, in Northern Italy, was struck by a ML=5.2 earthquake on November 24, 2004. The felt area is rather large (from Venice to Milan) and the damaged area consists of 66 municipalities, with a number of homeless of about 2200 and estimated direct damages of 215 millions of euros. Most of the damaged structures are old masonry buildings and churches, while there were almost no damage to reinforced concrete structures. The observed distribution of macroseismic intensity shows a strong azimuthal dependence, with high intensity level in a 10x10 km2 area located SW to the epicentre and rather large dispersion of values (ranging from V to VII-VIII) in the first 10 km epicentral distance. Taking into account the vulnerability level of the damaged structures and the features of the geological formations, we tried to explain the observed damage distribution in terms of finite fault properties of the source, despite the moderate magnitude of the event. Thus we hypothesised a fault geometry from seismotectonic considerations and we simulated the event by a high frequency simulation technique (Deterministic Stochastic Method, DSM). The synthetic ground motion parameters were converted into intensity values by empirical relationships and local geological conditions were considered to explain some discrepancies between simulated and observed intensities. It was possible to adequately reproduce both the observed distribution of macroseismic intensity and the ground motion recorded by an accelerometric station located at about 13 km epicentral distance.
    Description: Unpublished
    Description: Geneva, Switzerland
    Description: open
    Keywords: Damage ; Seismology ; 04. Solid Earth::04.06. Seismology::04.06.04. Ground motion
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Conference paper
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 5
    facet.materialart.
    Unknown
    Understanding crust dynamics and subduction in southern Italy (2008)
    Details
    Publication Date: 2017-04-04
    Description: To mark the centennial anniversary of the 1908 earthquake that shook Messina, Italy, the Istituto Nazionale di Geofisica e Vulcanologia (INGV) began the “Messina 1908–2008” research project. The aim is to clarify the extension deformation processes that occur in the Strait of Messina and to understand relationships between subduction and crustal deformation there by merging existing data and studies, and by collecting new and more detailed seismological, geodetic, historical, and satellite observations.
    Description: INGV
    Description: Published
    Description: 225–226
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: N/A or not JCR
    Description: reserved
    Keywords: Seismology ; geodesy ; 01. Atmosphere::01.03. Magnetosphere::01.03.04. Structure and dynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 6
    facet.materialart.
    Unknown
    Seismology and Tectonic Setting of the 2002 Molise, Italy, Earthquake (2006)
    Earthquake Engineering Research Institute
    Details
    Publication Date: 2017-04-04
    Description: Two earthquakes (both having Mw 5.7) struck the eastern portion of Molise on October 31 and November 1, 2002. Both caused severe damage over a 2000 km2 region straddling Molise and Puglia. The two larger shocks and the rather unusual aftershock sequence surprised most Italian seismologists and tectonicists. Although Italy has a good record of historical and instrumental seismicity and its main seismogenic trends are quite established, the epicentral location, depth and kinematics of this earthquake sequence were largely unexpected. In fact, the 2002 Molise earthquakes shed light on a previously unsuspected style of seismogenic faulting in this region. From the seismotectonic perspective, much of the significance of the two quakes arises from the possibility that this style of faulting might be shared by several much larger quakes that took place on the Adriatic side of the southern Apennines. In the first part of this paper we briefly describe the main seismological characteristics of the sequence. These were largely derived from the analysis of data supplied by permanent networks and from a preliminary analysis of data recorded by a portable network deployed a few hours after the first shock. In the second part of the paper we discuss the seismotectonic characteristics of the sequence in the framework of Italian tectonics and the implications for future earthquakes in the same region.
    Description: Published
    Description: S23-S37
    Description: reserved
    Keywords: Earthquake ; Molise 2002 ; Seismology ; Tectonic ; 04. Solid Earth::04.06. Seismology::04.06.04. Ground motion ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Format: 1422638 bytes
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 7
    facet.materialart.
    Unknown
    The 1997 Umbria-Marche (Italy) earthquake sequence: relationship between ground deformation and seismogenic structure (2005)
    American Geophysical Union
    Details
    Publication Date: 2017-04-04
    Description: A field survey performed during the 1997 Umbria-Marche earthquake sequence led us to recognize ground and pavement ruptures associated with the three largest shocks (M〉= 5.7). The ruptures are concentrated in narrow bands that, in part, are on and near previously mapped high-angle normal fauts. The geometry of the ground deformation is consistent with the NE-trending extension indicated by CMT focal solutions of the mainshocks. The distribution of aftershocks suggests that the three mainshocks occurred on ~40 degree SW-dipping normal faults. Geological investigations, modelling of expected coseismic elevation changes, and seismic data, suggest that the surface deformation is not the direct result of primary rupture of faults at depth.
    Description: Published
    Description: 895-898
    Description: reserved
    Keywords: Structural geology ; Fractures and faults ; Seismology ; Seismicity and seismotectonics ; Europe ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Format: 1724979 bytes
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 8
    facet.materialart.
    Unknown
    Phenomenological evidence in favor of a remote seismic coupling for large volcanic eruptions (2006)
    AGU
    Details
    Publication Date: 2017-04-04
    Description: A correlation has been recently found between large earthquakes and the succeeding largest 9 explosive eruptions of the last century, which has been interpreted as a product of co- and post-seismic stress diffusion. Here, we check the statistical significance of the proposed coupling by using a larger dataset, and investigate the reliability of the causality hypothesis. We find that the volcanoes with VEI ≥ 4 eruptions underwent, in the few decades before the volcanic event, higher seismic stress perturbations due to large earthquakes compared to other volcanic areas. The correlation is statistically significant and it is not explained by a spatio-temporal clustering of eruptions and earthquakes due to tectonic pulses. This implies that the large earthquakes indeed triggered the eruptions.
    Description: Gruppo Nazionale di Vulcanologia and e-Ruption projects
    Description: Published
    Description: reserved
    Keywords: Volcanology ; Eruption mechanisms ; Seismology ; Volcano seismology ; Tectonophysics ; Stresses - general ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Format: 1019925 bytes
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 9
    facet.materialart.
    Unknown
    DISSEMINATING SEISMOLOGY IN LIGURIA, NORTHERN ITALY (2009)
    Details
    Publication Date: 2017-04-03
    Description: We describe and discuss some activities of our working group to disseminate scientific issues concerning seismology to the students of the Region Liguria.
    Description: Published
    Description: Rimini, Italy
    Description: 5.9. Formazione e informazione
    Description: open
    Keywords: Education ; Seismology ; Preparedness ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Abstract
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 10
    facet.materialart.
    Unknown
    A technical note on the bias in the estimation of the b-value and its uncertainty through the Least Squares technique (2006)
    Details
    Publication Date: 2019-11-04
    Description: We investigate conceptually, analytically, and numerically the biases in the estimation of the b-value of the Gutenberg-Richter law and of its uncertainty made through the least squares technique. The biases are introduced by the cumulation operation for the cumulative form of the Gutenberg-Richter law, by the logarithmic transformation, and by the measurement errors on the magnitude. We find that the least squares technique, applied to the cumulative and binned form of the Gutenberg-Richter law, produces strong bias in the b-value and its uncertainty, whose amplitudes depend on the size of the sample. Furthermore, the logarithmic transformation produces two different endemic bends in the Log(N) versus M curve. This means that this plot might produce fake significant departures from the Gutenberg-Richter law. The effect of the measurement errors is negligible compared to those of cumulation operation and logarithmic transformation. The results obtained show that the least squares technique should never be used to determine the slope of the Gutenberg-Richter law and its uncertainty.
    Description: Submitted
    Description: JCR Journal
    Description: open
    Keywords: b-value ; Seismology ; Least Squares technique ; Synthetic-earthquake catalogs ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Format: 323778 bytes
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 11
    facet.materialart.
    Unknown
    Experimental and seismological constraints on the rheology, evolution, and alteration of the lithosphere at oceanic spreading centers (2007)
    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Details
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2007
    Description: Oceanic spreading centers are sites of magmatic, tectonic, and hydrothermal processes. In this thesis I present experimental and seismological constraints on the evolution of these complex regions of focused crustal accretion and extension. Experimental results from drained, triaxial deformation experiments on partially molten olivine reveal that melt extraction rates are linearly dependent on effective mean stress when the effective mean stress is low and non-linearly dependent on effective mean stress when it is high. Microearthquakes recorded above an inferred magma reservoir along the TAG segment of the Mid-Atlantic Ridge delineate for the first time the arcuate, subsurface structure of a long-lived, active detachment fault. This fault penetrates the entire oceanic crust and forms the high-permeability pathway necessary to sustain long-lived, high-temperature hydrothermal venting in this region. Long-lived detachment faulting exhumes lower crustal and mantle rocks. Residual stresses generated by thermal expansion anisotropy and mismatch in the uplifting, cooling rock trigger grain boundary microfractures if stress intensities at the tips of naturally occurring flaws exceed a critical stress intensity factor. Experimental results coupled with geomechanical models indicate that pervasive grain boundary cracking occurs in mantle peridotite when it is uplifted to within 4 km of the seafloor. Whereas faults provide the high-permeability pathways necessary to sustain high-temperature fluid circulation, grain boundary cracks form the interconnected network required for pervasive alteration of the oceanic lithosphere. This thesis provides fundamental constraints on the rheology, evolution, and alteration of the lithosphere at oceanic spreading centers.
    Description: Research was funded by a MIT Presidential Fellowship and NSF grants OCE-0095936, OCE-9907224, OCE-0137329, OCE-6892222, and OCE-6897400.
    Keywords: Seismology ; Sea-floor spreading
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 12
    facet.materialart.
    Unknown
    Ocean Seismic Network Pilot Experiment (2005)
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2003. It is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 4 (2003): 1092, doi:10.1029/2002GC000485.
    Description: The primary goal of the Ocean Seismic Network Pilot Experiment (OSNPE) was to learn how to make high quality broadband seismic measurements on the ocean bottom in preparation for a permanent ocean seismic network. The experiment also had implications for the development of a capability for temporary (e.g., 1 year duration) seismic experiments on the ocean floor. Equipment for installing, operating and monitoring borehole observatories in the deep sea was also tested including a lead-in package, a logging probe, a wire line packer and a control vehicle. The control vehicle was used in three modes during the experiment: for observation of seafloor features and equipment, for equipment launch and recovery, and for power supply and telemetry between ocean bottom units and the ship. The OSNPE which was completed in June 1998 acquired almost four months of continuous data and it demonstrated clearly that a combination of shallow buried and borehole broadband sensors could provide comparable quality data to broadband seismic installations on islands and continents. Burial in soft mud appears to be adequate at frequencies below the microseism peak. Although the borehole sensor was subject to installation noise at low frequencies (0.6 to 50 mHz), analysis of the OSNPE data provides new insights into our understanding of ocean bottom ambient noise. The OSNPE results clearly demonstrate the importance of sediment borne shear modes in ocean bottom ambient noise behavior. Ambient noise drops significantly at high frequencies for a sensor placed just at the sediment basalt interface. At frequencies above the microseism peak, there are two reasons that ocean bottom stations have been generally regarded as noisier than island or land stations: ocean bottom stations are closer to the noise source (the surface gravity waves) and most ocean bottom stations to date have been installed on low rigidity sediments where they are subject to the effects of shear wave resonances. When sensors are placed in boreholes in basement the performance of ocean bottom seismic stations approaches that of continental and island stations. A broadband borehole seismic station should be included in any real-time ocean bottom observatory.
    Description: This work was sponsored by the National Science Foundation (NSF Grant Numbers: OCE-9522114, OCE-9523541 and OCE-9819439) with additional support from Incorporated Research Institutions for Seismology (IRIS), Joint Oceanographic Institutions, Inc. (JOI Contract No: 12-94), Scripps Institution of Oceanography, a Mellon Grant from Woods Hole Oceanographic Institution, and the Earthquake Research Institute at the University of Tokyo (Visiting Professorship for RAS).
    Keywords: Ocean Seismic Network Pilot Experiment (OSNPE) ; Seismology ; Instruments and techniques ; Body wave propagation ; Surface waves and free oscillations
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: 2963663 bytes
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 13
    facet.materialart.
    Unknown
    Underwater tunable organ-pipe sound source (2008)
    Acoustical Society of America
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © Acoustical Society of America, 2007. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 122 (2007): 777-785, doi:10.1121/1.2751268.
    Description: A highly efficient frequency-controlled sound source based on a tunable high-Q underwater acoustic resonator is described. The required spectrum width was achieved by transmitting a linear frequency-modulated signal and simultaneously tuning the resonance frequency, keeping the sound source in resonance at the instantaneous frequency of the signal transmitted. Such sound sources have applications in ocean-acoustic tomography and deep-penetration seismic tomography. Mathematical analysis and numerical simulation show the Helmholtz resonator's ability for instant resonant frequency switching and quick adjustment of its resonant frequency to the instantaneous frequency signal. The concept of a quick frequency adjustment filter is considered. The discussion includes the simplest lumped resonant source as well as the complicated distributed system of a tunable organ pipe. A numerical model of the tunable organ pipe is shown to have a form similar to a transmission line segment. This provides a general form for the principal results, which can be applied to tunable resonators of a different physical nature. The numerical simulation shows that the “state-switched” concept also works in the high-Q tunable organ pipe, and the speed of frequency sweeping in a high-Q tunable organ pipe is analyzed. The simulation results were applied to a projector design for ocean-acoustic tomography.
    Description: The work was supported by ONR.
    Keywords: Acoustic generators ; Underwater sound ; Acoustic resonators ; Oceanographic equipment ; Seismology
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 14
    facet.materialart.
    Unknown
    Structure and dynamics of the Pacific upper mantle (2007)
    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Details
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution December 1997
    Description: A new tomographic technique is employed to investigate the structure and dynamics of the Pacific upper mantle. We invert band-center travel times of ScS reverberations and frequency-dependent travel times of direct S phases, upper-mantle guided waves such as SS and SSS, and the R1 and G1 surface waves for the 2D composite structure in the plane of two Pacific corridors. The frequency-dependent travel times of the turning and surface waves are measured from all three components of ground motion as phase delays relative to a radially-anisotropic, spherically-symmetric oceanic mantle model, and their 2D Fréchet kernels are constructed by a coupled-mode algorithm. The travel times of the primary ScSn and sScSn phases and their first-order reverberations from the 410 and 660 discontinuities are measured as individual phases and the 2D Fréchet kernels for these band-limited signals are calculated using the paraxial ray approximation. The model parameters include shear-speed variations throughout the mantle, perturbations to radial shear-wave anisotropy in the uppermost mantle, and the topography of the 410 and 660 discontinuities. We construct vertical tomograms through two mantle corridors: one between the Tonga subduction zone and Oahu, Hawaii, which traverses the central Pacific Ocean; and the other between the Ryukyu subduction zone and Oahu, which samples the northern Philippine Sea, the western Pacific, and the entire Hawaiian swell. Tests demonstrate that the data sets for the two corridors resolve the lateral structure in the upper mantle with a scale length of a few hundreds kilometers and greater but that the resolving power decreases rapidly in the lower mantle. The model for the Tonga-Hawaii corridor reveals several interesting features, the most significant being a regular pattern of high and low shear velocities in the upper mantle between Tonga and Hawaii. These variations, which are well resolved by the data set, have a horizontal wavelength of 1500 km, a vertical dimension of 700 km, and an amplitude of about 3%, and they show a strong positive correlation with seafloor topography and geoid-height variations along this corridor. The geoid highs correspond to a series of northwest-trending swells associated with the major hotspots of the Society, Marquesas, and Hawaiian Islands. Where these swells cross the corridor, they are underlain by high shear velocities throughout the uppermost mantle, so it is unlikely that their topography is supported by thermal buoyancy. This result is substantiated by the model from the Ryukyu-Hawaii corridor, which exhibits a prominent, fast region that extends beneath the entire Hawaiian swell. This anomaly, which resides in the uppermost 200-300 km of the mantle, is also positively correlated with the undulations of the Hawaiian-swell height. The other dominant features in the Ryukyu-Hawaii model include the high-velocity subducting slabs beneath the Ryukyu and Izu-Bonin seismic zones, which extend throughout the entire upper mantle; a very low-velocity in the uppermost 160 km of the mantle beneath the northern Philippine Sea, which is ascribed to the presence of extra water in this region; and a pronounced minimum in the amount of radial anisotropy near Hawaii, which is also seen along the Tonga-Hawaii corridor. A joint inversion of the data from the two corridors reveals the same anomaly pattern and clearly demonstrates that the swells in the Central Pacific are underlain by fast velocities. It is therefore implied that the topography of the swells in the central Pacific is supported by a chemical buoyancy mechanism which is generated by basaltic volcanism and the formation of its low-density peridotitic residuum. While the basaltic depletion mechanism can produce high shear velocities in the uppermost 200 km, it cannot explain the depth extent of the fast anomalies beneath the swells which, along Tonga-Hawaii corridor, extend well into the transition zone. It is therefore hypothesized that the central Pacific is underlain by a system of convective rolls that are confined above the 660-km discontinuity. It is likely that these rolls are predominantly oriented in the direction of plate motion (like "Richter rolls ") but the limited depth of the fast anomaly beneath the Hawaiian swell (200-300 km) suggests that their pattern is probably more complicated. Nevertheless, this convection pattern appears to be strongly correlated with the locations of the Tahitian, Marquesan, and Hawaiian hotspots, which raises interesting questions for Morgan's hypothesis that these hotspots are the surface manifestations of deep-mantle plumes.
    Description: This research was supported by the National Science Foundation under grant EAR- 9628351 and by the Defense Special Weapons Agency under grant DSW A-F49620-95-1- 0051.
    Keywords: Seismic tomography ; Seismology ; Upwelling ; Ocean waves
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 15
    facet.materialart.
    Unknown
    Ambient noise analysis and finite difference modelling of VLF borehole seismic data (2009)
    Woods Hole Oceanographic Institution
    Details
    Publication Date: 2022-05-25
    Description: This report describes a preliminary analysis of borehole seismic data to determine VLF/Sub-bottom Seismic Noise in the Atlantic and the preliminary results of finite difference modelling for a Cape Fear environment. Noise levels were not a simple function of depth and there are indications that noise levels may depend on local geology about a given receiver position and/or on clamping. Coherency of the noise was generally poor (〈0.8) and was independent of depth. There is no evidence for distinct polarizations or directionality of the noise. The lowest determined value for ambient noise power on the vertical component was 10-4 nm2/Hz in the frequency range from 5-50 Hz. The better clamped horizontal component had comparable power values. In conclusion, although the drill ship was on the site and drill pipe was in the hole, analysis of the data for a large number of windows can provide meaningful upper bounds on the ambient noise levels in the upper crust.
    Description: Prepared for the Naval Ocean Research and Development Activity as the final report for Contract Purchase Order No. N62306-86-l4-7589
    Keywords: Ambient sounds ; Seismology
    Repository Name: Woods Hole Open Access Server
    Type: Working Paper
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 16
    facet.materialart.
    Unknown
    Reconstructing long term sediment flux from the Brooks Range, Alaska using shelf edge clinoforms (2007)
    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Details
    Publication Date: 2022-05-26
    Description: Submitted in partial fulfillment of the requirements of the degree of Master of Science at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June 2004
    Description: Laterally extensive, well-developed clinoforms have been mapped in Early Cretaceous deposits located in the northeastern 27,000 km2 of the Colvile Basin, North Slope of Alaska. Using public domain 2-D seismic data, well logs, core photographs, and grain size data, depositional geometries within the Nanushuk and Torok formations were interpreted in order to constrain the transport conditions associated with progradation of the shoreline and construction of the continental margin out of detritus shed from the ancestral Brooks Range. Using STRATA, a synthetic stratigraphic modeling package, constructional clinoform geometries similar to those preserved in the North Slope clinoform volume (32,400 km3) were simulated. Sediment flux, marine and nonmarine diffusivities, and basin subsidence were systematically varied until a match was found for the foreset and topset slopes, as well as progradation rates over a 6 milion year period. The ability of STRATA to match the seismically interpreted geometries allows us to constrain measures of possible water and sediment discharges consistent with the observed development of the Early Cretaceous c1inoform suite. Simulations indicate that, in order to reproduce observed geometries and trends using constant input parameters, the subsidence rate must be very small, only a fraction of the most likely rate calculated from the seismic data. Constant sediment transport parameters can successfully describe the evolution of the prograding margin only in the absence of tectonic subsidence. However, further work is needed to constrain the absolute magnitude of these values and determine a unique solution for the NPR-A clinoforms.
    Keywords: Sediment transport ; Seismology ; Drill cores
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 17
    facet.materialart.
    Unknown
    Geoacoustic inversion by mode amplitude perturbation (2008)
    Acoustical Society of America
    Details
    Publication Date: 2022-05-26
    Description: Author Posting. © Acoustical Society of America, 2008. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 123 (2008): 667-678, doi:10.1121/1.2821975.
    Description: This paper introduces a perturbative inversion algorithm for determining sea floor acoustic properties, which uses modal amplitudes as input data. Perturbative inverse methods have been used in the past to estimate bottom acoustic properties in sediments, but up to this point these methods have used only the modal eigenvalues as input data. As with previous perturbative inversion methods, the one developed in this paper solves the nonlinear inverse problem using a series of approximate, linear steps. Examples of the method applied to synthetic and experimental data are provided to demonstrate the method's feasibility. Finally, it is shown that modal eigenvalue and amplitude perturbation can be combined into a single inversion algorithm that uses all of the potentially available modal data.
    Description: Funding for the research presented here was provided by the Office of Naval Research, and the WHOI Academic Programs Office.
    Keywords: Geophysical techniques ; Inverse problems ; Sediments ; Seismology
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 18
    facet.materialart.
    Unknown
    Understanding Micropolar Theory in the Earth Sciences II: The Seismic Moment Tensor (2021)
    Springer International Publishing
    Details
    Publication Date: 2023-06-12
    Description: Seismic events produced by block rotations about vertical axis occur in many geodynamic contexts. In this study, we show that these rotations can be accounted for using the proper theory, namely micropolar theory, and a new asymmetric moment tensor can be derived. We then apply this new theory to the Kaikōura earthquake (2016/11/14), Mw 7.8, one of the most complex earthquakes ever recorded with modern instrumental techniques. Using advanced numerical techniques, we compute synthetic seismograms including a full asymmetric moment tensor and we show that it induces measurable differences in the waveforms proving that seismic data can record the effects of the block rotations observed in the field. Therefore, the theory developed in this work provides a full framework for future dynamic source inversions of asymmetric moment tensors.
    Description: Westfälische Wilhelms-Universität Münster (1056)
    Keywords: ddc:551.22 ; Seismology ; asymmetric moment tensor ; micropolar theory ; Kaikōura earthquake
    Language: English
    Type: doc-type:article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    CITATION GEO-LEO
  • 19
    facet.materialart.
    Unknown
    Role of crustal fluids and thermo-mechanical structure for lower crustal seismicity: The Gargano Promontory (southern Italy) (2023)
    Elsevier
    Details
    Publication Date: 2023-02-20
    Description: Several regions around the globe are characterized by a seismically active lower crust, at depths where litho­logical and thermal conditions suggest stress release by ductile flow. The Gargano Promontory (GP, southern Italy) is an example where a recently installed seismic network has recorded an intense seismic activity at depths between 20 and 30 km, i.e. in the lower crust. The GP is located in proximity of the Gargano-Dubrovnik line­ament, a seismogenic zone separating the central and southern Adriatic basins. These two basins constitute sites of sediments accumulation since Tertiary times. Another important basin in the region is represented by the Apennine foredeep, that includes the Candelaro area. We analyze the possible mechanisms controlling the dis­tribution of seismicity in the GP to identify the factors that make the lower crust seismically active. To this aim, we construct a thermo-rheological model of a layered continental crust, calibrated on the basis of geometrical, lithological and thermal constraints. The model takes into account various crustal lithologies, the presence of fluids in the crystalline basement, lateral variations of geotherm and stress field. The numerical simulations show that the presence of fluids is a key factor controlling the cluster of seismicity in the lower crust. Moreover, the presence of water in the upper crystalline basement and sedimentary cover provides a plausible explanation for upper crustal seismicity in a zone of very high heat flow SW of the GP. The distribution of the seismicity is probably affected by the composition of the crystalline basement, with mafic bodies injected into the crust during the Paleocene magmatic phase that affected the Mediterranean region. In addition, fluid accumulation and overpressure may occur along detachment levels in the lower crust, leading to clustering of the earthquakes. Based on our findings, we hypothesize that the presence of hydrous diapiric upwelling(s) in the upper mantle can feed a deep fluid circulation system, inducing lower crustal seismicity.
    Description: Published
    Description: 103929
    Description: 4T. Sismicità dell'Italia
    Description: JCR Journal
    Keywords: Lower crust ; Rheology ; Seismology ; Geotherm ; Numerical modeling ; Gargano Promontory (southern Italy)
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 20
    facet.materialart.
    Unknown
    Quantification of bone surface textures: exploring a new method of ontogenetic ageing (2023)
    In:  Journal of Analytical Science and Technology vol. 14 no. 1
    Details
    Publication Date: 2024-02-26
    Description: Identifcation of ontogenetic age classes plays an important role in the felds of zoology, palaeontology and archaeology, where accurate age classifcations of (sub)fossil remains are a crucial component for the reconstruction \nof past life. Textural ageing\xe2\x80\x94the identifcation of age-related bone surface textures\xe2\x80\x94provides a size-independent \nmethod for age assessment of vertebrate material. However, most of the work so far is limited to qualitative results. \nWhile qualitative approaches provide helpful insights on textural ageing patterns, they are heavily subject to observer \nbias and fall short of quantitative data relevant for detailed statistical analyses and cross-comparisons. Here, we present a pilot study on the application of 3D surface digital microscopy to quantify bone surface textures on the long \nbones of the grey heron (Ardea cinerea) and the Canada goose (Branta canadensis) using internationally verifed \nroughness parameters. Using a standardised measuring protocol, computed roughness values show a strong correlation with qualitative descriptions of textural patterns. Overall, higher roughness values correspond to increased numbers of grooves and pits and vice versa. Most of the roughness parameters allowed distinguishing between diferent \nontogenetic classes and closely followed the typical sigmoidal animal growth curve. Our results show that bone \ntexture quantifcation is a feasible approach to identifying ontogenetic age classes.
    Keywords: General Physics and Astronomy ; General Environmental Science ; General Biochemistry ; Genetics and Molecular Biology ; General Materials Science ; General Chemistry ; Roughness ; Surfaces ; Taphonomy ; Topography ; Bone ; Ontogeny ; Digital microscopy
    Repository Name: National Museum of Natural History, Netherlands
    Type: info:eu-repo/semantics/article
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 21
    facet.materialart.
    Unknown
    Imaging seismic wave-fields with AlpArray and neighboring European networks (2021)
    Springer Berlin Heidelberg
    Details
    Publication Date: 2024-02-28
    Description: The AlpArray experiment and the deployment of Swath-D together with the dense permanent network in Italy allow for detailed imaging of the spatio-temporal imaging complexity of seismic wave-fields within the greater Alpine region. The distance of any point within the area to the nearest station is less than 30 km, resulting in an average inter-station distance of about 45 km. With a much denser deployment in a smaller region of the Alps (320 km in length and 140 km wide), the Swath-D network possesses an average inter-station distance of about 15 km. We show that seismogram sections with a spatial sampling of less than 5 km can be obtained using recordings of these regional arrays for just a single event. Multiply reflected body waves can be observed for up to 2 h after source time. In addition, we provide and describe animations of long-period seismic wave-fields using recordings of about 1300–1600 broadband stations for six representative earthquakes. These illustrate the considerable spatio-temporal variability of the wave-field’s properties at a high lateral resolution. Within denser station distributions like those provided by Swath-D, even shorter period body and surface wave features can be recovered. The decrease of the horizontal wavelength from P to S to surface waves, deviations from spherically symmetric wavefronts, and the capability to detect multi-orbit arrivals are demonstrated qualitatively by the presented wave-field animations, which are a valuable tool for educational, quality control, and research purposes. We note that the information content of the acquired datasets can only be adequately explored by application of appropriate quantitative methods accounting for the considerable complexity of the seismic wave-fields as revealed by the now available station configuration.
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: Christian-Albrechts-Universität zu Kiel (3094)
    Keywords: ddc:551.22 ; Seismology ; Wave-fields ; Animations ; Alps ; AlpArray ; Swath-D
    Language: English
    Type: doc-type:article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    CITATION GEO-LEO
  • 22
    facet.materialart.
    Unknown
    SISMIKO: INGV operational task force for rapid deployment of seismic network during earthquake emergencies (2023)
    Frontiers Media S.A.
    Details
    Publication Date: 2024-04-23
    Description: The National Institute of Geophysics and Volcanology (INGV, Istituto Nazionale di Geofisica e Vulcanologia), is an italian public research institute established in 1999. Since its inception, the mission of INGV included seismic surveillance and earthquake monitoring in Italy. INGV is part of the Civil Defence system (Margheriti et al., 2021). INGV has offices in different parts of Italy and operates the Italian National Seismic Network (Rete Sismica Nazionale—RSN; INGV Seismological Data Centre, 2006) and other networks at national scale (Michelini et al., 2017). INGV also operates a temporary seismic network infrastructure, a pool of instruments used to densify seismic networks for scientific experiments or in response to damaging earthquakes and to increase monitoring capabilities during seismic sequences. SISMIKO is the operational task force of INGV whose core purpose is to rapidly deploy temporary seismic stations in response to moderate—large magnitude earthquakes or in areas where a seismic sequence is causing concerns and/or scientific interest (Moretti et al., 2016). By reducing the spatial distance between the seismic stations, temporary deployments can improve the RSN detection capability and the accuracy of the earthquake locations. SISMIKO was established in 2015 by Lucia Margheriti and Milena Moretti, so they became responsible for INGV emergency deployments of the temporary networks. SISMIKO involves INGV technicians and researchers from all over Italy, from Milano to Catania (see acknowledgments), grouped together by common interest technical and scientific issues. SISMIKO coordinates all INGV groups working on seismic emergencies (Figure 1). The data acquired by the SISMIKO temporary networks, are made available to the scientific community, without any restrictions, via italian node of the European Integrated Data Archive portal (EIDA1; Danecek et al., 2021). Datasets are archived in near real-time in the “Standard for the Exchange of Earthquake Data (SEED)” format and have an associated Digital Object Identifier (DOI). The data are used for monitoring, surveillance and for scientific research. Since its establishment, SISMIKO has installed seven temporary seismic networks, including the one used to monitor the 2016–2018 seismic sequence in central Italy (Moretti et al., 2016). The most recent activations of SISMIKO were in May and November 2022: Chianti-Fiorentino (Piccinini et al., 2022; 2023) and North Marche coast (D’Alema et al., 2022b), respectively. The following section briefly describes the history of the INGV emergency mobile network.
    Description: Published
    Description: 1146579
    Description: OST5 Verso un nuovo Monitoraggio
    Description: JCR Journal
    Keywords: SISMIKO ; Seismic emergency ; Temporary seismic network ; Real time transmission ; Seismology ; 05.04. Instrumentation and techniques of general interest
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 23
    facet.materialart.
    Unknown
    Homogenization of magnitudes of the ISC Bulletin (2024)
    Oxford Academic
    Details
    Publication Date: 2024-04-05
    Description: This article has been accepted for publication in Geophysical Journal International ©:The Author(s) 2023. Published by Oxford University Press on behalf of the Royal Astronomical Society. All rights reserved.Uploaded in accordance with the publisher's self-archiving policy. All rights reserved.
    Description: We implemented an automatic procedure to download the hypocentral data of the online Bulletin of the International Seismological Centre (ISC) in order to produce in near real-time a homogeneous catalogue of the Global and EuroMediterranean instrumental seismicity to be used for forecasting experiments and other statistical analyses. For the interval covered by the reviewed ISC Bulletin, we adopt the ISC locations and convert the surface wave magnitude (Ms) and short-period body-wave magnitude (mb) as computed by the ISC to moment magnitude (Mw), using empirical relations. We merge the so obtained proxies with real Mw provided by global and EuroMediterranean moment tensor catalogues. For the most recent time interval (about 2 yr) for which the reviewed ISC Bulletin is not available, we do the same but using the preferred (prime) location provided by the ISC Bulletin and converting to Mw the Ms and mb provided by some authoritative agencies. For computing magnitude conversion equations, we use curvilinear relations defined in a previous work and the chi-square regression method that accounts for the uncertainties of both x and y variables.
    Description: H2020 EU project RISE contract n. 821115
    Description: Published
    Description: 1771-1785
    Description: OST2 Deformazione e Hazard sismico e da maremoto
    Description: JCR Journal
    Keywords: Statistical methods ; Statistical seismology ; Earthquake source observations ; Seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 24
    Electronic Resource
    Electronic Resource
    Einfluß der Substituenten auf Aktivierungsenthalpie-,-entropie und -volumen beim Zerfall organischer Perester (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 240-245 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Influence of Substituents on the Enthalpy, Entropy and Volume of Activation in the Decomposition of Organic PerestersThe influence of the ester group on the decomposition of organic peroxides was studied on peresters of the pivalic and neodecanoic acid with tert-butyl, tert-amyl, 1-methyl-1-propylpentyl and 1,1,4-trimethylpentyl groups at temperatures of 393 to 473 K and pressures up to 3000 bar using a flow method. As expected the half-live times decrease with increasing temperature and increase with rising pressure. With increasing bulkiness of the substituents the rates of decomposition as well as the enthalpies of activation increase. This surprising fact can be explained by the simultaneous increase of the entropies and the volumes of activation.
    Notes: Der Einfluß der Estergruppe auf den Zerfall organischer Peroxide wurde an Perestern der Pivalin- und der Neodecansäure mit tert-Butyl-, tert-Amyl-, 1-Methyl-propylpentyl- sowie 1,1,4-Trimethylpentylresten bei Temperaturen von 393 bis 473 K und Drücken bis 3000 bar in einer Strömungsapparatur untersucht. Die Zerfallshalbwertszeiten nehmen erwartungsgemäß mit steigender Temperatur stark ab und mit steigendem Druck zu. Mit zunehmender Größe der Substituenten steigen sowohl die Zerfallsgeschwindigkeiten als auch die Aktivierungsenthalpien. Dieser überraschende Effekt kann durch die Vergrößerung der Aktivierungsentropie und des Aktivierungsvolumens erklärt werden.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180123
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 25
    Electronic Resource
    Electronic Resource
    Zur Lewis-Acidität von Nickel(0), III. Alkalimetall-hydridotrialkylaluminat-Komplexe von Ni(CDT) (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 313-322 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Lewis Acidity of Nickel(0), III. Alkali Metal Hydridotrialkylaluminate Complexes of Ni(CDT)Ni(CDT) reacts with hydridotrialkylaluminates of the alkali metals in ether/THF or ether/amine mixtures at temperatures below -50°C to form the temperature-sensitive compounds [MA(n-Donor)n]+[R3Al—H—Ni(CDT)]- (1-7) (MA = Li, Na; R = Me, Et, iBu). An Al—H—Ni three-centre bond is present in these complexes. On the basis of NMR data, the strength of the hydridoaluminate-nickel bond and the charge on nickel, caused by the hydridoaluminate residue, are compared with the corresponding characteristics of other ligand-Ni(CDT) complexes in which donor-acceptor σ-bonds are present.
    Notes: Ni(CDT)Abkürzungen: CDT = trans, trans, trans-1,5,9-Cyclododecatrien, COD = 1,5-Cyclooctadien, MA+ (solvatisiertes) Alkalimetall-Ion, PMDTA = N,N,N′,N″N″-Pentamethyldiethylentriamin, TMEDA = N,N,N′,N′-Tetramethylethylendiamin. reagiert mit Alkalimetall-hydridotrialkylaluminaten in Ether/THF-oder Ether/Amin-Mischungen als Lösungsmittel unterhalb von -50°C zu den thermisch labilen Verbindungen [MA(n-Donor)n]+[R3Al—H—Ni(CDT)]- (1-7) (MA = Li, Na; R = Me, Et, iBu). In diesen Komplexen liegt eine Al—H—Ni-Mehrzentrenbindung vor. Anhand NMR-spektroskopischer Daten lassen sich die Stärke der Hydridoaluminat-Nickel-Bindung und die Beladung des Nickels durch den Hydridoaluminat-Rest mit den Bindungsverhältnissen in anderen Ligand-Ni(CDT)-Komplexen mit Donor-Akzeptor-σ-Bindungen vergleichen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180128
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 26
    Electronic Resource
    Electronic Resource
    Zur Lewis-Acidität von Nickel(0), I. Methyllithium-Komplexe von Nickel(0) (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 275-297 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Lewis Acidity of Nickel(0), I. Methyllithium Complexes of Nickel(0)The synthesis and properties of the methyllithium complexes of nickel(0) of the type (n-Donor)m-(LiCH3)Ni0(π-Ligand)n (1a-c, 16a-c, 20a-c) [n-Donor = chelating amine or THF; π-Ligand = CDT, ethene, or CO] are described. The structure of (PMDTA)(LiCH3)Ni(C2H4)2 (1b) has been determined by X-ray crystallography.  -  In these ate complexes, a carbanionic methyl group is σ-bonded to a nickel atom, the acceptor strength of which depend on the π-ligands. The chemical and spectroscopic properties indicate that the Ni—CH3 bond in the carbonyl complex is largely covalent whereas in the CDT and ethene compounds it is more polar. The CDT complex is thermolabile in solution. The findings are in agreement with the following series of increasing acceptor strength: Ni(CDT) 〈 Ni(C2H4)2 〈 Ni(CO)3.
    Notes: Es wird über die Synthese und Eigenschaften der Methyllithium-Komplexe von Nickel(0) (n-Donor)m(LiCH3)Ni0(π-Ligand)n Wir bezeichnen mitπ-Liganden solche Liganden, die als π-Akzeptoren mit einem Übergangsmetallatom dπ—pπ—oder dπ—dπ-Rückbindungen auszubilden vermögen (Alkene, CO, auch Phosphane);n-Donoren solche Liganden, die als „harte Basen“ (Ether, Amine) über ihre freien Elektronenpaare vornehmlich Hauptgruppenmetall-Ionen, d.h. „harte Säuren“ komplexieren;σ-Donoren solche Liganden, die  -  ohne über Akzeptororbitale zu verfügen  -  entweder polare Bindungen enthalten und Mehrzentrenbindungen eingehen können (Metallalkyle und -hydride) oder ein freies Elektronenpaar bereitstellen (Carbanionen, Phosphorane, Hydrid-Ion), wobei σ-Bindungen zu einem niederwertigen Übergangsmetallatom ausgebildet werden. (1a-c, 16a-c, 20a-c) mit Chelataminen oder THF als n-Donoren und CDTAbkürzungen: CDT = trans,trans,trans-l,5,9-Cyclooctadien; COT = Cyclooctatetraen; PMDTA = Pentamethyldiethylentriamin; TMEDA = Tetramethylethylendiamin; MA+A = Alkalimetall- bzw. quartäres Ammonium-Kation., Ethen oder CO als π-Liganden berichtet. Die Struktur von (PMDTA)(LiCH3)Ni(C2H4)2 (1b) wurde röntgenographisch bestimmt.  -  In diesen at-Komplexen ist eine carbanionische Methylgruppe über eine σ-Bindung an ein Nickelatom gebunden, dessen Akzeptorstärke von den π-Liganden abhängt. Chemische und spektroskopische Eigenschaften der Komplexe lassen für CDT oder Ethen als π-Liganden auf vergleichsweise polare, für den CDT-Komplex in Lösung dazu thermolabile Ni—CH3-Bindungen schließen, während für den Carbonyl-Komplex aufgrund von 13C-NMR-Daten eine überwiegend kovalente Ni—CH3-Bindung anzunehmen ist. Die Befunde stehen mit folgender Reihe zunehmender Akzeptorstärke im Einklang: Ni(CDT) 〈 Ni(C2H4)2 〈 Ni(CO)3.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180126
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 27
    Electronic Resource
    Electronic Resource
    Über das korrespondierende Verhalten von heteroatom-stabilisierten Carbokationen und dem Cycloheptatrien-Norcaradien-Gleichgewicht (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 620-633 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Correspondence of Heteroatom-stabilized Carbocations and the Cycloheptatriene-Norcaradiene EquilibriumThe effects of alkoxyiminium substituents on the cycloheptatriene-norcaradiene equilibria 1 ⇄ 2 have been investigated. Due to the energetics two classes of compounds were found (ΔH° 〈 0, and ΔH° 〉 0). The transfer of the substituent effect from carbocation to carbocyclus is inhibited by a p-phenylene group. From 1H and 13C NMR spectra at variable temperatures thermodynamic parameters are deduced and correlated with σR-constants obtained from 19F NMR spectroscopy. By extrapolation, the enthalpy difference for the unsubstituted cycloheptatriene and norcaradiene is calculated as 9.3 kcal/mol.
    Notes: Der Einfluß von Alkoxyiminium-Substituenten an C-7 auf die Lage des Cycloheptatrien-Norcaradien-Gleichgewichts 1 ⇄ 2 wird untersucht. Auf Grund der Energetik gibt es Verbindungen, bei denen Temperaturabsenkung eine Verschiebung des Gleichgewichts zum Norcaradien (ΔH° 〈 0) ergibt, bei anderen Beispielen ist ΔH° 〈 0. Eine p-Phenylenbrücke zwischen Kation und Carbocyclus blockiert den Substituenteneffekt. Aus den 1H- und 13C-NMR-Spektren bei verschiedenen Temperaturen wurden thermodynamische Daten ermittelt und mit den durch 19F-NMR bestimmten σR-Konstanten korreliert. Durch Extrapolation konnte die Enthalpiedifferenz des unsubstituierten Cycloheptatriens und Norcaradiens zu 9.3 kcal/mol abgeschätzt werden.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180221
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 28
    Electronic Resource
    Electronic Resource
    Hydrated oxocarbons, IV. Silylation of 1,1-dihydroxy compounds (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 661-669 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydratisierte Oxokohlenwasserstoffe, IV. Silylierung von 1,1-Dihydroxy-VerbindungenDie Anwendung von verschiedenen Silylierungsreagenzien auf mono- und polyvicinale 1,1-Di-hydroxy-Verbindungen wurde untersucht. Mit einigen dieser Reagenzien konnten aus Ninhydrin (2) und Rhodizonsäure (17) die entsprechenden geminalen Bis(trimethylsilyloxy)-Derivate 1 und 20 gewonnen werden. Während 1 leicht zu Hexamethyldisiloxan und Indantrion (4) fragmentiert, ist 20 thermisch relativ stabil, es gibt pyrolytisch bei 500°C nur Spuren des Tetraketons 21 ab. Andere Silylierungsreagenzien bewirken unerwartete C-Alkylierung oder C-Amidierung am Dihydroxykohlenstoff. Silylierungen von Perhydroxycyclobutan und -cyclohexan führen zu Ringaufspaltungs- bzw. Verengungsprodukten.
    Notes: The action of various silylating agents on mono- and polyvicinal 1,1-dihydroxy compounds has been investigated. Some of these reagents converted ninhydrin (2) and rhodizonic acid (17) into the corresponding geminal bis(trimethylsilyloxy) derivatives 1 and 20, respectively. Compound 1 readily fragments to form hexamethyldisiloxane and indantrione (4). The rhodizonic acid derivative 20 is, however, rather stable and even on pyrolysis at 500°C gives only traces of the tetraketone 21. With other silylating agents unexpected C-alkylation or C-amidation at the dihydroxy carbon is observed. Silylation of perhydroxycyclobutane and -cyclohexane leads to ring opened and contracted products.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180225
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 29
    Electronic Resource
    Electronic Resource
    Cycloadditionen des Triphenylallenyl-Kations mit Cyclopentadien  -  Studium des Reaktionsmechanismus unter stabilen Ionen-Bedingungen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 694-703 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloadditions of the Triphenylallenyl Cation with Cyclopentadiene  -  Investigation of the Reaction Mechanism under Stable Ion ConditionsThe triphenylallenyl cation (5) reacts with cyclopentadiene in a concerted [4 + 2] and a stepwise [2 + 2] cycloaddition. The reaction mechanisms are elucidated by NMR spectroscopic observation of the intermediate carbenium ions.
    Notes: Das Triphenylallenyl-Kation (5) geht mit Cyclopentadien eine konzertierte [4 + 2]- sowie eine stufenweise [2 + 2]-Cycloaddition ein. Die Reaktionsmechanismen werden durch NMR-spektro-skopische Beobachtung der intermediären Carbenium-Ionen aufgeklärt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180229
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 30
    Electronic Resource
    Electronic Resource
    Synthese und Struktur Platin-haltiger Tripeldecker- und Tetradecker-Komplexe (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 729-740 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of Platinum-Containing Triple-Decker and Tetra-Decker ComplexesStacking of the acceptor sandwich bis(η5-2,3-dihydro-1H-1,3-diborolyl)platinum 1 (≙ (C2B2C)2Pt) with (C5H5)M fragments leads to the unsymmetrical triple-decker complexes (η5-C5H5)M-μ-(η5-C2B2C)Pt(η5-C2B2C) 2 (M = Co) and 3 (M = Ni) as well as to the symmetrical tetra-decker complexes [(η5-C5H5)M-μ-(η5-C2B2C)]2Pt 4 (M = Fe) and 5 (M = Ni). In these reactions 1 and (C5H5)Fe(C8H12) yield the tetra-decker 4, whereas with (C5H5)Co(C2H4)2 only the triple-decker 2 is formed. With [(C5H5)Ni(CO)]2 both the triple-decker 3 and the tetra-decker 5 are obtained. NMR studies on the diamagnetic complexes 2 (30 valence electrons), 4 (42 VE), and 5 (46 VE) indicate high-symmetrical conformations, or free rotation of the ligands. 2 and 3 crystallize isotypic; the X-ray structure analyses exhibit the triple-decker arrangement with antiperiplanar conformation of the heterocycles. 3 in comparison with 2 is elongated along the molecular axis. The tetra-deckers 4 and 5 also crystallize isotypic; for the first time a synclinale conformation of the bridging ligands is found.
    Notes: Aufstockung des Akzeptor-Sandwichs Bis(η5-2,3-dihydro-1H-1,3-diborolyl)platin 1 (≙ (C2B2C)2Pt) mit (C5H5)M-Fragmenten führt zu den unsymmetrischen Tripeldecker-Komplexen (η5-C5H5)M-μ(η5-C2B2C)Pt(η5-C2B2C) 2 (M = Co) und 3 (M = Ni) sowie zu den symmetrischen Tetradecker-Komplexen [(η5-C5H5)M-μ-(η5-C2B2C)]2Pt 4 (M = Fe) und 5 (M = Ni). Dabei ergibt die Reaktion von 1 mit (C5H5Fe(C8H12) den Tetradecker 4, während mit (C5H5)Co(C2H4)2 nur der Tripeldecker 2 entsteht. Mit [(C5H5)Ni(CO)]2 werden der Tripeldecker 3 und der Tetradecker 5 gebildet. NMR-Untersuchungen an den diamagnetischen Komplexen 2 (30 Valenzelektronen), 4 (42 VE) und 5 (46 VE) sprechen für hochsymmetrische Konformationen oder freie Rotation der Liganden. 2 und 3 kristallisieren isotyp; die Röntgenstrukturanalysen zeigen die Tripeldeckeranordnung mit antiperiplanarer Konformation der Heterocyclen. 3 ist im Vergleich zu 2 entlang der Molekülachse aufgeweitet. Die Tetradecker 4 und 5 kristallisieren ebenfalls isotyp, es wird erstmals eine synclinale Konformation der Brückenliganden gefunden.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180232
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 31
    Electronic Resource
    Electronic Resource
    Ein neuer Zugang zu Alkylthio(trifluoracetyl)furanen durch thermische [3 + 2]-Cycloadditionen neuer mesoionischer 1,3-Oxathiol-4-one an Alkine (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 785-795 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Entry to Alkylthio(trifluoroacetyl)furans by Way of Thermal [3 + 2]Cycloaddition Reactions of New Mesoionic 1,3-Oxathiol-4-ones to AlkynesAs cyclic carbonyl ylides, the novel 2-alkylthio-5-trifluoroacetyl-1,3-oxathiolylium-4-olates of type 1a-d combine with dimethyl acetylenedicarboxylate across the 2,5-position with formation of non-isolable primary adducts, which release COS to give the furandicarboxylic diesters 3a-d. Methyl propiolate reacts with 1a-c to produce mixtures of the regioisomeric furancarboxylic esters 4a-c and 5a-c, whose main components 4a-c are isolable. On the other hand, the reactions of phenylacetylene, 1-diethylaminopropyne, or (Z)-1-methoxy-1-buten-3-yne with 1a proceed with regiospecific formation of the furan derivatives 6, 7, or 8, respectively. The observed regioselectivities are qualitatively discussed on the basis of MO-perturbation theory.
    Notes: Als cyclische Carbonyl-ylide nehmen die neuen 2-Alkylthio-5-trifluoracetyl-1,3-oxathiolylium-4-olate vom Typ 1a-d in 2,5-Stellung Acetylendicarbonsäure-dimethylester unter Bildung nicht-isolierbarer Primäraddukte auf, die unter COS-Abspaltung Furandicarbonester 3a-d liefern. Mit Propiolsäure-methylester reagiert 1a-c zu Gemischen aus den regioisomeren Furancarbonestern 4a-c und 5a-c, deren Hauptkomponenten 4a-c isolierbar sind. Dagegen vereinigen sich Phenylacetylen, 1-Diethylaminopropin bzw. (Z)-1-Methoxy-1-buten-3-in mit 1a regiospezifisch zu den Furan-Derivaten 6, 7 bzw. 8. Die beobachteten Regioselektivitäten werden qualitativ auf der Basis der MO-Störungstheorie diskutiert.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180237
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 32
    Electronic Resource
    Electronic Resource
    Notizen. Thermolysis and photolysis of hexachloro-tris-σ-homotropone and related compounds (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 840-844 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermolyse und Photolyse von Hexachlor-tris-σ-homotropon und verwandten VerbindungenTroponethylenacetal (2) reagiert mit überschüssigem CCl2 zu den Mono-, Bis- und Tris-Addukten 3, 4a, b und 5. Thermolyse von 5 führt nicht zum Hexachlor-tris-σ-homobenzol (1), ebensowenig wie die Photolyse des Ketons 6a, bei der unter Öffnung einer Cyclopropan-Brückenbindung das sterisch mehr gehinderte Isomere 6b erhalten wird. Die Photolyse von 8 verläuft ebenfalls nicht unter Decarbonylierung (→ 7) sondern unter Cyclopropanring-Öffnung zu 9 bzw. 10, wobei hier die von der Carbonylgruppe am weitesten entfernten Bindungen geöffnet werden.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180241
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 33
    Electronic Resource
    Electronic Resource
    Schwefelextrusion aus 5(2H)-Isothiazolonen und 5(2H)-Isothiazolthionen zu intermediären Imidoylketenen und -thioketenen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 851-862 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sulfur Extrusion from 5(2H)-Isothiazolones and 5(2H)-Isothiazolethiones to give Intermediate Imidoyl Ketenes and Imidoyl ThioketenesFrom 5(2H-isothiazolethiones (2) and propylene oxide a series of new 5(2H-isothiazolones (7) was prepared. With tributylphosphane (or cyanide ions) 2 and 7 eliminated one sulfur atom. The resulting assumed imidoyl ketenes (8) and imidoyl thioketenes (3) could not be detected spectro-scopically. But by isolation of dimeric imidoyl thioketenes (1,3-dithietanes, 1) and trapping with alcohols, amines, or benzylideneisopropylamine to give derivatives of acrylic acid (4-6) or dihydropyrimidones (9) it is shown that 3 and 8 are probably intermediates.
    Notes: Aus 5(2H)-Isothiazolthionen (2) wurde mittels Propylenoxid eine Reihe neuer 5(2H)-Isothiazolone (7) hergestellt. Beide Substanzklassen reagieren mit Tributylphosphan (oder Cyanid-Ionen) unter Abspaltung eines Schwefelatoms zu vermuteten, spektroskopisch aber nicht nachgewiesenen Imidoyl-thioketenen (3) bzw. Imidoylketenen (8). Ihr intermediäres Auftreten wurde durch die Isolierung von dimeren Imidoyl-thioketenen (1,3-Dithietanen, 1) und durch Abfangreaktionen mit Alkoholen, Aminen oder Benzylidenisopropylamin zu den Derivaten der Acrylsäure 4-6 bzw. den Dihydropyrimidonen 9 wahrscheinlich gemacht.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180302
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 34
    Electronic Resource
    Electronic Resource
    Heterocyclische β-Enaminoester, 36. Das Cycloadditions-Ringerweiterungsprinzip beim 4,5-Dihydropyrrol: 6,7-Dihydro-1H-azepine, Pyrimido[4,5-b]azepine und 1,2,4-Triazolo[5′,1′: 2,3]pyrimido[4,5-b]azepin (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 863-872 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic β-Enamino Esters, 36. The Cycloaddition-Ring Enlargement Principle on 4,5-Dihydropyrroles: 6,7-Dihydro-1H-azepines, Pyrimido[4,5-b]azepines, and 1,2,4-Triazolo[5′,1′: 2,3]pyrimido[4,5-b]azepineThe 2-amino-1-tosyl-Δ2-pyrroline enamino esters 2a, b react with dichlorotriphenylphosphorane to give the iminophosphoranes 3a, b. With acetylenic esters (4a-c) the 6,7-dihydro-1H-azepines 6a-d are formed according to the cycloaddition-ring enlargement principle. Acids hydrolyze to afford the free azepine enamino esters 7a, c, d. With phenyl isocyanate 6a gives the carbodiimide 9, which upon treatment with 5% aq. NaOH cyclizes to give the pyrimido[4,5-b]azepine 10. Analogously, isopropylamine and hydrazine lead to the 2-N-substituted bicycles 11a, b; with triethyl orthoformiate 11a yields the novel 5:6:7-tricycle 13.
    Notes: Die 2-Amino-1-tosyl-Δ2-pyrrolin-enaminoester 2a, b reagieren mit Dichlortriphenylphosphoran zu den Iminophosphoranen 3a, b. Mit Acetylenestern (4a-c) entstehen nach dem Prinzip Cycloaddition-Ringerweiterung die 6,7-Dihydro-1H-azepine 6a-d. Säuren hydrolysieren zu den freien Azepin-enaminoestern 7a, c, d. Mit Phenylisocyanat ergibt 6a das Carbodiimid 9, das sich mit 5proz. Natronlauge zum Pyrimido[4,5-b]azepin 10 ringschließen läßt; Isopropylamin und Hydrazin führt analog zu den 2-N-substituierten Bicyclen 11a, b, 11a ergibt mit Orthoameisensäure-triethylester den neuen 5:6:7-Tricyclus 13.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180303
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 35
    Electronic Resource
    Electronic Resource
    Carbonylvanadate(-I) mit ungesättigten Liganden: 51V-NMR-und IR-spektroskopische Charakterisierung der Tieftemperaturspezies [V(CO)5L]-; L = N2, Alkin, Alken, CS2 und SO2 (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 895-904 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Carbonylvanadates(-I) Containing Unsaturated Ligands:51V NMR and IR Characterization of Low-temperature [V(CO)5L]- Complexes; L = N2, Alkyne, Alkene, CS2, and SO2UV irradiation of [Et4N]V(CO)6 + L in THF (L = alkyne, alkene) or 2-Me-THF (L = N2) at 200 K yields the pentacarbonylvanadates [V(CO)5L]- with end-on (N2) and side-on (alkynes, alkenes) coordinated ligands, respectively. [V(CO)5SO2]- (η1S) and [V(CO)5CS2]- (η2-C,S) were obtained from the reaction between [V(CO)5THF]- and L at 200 K. The N2 complex is also formed from [V(CO)5OCMe2]- and N2. The complexes are characterized by their IR and 51V NMR spectra. Shielding of the 51V nucleus decreases in the order alkene 〉 alkyne ≍ N2 〉 SO2 〉 CS2 〉 {O}. Compared to η1-coordination, η2-coordination gives rise to a deshielding contribution of 110 to 280 ppm. The compounds decompose at temperatures above 225 K (L = N2, 2-pentyne, 3-hexyne, cyclopentene, cyclohexene), 240 - 250 K (SO2, CS2, 1-pentene), or 285 K (1-hexyne); with PPh3, [V(CO)5PPh3]- is formed.
    Notes: Die UV-Bestrahlung von [Et4N][V(CO)6] + L in THF (L = Alkin, Alken) oder 2-Me THF (L = N2) bei 200 K führt zu Pentacarbonylvanadaten [V(CO)5L]- mit end-on (N2) bzw. side-on (Alkine, Alkene) gebundenen Liganden. [V(CO)5SO2]- (η1-S und [V(CO)5CS2]- (η2C,S) wurden durch Umsetzung von [V(CO)5THF]- mit L bei 200 K erhalten. Der N2-Komplex entsteht auch aus [V(CO)5OCMe2]- und N2. Die Komplexe werden durch ihre IR- und 51V-NMR-Spektren charakterisiert. Die Abschirmung am Kern 51V nimmt in der Reihe Alken 〉 Alkin ≍ N2 〉 SO2 〉 CS2 〉 {O} ab. Die η2-Koordination liefert gegenüber der η1-Koordination einen Entschirmugsbeitrag von 110 - 280 ppm. Die Verbindungen zersetzen sich bei Temperaturen oberhalb 225 K (L = N2, 2-Pentin, 3-Hexin, Cyclopenten, Cyclohexen), 240 - 250 K (SO2, CS2, 1-Penten) bzw. 285 K (1-Hexin); mit PPh3 erfolgt Umsetzung zu [V(CO)5PPh3]-.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180307
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 36
    Electronic Resource
    Electronic Resource
    (Trifluormethyl)selen(VI)-Verbindungen, Synthese und Eigenschaften von Tetrafluor(trifluormethyl)selen-halogeniden sowie Trifluormethanselenonaten (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 943-951 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (Trifluoromethyl)selenium(VI) Compounds, Synthesis and Properties of Tetrafluoro(trifluoromethyl)selenium Halides and TrifluoromethaneselenonatesFluorination of CF3SeF3 with liquid F2 or AgF2 leads to CF3SeF5, which decomposes to CF4 and SeF4. With water CF4 and SeOF2 are formed. Addition of ClF to CF3SeF3 gives CF3SeF4Cl, which splits mainly into CF3Cl and SeF4. Hydrolysis provides analogously CF3Cl and SeOF2. A neutral concentrated solution of KMnO4 oxydizes CF3SeO2H in water in good yields to CF3SeO3K, the free acid of which is obtained with 74% HClO4. The aqueous solution can be concentrated up to 90%, but above this concentration spontaneous decomposition to CF4, COF2, and SeO2 occurs. Trifluoromethaneselenonates are stable at room temperature but decompose when heated.
    Notes: Die Fluorierung von CF3SeF3 mit flüssigem Fluor bzw. AgF2 führt zu CF3SeF5 das thermisch in CF4 sowie SeF4 zerfällt und mit H2O zu CF4 und SeOF2 hydrolysiert. Durch Addition von ClF an CF3SeF3 entsteht CF3SeF4Cl, das sich hauptsächlich zu CF3Cl und SeF4 zersetzt. Die Hydrolyse liefert analog CF3Cl und SeOF2. Mit wäßr., gesättigter KMnO4 liefert CF3SeO2H in guter Ausbeute CF3SeO3K, aus dem die freie Säure mit 74proz. HClO4 erhalten wird. Sie läßt sich in wäßriger Lösung bis zu 90% anreichern und zerfällt bei weiterem Konzentrieren spontan zu CF4, COF2 und SeO2. Ihre Salze sind bei Raumtemperatur stabil und explodieren beim Erhitzen.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180312
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 37
    Electronic Resource
    Electronic Resource
    Metallkomplexe mit biologisch wichtigen Liganden, XXXIV. Allyl-Palladium(II)- und Triphenylphosphan-Gold(I)-Komplexe mit Nucleobasen und Nucleosiden (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 931-942 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes with Biologically Important Ligands, XXXIV. Allyl-Palladium(II) and Triphenylphosphane Gold(I) Complexes with Nucleobases and NucleosidesThe reactions of (η3-allyl)Pd(μ-Cl)2Pd(η3-allyl) (A) and (COD)Rh(μ-Cl)2Rh(COD) with nucleobases and nucleosides give the complexes (η3-C3H5)Pd(L)Cl (1) (L = inosine, adenosine, guanosine, cytosine, cytidine, 2-thiouracil, 2-thiocytosine) and (COD)Rh(cytosine)Cl (2), respectively. With adenosine and purine also ligand bridged complexes (η3-C3H5)(Cl)Pd—L—Pd(Cl)(η3-C3H5) (3) have been obtained. Ph3PAuCl reacts with the anions L′ of purine, adenine, uridine, and inosine to give the complexes Ph3PAuL′ (5). Ph3PAu+ is added to both N atoms of the dianion of uracil with formation of 6. The coordination of the nucleobases is discussed on the basis of the 1H and 13C NMR spectra. The X-ray structure of Ph3PAu(adeninate) (5b) has been determined.
    Notes: Die Umsetzung von (η3-Allyl)Pd(μ-Cl)2Pd(η3-Allyl) (A) sowie von (COD)Rh(μ-Cl)2Rh(COD) mit Nucleobasen und Nucleosiden liefert unter Spaltung der Chlorobrücken die Komplexe (η3C3H5)-Pd(L)Cl (1) (L = Inosin, Adenosin, Guanosin, Cytosin, Cytidin, 2-Thiouracil, 2-Thiocytosin) bzw. (COD)Rh(Cytosin)Cl (2). Mit Adenosin und Purin wurden auch Ligand-verbrückte Komplexe (η3-C3H5)(Cl)Pd—L—Pd(Cl)(η3-C3H5) (3) erhalten. Ph3PAuCl setzt sich mit den Anionen L′ von Purin, Adenin, Uridin und Inosin zu Ph3PAuL′ (5) um; Ph3PAu+ addiert sich an die beiden N-Atome des Dianions von Uracil unter Bildung von 6. Die Koordination der Nucleobasen wird anhand der 1H- und 13C-NMR-Spektren diskutiert. Die Struktur von Ph3PAu (Adeninat) (5b) wurde röntgenographisch bestimmt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180311
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 38
    Electronic Resource
    Electronic Resource
    Bicyclofulvene, XI. Zur Frage der Spirokonjugation bei Spiro[cycloheptatrien-7,7′-norbornadien] (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1000-1007 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bicyclofulvenes, XI. On the Question of Spiroconjugation in Spiro[cycloheptatriene-7,7′-norbornadiene]The title compound 4 as well as the derivatives 5 und 6 have been prepared. The first band in the UV spectrum of 4 in n-heptane is blue-shifted by ca. 20 nm with respect to those of 5 and 6. Model calculations with the CNDO/S-CI method indicate that this hypsochromic shift as well as the bathochromic shift of the corresponding band of 2 relative to that of 3, cannot be explained by spiroconjugation. The thermolysis of 4 yields benzene, heptafulvalene (15), and fulveneallene (16). The latter products are probably derived from cycloheptatrienylidene (14) as an intermediate.
    Notes: Die Titelverbindung 4 sowie die Derivate 5 und 6 wurden dargestellt. Die erste Bande im UV-Spektrum von 4 in n-Heptan zeigt eine hypsochrome Verschiebung um ca. 20 nm verglichen mit den Banden in 5 und 6. Modellrechungen mit der CNDO/S-CI-Methode zeigen, daß, sowohl diese hypsochrome Verschiebung als auch die bathochrome Verschiebung der entsprechenden Bande von 2 im Vergleich zu 3 nicht auf Spirokonjugation beruht. Die Thermolyse von 4 ergibt neben Benzol Heptafulvalen (15) und Fulvenallen (16). Diese Produkte machen eine Spaltung von 4 in Benzol und Cycloheptatrienyliden (14) wahrscheinlich.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180316
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 39
    Electronic Resource
    Electronic Resource
    Neue Reagenzien, XXXII. Alkyldiphenylbismutane: Synthese, Eigenschaften und Halogenolyse (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1031-1038 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Reagents, XXXII. Alkyldiphenylbismutanes: Synthesis, Properties, and HalogenolysisAlkyldiphenylbismutanes 1 have been synthesized for the first time (61-92%). These compounds are air sensitive, not spontaneously inflammable liquids which decompose not below ≍ 170°C. The diphenylbismutino group is a very good equivalent for Cl- or Br-substituents at aliphatic residues since halogenolysis of the Bi-Alk bond with SO2Cl2 or Br2 already occurs at -40 to 0°C (corresponding fissions of As-Alk and Sb-Alk bonds afford heating to ≍ 130 or ≍ 220°C).
    Notes: Erstmals konnten Alkyldiphenylbismutane 1 synthetisiert werden (61-92%). Es sind luftempfindliche, nicht selbstentzündliche Flüssigkeiten, die sich erst bei ≍ 170°C zersetzen. Die Diphenylbismutino-Gruppe ist ein sehr gutes Äquivalent für aliphatisch gebundenes Chlor oder Brom, da die Halogenolyse der Bi-Alk-Bindung mit SO2Cl2 oder Br2 bereits bei - 40 bis 0°C abläuft (entsprechende Spaltungen von As-Alk- und Sb-Alk-Bindungen erfolgen bei ≍ 130 bzw. ≍ 220°C).
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180319
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 40
    Electronic Resource
    Electronic Resource
    Dimere Phospha- und Thiastannylene: Ylidartige Diphospha- und Dithiadistannetane (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1045-1049 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dimeric Phospha- and Thiastannylenes: Ylide-type Diphospha- and DithiadistannetanesBis(di-tert-butylphosphino)tin(II) (1) is obtained from the reaction of potassium di-tert-butyl-phosphide with stannous chloride or with the stannous chloride-triethylphosphane complex. Bis(tert-butylthio)tin(II) (2) is prepared by reaction of (η5-C5H5)2Sn with 2-methyl-2-propanethiol or from stannous chloride and (tert-butylthio)trimethylsilane. In solution, 1 and 2 are PR2-and SR-bridged dimers, respectively. NMR spectra indicate that rapid scrambling of terminal and bridging substituents occurs in 2 but not in the cyclic \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm P}\limits^ + - \mathop {\rm S}\limits^{\rm - } {\rm n} $\end{document} ylide 1.
    Notes: Bis(di-tert-butylphosphino)zinn(II) (1) entsteht durch Reaktion von Kalium-di-tert-butylphos-phid mit Zinndichlorid oder dem Zinndichlorid-Triethylphosphan-Komplex. Bis(tert-butylthio)-zinn(II) (2) wird hergestellt durch Umsetzung von (η5-C5H5)2Sn mit 2-Methyl-2-propanthiol und entsteht auch bei der Reaktion von Zinndichlorid mit (tert-Butylthio)trimethylsilan. 1 und 2 liegen in Lösung als PR2- bzw. SR-verbrückte Dimere vor. Kernresonanzspektren zeigen, daß bei dem cyclischen \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm P}\limits^ + - \mathop {\rm S}\limits^{\rm - } {\rm n} $\end{document}-Ylid 1 im Gegensatz zu 2 auch in Ethern keine raschen Platzwechselvorgänge (Brücke/terminal) ablaufen.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180321
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 41
    Electronic Resource
    Electronic Resource
    Regioselektive Addition von Grignard-Reagenzien an 3-Methoxy- und 3-Nitrophthalsäureanhydrid (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1058-1070 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Regioselective Addition of Grignard Reagents to 3-Methoxy- and 3-Nitrophthalic AnhydrideThe regioselectivity in the addition of the grignard reagents 5a and 6a to the anhydrides 1 and 2 is determined by the solvent system: in a highly selective manner (3: 97), the meta carbonyl group is attacked in tetrahydrofuran/tetramethylethylenediamine, while predominant, but relatively unselective (maximum 78:22) addition to the ortho carbonyl group is observed in diethyl ether. The influence of the solvent system on the regioselectivity is discussed. The LUMO-coefficients of the carbonyl carbon atoms in 1 and 2 were calculated.
    Notes: Die Addition der Grignard-Reagenzien 5a und 6a an die Anhydride 1 und 2 wird entscheidend vom Reaktionsmedium beeinflußt: in Tetrathydrofuran/Tetramethylethylendiamin wird hochselektiv (3: 97) die meta-ständige, in Diethylether dagegen überwiegend, aber mit nur geringer Selektivität (maximal 78: 22), die ortho-Carbonylgruppe angegriffen. Die Strukturen der dabei erhaltenen Addukte werden durch Umwandlung in die Ester 7-10, in die Lactone 11 sowie in die Ketone 12 und 13 bewiesen. Im Zusammenhang mit dem Versuch, die lösungsmittelabhängige Regioselektivität zu interpretieren, wurden die LUMO-Koeffizienten der Carbonylkohlenstoff-atome in 1 und 2 berechnet.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180323
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 42
    Electronic Resource
    Electronic Resource
    Cyanphosphorverbindungen, 8. Das ungewöhnliche Anion P2C10N102- (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1078-1085 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyanophosphorus Compounds, 8. The Unusual Anion P2C10N102-The reaction P(CN)3 + CN- (as [18]crown-6-sodium salt) leads via the spectroscopically identified P(CN)4 - to a disproportionation PIII → PI + PV. P(CN)2 - and P2C10N102- (1) have been isolated as products (with Ph3PCHPPh3 + as counter ion). In the latter an anionic aminomalononitrile bridge connects a dicyanophosphino and a pentacyanophosphate group, -P(CN)2 and - P(CN)5-, respectively.
    Notes: Die Reaktion P(CN)3 + CN- (als [18]Krone-6-Natriumsalz) führt über das nur spektroskopisch erkennbare P(CN)4- zur Disproportionierung PIII → PI + PV. Als Produkte können (mit Ph3PCHPPh3 + als Kation) P(CN)2- und P2C10N102- (1) gefaßt werden. In letzterem sind ein Dicyanphosphino-und ein Pentacyanophosphatrest, -P(CN)2 bzw. - P(CN)5-, über eine anionische Aminomalononitrilbrücke miteinander verbunden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180325
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 43
    Electronic Resource
    Electronic Resource
    Addition von Aldehyden an aktivierte Doppelbindungen, XXXV. α-Ketosäuren als Äquivalent für Aldehyde in der Thiazoliumsalz-katalysierten Addition (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1115-1125 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Addition of Aldehydes to Activated Double Bonds, XXXV. α-Keto Acids as an Equivalent for Aldehydes in the Thiazolium Salt-Catalyzed Additionα-Keto acids can be used instead of aldehydes in the thiazolium salt-catalyzed addition to vinyl ketones. The yields of γ-diketones 1-7 resulting from the aliphatic α-keto acids are equivalent with those obtained from the aldehydes. The diketo acids 9-19 are prepared from the easily accessible 2-oxodiacids. Phenylpyruvic acids are easier to prepare than the phenylacetalehydes and give better yields compared with the corresponding aldehydes in the addition to vinyl ketones leading to the γ-diketones 20-29. These diketones are converted to cyclopentenones. The dihydrofurylglyoxylic ester 40 leads to the diketone 43, which is converted to the diketone 44. There is no aldehyde known equivalent to that keto acid.
    Notes: α-Ketosäuren können anstelle von Aldehyden in die Thiazoliumsalz-katalysierte Addition an Vinylketone eingesetzt werden. So entstehen die γ-Diketone 1-7 aus den α-Ketosäuren der aliphatischen Reihe in Ausbeuten, die der Aldehydaddition entsprechen. Aus den gut zugänglichen 2-Oxodisäuren werden die Diketosäuren 9-19 erhalten. Phenylbrenztraubensäuren sind besser als Phenylacetaldehyde zu synthetisieren und liefern in der Addition an Vinylketone zu den γ-Diketonen 20-29 bessere Ausbeuten. Diese Diketone wurden in Cyclopentenone übergeführt. Aus dem Dihydrofurylglyoxylsäure-ethylester 40 kann das Diketon 43 und daraus das Diketon 44, erhalten werden, ein entsprechender Aldehyd ist nicht bekannt.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180328
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 44
    Electronic Resource
    Electronic Resource
    Masthead (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180501
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 45
    Electronic Resource
    Electronic Resource
    Heterocyclische 8π-Systeme, 16. Eliminierung an 2-Alkoxy-3-hydroxyindolinen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1726-1731 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heterocyclic 8π-Systems, 16. Elimination Reactions of 2-Alkoxy-3-hydroxyindolinesThermolysis of 2-ethoxy-3-hydroxyindolines 1a-f affords oxindoles 3a-f as main products and the corresponding 3-indolinones 2a-f as by-products. The reaction course via indole 2,3-oxide intermediates is discussed. For this reason rearrangement reactions of 3-hydroxyindoleninium salts 4a, f are investigated.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180439
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 46
    Electronic Resource
    Electronic Resource
    Chirale Lactole, IV. Selektivitäten bei Acetalisierungsreaktionen enantiomerenreiner Lactole am Beispiel von Octahydro-8,9,9-trimethyl-5,8-methano-2H-1-benzopyran-2-ol (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1733-1745 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chiral Lactols, IV. Selectivities in Acetal Formation Reactions of Enantiomerically Pure Lactols using Octahydro-8,9,9-trimethyl-5,8-methano-2H-1-benzopyran-2-ol as a ModelA synthesis of the lactol 1 is described and its application as a reagent for the resolution of racemates is demonstrated in several examples. By means of X-ray and conformation analysis a general rule is given, which allows to predict the absolute configuration of acyclic alkyl-aryl-carbinols from the course of acetal formation between an enantiomerically pure lactol and the racemic alcohol.
    Notes: Eine Synthese für das Lactol 1 wird beschrieben und seine Eignung als Reagens zur Racemattrennung an einigen Beispielen gezeigt. Aufgrund einer Röntgenstruktur und konformationsanalytischer Überlegungen wird eine allgemeine Regel erarbeitet, nach welcher die Absolutkonfiguration acyclischer Alkyl-aryl-carbinole aus dem Verlauf der Acetalisierungsreaktion eines enantiomerenreinen Lactols mit dem racemischen Alkohol vorhergesagt werden kann.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180502
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 47
    Electronic Resource
    Electronic Resource
    Aufbau Germylidin-verbrückter Drei- und Vierkerncluster (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1746-1757 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Buildup of Germylidyne-bridged Tri- and Tetranuclear ClustersReaction of organogermanium trihalides with KCo(CO)4 yields the trinuclear clusters RGeCo3(CO)9 (1, R = Me, Ph, tBu) as well as the new tetranuclear clusters (RGe)2Co4(CO)11 (3, R = Ph, tBu). The dinuclear complexes LnM — GeI2 — MLn (4-6, = FeCp(CO)2, Co(CO)4, NiCpCO) resulting from insertion of GeI2 into metal-metal bonds react with KCo(CO)4 to form the clusters LnM — GeCO3(CO)9 (7-9). Metal exchange reactions produce the hetero tetranuclear clusters (tBuGe)2Co3(CO)8M′Ln = MoCp(CO)2, NiCp). Crystal structure analyses were performed for Cp(CO)2Fe — GeCo3(CO)9 (7) and (tBuGe)2Co3(CO)8NiCp (11).
    Notes: Die Umsetzung von Organogermaniumtrihalogeniden mit KCo(CO)4 liefert sowohl die Dreikerncluster RGeCo3(CO)9 (1, R = Me, Ph, tBu) als auch die neuen Vierkerncluster (RGe)2Co4(CO)11 (3, R = Ph, tBu). Die durch Insertion von Gel2 in Metall-Metall-Bindungen entstehenden Zweikernkomplexe LnM — GeI2 — MLn (4-6, MLn = FeCp(CO)2, Co(CO)4, NiCpCO) setzen sich mit KCo(CO)4 zu den Clustern LnM — GeCO3(CO)9 (7-9) um. Metallaustauschreaktionen liefern die Heterovierkerncluster (tBuGe)2Co3(CO)8M′Ln (10, 11, M′Ln = MoCp(CO)2, NiCp). Von Cp(CO)2Fe — GeCo3(CO)9 (7) und (tBuGe)2Co3(CO)8NiCp (11) wurden Kristallstrukturanalysen durchgeführt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180503
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 48
    Electronic Resource
    Electronic Resource
    1,3-Dithienium- und 1,3-Dithioleniumsalze, II. Synthese monocyclothioacetalisierter 1,3-Diketone aus Silylenolethern (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1798-1808 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,3-Dithienium- and 1,3-Dithiolenium Salts, II. Synthesis of Monocyclothioacetalized 1,3-Diketones from Silyl Enol EthersThe 1,3-dithienium and 1,3-dithiolenium salts 3, available from the dithiols 1 or the cyclic thioacetals 4 (n = 2, 3) by reaction with the acyl chlorides 2, trityl tetrafluoroborate (5), and sulfuryl chloride (7), react in good yields with the silyl enol ethers 10 to give the new monocyclothioacetalized 1,3-Diketones 11. The synthetic of 11 as partially protected 1,3-Diketones is demonstrated exemplarily by dethioacetalization to the 1,3-dicarbonyl compounds 13.
    Notes: Die aus den Dithiolen 1 oder den cyclischen Thioacetalen 4 (n = 2, 3) durch Umsetzung mit den Acylchloriden 2, Trityl-tetrafluoroborat (5) und Sulfurylchlorid (7) erhältlichen 1,3-Dithienium-bzw. 1,3-Dithioleniumsalze 3 reagieren in guten Ausbeuten mit den Silylenolethern 10 zu den neuen monocyclothioacetalisierten 1,3-Diketonen 11. Das synthetische Potential von 11 als partiell geschützten 1,3-Diketonen wird exemplarisch durch Dethioacetalisierung zu den 1,3-Dicarbonylverbindungen 13 demonstriert.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180507
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 49
    Electronic Resource
    Electronic Resource
    Syntheses and ENDOR studies of selectively deuterated galvinoxyl radicals. Complete Determination of the 13C hyperfine coupling constants of Coppinger's radical (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1782-1797 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesen und ENDOR-Untersuchungen selektiv deuterierter Galvinoxyl-Radikale. Vollständige Bestimmung der 13C-Hyperfeinkopplungskonstanten von Coppingers RadikalDie Synthese einiger selektiv deuterierter Galvinole und deren Oxidation zu den korrespondierenden Galvinoxyl-Radikalen, z.B. Coppingers Radikal und Yangs Biradikal, wird beschrieben. Am Beispiel der Dublettradikale wird gezeigt, daß 13C-ENDOR-Spektroskopie auch ohne 13C-Isotopenanreicherung möglich ist. Im Falle von Coppingers Radikal gelang die vollständige Ermittlung der 13C-Hyperfeinkopplungskonstanten. Die ENDOR-Untersuchung von selektiv deuteriertem Yangs Biradikal in glasartiger Matrix erlaubte eine eindeutige Zuordnung der Singale zu Molekülpositionen, und es ließen sich Rückschlüsse auf die Radikalsymmetrie und die behinderte Rotation der tert-Butylgruppen ziehen. In den ENDOR-Spektren regellos orientierter Bisgalvinoxyl-Biradikale im Triplettzustand findet man scharfe Signale bei den freien Kern-Zeeman-Frequenzen, die von NMR-Übergängen im Ms = 0-Spinzustand herrühren. Es wird gezeigt, daß die betreffenden Deuterium-Signale infolge der Quadrupolwechselwirkung der Deuteriumkerne aufgespalten sind.
    Notes: The synthesis of selectively deuterated galvinols is described. Oxidation results in the formation of the respective galvinoxyl free radicals, e.g., Coppinger's radical and Yang's biradical. It is shown that 13C ENDOR signals can be detected for the doublet radicals without 13C labelling, i.e., in natural abundance. The complete set of 13C hyperfine coupling constants of Coppinger's radical could be determined. The ENDOR study of selectively deuterated Yang's biradical in a glassy matrix allowed an unambiguous assignment of the signals to molecular positions, and conclusions with respect to the symmetry of the radical and the hindered rotation of the tert-butyl groups could be drawn. Randomly oriented bisgalvinoxyl biradicals in the triplet spin state give rise to sharp ENDOR lines at the free nuclear Zeeman frequencies due to NMR transitions in the Ms = 0 electron spin manifold, and it is demonstrated that the respective 2H ENDOR lines show quadrupole splittings.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180506
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 50
    Electronic Resource
    Electronic Resource
    Darstellung von (η6-Aren)2Cr2(CO)3-Komplexen mit einer formalen Cr ≡ Cr-Dreifachbindung aus η6-ArenCr(CO)2NCCH3 (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1825-1835 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of (η6-arene)2Cr2(CO)3 Complexes Containing a Formal Cr ≡ Cr Triple Bond Starting from η6-areneCr(CO)2NCCH3The photochemical reaction of η6-ArCr(CO)3 (Ar = benzene, toluene, m-xylene, mesitylene, methyl benzoate, and fluorobenzene) with acetonitrile in hexane or p-tolunitrile in THF, resp., yields complexes η6-ArCr(CO)2NCR (1 - 10). Solutions of the red acetonitrile complexes yield on warming or UV photolysis by dissoziation of the nitrile and one CO ligand in the presence of benzene the new black coordination compounds (η6-Ar)2Cr2(CO)3 (11 - 16). The spectra and an X-ray structure determination of the benzene derivative 11 verify a Cr2-unit with a formal triple bond bridged by three CO ligands. The asymmetric unit of 11 contains two halves of molecules with Cr — Cr distances of 222.6 and 221.6 pm.
    Notes: Bei der photochemischen Umsetzung von η6-ArCr(CO)3 (Ar = Benzol, Toluol, m-Xylol, Mesitylen, Benzoesäure-methylester und Fluorbenzol) mit Acetonitril in Hexan bzw. p-Tolunitril in THF entstehen Komplexe η6-ArCr(CO)2NCR (1-10). Lösungen der roten Acetonitrilkomplexe bilden in der Wärme oder bei UV-Bestrahlung unter Abspaltung des Nitril- und eines CO-Liganden in Gegenwart von Benzol die neuen schwarzen Komplexe (η6-Ar)2Cr2(CO)3 (11-16). Die Spektren und die Röntgenstrukturanalyse des Benzolderivats 11 belegen eine von drei CO-Liganden verbrückte, formal eine Dreifachbindung aufweisende Cr2-Einheit. Die asymmetrische Enheit von 11 enthält zwei Molekülhälften mit Cr — Cr-Abständen von 222.6 bzw. 221.6 pm.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180509
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 51
    Electronic Resource
    Electronic Resource
    Reaction of 1-oxa-3-azabutatrienium salts with tertiary carboxamides (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1876-1886 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaktion von 1-Oxa-3-azabutatrienium-Salzen mit tertiären CarbonsäureamidenDie α-Chlorisocyanate 1 reagieren mit tertiären Carbonsäureamiden oder Acyliminen 3 in Gegenwart von Lewis-Säuren (SbCl5, FeCl3) unter milden Bedingungen zu den aminosubstituierten 2-Azaallenium-Salzen 5a - t. Die nur mäßig starken Elektrophile 5 setzen sich mit Methanol zu den Acetalen 8 und 10 um. Eine Röntgenstrukturanlyse von 5a zeigt, daß die -Einheit dieses Moleküls gewinkelt ist (128°). Es besteht eine Proportionalität zwischen der Wellenzahl der antisymmetrischen Valenzschwingung von 2-Azaallenium-Salzen und dem -Bindungswinkel. Die durch die sp2-Kohlenstoffe der -Einheit von 5a definierten Ebenen stehen nahezu senkrecht (84°) aufeinander.
    Notes: α-Chloro isocyanates 1 react with tertiary carboxamides or acylimines 3 in the presence of Lewis acids (SbCl5, FeCl3) to give the amino-substituted 2-azaallenium salts 5a - t under mild conditions. With methanol the moderately strong electrophiles 5 afford the acetals 8 and 10. According to an X-ray structural analysis, the C = N = C unit of 5a is bent by 128°. There exists a linear relationship between the wave number of the antisymmetric stretching vibration of 2-azaallenium salts and the bond angle. The planes defined by the sp2 carbons of the moiety of 5a are almost perpendicular (84°) with respect to each other.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180513
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 52
    Electronic Resource
    Electronic Resource
    Bildung von Oxetanen bei der photosensibilisierten Oxidation von Enaminen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1927-1935 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation of Oxetanes via Photo-sensitized Oxidation of EnaminesPhotooxidations of the enamines 1 and 5 in toluene give rise to the formation of the usual reaction products. In methanol, however, the oxetanes 8 and 13, respectively, are isolated as the main photooxidation products. Both the mechanism of their formation as well as some reactions of 8 and 13 are discussed. Oxidation of 13 with m-chloroperbenzoic acid produces the aldehyde 15 via a multi-step reaction.
    Notes: Die Photooxidation der Enamine 1 bzw. 5 in Toluol liefert die erwarteten Reaktionsprodukte. In Methanol entstehen dagegen die Oxetane 8 bzw. 13 als Hauptprodukt der Photooxidation. Die Reaktionen dieser Verbindungen werden beschrieben. Die Oxidation von 13 mit m-Chlorperbenzoesäure führt über einen mehrstufigen einheitlichen Reaktionsablauf zum Aldehyd 15. Der Bildungsmechanismus der Oxetane 8 und 13 wird diskutiert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180517
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 53
    Electronic Resource
    Electronic Resource
    Die Elektronenstruktur von 1,4-disubstituierten Butantetronen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1917-1926 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Electronic Structure of 1,4-Disubstituted ButanetetronesThe He(I) photoelectron (PE) spectra of the disubstituted butanetetrones 1 a - e have been recorded. The assignment of the first PE bands is based on semiempirical calculations. For 1 a - e the first bands could be assigned to ionization events from lone pair combinations on the oxygen atoms and in the case of 1 b - e additionally to ionizations from π-orbitals localized on the aromatic rings. The comparison between the PE bands of 1 d, 1,3-diphenyl-1,2,3-propanetrione, benzil, and benzophenone yields the result that the energy split between the n-orbital energies con-verges towards a value of about 3 eV. The interactions among the lone pairs and between lone pairs and the σ frame in 2 b - d are discussed, based on INDO calculations using localized orbitals.
    Notes: Die He(I)-Photoelektronen(PE)-Spektren der 1,4-disubstituierten Butantetrone 1 a - e wurden gemessen und anhand semiempirischer Rechnungen zugeordnet. Bei 1 a - e wurden die ersten Banden Ionisationen aus Linearkombinationen der einsamen Elektronenpaare an den Sauerstoffen und im Fall von 1 b - e noch zusätzlich Ionisationen aus den aromatischen π-Orbitalen zugeordnet. Der Vergleich zwischen den PE-Banden von 1 d, 1,3-Diphenyl-1,2,3-propantrion, Benzil und Benzophenon zeigt, daß die Aufspaltung zwischen den n-Orbitalenergien einem Grenzwert von etwa 3 eV zustrebt. Die Wechselwirkung zwischen den n-Orbitalen, den n-Orbitalen und dem σ-Gerüst (Through-Space- und Through-Bond-Wechselwirkung) in den vic. Di-, Tri- und Tetra-ketonen 2 b - d wird anhand von lokalisierten Orbitalen, die nach der INDO-Methode erhalten werden, diskutiert.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180516
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 54
    Electronic Resource
    Electronic Resource
    Azaborolinyl-Komplexe, XVI. Synthese und Untersuchung von (1,2-Azaborolinyl)tricarbonyl-Komplexen des Chroms, Molybdäns und Wolframs (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1949-1958 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azaborolinyl Complexes, XVI. Synthesis and Investigation of (1,2-Azaborolinyl)tricarbonyl Complexes of Chromium, Molybdenum, and Tungsten1-tert-Butyl-2-methyl-1,2-azaborolinyllithium reacts with the hexacarbonyls of chromium, molybdenum, and tungsten to give the complex salts Li[(Ab)M(CO)3] (Ab = azaborolinyl ligand, M = Cr (2), Mo (3), and W (4)). With Me3ECl (E = Ge, Sn, Pb) they form the corresponding germyl, stannyl, and plumbyl derivatives. The molecular and crystal structures of (Ab)(CO)3Cr—SnMe3 (2b) and (Ab)(CO)3Mo—SnMe3 (3b) show the azaborolinyl rings to be pentahapto-bonded, inspite of a small folding of the rings, leading to a longer distance of the boron atoms to the metal atoms. The IR, 1H, 11B, and 13C NMR data prove equivalent structures for the other complexes. The existence of enantiomers in the cell results from the crystal structure investigations of 2b and 3b and is caused by the prochiral character of the azaborolinyl rings.
    Notes: 1-tert-Butyl-2-methyl-1,2-azaborolinyllithium reagiert mit den Hexacarbonylen von Chrom, Molybdän und Wolfram zu den komplexen Salzen Li[(Ab)M(CO)3] (Ab = Azaborolinyl-Ligand, M = Cr (2), Mo (3) und W (4)). Diese bilden mit Me3ECl (E = Ge, Sn, Pb) die entsprechenden Germyl-, Stannyl- und Plumbylderivate. Die Molekül- und Kristallstrukturen von (Ab)(CO)3Cr—SnMe3 und (2b) und (Ab)(CO)3Mo—SnMe3 (3b) weisen die Azaborolinylringe als pentahapto-gebunden aus, trotz einer leichten Faltung der Ringe, durch die die Boratome einen größeren Abstand zu den Metallatomen erreichen. Die IR-, 1H-, 11B- und 13C-NMR-Daten beweisen äquivalente Strukturen für die übrigen Komplexe. Aus den Kristallstrukturuntersuchungen von 2b und 3b geht die Anwesenheit von Enantiomeren in der Zelle hervor, verursacht durch den prochiralen Charakter der Azaborolinylringe.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180519
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 55
    Electronic Resource
    Electronic Resource
    2,4-Diazabicyclo[3.3.1]nonan-Gerüste aus cis-Benzoltrioxid (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2044-2078 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2,4-Diazabicyclo[3.3.1]nonane Skeletons from cis-Benzene TrioxideBy treating cis-benzene trioxide (1) with guanidine in buffered tert-butyl alcohol solution the 1:1-adducts DL-(1α,2β,4β,5α,6α,10α)- 8-imino-3-oxa-7,9-diazatricyclo[4.3.1.02,4]decane-5,10-diol (13a) and DL-(1α,2α,3β,5β,6α,7α)- 9-imino-4-oxa-8,10-diazatricyclo[5.3.0.03,5]decane-2,6-diol (12a) resulting from 1,3(1,2)-bridging in 1 are obtained in 88 - 91% (9 - 12%) yields. Trifluoroacetamidine (acetamidine) is also selectively 1,3-added to 1. From 13a via generally regiospecific hydrolysis (26a), thiolysis (30a, d) ammonolysis (34a), hydrazinolysis (34d), and HCl-/HBr- addition (39a, c) access to highly functionalised 2,4-diazabicyclo[3.3.1]nonane derivatives is opened. During the “ring-chain tautomerism” observed for 26a and 34d (28a, 36d) the adamantoid orthocarbonic acid intermediates (27a, 35d) cannot be identified directly. The spectroscopic structure elucidations (not always unequivocal because i.a. of conformational flexibility of the skeletons) are confirmed by X-ray structural analysis for 29f, 36e, 38, und 43.
    Notes: Bei der Umsetzung von cis-Benzoltrioxid (1) mit Guanidin in gepufferter tert-Butylalkohol-Lösung werden mit 88 - 91% (9 - 12%) Ausbeute die aus der 1,3(1,2)-Überbrückung in 1 hervorgehenden 1:1-Addukte DL-(1α,2β,4β,5α,6α,10α)- 8-Imino-3-oxa-7,9-diazatricyclo[4.3.1.02,4]decan5,10-diol (13a) und DL-(1α,2α,3β,5β,6α,7α)- 9-Imino-4-oxa-8,10-diazatricyclo[5.3.0.03,5]decan-2,6-diol (12a) gewonnen. Auch Trifluoracetamidin (Acetamidin) wird an 1 bevorzugt 1,3-addiert. Aus 13a gewinnt man durch jeweils regiospezifische Hydrolyse (26a), Thiolyse (30a, d), Ammonolyse (34a), Hydrazinolyse (34d) und HCl/HBr-Addition (39a, c) Zugang zu hochfunktionalisierten 2,4-Diazabicyclo[3.3.1]nonan-Derivaten. Bei der für 26a und 34d beobachteten „Ring-Ketten-Tautomerie“ (28a, 36d) sind die adamantoiden Orthokohlensäure-Intermediate (27a, 35d) nicht nachweisbar. Die u. a. wegen der konformativen Flexibilität der Gerüste nicht immer eindeutigen spektroskopischen Strukturzuordnungen werden durch Röntgenstrukturanalysen für 29f, 36e, 38 und 43 gesichert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180527
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 56
    Electronic Resource
    Electronic Resource
    Untersuchungen an Diazoverbindungen und Aziden, 58. Dikation-ether, 5. Formamidinium-substituierte Diazophosphoryl-Verbindungen: Synthese, Eigenschaften und Reaktionen zu Tetrazolen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2105-2117 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on Diazo Compounds and Azides, 58. Dication Ethers, 5. Formamidinium-substituted Diazophosphoryl Compounds: Synthesis, Properties, and Reactions Leading to TetrazolesElectrophilic diazoalkane substitution of diazophosphoryl compounds 4a - c by bis(formamidinium) ethers 3a, b leads to formamidinium-substituted (diazomethyl)phosphoryl compounds 5. These can also be considered as alkenediazonium salts, but the contribution from this resonance structure is low according to 1H NMR and IR data. Reaction of 5a - c with another equivalent of 4a - c under slightly modified conditions yields 2-vinyl-2H-tetrazoles 6 and 7. The identity of the tetrazoles has been confirmed by X-ray structure analysis of 6c as well as by thermolysis of 6c leading to pyrazole 12 which then was hydrolyzed to give the NH-pyrazole 13.
    Notes: Die Diazophosphoryl-Verbindungen 4a - c reagieren mit den Bis(formamidinium)ethern 3a, b im Sinne einer elektrophilen Diazoalkan-Substitution zu Formamidinium-substituierten (Diazomethyl)phosphoryl-Verbindungen 5. Diese lassen sich auch als Olefindiazoniumsalze auffassen, jedoch deuten 1H-NMR- und IR-Daten nur auf einen geringen Anteil dieses Bindungszustandes hin. Unter leicht modifzierten Reaktionsbedingungen reagieren 5a - c mit einem weiteren Äquivalent von 4a - c zu den 2-Vinyl-2H-tetrazolen 6 und 7. Die Identität der Tetrazole wird durch eine Röntgenstrukturanalyse von 6c sowie die Thermolyse von 6c zum Pyrazol 12 und dessen Hydrolyse zum NH-Pyrazol 13 belegt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180530
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 57
    Electronic Resource
    Electronic Resource
    The molecular and electronic structure of dipiperidinosquaraine (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2118-2126 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Molekulare und elektronische Struktur von DipiperidinoquadratainDipiperidinoquadratain (9) kristallisiert im orthorhombischen Gitter, Raumgruppe Pnab, mit 4 Molekülen in einer Elementarzelle mit den Abmessungen a = 7.1798(9), b = 9.5362(8) und c = 18.788(2) Å. Das Molekül liegt auf einem Symmetriezentrum, d.h. der Vierring (C — C = 1.456(1) Å) ist genau planar; die Stickstoff- und Sauerstoffatome sind fast mit dem Ring coplanar, mit C — O = 1.2396(7) und C — N = 1.3112(7) Å. Sowohl die experimentellen als auch die theoretischen Daten zeigen beachtliche C — N- und C — O-π-Bindungen, aber nur eine geringfügige C — C-π-Bindung im Quadratainsystem. Die Berechnungen ergeben starke 1,3-abstoßende Wechselwirkungen im Vierring. Ringfaltung, ein sonst üblicher Mechanismus bei der Vermeidung solcher Abstoßungen, wird hier durch die starke C — N-π-Bindung verhindert.
    Notes: Dipiperidinosquaraine (9) crystallizes in the orthorhombic system, space group Pnab, with four molecules in a cell of dimensions a = 7.1798(9), b = 9.5362(8), and c = 18.788(2) Å. The molecule is located over a center of symmetry, so the four-membered ring (C - C = 1.456(1) Å av) is exactly planar; the nitrogen and oxygen atoms are nearly coplanar with the ring, with C — O = 1.2396(7) and C — N = 1.3112(7) Å. Both experimental and theoretical evidence indicates the presence of considerable C — N and C — O π-bonding, but only a small amount of C — C π-bonding in the squaraine system. The calculations indicate the presence of strong 1,3-repulsive interactions within the four-membered ring. Ring puckering, which is a common mechanism to alleviate these repulsions, is prevented here by the extensive C — N π-bonding.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180531
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 58
    Electronic Resource
    Electronic Resource
    The He(Iα) PE spectra and electronic absorption spectra of hexafluorocyclobutanone and of tetrafluoro-1,2-cyclobutane-dione (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2127-2133 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die He(Iα)-PE-Spektren und Elektronenabsorptionsspektren von Hexafluorcyclobutanon und Tetrafluor-1,2-cyclobutandionDie He(Iα)-PE-Spektren und die Elektronenabsorptionsspektren von Hexafluorcyclobutanon (3) und Tetrafluor-1,2-cyclobutandion (4) wurden gemessen. Die Zuordnung der ersten Banden beider Spektrentypen basiert hauptsächlich auf der Korrelation mit den entsprechenden Spektren der unsubstituierten Verbindungen Cyclobutanon (1) und 1,2-Cyclobutandion (2) sowie auf den Resultaten semiempirischer Rechnungen. Die Banden in den PE-Spektren von 3 und 4 werden im Vergleich zu den PE-Banden von 1 und 2 durch den Perfluor-Effekt um 1.6 bzw. 1.5 eV zu höheren Energien verschoben. Vergleicht man die Energie der ersten Bande in den Elektronenspektren von 1 und 3 bzw. 2 und 4, so findet man, daß diese Bande bathochrom um etwa 5000 cm-1 durch die Perfluor-Substitution verschoben wird. Dies wird dadurch erklärt, daß beim Ersatz der H-Atome durch F-Atome die Energie des LUMOs (π*) stärker abgesenkt wird als die des HOMOs (n).
    Notes: The He(Iα) PE and the electronic absorption spectra of hexafluorocyclobutanone (3) and tetrafluoro-1,2-cyclobutanedione (4) have been recorded. The assignment of the observed bands in both types of spectra is mainly based on the correlation with the corresponding spectra of the parent compounds cyclobutanone (1) and 1,2-cyclobutanedione (2), and in addition on the results of semiempirical calculations. As a result of the perfluoro effect, the bands in the PE spectra of 3 and 4 are shifted towards higher ionization energies by 1.6 eV and 1.5 eV relative to the corresponding bands in the PE spectra of 1 and 2. A comparison of the positions of the first band in the electronic spectra of 1 and 3, as well as of 2 and 4, shows that this band is shifted bathochromically by about 5000 cm-1 as a consequence of the perfluoro substitution. This is explained as being due to a stronger lowering of the LUMO (π*) energy than that of the HOMO (n) energy, induced by the replacement of the H-by F-atoms.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180532
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 59
    Electronic Resource
    Electronic Resource
    Cycloadditionen des 1-(4-Methoxyphenyl)-2,2-dimethylvinyl-Kations an Olefine (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2974-2992 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloadditions of 1-(4-Methoxyphenyl)-2,2-dimethylvinyl Cation to Olefins1-Bromo-1-(4-methoxyphenyl)-2-methyl-1-propene (1) reacts with cyclohexene, cycloheptene, (Z)-cyclooctene and the silver salts AgBF4, via the vinyl cation 2 by cycloaddition to form the cyclobutenes 7b-d. Cyclobutene 8 is obtained from (Z)- and (E)- and (E)-2-butene. Besides the cyclobutene derivatives, the isomeric cyclopropane compound 10d is also formed in the reaction of 1 with (Z)-cyclooctene under the same conditions, with cyclopentene only the cyclopropane derivative is formed. Copper (I) triflate-olefin complexes can be used in place of silver slats to generate the vinyl cation 2, whereby cyclobutenes 7 are formed preferably. - In contrast to vinyl bromide 1, 1-(4-methoxyphenyl)-2-methyl-1-propenyl triflate (5) reacts with cyclopentene, cyclohexene, cyloheptene, (Z)- and (E)-cyclooctene to give mostly the corresponding cyclopropane derivatives 10. The stereoisomeric cyclopropyl compounds 19 are obtained from (Z)- and (E)-2-butene. - The mechanisms of silver-catalysed and silver-free cycloaddition reactions are discussed.
    Notes: 1-Brom-1-(4-methoxyphenyl)-2-methyl-1-propen (1) reagiert mit Cyclohexen, Cyclohepten, (Z)-Cycloocten und den Silbersalzen AgBF4 bzw. AgSbF6 über das Vinylkation 2 unter Cycloaddition überwiegend zu den Cyclobutenen 7b-d. Mit (Z)- und (E)-2- Buten wird das Cyclobuten 8 erhalten. Bei der Umsetzung von 1 unter den gleichen Bedingungen entsteht mit Cyclopenten das Cyclopropanderivat 10a, mit (Z)-Cycloocten entsteht neben dem Cyclobutenderivat 7d die isomere Cyclopropanverbindung 10d. An Stelle der Silbersalze können auch Kupfer(I)-triflat-Olefin-Komplexe zur Erzeugung des Vinylkations 2 verwendet werden, wobei ebenfalls bevorzugt die Cyclobutene 7 erhalten werden. - Im Gegensatz zum Vinylbromid 1 reagiert das 1-(4-Methoxyphenyl)-2-methyl-1-propenyl-triflat (5) mit Cyclopenten, Cyclohexen, Cyclohepten und (Z)- bzw. (E)-Cycloocten überwiegend zu den entsprechenden Cyclopropanderivaten 10. Mit (Z)- und (E)-2-Buten werden die stereoisomeren Cyclopropylverbindungen 19 erhalten. - Die Mechanismen der silbersalzkatalysierten und silberfreien Cycloadditionsreaktionen werden diskutiert.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180731
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 60
    Electronic Resource
    Electronic Resource
    Basische Metalle, LVI Reaktionen von (Pentamethylcyclopentadienyl)rhodium(I)-Komplexen mit Dihalogen- und Trihalogenmethanen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 3032-3040 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals, LVI. Reactions of (Pentamethylcyclopentadienyl)rhodium(I) Complexes with Dihalo- and TrihalomethanesC5Me5Rh(CO)2 and C5Me5Rh(CO)L (L=PMe3, PMe2Ph, P(OMe)3) react with dihalo- and trihalomethanes to give (pentamethylcyclopentadienyl)rhodium complexes containing CH2X and CHX2 (X=Cl, Br, I, CN) as ligands. The reactions of [C5Me5RhCH2I(L)I] (L=CO, PMe3) with NaOCH3, PMe3, and PPh3 lead in some cases to substitution (e.g., formation of [C5Me5RhCH2OMe(PMe3)I] and [C5Me5Rh(CH2PPh3)(PMe3)I]X), in some cases to cleavage of the Rh - C bond. [C5Me5RhCH2I(CO)I] reacts with CH2(PPh2)2 to form the cyclic ylide complex [Ph2(I)]I.
    Notes: Durch Reaktion von C5Me5Rh(CO)2 und C5Me5Rh(CO)L (L=PMe3, PMe2Ph, P(OMe)3) mit Dihalogen- und Trihalogenmethanen werden (Pentamethylcyclopentadienyl)rhodium-Komplexe mit CH2X und CHX2 (X=Cl, Br, I, CN) als Liganden synthetisiert. Die Umsetzungen von [C5Me5RhCH2I(L)I] (L=CO, PMe3) mit NaOCH3, PMe3 und PPh3 verlaufen teilweise unter Substitution (Bildung z.B. von [C5Me5RhCH2OMe(PMe3)I] und [C5Me5Rh(CH2PPh3)(PMe3)I]X), teilweise aber auch unter Spaltung der Rh - C-Bindung. [C5Me5RhCH2I(CO)I] reagiert mit CH2(PPh2)2 zu dem cyclischen Yild-Komplex [Ph2(I)]I.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180804
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 61
    Electronic Resource
    Electronic Resource
    Monoozonolysen von acyclischen konjugierten Dienen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 3041-3057 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Monoozonolyses of Acyclic Conjugated DienesMonoozonolyses of isoprene (1a), 2-methyl-3-phenyl-1,3-butadiene (1b), 2,3-diphenyl-1,3-butadiene (25), and 2,3,4,5-tetramethyl-2,4-hexadiene (34) have been examined in pentane and in methanol. The dienes 1a, b and 25 afforded all possible α,β-unsaturated monoozonides and α,β-unsaturated methoxy hydroperoxides, respectively, whereas diene 34 gave no ozonide and no α,β-unsaturated methoxy hydroperoxide. From the dienes 25 and 34, the corresponding monoepoxides have been formed additionally. The results allow some conclusions concerning the regioselectivity of ozone attack at the unsymmetrically substituted dienes 1a, b as well as concerning the cleavage directions of primary ozonides.
    Notes: Monoozonolysen von Isopren (1a), 2-Methyl-3-phenyl-1,3-butadien (1b), 2,3-Diphenyl-1,3-butadien (25) und 2,3,4,5-Tetramethyl-2,4-hexadien (34) in Pentan und in Methanol wurden untersucht. Die Diene 1a, b und 25 lieferten alle möglichen α,β-ungesättigten Monoozonide bzw. α,β-ungesättigten Methoxyhydroperoxide; das Dien 34 ergab kein Ozonid und kein α,β-ungesättigtes Methoxyhydroperoxid. Aus den Dienen 25 und 34 wurden zusätzlich auch die entsprechenden Monoepoxide erhalten. Die Ergebnisse erlauben Rückschlüsse auf die Regioselektivität des Ozonangriffes an den unsymmetrisch substituierten Dienen 1a, b sowie über die Spaltungsrichtungen von Primärozoniden.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180805
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 62
    Electronic Resource
    Electronic Resource
    Photolyse des 9-Azidotriptycens. - Struktur des Dimeren eines extrem gespannten Brückenkopfimins (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 3058-3069 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photolysis of 9-Azidotriptycene. - Structure of the Dimer of a Severely Strained Bridgehead IminePhotolysis of 9-azidotriptycene (4) in cyclohexane affords molecular nitrogen and a dimer of the intermediate bridgehead imine 5 in 69% yield. The dimer is very sensitive towards traces of acid and irradiation in the presence of oxygen. The structure of the dimer is elucidated by spectroscopic methods as well as by an X-ray diffraction analysis. In solution approximately equal amounts of the (racemic) diastereomers 10 A and B are present which interconvert via an energy barrier of ΔG413≠ = ca. 90 kJ · mol-1. In contrast, in the crystalline state only diastereomer 10 A exists. The distereomer 10 A crystallizes as a racemate in the monoclinic space group P21/n (No. 14) with four molecules per cell. As the first step in the formation of 10 A, B we assume a dimerization of the bridgehead imine 5 producing 12 which rearranges to 10 A, B via a proton shift (→13) and subsequent opening of one of the 4H-azepine rings. The results are indicative of some diradical character of the bridgehead imine 5.
    Notes: Die Photolyse des 9-Azidotriptycens (4) in Cyclohexan ergibt neben Stickstoff mit 69% Ausbeute ein Dimeres des intermediären Brückenkopfimins 5. Das Dimere ist sehr empfindlich gegen Säurespuren und Belichten in Gegenwart von Luftsauerstoff. Die Struktur des Dimeren wird spektroskopisch und durch Röntgenbeugungsanalyse aufgeklärt. In Lösung liegen etwa gleiche Mengen der Diastereomeren 10 A und B vor, die sich mit ΔG413≠ =ca. 90 kJ · mol-1 ineinander umwandeln. Im Kristall existiert dagegen nur das Diastereomere 10 A, das als Racemat monoklin in der Raumgruppe P21/n (Nr. 14) mit vier Molekülen in der Elementarzelle kristallisiert. Als ersten Schritt der Bildung von 10 A, B nehmen wir eine Dimerisierung des Brückenkopfimins 5 zu 12 an, das sich durch Protonenwanderung (→13) und Öffnung eines 4H-Azepinrings in 10A, B umlagert. Die Ergebnisse sprechen für einen gewissen Diradikalcharakter des Brückenkopfimins 5.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180806
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 63
    Electronic Resource
    Electronic Resource
    Über sterisch gehinderte freie Radikale, XII. Das Radikal tert-Butyldiphenylmethyl, sein Dimeres sowie deren Autoxidation. Eine Neuuntersuchung (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 450-456 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Hindered Free Radicals, XII. The Radical tert-Butyldiphenylmethyl, Its Dimer, and Their Autoxidation. A ReinvestigationThe radical Ph2C.  -  tBu (1) dimerizes giving reversibly the quinonoid derivative 3, and not the ethane-like 2 as reported in the literature. In equilibrium there are less radicals 1 than in the case of triphenylmethyl, ΔHdiss = 18.5 ± 2 kcal/mol for 3. Both the radical 1 and its dimer 3 are rapidly oxidized by oxygen. 1 gives the dialkyl peroxide 6 which fragmentates already at 20°C mainly to benzophenone and tBu., 3 leads to the ketone 7, probably via the hydroperoxide 10. 3 rearranges catalysed by acid and by base as well via a 1,5-hydrogen migration forming the benzenoid derivative 4. Preparative and ESR details are given.
    Notes: Das Radikal Ph2C.  -  tBu (1) dimerisiert reversibel zum chinoiden Derivat 3 und nicht zum ethan-artigen 2, wie in der Literature berichtet. Im Gleichgewicht liegt weniger Radikal 1 vor als im Fall von Triphenylmethyl, ΔHDiss = 18.5 ± 2 kcal/mol für 3. Sowohl das Radikal 1 wie sein Dimeres 3 werden durch Sauerstoff rasch oxidiert. 1 gibt das Dialkylperoxid 6, das schon bei 20°C fragmentiert, hauptsächlich zu Benzophenon und tBu., 3 führt zum Keton 7, wahrscheinlich über das Hydroperoxid 10. 3 lagert sich, sowohl säure- wie basenkatalysiert, unter 1,5-H-Verschiebung um in das benzoide Derivat 4. Einzelheiten zu den Darstellungen sowie zur ESR-Spektroskopie werden angegeben.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180206
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 64
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 146. Über die Reaktion von Tetrazadiborinanen mit Heterokumulenen: Pseudodipolare [2 + 3]-Cycloadditionen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 483-494 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 146 Reactions of Tetrazadiborinanes with Heterocumulenes: Pseudodipolar [2 + 3]-CycloadditionsCO2, COS, and CS2 scavenge the 1,3-dipolar unit \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R'}\mathop {{\rm B - }}\limits^ \oplus {\rm NR - }\mathop {\rm N}\limits^{\rm \Theta } {\rm R} $\end{document} from the tetrazadiborinanes 3. [2 + 3]-Cycloadducts are formed in a pseudodipolar reaction, namely oxadiaza- and thiadiazaborolidines of type 7, 8 and 4. A reaction mechanism is suggested.  -  The thiadiazaborolidine 4b contains a planar five-membered ring according to an X-ray structure determination. Short BN, NN, and CN bond distances suggest a heteroaromatic ring system. High polarity is associated with the thioxo group. In contrast, the oxadiazaborolidinones 8a, b are in an equilibrium with their dimers in solution.
    Notes: CO2, COS und CS2 fangen aus den Tetrazadiborinanen 3e) den 1,3-Dipol \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R'}\mathop {{\rm B - }}\limits^ \oplus {\rm NR - }\mathop {\rm N}\limits^{\rm \Theta } {\rm R} $\end{document} ab. In einer pseudodipolaren Reaktion bilden sich als [2 + 3]-Cycloaddukte die Oxadiaza- und Thiadiazaborolidine 7, 8 und 4. Ein Reaktionsmechanismus wird diskutiert.  -  Nach Röntgenstrukturanalyse enthält 4b einen planaren Fünfring. Kurze BN-, NN- und CN-Abstände legen ein heteroaromatisches System nahe, wobei der Thioxo-Gruppe eine erhebliche Polarität zuzuweisen ist. Die Oxadiazaborolidinone 8a, b stehen in Lösung im Gleichgewicht mit ihrem Dimeren.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180210
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 65
    Electronic Resource
    Electronic Resource
    The colour of chelates of boron. An X-ray structural investigation of bis(4-methylphenyl)boryl and 9-borabicyclo-[3.3.1]nonyl acetylacetonates (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 670-675 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die Farbe von Bor-Chelaten. Röntgenstruktur-Untersuchung von Bis(4-methylphenyl)boryl- und 9-Borabicyclo[3.3.1]nonyl-acetylacetonatenDie Molekülstrukturen des farblosen Bis(4-methylphenyl)boryl- und des orangefarbenen 9-Borabicyclo[3.3.1]non-9-yl-acetylacetonats (4 und 5) wurden durch Röntgenstrukturanalyse ermittelt. Die C—O-Abstände in 4 sind merklich (ca. 0.029 Å) länger als die in 5. Es wird vermutet, daß der unterschiedliche π-Charakter in den C—O-Bindungen die Verschiebungen im Elektronenspektrum der verschiedenen Chelate von 1,3-Diketonen und verwandten Verbindungen verursacht.
    Notes: The molecular structures of the colourless bis(4-methylphenyl)boryl and the orange coloured 9-borabicyclo[3.3.1]non-9-yl acetylacetonates (4 and 5, respectively) have been determined by X-ray analysis. The C—O bond lengths in 4 are significantly (about 0.029 Å) longer than in 5. It is suggested that variation of the π bond order in the C—O bonds is responsible for the shifts in the electronic spectra observed for the various chelates of 1,3-diketones and related compounds.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180226
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 66
    Electronic Resource
    Electronic Resource
    2-Azaallenium salts from the reaction of 1-oxa-3-azabutatrienium salts with cyanamides and carbodiimides (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1887-1902 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Darstellung von 2-Azaallenium-Salzen durch Reaktionen von 1-Oxa-3-azabutatrienium-Salzen mit Cyanamiden und CarbodiimidenDie 1-Oxa-3-azabutatrienium-Salze 2 reagieren mit disubstituierten Cyanamiden unter [2 + 2 + 2]-Cycloaddition zu den 2-(Alkylidenamino)-4,6-diamino-1,3,5-oxadiazinium-Salzen 7a - o, die man als oxysubstituierte 2-Azaallenium-Salze betrachten kann. Durch Anlagerung von Methanol entstehen die Oxadiazinium-Salze 8a, d, p. Aus 2n und Dimethylcyanamid erhält man das 2-Azaallenium-Salze 11, dessen Bildung eine [1,5]-isocyanatotrope Umlagerung einschließt. Die Butatrienium-Salze 2 reagieren meist mit zwei Äquivalenten Carbodiimid vom Typ R1 — N = C = N — CHR22 zu den 2-Azaallenium-Salzen 17a - k, die durch eine [1,5]-Hydridverschiebung entstehen. Sterisch anspruchsvoll substituierte Butatrienium-Salze 2 lagern drei Moleküle Diisopropylcarbodiimid and und ergeben die 1,3,5-Triazinium-Salze 20n, o. Es werden Röntgenstruktur-analysen der Verbindungen 7a und 17a angegeben.
    Notes: 1-Oxa-3-azabutatrienium salts 2 react with disubstituted cyanamides under [2 + 2 + 2] cycloaddition affording the 2-(alkylideneamino)-4,6-diamino-1,3,5-oxadiazinium salts 7a - o, which can be regarded as oxy-substituted 2-azaallenium salts. Addition of methanol leads to the oxadiazinium salts 8a, d, p. From 2n and dimethylcyanamide the 2-azaallenium salt 11 was obtained, which must be formed by an [1,5] isocyanatotropic rearrangement. Most butatrienium salts 2 react with two equivalents of carbodiimides R1 — N = C = N — CHR22 to form the 2-azaallenium salts 17a - k. The reaction mechanism includes an [1,5] hydride shift. Bulky substituted butatrienium salts 2 add three molecules of diisopropylcarbodiimide to give the 1,3,5-triazinium salts 20n, o. X-Ray structural analyses for 7a and 17a are reported.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180514
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 67
    Electronic Resource
    Electronic Resource
    Iminokohlenstoff-Dianionen der C4-Reihe mit Cyaniminofunktionen (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1903-1916 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Iminocarbon Dianions of the C4-Series with Cyanoimino GroupsSuitable activated squaric acid derivatives react with the anion of cyanamide to yield novel iminocarbon dianions of the C4-series 8 - 11, in which the oxygens of the squarate dianion are successively replaced by one, two, three, or four cyanoimino groups. Besides the synthesis of mixed substituted iminocaron monoanions such as 12, 13, 25, and 26 is described. Spectroscopic data are discussed, 13C NMR data are compared with those of other pseudooxocarbons of the C3- and C4-series. The structure of the first isolable C4-iminocarbon 11′ is proved by X-ray diffraction, which confirmed 11′ to be a delocalized bond system just like the squarate dianion or the other pseudooxocarbons of the C4-series.
    Notes: Geeignet aktivierte Quadratsäurederivate lassen sich mit dem Anion des Cyanamids zu neuen Iminokohlenstoff-Dianionen der C4-Reihe 8 - 11 umsetzen, in denen die Sauerstoffunktionen des Quadratats sukzessive durch ein, zwei, drei oder vier Cyaniminogruppen ersetzt sind. Daneben wird die Darstellung gemischt substituierter Iminokohlenstoff-Monoanionen wie 12, 13, 25 und 26 beschrieben. Spektroskopische Daten werden diskutiert, 13C-NMR-Daten mit denen anderer Pseudooxokohlenstoffe der C3- und C4-Serie verglichen. Die Konstitution des ersten isolierbaren C4-Iminokohlenstoffs 11′ wird durch eine Röntgenstrukturanalyse belegt, die bestätigt, daß 11′ analog dem Quadratat und den anderen Pseudooxokohlenstoffen der C4-Reihe ein delokalisiertes Bindungssystem besitzt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180515
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 68
    Electronic Resource
    Electronic Resource
    Anisotropieeffekte konjugierter cyclischer Systeme, VI. Struktur und magnetische Anisotropie mesitylsubstituierter Ferrocene (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1968-1982 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Anisotropy Effects of Conjugated Cyclic Systems, VI. Structure and Magnetic Anisotropy of Mesityl-substituted FerrocenesTwo isomeric ferrocene derivatives have been obtained from 2-(2-ethyl-4,6-dimethylphenyl)-1,3-dimethylcyclopentadiene (22a). The exo,exo- (9) as well as the endo,endo-configuration (10) of these were determined by X-ray structure analysis. The assignment of the 1H NMR signals of the methyl groups in the spectrum of 1,1′,3,3′-tetramethyl-2,2′-dimesitylferrocene (7) is derived from the spectra of 9 and 10. Signals of methyl groups in exo-position of the mesitylferrocene are shifted by -0.74 ppm to higher magnetic field. Signals of methyl groups in endo-position directed towards the iron atom are shifted downfield by +0.71 ppm. Therefore, ferrocene develops a diamagnetic anisotropy which is similar to that of benzene.
    Notes: Aus 2-(2-Ethyl-4,6-dimethylphenyl)-1,3-dimethylcyclopentadien (22a) werden zwei isomere Ferrocenderivate erhalten. Durch Röntgenstrukturanalysen wird deren exo,exo-(9) bzw. endo,endo-Konfiguration (10) bestimmt. Anhand der 1H-NMR-Spektren dieser Ferrocene ist die Zuordnung der Methylgruppensignale im 1H-NMR-Spektrum des 1,1′,3,3′-Tetramethyl-2,2′-dimesitylferrocens (7) bewiesen. Signale von Methylgruppen in exo-Stellung des Mesitylferrocens werden um -0.74 ppm nach hohem Magnetfeld und solche von zum Eisenatom gerichteten in endo-Stellung um +0.71 ppm nach tiefem Feld verschoben. Daraus leitet sich für Ferrocen eine dem Benzol ähnliche diamagnetische Anisotropieverteilung ab.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180521
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 69
    Electronic Resource
    Electronic Resource
    Synthese und Struktur von Lithiumkomplexen mit pentahapto-gebundenen Tris(trimethylsilyl)cyclopentadienyl-Liganden (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1959-1967 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of Lithium Complexes with pentahapto-Bonded Tris(trimethylsilyl)cyclo-pentadienyl LigandsReaction of tris(trimethylsilyl)cyclopentadienyllithium (2) with the nitrogen bases quinuclidine, tetramethylethylenediamine, and pentamethyldiethylenetriamine leads to the isolation of the crystalline, air-sensitive 1:1-adducts 3, 4, and 5, resp., which are monomeric in the gas phase, in solution, and in the solid state. X-Ray structure determinations show that in 3-5 the cyclopentadienyl ring is pentahapto-bonded to the lithium atom. The bonding in these π-complexes is discussed; the complex 3 fulfills the criteria for a nido-cluster.
    Notes: Umsetzung von Tris(trimethylsilyl)cyclopentadienyllithium (2) mit den Stickstoffbasen Chinuclidin, Tetramethylethylendiamin und Pentamethyldiethylentriamin führt zur Isolierung der kristallinen, luftempfindlichen 1:1-Addukte 3, 4 und 5, die in der Gasphase, in Lösung und im festen Zustand monomer vorliegen. Kristallstrukturuntersuchungen zeigen, daß in 3-5 der Cyclopentadienylring pentahapto an das Lithiumatom gebunden ist. Die Bindungsverhältnisse in diesen π-Komplexen werden diskutiert; der Komplex 3 erfüllt die Kriterien für einen nido-Cluster.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180520
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 70
    Electronic Resource
    Electronic Resource
    Selektive Reduktion von Cyclohexadienonen mit Fe2(CO)9 und Wasser (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1983-1995 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Selective Reduction of Cyclohexadienones with Fe2(CO)9 and waterSelective monohydrogenation of cross conjugated 2,5-cyclohexadien-1-ones 1 with Fe2(CO)9 and water forming under unusually mild conditions the cyclohexadienol complexes 2 is applied to various related compounds. The regioselectivity of this reaction is tested with differently substituted derivatives. A mechanism explaining the observed regioselectivities and the pH dependence of the stereochemistry is discussed.
    Notes: Die unter ungewöhnlich milden Bedingungen verlaufende selektive Monohydrierung gekreuzt konjugierter 2,5-Cyclohexadien-1-one 1 mit Fe2(CO)9 und Wasser zu den Cyclohexadienol-Komplexen 2 wird auf verschiedene verwandte Verbindungen übertragen. Die Regioselektivität der Reaktion wird an unterschiedlich substituierten Derivaten geprüft. Es wird ein Mechanismus diskutiert, der die beobachteten Regioselektivitäten und die pH-Abhängigkeit der Stereochemie erklärt.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180522
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 71
    Electronic Resource
    Electronic Resource
    Synthese mittlerer und großer Ringe, X. (+)- und (-)-[6]Paracyclophan-8-carbonsäure aus (+)- und (-)-3,6-Hexanooxepin-4-carbonsäure (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1996-2010 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Medium and Large Rings, X. (+)- and (-)-[6]Paracyclophane-8-carboxylic Acid from (+)- and (-)-3,6-Hexanooxepin-4-carboxylic AcidThe racemic 3,6-hexanooxepin-4-carboxylic acid ((±)-2d), available in five steps from cyclooctyne and 3-(acetoxymethyl)furan, can be resolved into the enantiomers (+)- and (-)-2d using (+)(R)-1-(1-naphthyl)ethylamine. A stereospecific synthesis of (+)- and (-)-[6]paracyclophane-8-carboxylic acid ((+)- and (-)-4b) is possible from (+)- and (-)-2d as starting materials. Key steps of this synthesis are the transannular addition of bromine to give (-)- and (+)-3a and a subsequent McMurry reaction. The problems involved in the interpretation of the CD-spectra of the oxepin ester (+)-2e and of (+)-4b are discussed in detail.
    Notes: Die aus Cyclooctin und 3-(Acetoxymethyl)furan in fünf Stufen erhältliche racemische 3,6-Hexanooxepin-4-carbonsäure ((±)-2d) kann mit (+)(R)-1-(1-Naphthyl)ethylamin in die Enantiomeren (+)- und (-)-2d gespalten werden. Ausgehend von (+)- und (-)-2d ist eine stereospezifische Synthese von (+)- und (-)-[6]Paracyclophan-8-carbonsäure ((+)- und (-)-4b) möglich. Schlüsselschritte sind dabei die transannulare Bromaddition zu (-)- und (+)-3a und eine anschließende McMurry-Reaktion. Die Probleme der Interpretation der CD-Spektren des Oxepinesters (+)-2e und der Phancarbonsäure (+)-4b werden eingehend diskutiert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180523
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 72
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 152. 1,3,2,4-Diazaphosphaboretidine und 1,3,2,4-Diazasilaboretidine durch intra- und intermolekulare Cyclokondensation (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2030-2043 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 152. 1,3,2,4-Diazaphosphaboretidines and 1,3,2,4-Diazasilaboretidines Prepared via Intra- and Intermolecular Cyclocondensation1,3,2,4-Diazaphospha(sila)boretidines 5 and 9 are accessible via thermal decomposition of compounds of type E(NR′—BR2)2 (8) or from organoboron dihalides or boron trihalides and E(NR′Li)2 [E = Si(CH3)2, CH3(O)P, R(S)P, CH3P]. The formation of 1,3-di-tert-butyl-4-methyl-(or ethyl)-1,3,2,4-diazaphospha(sila)boretidines from the precursor E(NR′—BR2)2 proceeds by an intramolecular cyclocondensation. NMR data reveal less shielded B and P atoms in the new heterocycles as compared with noncyclic compounds; this is attributed to a strained ring system. A tetracoordinated as well as a tricoordinated boron atom is observed in CH3(O)P(NR′BR2)2 compounds resulting from intramolecular BO coordination.
    Notes: 1,3,2,4-Diazaphospha(sila)boretidine 5 und 9 sind über die thermische Zersetzung von Verbindungen des Typs E(NR′-BR2)2 (8) oder durch Umsetzung von Organylbordihalogeniden bzw. Bortrihalogeniden mit N-Lithio-Verbindungen E(NR′Li)2 [E = Si(CH3)2, CH3(O)P, R(S)P, CH3P] zugänglich. Es wird gezeigt, daß die 1,3-Di-tert-butyl-4-methyl-bzw. -4-ethyl-1,3,2,4-diazaphospha(sila)boretidine aus der Vorstufe E(NR′-BR2)2 durch eine intramolekulare Cyclokondensation entstehen. Nach NMR-Daten sind die Bor- und Phosphor-Kerne in den Vierring-Heterocyclen als Folge der Ringspannung schlechter abgeschirmt als in nichtcyclischen Derivaten. Vierfach koordiniertes Bor liegt neben dreifach koordiniertem in den Verbindungen CH3(O)P-(NR′BR2)2 vor. Dies geht auf intramolekulare BO-Koordination zurück.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180526
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 73
    Electronic Resource
    Electronic Resource
    Synthese von 4-Oxo-4H-benzothiazolo[3,2-a]pyrimidin-1-ium-2-olaten und ihre Cycloadditionen an elektronenarme und elektronenreiche Alkine sowie an o-Chloranil (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2079-2094 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 4-Oxo-4H-benzothiazolo[3,2-a]pyrimidin-1-ium-2-olates and their Cycloaddition Reactions to Electron-poor and Electron-rich Alkynes as well as to o-ChloranilThe synthesis and physical properties of the title compounds 3a - d, prepared from 1 and bis(2,4,6-trichlorophenyl) malonates 2a - d, are described. As cyclic 1,4-dipoles, the betaines 3 combine with dimethyl acetylenedicarboxylate, dibenzoylethyne or bis(diethylamino)ethyne with formation of primary adducts of type 4, which release methyl isocyanate to give pyrido[2,1-b]-benzothiazole derivatives 5a - g, whereas the reaction of 3a with bis(diethylamino)ethyne yields the betaine 7. With unsymmetrically substituted alkynes like methyl propiolate or 1-(diethyl-amino)propyne, 3 reacts with regiospecific formation of 8a - f. On the other hand, the reaction of 3a with o-chloranil proceeds with regiospecific formation of the 1,4-benzodioxin derivative 11. In the case of 8, the observed regiospecificities are in agreement with the results of MNDO calculations and MO-perturbation theory.
    Notes: Die Synthese und physikalischen Eigenschaften der Titelverbindungen 3a - d aus 1 und Malonsäure-bis(2,4,6-trichlorphenylestern) 2a - d werden beschrieben. Als cyclische 1,4-Dipole vereinigen sich die Betaine 3 mit Acetylendicarbonsäure-dimethylester, Dibenzoylethin oder Bis(diethyl-amino)ethin zu Primäraddukten vom Typ 4, die unter Methylisocyanat-Abspaltung Pyrido-[2,1-b]benzothiazol-Derivate 5a - g liefern, während 3a mit Bis(diethylamino)ethin das Betain 7 ergibt. Mit unsymmetrisch substituierten Alkinen, wie Propiolsäure-methylester oder 1-(Diethyl-amino)propin, reagiert 3 regiospezifisch zu 8a - f. Andererseits führt die Umsetzung von 3a mit o-Chloranil regiospezifisch zu dem 1,4-Benzodioxin-Derivat 11. Die bei 8 beobachteten Regiospezifitäten sind mit den Ergebnissen aus MNDO-Rechnungen und der MO-Störungstheorie in Einklang.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180528
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 74
    Electronic Resource
    Electronic Resource
    Thermolabile Hydrocarbons, XXVII. 2,3-Di-1-adamantyl-2,3-dimethylbutane; Long Bonds and Low Thermal Stability (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 4665-4673 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermolabile Kohlenwasserstoffe, XXVII. 2,3-Di-1-adamantyl-2,3-dimethylbutan; lange Bindungen und geringe thermische StabilitätDie Titelverbindung 2 wurde durch Wurtz-Synthese dargestellt und eine Kristallstrukturanalyse durchgeführt. Die Strukturdaten des sehr stark deformierten Molekülgerüstes - drei benachbarte CqCq-Bindungen sind länger als 164 pm, CqCqCq-Bindungswinkel sind bis 118° aufgeweitet - werden durch Rechnungen mit dem MM 2-Kraftfeld sehr gut wiedergegeben. Nach den Kraftfeldrechnungen ist 2 der am stärksten gespannte, nach kinetischen Messungen der thermisch labilste Vertreter der bereits früher bearbeiteten CqCq-Alkane.
    Notes: The title compound 2 was prepared by a Wurtz procedure. Its highly deformed structure was determined by X-ray analysis and matched with high precision by MM 2 force field calculations. The three neighbouring CqCq bonds are longer than 164 pm and the CqCqCq bond angles are 118°. According to MM 2 calculations and a kinetic investigation 2 is the most strained and least stable member of the CqCq alkane series investigated previously2).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851181203
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 75
    Electronic Resource
    Electronic Resource
    Hauptgruppenelement-Übergangsmetall-Mehrfachbindungen, IV. Katalytische Assistenz von [Cp(CO)3Mo]2 bei der Aggregation von Metallo-arsanen über Arsen-Metall-Doppelbindungskomplexe (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 378-382 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Main Group Element Transition Metal Multiple Bonds, IV. Catalytic Assistance by [Cp(CO)3Mo]2 in the Aggregation of Metallo-arsanes via Arsenic Metal Double Bond Complexes2)The metallo-arsanes Cp(CO)3M—AsMe2 (1a, b) (M = Mo, W) are converted to the double arsenido-bridged dinuclear complexes [(μ-AsMe2)Mo(CO)2Cp]2 (3a, b) in the presence of [Cp(CO)3Mo]2. Due to the unusual mild conditions of aggregation the intermediate formation of the double bonded species Cp(CO)2M=AsMe2 (2a, b) is postulated. The crystal structure of 3a is reported, which shows mutual trans arrangement of the cyclopentadienyl and CO ligands.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190133
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 76
    Electronic Resource
    Electronic Resource
    Aliphatische Flüssigkristalle, 7. Einige mesogene Tercyclohexylderivate (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 387-400 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aliphatic Liquid Crystals, 7. Some Mesogenic Tercyclohexyl DerivativesStarting from bicyclohexyl-4-one 1 the tercyclohexyl-3-one 6 is synthesized via the acetyl derivatives 3a,b. Methoxycarbonylation of 6 gives the keto ester 12 which on the one hand is tranformed to the esters 15a,b and 17 - 20 and the nitriles 21a,b, on the other hand to the methylated keto esters 23a,b and 24a,b. From 23a the ester 26 with an axial 1-methyl group is obtained. Nearly all the products are mesogenic.
    Notes: Aus dem Bicyclohexyl-4-on 1 wird über die Acetylderivate 3a,b das Tercyclohexyl-3-on 6 aufgebaut, daraus durch Methoxycarbonylierung der Ketoester 12, der einerseits zu den Estern 15a,b und 17 - 20 und den Nitrilen 21a,b, andererseits zu den methylierten Ketoestern 23a,b und 24a,b umgesetzt wird. Aus 23a erhält man den Ester 26 mit axialer 1-Methylgruppe. Fast alle Produkte sind mesogen.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190202
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 77
    Electronic Resource
    Electronic Resource
    Vitamin-Synthese mit Carben-Komplexen, VI. Stereospezifische Darstellung von Pentacarbonyl[(Z)-dimethoxy-vinyl]carben-Komplexen des Chroms und Wolframs (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1126-1132 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vitamin Syntheses via Carbene Complexes, VI. Stereospecific Synthesis of Pentacarbonyl[(Z)-dimethoxyvinyl]carbene Complexes of Chromium and TungstenThe addition of (E,Z)-1-lithio-1,2-dimethoxyethene (1) to hexacarbonylchromium and -tungsten followed by protonation or alkylation, respectively, provides a stereospecific route to pentacabonyl[(Z)-1,2-dimethoxyvinyl]carbene complexes 2-5. Established by X-ray analysis, the carbene ligand of the methoxycarbene chromium complex 3 is nearly coplanar.
    Notes: Die Addition von (E,Z)-1-Lithio-1,2-dimethoxyethen (1) an Hexacarbonylchrom und -wolfram liefert nach Protonierung bzw. Alkylierung stereospezifisch die Pentacarbonyl[(Z)-1,2-dimeth-oxyvinyl]carben-Komplexe 2-5. Nach der Röntgenstrukturanalyse des (Methoxycarben)chrom-Komplexes 3 ist der gesamte Carbenligand annähernd koplanar.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180329
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 78
    Electronic Resource
    Electronic Resource
    Zwei neue Metallcarbonyle: Darstellung und Struktur von RuCo2(CO)11 und Ru2Co2(CO)13 (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1133-1142 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Two New Metal Carbonyls: Preparation and Structure of RuCo2(CO)11 and Ru2Co2(CO)13RuCo2(CO)11 (1) results from the stoichiometric and heterogeneous reaction between KCo(CO)4 and [Ru(CO)3Cl2]2 in water. Its decomposition in hexane at 65°C yields Ru2Co2(CO)13 (2). The crystallographically determined molecular structures of both compounds show that their metal atom cores are located inside approximately regular ligand polyhedra.
    Notes: RuCo2(CO)11 (1) entsteht durch stöchiometrische heterogene Umsetzung von KCo(CO)4 und [Ru(CO)3Cl2]2 in Wasser. Seine Zersetzung bei 65°C in Hexan liefert Ru2Co2(CO)13 (2). Die kristallographisch bestimmten Molekülstrukturen beider Verbindungen lassen erkennen, daß ihre Metallatom-Kerne sich in annähernd regelmäßigen Ligandenpolyedern befinden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180330
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 79
    Electronic Resource
    Electronic Resource
    Synthese und Struktur eines hochsubstituierten Tetracyclo[3.3.0.02,8.04,6]octans (Nortriasteran) (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1176-1182 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of a Highly Substituted Tetracyclo[3.3.0.02,8.04,6]octane (Nortriasterane)The 4,8-dibromobicyclo[3.3.0]octa-2,6-diene-2,6-dicarbonitrile 2 reacts with sodium methoxide in methanol quantitatively and with complete stereoselectivity to afford the nortriasteranedicarbonitrile 5. This dinitrile crystallizes triclinically in the space group P1 with two enantiomorphous molecules per cell. Some geometric parameters involving the cyclopropane rings and the mechanism of formation of 5 are discussed.
    Notes: Das 4,8-Dibrombicyclo[3.3.0]octa-2,6-dien-2,6-dicarbonitril 2 reagiert mit Natriummethanolat in Methanol quantitativ und vollständig stereoselektiv zum Nortriasterandicarbonitril 5. Dieses kristallisiert triklin in der Raumgruppe P1 mit zwei enantiomorphen Molekülen in der Elementarzelle. Einige geometrische Parameter der Cyclopropanringe und der Bildungsmechanismus von 5 werden diskutiert.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180333
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 80
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 169. Sterisch anspruchsvolle N-Lithioaminoborane: Reagentien zur Synthese symmetrisch und unsymmetrisch substituierter Diborylamine (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1361-1373 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 169. Sterically Demanding N-Lithioaminoboranes: Reagents for the Synthesis of Symmetrically and Unsymmetrically Substituted DiborylaminesN-Metalation of R2BNH2 or R2BNMeH yields lithium amides R2BNR′Li with sterically demanding R groups (R = tBu, iPr). These compounds are synthons for symmetrically or unsymmetrically substituted diborylamines as well as for B-functional diborylamines. NMR data reveal the conformation of these diborylamines. Compounds of the type tBu2B—NMe—BR2 contain tBu2B groups whose BC2 plane stands nearly orthogonal to the B2NC skeleton. In contrast, the BRX group in diborylamines of the type tBu2B—NH—BRX is strongly twisted with respect to the B2NH plane.
    Notes: Durch N-Metallierung erhältliche Lithiumamide R2BNR′Li mit sperrigen Substituenten R = tBu, iPr eignen sich sowohl zur Darstellung symmetrisch und unsymmetrisch substituierter Diborylamine als auch zur Gewinnung B-funktioneller Diborylamine. Kernresonanzspektroskopische Untersuchungen zeigen, daß Diborylamine tBu2B—NMe—BR2 eine tBu2B-Gruppe enthalten, deren BC2-Ebene weitgehend orthogonal zur B2NC-Gerüstebene steht. In Diborylaminen tBu2B—NH—BRX ist hingegen die BRX-Gruppe gegen die B2NH-Ebene verdrillt.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190423
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 81
    Electronic Resource
    Electronic Resource
    Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen, XXV. Aufbau und Reaktivität von Se1- und Se2-Brücken in Organochrom-Komplexen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1437-1440 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multiple Bonds Between Main Group Elements and Transition Metals, XXV. Synthesis and Reactivity of Se1- and Se2-Bridges in Organochromium CompoundsReaction of the ionic complex K[(η5-C5Me5)Cr(CO)3] (1) with selenium(I) with selenium(I) chloride, Se2Cl2, yields the diselenium compounds 2 of composition (η5-C5Me5)Cr(CO)5Se2 which is converted to the Se1 derivative (μ-Se)[η5-C5Me5)Cr2(CO)2]2 (3) with triphenylphosphane. 3 exhibits a linear, multiple bonded CrSeCr core structure. Reaction of 2 with diazomethane gives the novel mononuclear, paramagnetic selenoformaldehyde complex (η5-C5Me5)-Cr(CO)2(SeCH2) (4).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190430
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 82
    Electronic Resource
    Electronic Resource
    Masthead (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190501
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 83
    Electronic Resource
    Electronic Resource
    N-tert-Butylpivalohydroxamsäure: s-trans-Konformation und H-Brückenbindungen im Kristall (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1441-1444 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-tert-Butylpivalohydroxamic Acid: s-trans-Conformation and H-Bonding in the CrystalIt is shown by an X-ray crystal structure analysis that, in the crystal, teh title compound has the s-trans-conformation and the molecules are linked by strong intermolecular H-bonds to linear chains.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190431
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 84
    Electronic Resource
    Electronic Resource
    Synthesen von 2,6,7-Triazabicyclo[2.2.2]oct-2-en-5,8-dionen und 4(3H)-Pyrimidinonen durch 1,4-Dipolare Cycloadditionen von Pyrimidinium-4-olaten an Nitrile (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1445-1454 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of 2,6,7-Triazabicyclo[2.2.2]oct-2-ene-5,8-diones and 4(3H)-Pyrimidinones via 1,4-Dipolar Cycloaddition Reactions of Pyrimidinium-4-olates to NitrilesThe 3,6-dihydro-6-oxo-1-pyrimidinium-4-olate 1a, which carry no substituent in the 2 position, undergoes 1,4-dipolar cycloaddition reactions with ethyl cyanoformate (2a) and benzoyl cyanide (2b) to produce novel bicyclic primary adducts 3a, b, respectively, which at higher temperature fragment into 4(3H)-pyrimidinones 4a, b with elimination of phenyl isocyanate. However, pyrimidinium-4-olates 1b - h or 5, which are substituted in the 2 position, react directly with nitriles 2a - c to form high yields of 4(3H)-pyrimidinone derivatives of type 4 or 7, respectively. Furthermore, the reactions of 1a with isocyanic acid as well as with cyan amide are described.
    Notes: Das in 2-Position unsubstituierte 3,6-Dihydro-6-oxo-1-pyrimidinium-4-olat 1a geht mit Cyanameisensäure-ethylester (2a) und Benzoylcyanid (2b) 1,4-Dipolare Cycloadditionen zu neuen bicyclischen Primäraddukten 3a bzw. b ein, die bei höherer Temperatur unter Phenylisocyanat-Abgabe in 4(3H)-Pyrimidinone 4a, b fragmentieren. Dagegen reagieren die in 2-Stellung substituierten Pyrimidinium-4-olate 1b - h oder 5 mit Nitrilen 2a - c in hohen Ausbeuten direkt zu den 4(3H)-Pyrimidinon-Derivaten vom Typ 4 bzw. 7. Weiterhin werden die Reaktionen von 1a mit Isocyansäure sowie mit Cyanamid beschrieben.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190502
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 85
    Electronic Resource
    Electronic Resource
    Über sterisch gehinderte freie Radikale, XV. Das erste unsymmetrische Dimere aus zwei stabilen Radikalen: 3-(tert-Butylphenylmethylen)-6-(triphenylmethyl)-1,4-cyclohexadien aus tert-Butyldiphenylmethyl und Triphenylmethyl (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2006-2012 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Hindered Free Radicals, XV. The First Unsymmetrical Dimer from Two Different Stable Radicals: 3-(tert-Butylphenylmethylene)-6-(triphenylmethyl)-1,4-cyclohexadiene from tert-Butyldiphenylmethyl and TriphenylmethylThe quinonoid title compound 6 is formed in an equilibrium to 95% and can be isolated, when the two title radicals 1 and 3 are generated in solution. The reason for this is the sterically less strained position of the bulky tBu group at the sp2-C atom of the methylene group. The structure of 6 is proved by 1,5-H migration giving 8 and autoxidation of the latter at -10°C giving tBuOH and 4-tritylbenzophenone (12). The synthesis of several analogous compounds are described.
    Notes: Die chinoide Titelverbindung 6 entsteht im Gleichgewicht zu 〉95% und kann isoliert werden, wenn die beiden Titelradikale 1 und 3 in Lösung erzeugt werden. Ursache hierfür ist die räumlich günstigere Unterbringung der sperrigen tBu-Gruppe am sp2-C-Atom der Methylengruppe. Die Struktur von 6 wird durch 1,5-H-Verschiebung zu 8 sowie dessen Autoxidation bei -10°C zu tBuOH und 4-Tritylbenzophenon (12) bewiesen. Synthesen analoger Verbindungen werden beschrieben.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190621
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 86
    Electronic Resource
    Electronic Resource
    Der Einfluß von Phenylgruppen auf die Homokonjugation im Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anion. Eine 13C-NMR-Studie (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2025-2049 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Effect of Phenyl Groups on the Homoconjugation in the Bicyclo[3.2.1]octa-3,6-dien-2-yl Anion. A 13C NMR StudyThe effects of deuterium atoms in the positions 2 and 4 of exo-6-bromo- (11) and endo-6-methoxytricyclo[3.2.1.02,7]oct-3-ene (12) as well as exo-4-methoxybicyclo[3.2.1]octa-2,6-diene (13) on their 13C chemical shifts are in line with the previous interpretation of the effects in correspondingly deuterated bicyclo[3.2.1]octa-3,6-dien-2-yl anions 1, and thus provide evidence for the homoconjugative interaction in 1. 3-Phenylbicyclo[3.2.1]octa-2,6-diene (16) and endo- (19a) as well as exo-4-phenylbicyclo[3.2.1]octa-2,6-diene (19b) have been prepared from bicyclo[3.2.1]oct-6-en-3-one (14) and bicyclo[3.1.0]hex-2-ene-endo-6-carbaldehyde (17), respectively. 2,4-Diphenylbicyclo[3.2.1]octa-2,6-diene (6) and 19a, b were deprotonated by methyllithium and n-butyllithium, respectively, whereas the proton abstraction from tricyclo[6.3.1.02,7]dodeca-2,4,6,9-triene (4) and from 16 required potassium tert-butoxide/n-butyllithium. As products the corresponding bicyclo[3.2.1]octa-3,6-dien-2-yl anion derivatives have been identified. By means of potassium tert-butoxide/n-butyllithium 19a, b were converted into 21K, i.e. the anion with K+ as counterion. The NMR spectra of 21Li turned out to depend upon the temperature in the range between +45 and -30°C in contrast to those of 21K. The 13C NMR spectra of the anions and of the corresponding hydrocarbons are discussed in detail in relation to the spectra of the unsubstituted species 1 and 2. In particular, the wide variations of the chemical shifts of C-6,7 depending upon the substituents of the allylic moiety of the bicyclo[3.2.1]octa-3,6-dien-2-yl anion system give strong support for the bishomoaromatic nature of these anions.
    Notes: Die Effekte von Deuteriumatomen in den Positionen 1 und 4 von exo-6-Brom- (11) und endo-6-Methoxytricyclo[3.2.1.02,7]oct-3-en (12) sowie exo-4-Methoxybicyclo[3.2.1]octa-2,6-dien (13) auf deren 13C-chemische Verschiebungen stützen die frühere Interpretation der Effekte bei entsprechend deuterierten Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionen 1 und belegen so die homokonjugative Wechselwirkung in 1.  -  Ausgehend von Bicyclo[3.2.1]oct-6-en-3-on (14) und Bicyclo[3.1.0]hex-2-en-endo-6-carbaldehyd (17) stellte man 3-Phenyl- (16) bzw. endo-4-Phenyl-(19a) und exo-4-Phenylbicyclo[3.2.1]octa-2,6-dien (19b) dar. 2,4-Diphenylbicyclo[3.2.1]octa-2,6-dien (6) und 19a, b wurden mit Methyllithium bzw. n-Butyllithium, Tricyclo[6.3.1.02,7]dodeca-2,4,6,9-tetraen (4) sowie 16 mit Kalium-tert-butoxid/n-Butyllithium deprotoniert, wobei die entsprechenden Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionderivate 7, 21Li, 5 und 22 entstanden. Aus 19a, b wurde mit Kalium-tert-butoxid/n-Butyllithium auch 21K, d. h. das zugehörige Anion mit K+ als Gegenion erhalten. Die NMR-Spektren von 21Li erwiesen sich im Gegensatz zu jenen von 21K im Bereich von +45 bis -30°C als temperaturabhängig. Die 13C-NMR-Spektren der Anionen und der zugehörigen Kohlenwasserstoffe werden im Vergleich mit den Spektren der unsubstituierten Verbindungen 1 und 2 ausführlich diskutiert. Insbesondere die starken Variationen der chemischen Verschiebungen von C-6,7 in Abhängigkeit von den Substitutenten am Allylteil des Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionsystems bieten ein starkes Argument für die bishomoaromatische Natur dieser Anionen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190623
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 87
    Electronic Resource
    Electronic Resource
    Synthese und physikalische Eigenschaften neuer 1,3-Dithiolylium-4-methanide und 1,3-Thiazolium-5-methanide (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2094-2103 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Physical Properties of Novel 1,3-Dithiolylium-4-methanides and 1,3-Thiazolium-5-methanidesThe synthesis and physical properties of the novel title compounds of type 9 from carboxylic acid derivatives 3 and CH acidic compounds 4 are described.
    Notes: Die Synthese und physikalischen Eigenschaften der neuen Titelverbindungen vom Typ 9 aus Carbonsäure-Derivaten 3 und CH-aciden Verbindungen 4 werden beschrieben.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190704
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 88
    Electronic Resource
    Electronic Resource
    Metallaheterocumulene, IV. 2-Azaallyliden-Komplexe  -  neuartige Verbindungen mit einem gewinkelten CNCR2-Fragment als Komplexligand (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2080-2093 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallaheterocumulenes, IV. 2-Azaallylidene Complexes  -  Novel Compounds with a Bent CNCR2 Fragment as Complex Ligand(2-Azoniaallenylidene)pentacarbonyltungsten tetrabromoaluminate complexes [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e)) Which are synthesized by the reaction of (CO)5W[C(OEt)N=CR2] (1) with AlBr3, react with freshly distilled tetrahydrofuran to give neural trans-bromo(2-azaallylidene) complexes trans-Br(CO)4W(CNCR2) (3) and small amounts of (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). The compounds 4 correspond to the product of a reductive dimerization of two cations 2. If 1b (or the corresponding methoxy compound 5) reacts with BBr3 instead of AlBr3/THF 4b is the main product. The spectroscopic data of 3 and the results of an X-ray analysis of 3b show that the replacement of a CO ligand in the cations 2 by Br- with formation of 3 results in a drastic change of the bonding situation within the CNCR2 ligand. 3a-e are the first compounds in which a strongly bent CNCR2 fragment functions as a complex ligand. The aminocarbyne complex trans-Br(CO)4W≡CNPh2 (7) was synthesized by BBr3-induced fragmentation of (CO)5W[C(NPh2)N=C(Ph)OMe] (6).
    Notes: (2-Azoniaallenyliden)pentacarbonylwolfram-tetrabromoaluminat-Komplexe [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e))  -  darstellbar durch Umsetzung von (CO)5W[C(OEt)N=CR2] (1) mit Albr3  -  reagieren mit frisch destillierten Tetrahydrofuran zu neutralen trans-Bromo(2-azaallyliden)-Komplexen trans-Br(CO)4W(CNCR2) (3) und wenig (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). Die Verbindungen 4. entsprechen dem Produkt einer reduktiven Dimerisierung zweier Kationen 2. 4b wird zum Hauptprodukt der Umsetzung, wenn 1b (oder der entsprechende Methoxy-Komplex 5) mit BBr3 anstatt AlBr3/THF umgesetzt wird. Wie die spektroskopischen Daten von 3 sowie die Ergebnisse der an 3b durchgeführten Röntgenstrukturanalyse zeigen, führt der Austausch eines CO-Liganden in den Kationen 2 gegen Br- unter Bildung von 3 zu einer drastischen Veränderung der Bindungsverhältnisse im CNCR2-Liganden. 3a-e sind die ersten Verbindungen, in denen ein stark gewinkeltes CNCR2-Fragment als Komplexligand fungiert. Durch BBr3-induzierte Fragmentierung von (CO)5W[C(NPh2)N=C(Ph)OMe] (6) wurde der Aminocarbin-Komplex trans-Br(CO)4W≡CNPh2 (7) dargestellt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190703
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 89
    Electronic Resource
    Electronic Resource
    Heterocyclische β-Enaminoester, 41. Vinylogieprinzip bei 6,7-Dihydro-1H-azepinen; Cycloaddition und neuartige Umlagerung zu 2,3,3a,7a-Tetrahydroindolen.  -  Thermische [2 + 2]-Cycloadditionen mit 4-R-TAD (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2114-2126 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic β-Enamino Esters, 41. Vinylogeous Principle on 6,7-Dihydro-1H-azepines; Cycloaddition and Novel Rearrangement to 2,3,3a,7a-Tetrahydroindoles.  -  Thermal [2 + 2]-Cycloadditions with 4-R-TADThe conjugated π-Systems of 6,7-dihydrooxepines, -thiepines, and -azepines (1-5) show a remarkable alternance of their 13C NMR shifts. In a cycloaddition-ring enlargement sequence the 6,7-dihydroazepine 3 reacts with acetylenedicarboxylates at the 4,5-double bond to afford first the intermediary 8,9-dihydro-1H-azonines 6B. These give in turn the indoles 7a,b via thermal 6π-electron cyclization. Under subsequent rearrangement 2,3,3a,7a-tetrahydroindoles 8a,b are formed. The structure of 8a is established by X-ray diffraction. In a polar [2 + 2]-cycloaddition 4-R-1,2,4-triazoline-3,5-dione (4-R-TAD) gives with 3 and 5 the [1,2,4]triazolo[1′,2′:1,2]diazet-[3,4-d]azepines 10a-d and 11a,b resp., and with the bis-TAD 12 the 2:1-adduct 13. Treatment of 10a with phenyl isocyanate originates the carbodiimide 14 which is converted with basic ring closure into the pyrimido[4,5-b]azepine 15.
    Notes: 6,7-Dihydrooxepine, -thiepine und -azepine (1-5) zeigen eine ausgeprägte Alternanz ihrer 13C-NMR-Verschiebungen im konjugierten π-System. Das 6,7-Dihydroazepin 3 reagiert mit Acetylendicarbonsäureestern zunächst unter Cycloaddition-Ringerweiterung an der 4,5-Doppelbindung zu den intermediären 8,9-Dihydro-1H-azoninen 6b. Diese ergeben sogleich unter thermischem 6π-Elektronenringschluß die Indole 7a,b. Nach erneuter Umlagerung entstehen 2,3,3a,7a-Tetrahydroindole 8a,b; die Konstitution von 8a wird durch Röntgenstrukturanalyse ermittelt. Mit 4-R-1,2,4-Triazolin-3,5-dionen (4-R-TAD) entstehen aus 3 und 5 in polarer [2 + 2]-Cycloaddition die [1,2,4]Triazolo[1′,2′:1,2]diazet[3,4-d]azepine 10a-d und 11a,b mit dem Bis-TAD 12 das 2:1-Addukt 13. 10a ergibt mit Phenylisocyanat das Carbodiimid 14 und beim basischen Ringschluß das Pyrimido[4,5-b]azepin 15.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190706
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 90
    Electronic Resource
    Electronic Resource
    Neue Reagenzien, XXXVII. (α-Lithioalkyl)diphenylarsanoxide: Synthese und Anwendung zur indirekten nucleophilen Haloalkylierung (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2135-2142 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Reagents, XXXVII. (α-Lithioalkyl)diphenylarsane Oxides: Synthesis and Application for the Indirect Nucleophilic HaloalkylationDue to ready accessibility and high nucleophilicity (α-lithioalkyl)diphenylarsane oxides (2) are favorable reagents for the synthesis of many organoarsenic compounds. In organic synthesis they are recommendable as reagents for indirect nucleophilic haloalkylation reactions (Hal=Cl, Br, I).
    Notes: (α-Lithioalkyl)diphenylarsanoxide (2) sind wegen ihrer bequemen Zugänglichkeit und hohen Nucleophilie günstige Reagenzien zur Darstellung zahlreicher Organoarsenverbindungen. In der organischen Synthese sind sie als Reagenzien für indirekte nucleophile Haloalkylierungen (Hal=Cl, Br, I) empfehlenswert.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190708
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 91
    Electronic Resource
    Electronic Resource
    Synthesen mit Cyclobutadienen, 13. Azapentafulvene aus 2,3,4-Tri-tert-butylcyclobutadien-1-carbonsäureestern und Isonitrilen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2159-2172 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese with Cyclobutadienes, 13. Azapentafulvenes from 2,3,4-Tri-tert-butylcyclobutadiene-1-carboxylic Esters and IsonitrilesFrom kinetically stabilized cyclobutadienes 6a and b and isonitriles 7a-c the azapentafulvenes 9a-d are obtained. In contrast, 6a reacts with 7d exclusively to form the constitution isomeric azapentafulvene 11e. Both isomers (9f and 11f) are realized in the reaction of 6a with 7e. The structural assignment of the isomers 9 and 11 is based on 13C NMR investigations as well as on an X-ray analysis performed for 9a. Hydrolysis of 9 and 11 yields the tri-tert-butyl substituted cyclopentadienones 20a,b and 21. By photochemical means 21 is transformed into the isomer 20a, which can also be obtained directly from the cyclobutadiene 6a and carbon monoxide.
    Notes: Aus den kinetisch stabilisierten Cyclobutadienen 6a bzw. b und den Isonitrilen 7a-c erhält man die Azapentafulvene 9a-d. Im Gegensatz dazu reagiert 6a mit 7d ausschließlich unter Bildung des konstitutionsisomeren Azapentafulvens 11e. Beide Möglichkeiten (9f und 11f) werden bei der Umsetzung von 6a mit 7e wahrgenommen. Die Strukturzuordnung der Isomeren 9 und 11 beruht auf 13C-NMR-Untersuchungen sowie auf der Röntgenstrukturanalyse für 9a. Hydrolyse von 9 und 11 macht die tri-tert-butylsubstituierten Cyclopentadienone 20a,b und 21 zugänglich. Photochemisch läßt sich 21 in das Isomere 20a umwandeln, das auch unmittelbar aus dem Cyclobutadien 6a und Kohlenmonoxid erhalten werden kann.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190711
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 92
    Electronic Resource
    Electronic Resource
    Enantioselective diastereospecific synthesis of anti-α-alkyl-β-hydroxy esters through cuprate opening of glycidic esters (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2178-2190 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enantioselektive diastereospezifische Synthese von anti-α-Alkyl-β-hydroxycarbonsäureestern durch Cuprat-Ringöffnung von GlycidesternEine über die Zwischenglieder 4-7 ablaufende diastereospezifische Kettenverlängerung von Aldehyden 1 zu anti-α-Alkyl-β-hydroxyestern 2 wird beschrieben. Durch Verwendung der Sharpless-Epoxidierung kann 2 mit Enantiomerenüberschüssen von 〉90% in Form beider Antipoden erhalten werden.
    Notes: A diastereospecific chain elongation of the aldehydes 1 of anti-α-alkyl-β-hydroxy esters 2 via the intermediates 4-7 is described. By means of the Sharpless epoxidation, 2 may be obtained with 〉90% ee in either enantiomer.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190713
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 93
    Electronic Resource
    Electronic Resource
    Stereoselektive Aldolreaktion mit chiralen sekundären Acetamiden (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2191-2207 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereoselective Aldol Reaction with Chiral Secondary AcetamidesThe deprotonated acetamides 4a-c und 5a-c are added to prochiral carbonyl compounds. The influence of the solvent, of the reaction temperature, and of the enolate gegenion on the ratio of the isomeric products 8/9, 18/19, and 26/27, respectively, are studied. The highest degrees of diastereoselectivity are observed, when the titanium enolate of the acetamide 4a or the threefold deprotonated N-acetyl-α-phenylglycinol (5a) is used. The diastereomers 18a-d, formed in excess in the addition of 5a to aldehydes, are isolated in a pure form by a single recrystallization, and afford the enantiomerically pure β-hydroxy carboxylic acids 3a-d. Thereby, the chiral auxiliary, α-phenylglycinol (14), is recovered.
    Notes: Die deprotonierten Acetamide 4a-c und 5a-c werden an prochirale Carbonylverbindungen addiert. Dabei wird der Einfluß von Lösungsmittel, Temperatur und Enolat-Gegenion auf das jeweilige Verhältnis der isomeren Produkte 8/9, 18/19 und 26/27 untersucht. Die höchsten Diastereoselektivitäten lassen sich mit dem Titan-enolat des Amids 4a und dem dreifach deprotonierten N-Acetyl-α-phenylglycinol (5a) erzielen. Die bei der Addition von 5a an Aldehyde im Überschuß gebildeten Diastereomeren 18a-d können durch einmaliges Umkristallisieren rein erhalten werden und liefern nach alkalischer Hydrolyse die enantiomerenreinen β-Hydroxycarbonsäuren 3a-d. Dabei wird der chirale Hilfsstoff, α-Phenylglycinol (14), zurückgewonnen.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190714
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 94
    Electronic Resource
    Electronic Resource
    Synthesis of ketene aminals with an imidazolidine ring by condensation of 4,5-dihydro-2-(methylithio)-1H-imidazoles with active methylene compounds and some addition and cyclocondensation reactions (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2208-2219 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese von Ketenaminalen mit Imidazolidinring durch Kondensation von 4,5-Dihydro-2-(methylthio)-1H-imidazolen mit CH-aciden Methylenverbindungen und einige Additions-und Cyclokondensations-Reaktionen4,5-Dihydro-2-(methylthio)-1H-imidazole 1a, b reagieren mit aktiven Methylenverbindungen 2a-f unter Eliminierung von Methanthiol zu den entsprechend substituierten Methylenimidazolidinen 3a-f und 4c-f. Die Verbindungen 2g-j, die eine aktivere Carbonylgruppe enthalten, ergeben mit 1a unter Eliminierung einer Methylthio- und Acylgruppe 3g-i. 3a, g-i reagieren mit Estern ungesättigter Säuren in einer Additions- und Cyclokondensations-Sequenz zu den entsprechenden Imidazo[1,2-a]pyridinen 5,6 und 7, ergeben aber mit Azodicarbonsäure-diethylester nur die Additionsprodukte 8.
    Notes: The 4,5-dihydro-2-(methylthio)-1H-imidazoles 1a,b react with active methylene compounds 2a-f to afford the corresponding substituted methyleneimidazolidines 3a-f and 4c-f by elimination of methanethiol. The reaction of compounds 2g-j, which contain a more active carbonyl group, with 1a gives 3g-i by elimination of a methylthio group as well as an acyl group, too. 3a,g-i react with esters of α,β-unsaturated acids to afford the corresponding imidazo[1,2-a]pyridines 5,6, and 7 in an addition and cyclocondensation reaction sequence, but with diethyl azodicarboxylate only to give the addition product 8.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190715
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 95
    Electronic Resource
    Electronic Resource
    Desaminierungsreaktionen, 43. Zum Einfluß von Trifluormethylgruppen auf die Reaktionen aliphatischer Diazonium-Ionen und Carbokationen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2233-2248 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Deamination Reactions, 43. The Effect of Trifluoromethyl Groups on the Reactivity of Aliphatic Diazonium Ions and CarbocationsVarious trifluoroalkanamines (9, 26, 35, 38, 45, 56, and 67) have been prepared and diazotized (water, pH 3.5) to probe the effect of trifluoromethyl groups on the reactivity of aliphatic diazonium ions. The product distributions reveal that α-CF3 groups enhance inverting displacement and enforce rearrangements (hydride shifts) separating the positive charge from CF3. Migrations of the positive charge from the β- to the γ-position are less strongly promoted than those from α to β. Enhancement factors of ca. 15 (α → β) and 4 (β → γ) may be derived by comparison with analogous alkanediazonium ions. The positive charge does not migrate in the reverse direction (β → α) except for minor amounts of a pinacolic rearrangement (68 → 7). A migration of the positive charge from γ to β has been detected with 36 but a tenfold decrease as compared to the analogous butanediazonium ion 37 is indicated. All observations are reasonably explained in terms of the relative stabilites of the intermediate trifluoroalkyl cations.
    Notes: Eine Reihe von Trifluoralkanaminen (9, 26, 35, 38, 45, 56 und 67) wurde dargestellt und diazotiert (Wasser, pH 3.5), um den Einfluß von Trifluormethylgruppen auf die Reaktionsweise aliphatischer Diazonium-Ionen zu untersuchen. Die Produktverteilungen zeigen, daß α-CF3-Gruppen die invertierende Substitution verstärken und Umlagerungen (Wasserstoffverschiebungen) fördern, welche die positive Ladung von der CF3-Gruppe trennen. Die Wanderung der positiven Ladung von der β- zur γ-Position wird weniger stark gefördert als die von α nach β. Aus dem Vergleich mit analogen Alkandiazonium-Ionen lassen sich Beschleunigungsfaktoren von ca. 15 (α → β) und 4 (β → γ) ableiten. In umgekehrter Richtung (β → α) wandert die positive Ladung nicht, abgesehen von einem kleinen Anteil Pinakol-Umlagerung (68 → 7). Eine Ladungsverschiebung von der γ- zur β-Position wurde bei 36 gefunden; im Vergleich zum analogen Butandiazonium-Ion 37 ist sie um den Faktor 10 verringert. Alle Beobachtungen sind im Einklang mit der relativen Stabilität der intermediären Trifluoralkyl-Kationen.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190717
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 96
    Electronic Resource
    Electronic Resource
    Neuartige 2,6-disubstituierte Azulene (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2272-2288 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel 2,6-Disubstituted AzulenesMethods are described to introduce varying residues into 2- and 6-positions of azulene, starting from diethyl 6-bromo-2-methoxy-1,3-azulenedicarboxylate (1). 2-Substitution is achieved by Grignard reaction or exchange of the alkoxy group and by aldol condensation of 2-methyl compounds whereas 6-substitution is conducted by nucleophilic displacement and by homo- and hetero-aromatic coupling. Consecutive dealkoxycarbonylation yields azulenes 20 with free 1,3-positions. Biazulenes 9a-c and 201, 20m, styryl- and bis(styryl)-azulenes 15-18 and 20i-k, and finally the azulenedialdehyde 19 are novel compounds which were difficult to prepare or were inaccessible so far.
    Notes: Ausgehend von 6-Brom-2-methoxy-1,3-azulendicarbonsäure-diethylester (1) werden Methoden zur Einführung unterschiedlicher Reste in 2- und 6-Position entwickelt. 2-Substitution gelingt durch Grignard-Reaktion oder Austausch der Alkoxygruppe sowie durch Aldol-Kondensation von 2-Methylverbindungen, während 6-Substitution durch nucleophilen Austausch und durch Homo- und Kreuz-Aromaten-Kupplungen erfolgt. Anschließende Dealkoxycarbonylierung erbringt Azulene 20 mit freien 1,3-Stellungen. Die Biazulene 9a-c und 201, 20m, die Styryl- und Bis(styryl)azulene 15-18 und 20i-k sowie der Azulendialdehyd 19 sind Verbindungen, die bisher schwierig oder nicht zugänglich waren.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190720
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 97
    Electronic Resource
    Electronic Resource
    Zur Frage der Stellungsisomerie bei disubstituierten Bullvalenen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2339-2349 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Concerning the Question of Positional Isomerism in Disubstituted BullvalenesWe report about 15 new disubstituted bullvalenes (2, 4, 5, 11, 12, 14-20, 22-24) and discuss their substitution pattern together with 9 known species (1, 3, 6-10, 13, 21). The results which are partly unexpected are put together phenomenologically. We have no reasonable explanation for some results, i.e. only a few substituents with „complementary“ properties like the pair CH2OH/Br or CH3/CN in compounds 16 and 18, respectively, prefer a vicinal arrangement at a double bond.
    Notes: Wir berichten über 15 neue disubstituierte Bullvalene (2, 4, 5, 11, 12, 14-20, 22-24) und diskutieren ihr Substitutionsmuster gemeinsam mit dem von 9 bekannten Vertretern (1, 3, 6-10, 13, 21). Die teilweise unerwarteten Ergebnisse werden phänomenologisch geordnet. Für einige Befunde fehlen befriedigende Erklärungen. So bevorzugen z. B. nur manche Substituenten mit „komplementären“ Eigenschaften wie das Paar CH2OH/Br oder CH3/CN in den Verbindungen 16 bzw. 18 eine vicinale Anordnung an der Doppelbindung.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190724
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 98
    Electronic Resource
    Electronic Resource
    Zur Regio- und Stereoselektivität neuer thermischer [3 + 2]-Cycloadditionen mesoionischer 1,3-Oxathiol-4-one an Alkine und Alkene (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2317-2338 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Regio- and Stereoselectivity of Novel Thermal [3 + 2] Cycloaddition Reactions of Mesonionic 1,3-Oxathiol-4-ones to Alkynes and AlkenesAs potential carbonyl ylides, the 1,3-oxathiolyium-4-olates 1c or 1d combine with dibenzoylacetylene or 1-(diethylamino)-1-propyne via nonisolable [3 + 2] primary adducts of type 2, which release COS to give the furan derivatives 3a or b, respectively. On the other hand, some representative of 1 reacts with symmetrically and unsymmetrically substituted olefinic substrates with regio- and/or stereoselective formation of the isolable [3 + 2] primary adducts 4-16. In the example of the reactions of 1c with trans- and cis-cyclooctene, the stereospecificities and the competition constant are determined. Furthermore, the thermolyses of the cycloadducts 4b,5,6, and 7a,b are investigated. The addition directions, derived from the FMO and PMO theory, are compared with the experimentally realized regiochemistry.
    Notes: Als potentielle Carbonyl-ylide vereinigen sich die 1,3-Oxathiolylium-4-olate 1c oder 1d mit Dibenzoylacetylen oder 1-(Diethylamino)-1-propin über nicht isolierbare [3 + 2]-Primäraddukte vom Typ 2 unter COS-Abspaltung zu Furan-Derivaten 3a bzw. b. Demgegenüber reagieren einige Vertreter von 1 mit symmetrisch und unsymmetrisch substituierten olefinischen Substraten regio- und/oder stereoselektiv zu isolierbaren [3 + 2]-Primäraddukten 4-16. Am Beispiel der Umsetzung von 1c mit trans- und cis-Cycloocten werden die Stereospezifitäten und die Konkurrenzkonstante ermittelt. Weiterhin werden die Thermolysen der Cycloaddukte 4b, 5, 6 und 7a,b untersucht. Die aus der FMO- und PMO-Theorie abgeleiteten Additionsrichtungen werden mit der experimentell realisierten Regiochemie verglichen.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190723
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 99
    Electronic Resource
    Electronic Resource
    Synthese und Reaktion von α-(Dimethylamino)alkanaldimethylhydrazonen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2397-2413 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Reaction of α-(Dimethylamino)alkanal DimethylhydrazonesSeveral α-(dimethylamino)aldehyde hydrazones of the general structure 11 have been obtained by alkylation of the lithium salt of 9 or by addition of Grignard reagents to 15 or 17. The compounds react with acyl chlorides to give hydrazones of unsaturated aldehydes. The same products 27 are obtained by thermal degradation of the ammonium salts 26. In the hydrazonoammonium salts 26a, g the trimethylammonium group can be substituted by a variety of nucleophiles (→ 34-39).
    Notes: Verschieden substituierte α-(Dimethylamino)aldehyd-hydrazone der allgemeinen Struktur 11 lassen sich aus dem Lithium-Salz des (Dimethylamino)acetaldehyd-dimethylhydrazons durch Alkylierung sowie durch Addition von Grignard-Verbindungen an das Ammoniumsalz 15 oder das N,O-Acetal 17 darstellen. Die Verbindungen 11 enthalten eine leicht eliminierbare Dimethylaminogruppe und gehen mit Säurechloriden oder nach Methylierung thermisch in Hydrazone 27 α,β-ungesättigter Aldehyde über. In den Salzen 26a, g läßt sich die Trimethylammoniumgruppe durch verschiedene Nucleophile verdrängen (→ 34-39).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190802
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 100
    Electronic Resource
    Electronic Resource
    Intramolekulare Wechselwirkungen in Radikalkationen von Di- und Tetra(α-methoxy)-9,10-dihydro-9,10-ethanoanthracenen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2414-2429 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Intramolecular Interactions in Radical Cations of Di- and Tetra(α-methoxy)-9,10-dihydro-9,10-ethanoanthracenes[4 + 2]-Cycloaddition of maleic anhydride, 2-chloropropenoyl chloride and (E)-dichloroethene to 1,4-di- (3a) and 1,4,5,8-tetramethoxyanthracene (3b) yields the dihydroethanoanthracenes 4, 5, and 8, respectively. The predominant maleic anhydride adduct 4a is assigned the exo-configuration on the basis of the ESR spectrum of the radical cations 4a+·. The cycloadducts 5 and 8 are converted to the dihydroethanoanthracenes 10 via the ketones 6 or the dihydroethenoanthracenes 9, respectively. Aluminium chloride in nitromethane oxidizes the α-methoxydihydroethanoanthracenes 4, 6a, 8, and 10 to radical cations the ESR spectra of which are analyzed. Besides the expected proton hyperfine splittings of the 1,4-dimethoxybenzene moiety, one observes long-range transfer of spin density to the unsubstituted benzene ring [a(4H) = 0.008-0.010 mT] as well as to the syn-[10a+·: a(2H) = 0.013 mT] and anti-protons [a(2H) = 0.059-0.069 mT] of the ethano bridge. Of the radical cations possessing two 1,4-dimethoxybenzene rings, 4b and 10b do not exhibit dynamic ESR spectroscopic phenomena. On the other hand, the unpaired electron is exchanged rapidly (with respect to the hyperfine splitting time scala) between the 1,4-dimethoxybenzene rings of the radical cation 8b+·. The dependence of the exchange frequency on the temperature and the aluminium chloride concentration is indicative of ion-pair effects.
    Notes: Durch [4 + 2]-Cycloaddition von Maleinsäureanhydrid, 2-Chlorpropenoylchlorid bzw. (E)-Dichlorethen an 1,4-Di- (3a) und 1,4,5,8-Tetramethoxyanthracen (3b) entstehen die Dihydroethanoanthracene 4, 5 bzw. 8. Dem überwiegenden der Maleinsäureanhydrid-Addukte 4a wird aufgrund des ESR-Spektrums der Radikalkationen 4a+· die exo-Konfiguration zugeordnet. Die Cycloaddukte 5 und 8 werden über die Ketone 6 bzw. Dihydroethenoanthracene 9 in die Dihydroethanoanthracene 10 übergeführt. Aluminiumchlorid in Nitromethan oxidiert die α-Methoxydihydroethanoanthracene 4, 6a, 8 und 10 zu Radikalkationen, deren ESR-Spektren analysiert werden. Neben den erwarteten Protonen-Hyperfeinaufspaltungen des 1,4-Dimethoxybenzolrings beobachtet man weitreichenden Transfer von Spindichte zum unsubstituierten Benzolring [a(4H) = 0.008-0.010 mT] sowie zu den syn-[10a+·: a(2H) = 0.013 mT] und anti-Protonen [a(2H) = 0.059-0.069 mT] der Ethanobrücke. Von den Radikalkationen mit zwei 1,4-Dimethoxybenzolringen zeigen die aus 4b und 10b erhaltenen keine dynamischen ESR-spektroskopischen Phänomene. Dagegen wird in 8b+· das ungepaarte Elektron rasch bezüglich der Hyperfeinaufspaltungs-Zeitskala zwischen den 1,4-Dimethoxybenzolringen ausgetauscht. Die Abhängigkeit der Austauschfrequenz von der Temperatur und der Aluminiumchlorid-Konzentration weist auf Ionenpaar-Effekte hin.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190803
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...