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  • Articles  (7,113)
  • Inorganic Chemistry  (5,390)
  • Industrial Chemistry  (1,701)
  • Seismology
  • 2005-2009  (14)
  • 1975-1979  (4,168)
  • 1950-1954  (2,931)
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  • 1
    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
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  • 2
    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
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  • 3
    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)
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  • 4
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    Acoustical Society of America
    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
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  • 5
    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
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  • 6
    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
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  • 7
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    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
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  • 8
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    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
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  • 9
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    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
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  • 10
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    Earthquake Engineering Research Institute
    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
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  • 11
    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)
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  • 12
    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
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  • 13
    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
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  • 14
    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
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Pure and applied geophysics 117 (1979), S. 1045-1049 
    ISSN: 1420-9136
    Keywords: Seismology ; Surface waves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Description / Table of Contents: Summary Alsop's method (1966) for the non-normal passage of surface waves through a vertical discontinuity is improved by using a new functional to be made stationary on the plane of discontinuity. The modified functional has the dimension of an energy flux and is characterized by the discontinuous surface wave displacements and stresses on the vertical discontinuity. Model calculations which were carried out for SV-waves and Love waves show that the new version of Alsop's method yields in all respects more consistent results than the old one.
    Notes: Zusammenfassung Die Methode von Alsop (1966) für den Durchgang von schräg einfallenden Oberflächenwellen durch eine vertikale Diskontinuität wird durch Verwendung eines neuen Funktionals, das auf der Diskontinuitätsfläche stationär sein soll, verbessert Das modifizierte Funktional hat die Dimension eines Energieflusses und wird durch diejenige Spannungs- und Verschiebungsdiskontinuität charakterisiert, die durch das Oberflächenwellenfeld auf der Diskontinuitätsfläche erzeugt wird. Modellrechnungen für SV-Wellen und Lovewellen zeigen, daß die neue Version von Alsoos Verfahren in jeder Hinsicht konsistentere Ergebnisse als die bisherige liefert.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1252-1259 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Macrocyclic and Linear Borazine-Arene CompoundsMacrocyclic oligomeric condensates formed by an alternate sequence of 2,4-difunctional borazines and aromatic 1,3-dihydroxy, 1,3-diamino, or l-amino-3-hydroxy compounds (1-4) are less stable than corresponding systems formed by O- or NH-linked borazines only. Besides of these compounds which have a pseudocage structure like the cyclic oligoborazines, several noncyclic oligomeric condensates have been prepared which exist of mono- or difunctional borazines and di- or monofunctional phenols, thiophenols, or aromatic amines (5- 13). The substances are characterized by analyses, mass and 1H-NMR spectroscopy.
    Notes: Oligomere, makrocyclische Kondensate, die alternierend aus 2,4-difunktionellen Borazinen und aromatischen 1,3-Dihydroxy-, 1,3-Diamino- oder 1-Amino-3-hydroxy-Verbindungen gebildet werden (1-4), sind weniger stabil als entsprechende Systeme, die nur aus O- oder NH-verbrückten Borazinen bestehen. Außer diesen Verbindungen, die ebenso wie die cyclischen Oligoborazine Pseudokäfigstruktur besitzen, wurden mehrere nicht cyclische oligomere Kondensate aus mono- oder difunktionellen Borazinen und di- bzw. monofunktionellen Phenolen, Thiophenolen bzw. aromatischen Aminen dargestellt (5-13). Die Verbindungen sind analytisch und durch ihre Massen- und 1H-NMR-Spektren charakterisiert.
    Additional Material: 5 Tab.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1464-1469 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and X-Ray Structural Analysis of an Adamantyl-spirophosphorane, C10HI5P(O2C6H4)Reaction of (1-adamantyl)tetrafluorophosphorane with catechol bis(trimethylsilyl ether) yielded the spirophosphorane C10H15P(O2C6H4)2 (4). Crystals of 4 are orthorhombic. P212121, with a = 668.5 (1), b = 1575.8 (2), c = 1755.1 (2) pm, Z = 4, R = 0.058. C2v,-distorted rectangular pyramidal coordination is observed at phosphorus.
    Notes: Durch Umsetzung von (1-Adamantyl)tetrafluorphosphoran mit Brenzcatechin-bis(trimethylsilylether) wurde das Spirophosphoran C10H15P(O2C6H4)2 (4) erhalten. 4 kristallisiert orthorhombisch, P212121, mit a = 668.5 (1), b = 1575.8 (2), c = 1755.1 (2) pm, Z = 4,. R, = 0.058. Es wird C2v-verzerrte rechteckig-pyramidale Koordination am Phosphor gefunden.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1470-1472 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of Enolic Sugar Derivatives, XIV. A New Synthesis of L-Fucosamine by „Azido-nitration“ of L-FucalStarting from 3,4-di-O-acetyl-L-fucal (2) 3,4-di-O-acetyl-2-azido-2-deoxy-α-L-fucopyranosyl nitrate (3) was prepared by azido-nitration. Ammonolysis and reacetylation led to 1-N,3,4-O-triacetyl-2-azido-2-deoxy-α-L-fucopyranosylamine (4). De-O-acetylated 4 (5) was hydrogenized to yield crude l-N-acetyl-2-amino-2-deoxy-α-L-fucopyranosylamine which after acid hydrolysis yielded L-fucosamine (1).
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  • 19
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1477-1479 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Yellow Isomer of (1,5-Diphenylformazanyl)glyoxylic AcidThe yellow isomer is shown to be 4,4-dihydroxy-l-phenyl-3-phenylazo-2-pyrazolin-5-one (3), the hydrate of the pyrazolin-4,5-dione 4. Treatment of 4 with a solution of potassium -tert- butoxide in dimethylsulfoxide leads to the formation of a radical anion identified as 5 by ESR.
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  • 20
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1486-1490 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of Complex Ligands, XV. Synthesis of the Furan Skeleton from a Carbene Ligand, a Carbonyl Ligand, and an AlkynePentacarbonyl[ferrocenyl(methoxy)carbene]chromium(0) (1) reacts with tolan (2) in dibutyl ether on warming to give tricarbonyl[(5-ferrocenyl-2-methoxy-3-η6-phenyl-4-phenyl)furan]-chromium(O) (3). The structure of the reaction product was established by an X-ray analysis.
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  • 21
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1491-1492 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies on the Field of Natural Products Chemistry, 71. Psoralen and Angelicin by Reaction of 7-Hydroxycoumarin with 4-Chloro-1,3-dioxolan-2-oneDirect condensation of umbelliferone (1) with 4-chloro-1,3-dioxolan-2-one (2) yields 15% psoralen (3) and 20% angelicin (4).
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  • 22
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1495-1497 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: About the Formation of 2-Ethylthio-3-phenylindene from 2-Ethylthio-1,1-diphenyl-2-propen-1-ol2-Ethylthio-3-phenylindene (6) is formed in 75% yield by heating the tertiary carbinol 2b in toluene with catalytic amounts of p-toluenesulfonic acid.
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  • 23
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    Berichte der deutschen chemischen Gesellschaft 112 (1979) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 24
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1-15 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrophilic Aromatic Substitution Reactions with Protonated 1,3-Diazines, I. Preparation and Properties of 4-Aryl-substituted 3,4-Dihydropyrimidine DerivativesIn the presence of trifluoroacetic acid, pyrimidine and 5-methylpyrimidine react with active aromatic compounds to form stable 4-aryl-substituted 3,4-dihydropyrimidinium salts, e.g. 1, 2, 6. From these, the dihydro bases 7 or 8 can be obtained which are readily oxidized to 4-aryl-substituted pyrimidines 9. 2- and/or 4-substituted pyrimidines as well as 2-amino- and 2-mercaptopyrimidines react with phenols to form benz[g][1,3,5]oxadiazocines 3 and 10. The mechanism of this novel reaction is apparently best described as an aromatic electrophilic substitution by the protonated pyrimidine derivative. The observed reactivity of different diazines is in accordance with frontier orbital arguments, using HMO-coefficients.
    Notes: Bei Gegenwart von Trifluoressigsäure reagieren Pyrimidin und 5-Methylpyrimidin mit aktiven aromatischen Verbindungen zu stabilen 4-arylsubstituierten 3,4-Dihydropyrimidinium-Salzen, z. B. 1, 2, 6, aus denen sich die zugrunde liegende Dihydrobase 7 bzw. 8 erhalten läßt, die ihrerseits leicht zu 4-arylsubstituierten Pyrimidinen 9 oxidiert werden kann. 2- und/oder 4-substituierte Pyrimidine sowie 2-Amino- und 2-Mercaptopyrimidine bilden mit Phenolen Benz[g][1,3,5]oxadiazocine der (Konstitution 3a - f und 10. Als Reaktionsmechanismus wird eine elektrophile Substitutionsreaktion durch das protonierte Pyrimidinderivat vorgeschlagen. Die beobachtete Reaktivität der verschiedenen Diazine steht im Einklang mit dem Grenzorbital-Modell auf der Basis der HMO-Koeffizienten.
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  • 25
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 42-56 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangements of Free Radicals, VII. Electrocyclic and Sigmatropic Rearrangements of Bicyclo[3.1.0]hexenyl RadicalAbstraction of an allylic hydrogen from bicyclo[3.1.0]hex-2-ene (1) leads to the bicyclic allyl radical 2. Electrocyclic ring opening to the cyclohexadienyl radical 3 could not be observed in solution up to + 70°C. Only the product analysis of a thermolysis (130°C) of di-tert-butylperoxide in presence of 1 evidenced the possibility of ring opening with the formation benzene. In adamantane matrix 2 rearranges at -50°C in 3 (ΔG≠ = 68.6 ± 2.0 kJ/mol). In matrix bimolecular termination reactions are prohibited. Therefore rearrangements with activation barriers greater than those of diffusion controlled reactions can easily be observed. By this method a degenerate 1,4-sigmatropic rearrangement of the methylene bridge in 2 could be proven. For this purpose specifically in 2- and 3-position deuterated derivatives of 1 were synthesized. The sigmatropic reaction follows from the statistical distribution of deuterium in the cyclohexadienyl radical over the carbon atoms of the former five-membered ring.
    Notes: Durch Abstraktion eines allylischen Wasserstoffatoms aus Bicyclo[3.1.0]hex-2-en (1) läßt sich das bicyclische Allylradikal 2 erzeugen. Eine Ringöffnung zum Cyclohexadienylradikal 3 konnte in Lösung ESR-spektroskopisch bis + 70°C nicht beobachtet werden. Die Produktanalyse einer Thermolyse (130°C) von Di-tert-butylperoxid in Gegenwart von 1 erwies mit dem Auftreten von Benzol die grundsätzliche Möglichkeit zur elektrocyclischen Ringöffnung. In Adamantanmatrix lagert das durch Röntgenbestrahlung aus 1 erzeugte 2 bereits bei -50°C in 3 um (ΔG≠ = 68.6 ± 2.0 kj/mol). Die Matrixmethode macht durch die Unterdrückung bimolekularer Abreaktionen von 2 auch den Nachweis einer degenerierten sigmatropen 1,4- Verschiebung der Methylenbrücke möglich. Hierzu wurden in 2- bzw. 3-Stellung deuterierte Derivate von 1 dargestellt. Der Nachweis der sigmatropen Wanderung ergibt sich aus der statistischen Verteilung des Deuteriums im Cyclohexadienylradikal über die C-Atome. des ehemals fünfgliedrigen Ringes.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 99-106 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Sulfur Ylide Complexes, VII. η5-Thiacyclohexadienyl 1-Oxide as Novel Ligand in Complex AnionsFrom the reaction of syn-tricarbonyl(1-methyl-3,5-diphenylthiabenzene 1-oxide)chromium, molybdenum, and -tungsten (2a-c) with disodium tetracarbonylferrate or lithium diphenyl-phosphide the alkali salts of complex anions (3a-c, 5a-c) are obtained. They contain the novel ligand η5 -thiacyclohexadienyl 1-oxide. The alkali salts are converted into the tetraethylammonium salts 4a-c, which are characterized by analytical and spectroscopical data.
    Notes: Bei der Umsetzung von syn- Tricarbonyl(1-methyl-3,5-diphenylthiabenzol-1-oxid)chrom, -molybdän und-wolfram (2a-c) mit Dinatrium-tetracarbonylferrat oder Lithium-diphenylphosphid entstehen die Alkalisalze komplexer Anionen mit η5-Thiacyclohexadienyl-1-oxid als neuartigem Liganden (3a-c, 5a-c). Diese werden in die Tetraethylammoniumsalze 4a-c übergeführt und als solche auf analytischem und spektroskopischem Wege charakterisiert.
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    Keywords: Chemistry ; Inorganic Chemistry
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Racemization of Spirocyclic Pentaaryl Derivatives of Group 5 A Elements. I H NMR Investigations with Overcrowded Asymmetric Phosphoranes, Arsoranes, and StiboranesThe two different methyl positions of bis-2,2′-biarylylenephosphorane 7, the corresponding arsoranes 8a, b, and the analogous stiborane 9 are reversibly equilibrated at elevated temperatures with free enthalpies of activation of 18.2 (76.0), 17.2 (72.2), ≈ 22.5 (94.2), and 15.4 (64.6) kcal(kJ)/mol. Starting with the trigonal bipyramidal ground state conformations C and ∪ (fig. 2) these ligand exchange phenomena can be interpreted in the framework of the pseudorotation process on the basis of trigonal bipyramidal transition states of type A with diequatorial biarylylene groups.
    Notes: Die beiden unterschiedlichen Methyl-Positionen des Bis-2,2′-biarylylenphosphorans 7, der entsprechenden Arsorane 8a, b und des analogen Stiborans 9 werden bei erhöhten Temperaturen mit freien Aktivierungsenthalpien von 18.2 (76.0), 17.2 (72.2). ≈ 22.5 (94.2) und 15.4 (64.6) kcal(kJ)/mol reversibel äquilibriert. Ausgehend von den trigonal-bipyramidalen Grundzustandskonformationen C und ∪ (Abb. 2) lassen sich diese Ligandenaustauschphänomene im Rahmen des Pseudorotationsprozesses auf der Basis trigonal-bipyramidaler Übergangszustände des Typs A (Abb. 2) mit diäquatorialen Biarylylen-Gruppen interpretieren.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 310-348 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Light-induced Reactions, XIII. On the Seco-isomeric Dienylketene Related to 2,4-Androstadien-1-oneThe steroidal 2.4-cyclohexadienone 3 photochemically affords the diastereomer 4. Both the configurational isomers differ exceedingly in their chiroptical properties. Their respective contribution to the photostationary state depends on the wave-length of the light and the solvent utilized. The dienylketene 5 can be determined spectroscopically as a transient. It is not trapped by 2,2,2-trifluoroethanol; cyclohexylamine, however, furnishes the 1,6-adduct 7a and/or the 1,2-adduct 6 a owing to the concentration and wave-length (365 or 313 nm) used.
    Notes: Das steroidale 2,4-Cyclohexadienon 3 geht photochemisch in das Diastereomere 4 über. Beide Konfigurationsisomere unterscheiden sich deutlich in ihren chiroptischen Eigenschaften. Ihr jeweiliger Anteil im photostationären Zustand hängt von der Wellenlänge des Lichts und dem Lösungsmittel ab. Das Dienylketen 5 läßt sich als Transient spektroskopisch nachweisen. Es wird von 2,2,2-Trifluorethanol nicht, von Cyclohexylamin je nach Konzentration und Wellenlänge (365 oder 313 nm) als 1,6-Addukt 7a und/oder als 1,2-Addukt 6a abgefangen.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 773-775 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimerization of Diphenyl(trifluoroacetyl)phosphane OxideAt -25°C the phosphane oxide CF3C[(O)P(O)Ph2]2OC(O)CF3 (1) dimerizes to the trifluoroacetate CF3C[(O) PPh2]2OC(O)CF3 (2a), which is sensitive to hydrolysis and, at 40°C is transformed irreversibly into the phosphinate CF3C[(O)PPh2][OP(O)Ph2]C(O)CF3(3a). In contrast to 2a, the thermally more stable homologous octanate C7F15C[(O)PPh2]2OC(O)C7F15 (2b) is obtained from Ph2PCI and C7F15CO2H.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 763-772 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Reactive Behaviour of Acyldiorganylphosphane OxidesThe acylphosphane oxides RC(O)P(O)R′R″ (3) are obtained in the case of 3a - e by oxidation of the acylphosphanes RC(O)PR′R″ (1a - e) with rigorously dried oxygen. 3c - e are also formed from the anhydrides (RCO)2O (R = CH3 CF3) and the phosphane oxides XP(O)R′R″ (2c′ d′). 3f only results from ClPPh2 and formic acid [eqs. (2a - c)]. 3d, e dimerize to the phosphinates RC[Ph2P(O)][OP(O)Ph2]C(O)R (4d, e)[eq.(3)] Heating of 3e with ClRh(PPh3)3 causes elimination of CO and formation of C2F6 and [Ph2P(O) — ]2 [eq. (4)]. Thermolysis of 3a - e generates the ketenes X2C2O (X = H, F) and the phosphane oxides 2a′ - e′ [eq. (5)], whereas 3f yields CO and 2d′ [eq. (6)]. 2c′ reacts with 3c to give the alcohol CH3C[(CH3)2P(O)]2OH (5c). With stoichiometric amounts of water 3a, b, d - f are hydrolyzed to the corresponding alcohols RC[R′R″P(O)]2 OH (5a, b, d - f), which isomerize with the exception of 5a to the phosphinates RC[R′R″P(O)][OP(O)R′R″]H (6b - f) [eqs. (7a, b)].
    Notes: Die Acylphosphanoxide RC(O)P(O)R′R″ (3) erhält man im Falle von 3a - e durch Oxidation der Acylphosphane RC(O)PR′R″ (1a - e) mit rigoros getrocknetem Sauerstoff. 3c - e bilden sich auch aus den Anhydriden (RCO)2O (R = CH3, CF3) und Phosphanoxiden XP(O)R′R″ (2c′, d′). 3f entsteht nur aus CIPPh2 und Ameisensäure [Gln. (2a - c)]:3d, e dimerisieren zu den Phosphinaten RC[Ph2P(O)][OP(O)Ph2]C(O)R (4d, e) [Gl. (3)]. Beim Erhitzen eliminiert 3e mit ClRh(PPh3)3 CO unter Bildung von C2F6 und [Ph2P(O)—]2 [Gl. (4)]. Während 3a - e bei der Thermolyse die Ketene X2C2O(X = H, F) und die Phosphanoxide 2a′-e′ liefern [Gl. (5)], gibt 3f CO und 2d′ [Gl. (6)]. 2c′ und 3c reagieren zum Alkohol CH3C[(CH3)2P(O)]2OH(5c). Mit stöchiometrischen Mengen Wasser hydrolysieren 3a, b, d - f zu den entsprechenden Alkoholen RC[R′R″(O)]2 OH (5a, b, d - f), welche sich mit Ausnahme von 5a in die Phosphinate RC[R′R″P(O)][OP(O)R′R″]H (6b - f) isomerisieren [Gln. (7a, b)].
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    Berichte der deutschen chemischen Gesellschaft 112 (1979) 
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    Keywords: Chemistry ; Inorganic Chemistry
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 781-792 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic Seven-membered Ring Compounds, XXII. Synthesis and Thermolysis of Substituted 4-Phenyl-l -benzothiepin 1-Oxides4-Phenyl-l-benzothiepin l-oxides 3a and b have been prepared as well via the benzothiepinone 1-oxide 2 as by direct oxidation of the parent 1-benzothiepins 6a and b. The synthesis of 3c and d was only accomplished by the second way. Further oxidation of 3a-d yielded the thermally stable dioxides 4a-d. Thermolysis of 3a-d produced the corresponding naphthalenes 5a-d by elimination of SO. The rates of the reaction 3→5 have been estimated for one temperature each.
    Notes: Die 4-Phenyl-l-benzothiepin-l-oxide 3a und b wurden sowohl über das Benzothiepinon-1-oxid 2 als auch durch direkte Oxidation der entsprechenden 4-Phenyl- 1-benzothiepine 6a und b dargestellt. Die Synthese von 3c und d erfolgte nur auf dem zweiten Weg. Weiteroxidation von 3a-d führte zu den thermisch stabilen Dioxiden 4a-d. Die Thermolyse von 3a-d lieferte unter Abspaltung von SO die entsprechenden Naphthaline 5a-d. Die Geschwindigkeitskonstanten der Reaktion 3→5 wurden für je eine Temperatur bestimmt.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 883-889 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Significance of Diene-1,4-Distance on the Reactivity in Diels-Alder ReactionsThe reactivity of cyclopentadiene and di-exo-methylene compounds in Diels-Alder reactions is investigated using the frontier molecular orbital method. It is shown that besides the HOMO-LUMO energy difference the diene 1,4-distance plays an important part for the rate of reaction. The shorter this distance is the higher becomes the reactivity. Experimentally this is shown by the rates of reaction of tetracyanoethylene and maleic anhydride with cyclopentadiene and di-exo-methylene compounds 2-6. The 1,4-distance of the latter is known from force field calculations. 1,4-Distance and log k2 exhibit a linear relationship which is supported by theoretical considerations.
    Notes: Die Reaktivität von Cyclopentadien und cis-fixierten Di-exo-methylenverbindungen in Diels-Alder-Reaktionen wird im Rahmen des Grenzorbitalmodells untersucht. Es wird gezeigt, daß neben der Energiedifferenz der dominanten Grenzorbitalwechselwirkung auch der Dien-1,4-Abstand eine wichtige Funktion besitzt. Je kürzer dieser ist, umso reaktiver ist das Dien. Dies zeigt die Kinetik der Umsetzung von Tetracyanethylen und Maleinsäureanhydrid mit Cyclopentadien und den Di-exo-methylenverbindungen 2-6, deren 1,4-Abstand auf Grund von Kraftfeldrechnungen bekannt ist. Zwischen 1,4-Abstand des Diens und log k2 der Cycloaddition besteht ein linearer Zusammenhang, der sich theoretisch begründen läßt.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1267-1271 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclopentadienide Syntheses with Iodonium Ylides: Cyclopentadienides with Sulfur, Selenium, Phosphorus, and Arsenic as Onium CenterThe aryliodonio-cyclopentadienides 1 react with thioethers or diphenyl selenide at temperatures of 65 - 140°C to give the corresponding sulfonio- or selenonio-cyclopentadienides 2. Thioureas yield the isothiuronium betaines 4. The reactions of 1 with triphenylphosphane and -arsane to the phosphonio- and arsonio-cyclopentadienides 6 require temperatures of 140 - 150°C and catalysis by Cu compounds.
    Notes: Die Aryliodonio-cyclopentadienide 1 reagieren mit Thioethern oder Diphenylselenid bei Temperaturen von 65-140°C zu den entsprechenden Sulfonio- und Selenonio-cyclopentadieniden 2. Thioharnstoffe ergeben die Isothiuronium-Betaine 4. Die Reaktionen von 1 mit Triphenylphosphan und -arsan zu den Phosphonio- und Arsonio-cyclopentadieniden 6 benötigen Temperaturen von 140-150°C und Katalyse durch Cu-Verbindungen.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1288-1296 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Decomposition Products of Imino-Δ3 1,2,4-thiadiazolinesImino-Δ3-1,2,4-thiadiazolines (2) are often instable, even at ambient temperature, especially those with R′ = alkyl or H. In case of 2, R = aryl, R′ = alkyl, two molecules combine with loss of one atom sulfur to yield the thiadiazolidines 3. The latter can be prepared alternatively from 2 and imidoylcarbodiimide or from sulfur and imidoylcarbodiimide. The decomposition of 2, R = phenyl. R′ = H, afforded the N-cyanobenzamidine 9b via an unknown red intermediate. From experiments and comparisons it is deduced that the possibility of fragmentation into sulfur and an acyl heterocumulene is a prerequisite for an easy decomposition of such a kind of molecules.
    Notes: Imino-Δ3-1,2,4-thiadiazoline (2) sind häufig schon bei Raumtemperatur instabil, besonders solche mit R′ = Alkyl oder H. Im Falle der Verbindungen 2, R = Aryl, R′ = Alkyl, vereinigen sich zwei Moleküle unter Austritt von einem Atom Schwefel zu den Thiadiazolidinen 3. Letztere können gezielt auch aus 2 und Imidoylcarbodiimiden oder aus Schwefel und Imidoylcarbodiimid hergestellt werden. Der Zerfall von 2, R = Phenyl, R′ = H, liefert über eine unbekannte rote Zwischenverbindung das N-Cyanbenzamidin 9b. Aus den Versuchen und Vergleichen wird abgeleitet, daß. Fragmentierbarkeit derartiger Moleküle in Schwefel und ein Acyl-heterocumulen Voraussetzung für den leichten Zerfall sind.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1304-1315 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Reactivity of Silicon Transition Metal Complexes, XII. Double Dicarbonyl(cyclopentadienyl)iron-substituted SilanesThe transition metal-substituted silanes [C5H5(CO)2Fe]2SiHR (R = CH3, Cl) (1, 2) are obtained via metallation of C5H5(CO)2Fe—SiHRCl with [C5H5(CO)2Fe]Na in cyclohexane. 1 is also formed together with C5H5(CO)2Fe—SiH2CH3 (3) by reaction of C5H5(CO)2Fe—SiH(CH3)Cl with sodium amalgam. CCl4 rapidly converts 1 and 2 to the chlorinated derivatives 4 and 5, which further react with AgBF4 to give the fluorosilyl complexes [C5H5(CO)2Fe]2SiFCH3 (6) and [C5H5(CO)2Fe]2SiF2 (8). The structure of the bimetallated silanes is determined by means of IR, NMR (1H, 13C, 19F, 29Si) and mass spectroscopy.
    Notes: Die übergangsmetall-substituierten Silane [C5H5(CO)2Fe]2SiHR (R = CH3, Cl) (I, 2) werden durch Metallierung von C5H5(CO)2Fe—SiHRCl mit [C5H5(CO)2Fe]Na in Cyclohexan erhalten. 1 bildet sich außerdem zusammen mit C5H5(CO)2Fe-SiH2CH3 (3) bei der Umsetzung von C5H5(CO)2Fe — SiH(CH3)Cl mit Natriumamalgam. CCl4 überführt 1 und 2 rasch in die chlorierten Abkömmlinge 4 und 5, die mit AgBF4 weiter zu den Fluorsilylkomplexen [C5H5(CO)2Fe]2SiFCH3 (6) und [C5H5(CO)2Fe]2SiF2 (8) reagieren. Die Struktur der bimetallierten Silane wird mit Hilfe von IR-, NMR (1H, 13C, 19F, 29Si)- und Massenspektroskopie bestimmt.
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  • 37
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1320-1328 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbyne Complexes, XLV. Cyclopentenylcarbene and -carbyne Metal Complexes of Chromium and TungstenThe cyclopentenylcarbene and-carbyne complexes (CO)5MC(OC2H5)(C5H7)(M = Cr. Mo. W) (1a-c) and trans-X(CO)4M≡CC5H7 (M = Cr, W; X = Cl, Br, I) (2a-e) are introduced as easily accessible, vinyl-substituted derivatives of this class of compounds. Complete characterization is achieved. An X-ray analysis of 2b rendered information about the influence of the carbon-carbon double bond of the cyclopentenyl group in conjugation to a metal-carbon triple bond.
    Notes: Mit den Cyclopentenylcarben- und -carbin-Komplexen (CO)5M C(OC2H5)(C5H7) (M = Cr, Mo, W) (1a-c) und trans-X(CO)4M≡CC 5H7 (M = Cr, W; X = Cl, Br, I) (2a-e) werden leicht zugängliche vinylsubstituierte Vertreter dieser Verbindungsklasse beschrieben und vollständig charakterisiert. Eine Röntgenstrukturbestimmung von 2b gab Aufschluß über den Einfluß der in Konjugation zur Metall-Kohlenstoff-Dreifachbindung stehenden C = C-Doppelbindung des Cyclopentenylrestes.
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  • 38
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1348-1358 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrophilic Aromatic Substitution Reactions with Protonated 1,3-Diazines, II. Preparation and Properties of 4-Aryl-substituted 3,4-Dihydroquinazoline DerivativesIn the presence of trifluoroacetic acid, quinazoline and 2-methylquinazoline react with a great variety of aromatic compounds to form 4-aryl-substituted 3,4-dihydroquinazolinium salts, e. g. 2, 3. From those, the dihydro bases 4 can be obtained which are readily oxidized to 4-aryl-substituted quinazolines 5, 6. Highly reactive compounds like indole are treated in formic acid or acetic acid, for better results. Also, some CH-acidic compounds react with quinazoline in trifluoroacetic acid.
    Notes: Bei Gegenwart von Trifluoressigsäure (TFE) reagieren Chinazolin und 2-Methylchinazolin mit einem weiten Spektrum aromatischer Verbindungen zu stabilen 4-arylsubstituierten 3,4-Dihydro-chinazoliniumsalzen, z. B. 2, 3, aus denen sich die zugrunde liegende Dihydrobase 4 erhalten läßt, die ihrerseits zu 4-arylsubstituierten Chinazolinen 5, 6 oxidiert werden kann. Im Fall besonders reaktiver Aromaten (z. B. Indol) läßt sich TFE vorteilhaft durch Eisessig oder Ameisensäure ersetzen. Auch eine Reihe CH-acider Verbindungen reagiert in TFE mit Chinazolin.
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  • 39
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1365-1371 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Structure of a Novel Spirobicyclic Phosphorane with λ3P-λ5P BondBy the reaction of [Si(CH3)3] (3-CF3C6H4) NC(O)NCH3 [Si(CH3)3] (1) with C6F5PCL2 the first λ3P-λ5P coordinated compound (2) is obtained. The structure was established by X-ray analysis. The λ3-phosphorus adopts an equatorial position in the larger ring of a spirobicyclic phosphorane which contains one four- and one five-membered ring. The coordination at the λ5-phosphorus displays a 21% distortion from an idealised trigonal bipyramid toward a square pyramidal geometry. The very different axial P—N bond lengths of 186.7 (3) and 174.3 (2) pm in the four and five-membered rings, respectively, are indicative of a significant degree of ring strain in the four and five-membered ring. The P—P bond length of 219.5 pm is slightly shorter than that which has been observed in diphosphanes with the coordination number 3.
    Notes: Durch Reaktion von [Si(CH3)3](3CF3C6H4)NC(O)NCH3[Si(CH3)3] (1) mit C6F5PCI2 konnte die erste Δ3P-λ5P-koordinierte Verbindung (2) erhalten werden. Die Struktur wurde durch eine Röntgenanalyse belegt. Der λ3- Phosphor nimmt eine äquatoriale Position im größeren Ring eines spirobicyclischen Phosphorans mit einem vier- und einem fünfgliedrigen Ring ein. Die Koordination am λ5- Phosphor zeigt eine Verzerrung von 21% von einer idealisierten trigonalen Bipyramide in Richtung einer quadratisch-pyramidalen Geometrie. Die sehr verschiedenen axialen P—N-Bindungsabstände von 186.7(3) und 1743.3(2) pm in den vier-bzw. fünfgliedrigen Ringen weisen auf eine erhebliche Ringspannung im Vierring hin. Die P—P-Bindungslänge ist mit 219.5 pm geringfügig kürzer als sie in Diphosphanen der Koordinationszahl 3 gefunden wird.
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  • 40
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1392-1399 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ligand Structure and Complexation, XXXVII. Three-Armed Multidonor Neutral Ligands - Synthesis, Complex Formation, and Cation SelectivityThe long-chain multidonor tripodand molecules 2a-f, 3a-e, 4 and the lipophilic analogue substances 5-7 have been synthesized. Crystalline 1:1 complexes with alkali and alkaline earth metal salts have been isolated. The complex stability constants depend on the ligand topology. The tripodand 2 f with quinoline terminal groups shows the highest constant with Ba2⊕ ions (log Ks = 4; table 1).
    Notes: Die langkettigen, multizähnigen Tripodanden 2a-f, 3a-e, 4 und die lipophilen Analoga 5-7 wurden synthetisiert. Kristalline 1:1-Komplexe mit Alkali- und Erdalkalimetallsalzen wurden isoliert. Die Komplexstabilitätskonstanten hängen von der Ligandtopologie ab. Der Tripodand 2 f mit Chinolin-Endgruppen ergibt mit Barium-Ionen die höchste Konstante (log Ks = 4: Tab 1).
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  • 41
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1410-1419 
    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, XX. Syntheses of Unsymmetrical 1,4,7-TriketonesThiazolium salt catalysed additions of aldehydes to vinyl diketones (1-4, 10-12) lead to unsymmetrical 1,4,7-triketones (13-26). The vinyl diketones were obtained by addition of 2-formylnorbornene to alkyl vinyl ketones (30-32) followed by pyrolysis, the latter by the reaction of 2-cyanonorbornene with alkylmagnesium halides followed by hydrolysis and pyrolysis.
    Notes: Thiazoliumsalz-katalysierte Additionen von Aldehyden an Vinyldiketone (1-4, 10-12) führen zu unsymmetrischen 1,4,7-Triketonen (13-26). Die Vinyldiketone entstehen durch Addition von Norbornen-2-carbaldehyd an Alkylvinylketone und nachfolgende Pyrolyse. Die Alkylvinylketone (30 - 32) werden durch Reaktion des Norbornen-2-carbonitrils mit Alkylmagnesiumhalogeniden nach Hydrolyse und Pyrolyse erhalten.
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  • 42
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1420-1439 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Applications of Magnesium Thioacrolein Dianions to the Synthesis of Sulfur-free Compounds (Vinyl- and Divinylepoxides, Acylcyclopentenes)Doubly lithiated allyl (la) and methallylmercaptan and MgBr 2. etherate furnish reagents (cf. lb) which add to aldehydes and ketones, including α,β-unsaturated ones, to give the α-1,2-products 2-5 after methylation (see tables 1 and 2). The isolated hydroxythioethers contain less than 10% γ-adducts (cf. A in table 1); with enones no Michael-addition occurs; if there are two centers of chirality in 2 - 5, diastereomeric mixtures are formed. - With CH3I or Meerwein reagent the hydroxysulfonium salts G (OH instead of O⊖;) are generated which give E/Z mixtures of vinyl and divinyl oxiranes 6 and 7, respectively, upon treatment with aqueous base in a two-phase system. - Oxide-Cope rearrangement of the potassium alkoxides of the 1,5-hexadienes 3, 5 in THF, HMPT, or mixtures of the two solvents produces ketoaldehyde thioenol ethers 8 in good yields (tables 3 and 4). The α- and γ-1,2-adducts (3d, 10) rearrange with high constitutional and stereochemical selectivity to the ketones (8b, 11), see scheme 1. This provides evidence for a pericyclic rather than ionic (dissociation/recombination) mechanism of the oxide-Cope rearrangement of the alkoxides 3, 5 (O⊖ instead of OH). - Hydrolysis of the products 8 of rearrangement and aldol ring closure leads to cyclopentenyl ketones 14 in modest overall yields. For the thioenol ether hydrolysis a two step procedure (8 → 13 → 12) is recommended. - Scheme 2 demonstrates the synthetic equivalence of the organometallic reagent l b with allylidene and propionaldehyde d3-synthon.
    Notes: Die Magnesiumderivate des Thioacrolein-Dianions (lb) und des doppelt deprotonierten Methallylmercaptans werden aus den entsprechenden Lithioverbindungen und Magnesiumbromid-Etherat erhalten und reagieren mit normalen und α,β-ungesättigten Aldehyden und Ketonen zu α - 1,2-Produkten 2 - 5 (nach der Methylierung), siehe Tab. 1 und 2. - Aus den Diastereomerengemischen 2, 3 entstehen durch, S-Methylierung und Eliminierung E/Z-isomere Vinyl-(6) und Divinyloxirane (7). - Oxid-Cope-Umlagerung der Methylthio-hexadienole 3, 5 mit Kaliumhydrid in THF oder THF/HMPT führt zu Thioenolethern 8 von 6-Ketoaldehyden (s. Tab. 3 und 4). Durch die in Schema 1 gezeigten Versuche wird bewiesen, daß die Umlagerung konstitutions- und stereoselektiv verläuft, also nicht über äquilibrierende Dissoziation/Rekombination. - Über die Dicarbonylverbindungen 12 werden aus 8a - c die Cyclopentenylketone 14a - c hergestellt. Zur Hydrolyse von Thioenolethern wird ein zweistufiges Verfahren (Mercaptanaddition zum Thio-acetal und dessen HgII-Spaltung) empfohlen (8 → 13 → 12). - In Schema 2 ist die Syntheseäquivalenz des Organometallreagenz lb mit Allyliden und Propionaldehyd-d3-Synthon als Zusammenfassung der hier beschriebenen Umsetzungen verdeutlicht.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1585-1594 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mesoionic Six-membered Heterocycles, XI. Synthesis and Reactions of Mesoionic 1,3-OxazinesThe reaction of (chloroformyl) ketenes 1 with cyclic amides such as 2-pyridone (2) and 2-quinolones (8) leads to bicyclic mesoionic oxazines (3 and 9). With phenyl isocyanate these compounds are converted into pyrimidine betaines (6 and 10) by 1, 4-dipolar cycloaddition and elimination of CO2 With acetylenedicarboxylate 3 yields the quinolizinonedicarboxylate 7. The more unstable monocyclic oxazine betaines 13 are formed from N-substituted amides 12 and 1 in the presence of triethylamine. Higher reaction temperature leads by rearrangement to the isomeric quinolinedione 15. However, 2-phenylacetamide (17) as an aliphatic N-unsubstituted amide gives the oxazinone 18.
    Notes: Die Reaktion der (Chlorcarbonyl) ketene 1 mit cyclischen Säureamiden wie 2-Pyridon (2) und 2 Chinolonen (8) führt zu bicyclischen mesoionischen Oxazinen (3 und 9). Diese setzen sich mit Phenylisocyanat unter 1,4-dipolarer Cycloaddition und CO2 - Eliminierung zu den Pyrimidin-Betainen 6 und 10 um, Mit Acetylendicarbonsäureester reagiert 3 zum Chinolizinondicarbonsäureester. 7. Die instabileren monocyclischen Oxazin- Betaine 13 werden aus N - substituierten aromatischen Säureamiden 12 und 1 unter Zusatz von Triethylamin erhalten. Höhere Reaktionstemperaturen führen dagegen unter Umlagerung zum isomeren Chinolindion 15. 2-Phenylacetamid (17) als aliphatisches N-unsubstituiertes Säureamid gibt das Oxazinon 18.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1595-1605 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Metal and Metalloid Compounds with Polyfunctional Molecules, XX. Reactions of N-(Trimethylsilyl)carboxamides with Dihalogenoorganylboranes and Trihalogenoboranes2,2,2-Trihalogeno-N-(trimethylsilyl)acetamides react with trichloroborane, tribromoborane, or dihalogenoorganylboranes to give the ring system of 1-oxa-3-azonia-5-aza-2-borata-3,5-cyclohexadiene (1-6). Trifluoroborane reacts with 2,2,2-trifluoro-N-(trimethylsilyl)acetamide to yield the trifluoroborane adduct 7 of trifluoroacetamide. The reaction of 2-chloro-N-(trimethylsilyl)acetamide with butyldichloroborane leads to the formation of the boryl chloroacetimidate 8 Analogous compounds are also obtained by substitution reactions of the chlorine atom in 3 with AgCN and NaN3 (→9, 10) or by the reaction of lithiated 2,2,2-trifluoro-N-(trimethylsilyl)acetamide with dihalogenoorganylboranes (→14, 15). Cleavage of both Si—N bonds in l-oxa-3,5-diaza-2,4-disila-5-cyclohexene 11 by dihalogenoorganylboranes leads to the corresponding 1-oxa-3,5-disila-2,4-dibora-5-cyclohexenes (12, 13). The 1H. 11B, and 19F NMR, Mass and 1R spectra are reported.
    Notes: Läßt man 2,2,2-Trihalogen-N-(trimethylsilyl)acetamide mit Trichlorboran. Tribromboran oder Dihalogenorganylboranen reagieren, So erhält man das Ringsystem des 1-Oxa-3-azonia-5-aza-2-borata-3,5-cyclohexadiens (1-6). Bei der Umsetzung von 2,2,2-Trifluor-N-(trimethylsilyl)acetamid mit Trifluorboran entsteht das Addukt 7 aus Trifluoracetamid und Trifluorboran. Die Reaktion von 2-Chlor-N-(trimethylsilyl)acetamid mit Butyldichlorboran ergibt den Chloracetimidsäure-borylester 8. Dazu analoge Verbindungen werden erhalten, wenn man in 3 das Chlor mit AgCN oder NaN3 reagieren läßt (→9, 10) oder lithiiertes 2,2,2-Trifluor-N-(Trimethylsilyl)-acetamid mit Dihalogenorganylboranen umsetzt(→14, 15). Durch Spaltung der beiden Si—N-Bindungen im 1-Oxa-3,5-diaza-2,4-disila-5-cyclohexen 11 durch Dihalogenorganylborane entstehen die entsprechenden 1-Oxa-3,5-diaza-2,4-dibora-5-cyclohexen-Verbindungen (12, 13). Die Verbindungen werden analytisch und spektroskopisch (NMR: 1H. 11B. 19F: MS: IR) charakterisiert.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1626-1634 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereochemistry of the Metal-Metal Bond. The Structures of three Complexes of the Type [L2M—PR2]2The molecular structures of the complexes [(NO)2Fe—P(C6H5)2]2 (2), and [CO(NO)Co—P(C6H5)2]2 (4) were determined crystallographically. Together with literature data they allow the discussion of the metal-metal bonding in two series of complexes. In the series [L2M P(C6H5)2]2 with L2M=(NO)2Fe, CO(NO)2Co, (CO)2Ni (1,4,5) the metal-metal-bond lengths are controlled by the electronic influence of the ligands L. In the series [(NO)2Fe—PR2]2 with R=C6H5, CH3, CF3 (1,2,3) the variation of the phosphorus substituents generates only minor changes of the molecular framework.
    Notes: Die Molekülstrukturen der Komplexe [(NO)2Fe—P(C6H5)2]2 (1), [(NO) 2Fe—P(CH3)2]2 (2) und [CO(NO)Co—P(C6H5)2]2 (4) wurden kristallographisch bestimmt. Sie erlauben zusammen mit Literaturangaben die Diskussion der Metall-Metall-Bindung in zwei Komplexreihen. In der Reihe [L2M—P(C6H5)2]2 mit L2M=(NO) 2Fe, CO(NO)Co, (CO) 2Ni (1,4,5) steuert der elektronische Einfluß der Liganden L die Metall-Metall-Bindungslängen. In der Reihe [NO) 2Fe—PR2]2mit R=C6 H5, CH3, CF3 (1,2,3) bewirkt die Variation der Phosphorsubstituenten R nur unwesentliche Veränderungen des Molekülgerüstes.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1660-1669 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminobenzenes, XV. Halo and Pseudohalo σ-Complexes of Symmetrical Tris(dialkylamino)benzenes - Synthesis and Characterization1,3,5-Tris(dialkylamino)benzenes 1 react with halides or dirhodane in inert solvents at low temperatures to give, in part isolable, cationic intermediates 2 (σ-complexes) of electrophilic aromatic substitution. Treatment of compounds 2 with base produces halo benzenes 4, reacidification of 4 gives rise to the identical σ-complexes 2. The stability of complexes 2 depends upon the different mesomeric stabilization by the various dialkylamino substituents.
    Notes: 1,3,5-Tris(dialkylamino)benzole 1 bilden mit Halogenen und Dirhodan in inerten Lösungsmitteln bei tiefen Temperaturen die zum Teil isolierbaren kationischen Zwischenverbindungen 2 (σ-Komplexe) der elektrophilen Aromatensubstitution. Mit Basen entstehen aus 2 durch Deprotonierung die Halogenbenzole 4, die mit Säuren wiederum die identischen σ-Komplexe 2 bilden. Die Stabilität der Komplexe 2 hängt von der unterschiedlichen Mesomeriestabilisierung durch die verschiedenen Dialkylaminosubstituenten ab.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1670-1676 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Halogenation of Enamines  -  Synthesis of β-Halo-immonium HalidesEnamines 4-6 react with halides in diethylether under exclusion of oxygene and moisture at -78°C to give the isolable β-halo-immonium halides 7-9, 13-15, and 19 in good yields. Acid hydrolysis leads to the α-halo ketones 10-12, 16-18, and 20.
    Notes: Die Enamine 4-6 bilden mit Halogenen in Diethylether bei -78°C unter Luft- und Feuchtigkeitsausschluß in sehr guter Ausbeute die isolierbaren β-Halogen-iminium-halogenide 7-9, 13-15 und 19. Die saure Hydrolyse führt zu den α-Halogenketone 10-12, 16-18, und 20.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1705-1711 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 3-O-Benzyl-D-ribose3-O-Benzyl-D-ribose (4) is synthesized from D-glucose and D-ribose via different routes; these methods were compared. For a characterization 4 is transformed into 3′-O-benzyl-adenosine (19). 1H NMR data of the synthesized compounds are compiled.
    Notes: Aus D-Glucose und aus D-Ribose wird in vergleichenden Untersuchungen auf verschiedenen Wegen 3-O-Benzyl-D-ribose (4) hergestellt. Zur Charakterisierung wird 4 in 3′-O-Benzyladenosin (19) übergeführt. 1H-NMR-Spektroskopische Daten der synthetisierten Verbindungen werden mitgeteilt.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 423-426 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rel. Configuration and Crystal Structure of a Bufadienolide AnalogueThe X-ray analysis of 4 surprisingly proved a cis substitution pattern within the five-membered ring. Furthermore a conformational similarity between 3 and 4 is shown.
    Notes: Die Röntgenstrukturanalyse am Perhydrostilben-α-Pyron 4 bringt den überraschenden Befund einer cis-Anordnung der Substituenten im Cyclopentanring. Im übrigen entspricht die Konformation des Moleküls weitgehend der Verbindung 3.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 397-407 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of (±)-“Isoalbene”In an attempt to synthesize the natural compound „albene“ it was shown that this material does not possess structure 1. Actually 1 is produced via the Diels-Alder adduct 10, followed by hydrogenation to 11 and Thorpe-Ziegler ring closure of the third carbocyclic ring by means of dinitrile 19. The resulting symmetrical ketone 3 is transformed into the thioenolether 21 with phenylmethanthiol. Desulfurization with Raney nickel yields 2.6-dimethyl-endo-tricyclo[5.2.1.02,6]dec-3-ene (1). which is not identical with natural „albene“.
    Notes: Bei dem Versuch einer Totalsynthese des Naturstoffs „Alben“ zeigte sich, daß diesem nicht die Strukturformel 1 zukommen kann. Die Darstellung von 1 erfolgte auf dem Wege über das Diels-Alder-Addukt 10, Hydrierung zu 11 und Schließen des dritten carbocyclischen Ringes mit Hilfe des Dinitrils 19 und Thorpe-Ziegler-Verfahrensweise. Das solcherart zugängliche symmetrische Keton 3 ließ sich mit Phenylmethanthiol in den Thioenolether 21 überführen. Entschwefelung mit Raney-Nickel ergab 2,6-Dimethyl-endo-tricyclo[5.2.1.0:2,6]dec-3-en (l), das mit natürlichem „Alben“ nicht übereinstimmte.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 408-422 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: First Total Synthesis of (-)-„Albene“By different routes the synthesis of (-)- „albene“ (2) is investigated. The tert. carbinol 8 is produced stereospecifically via 2 -norbornanone (5). Ionic cyclisation of the former leads to a chloroolefin the structure of which is presumably shown by 11. Starting with camphenilone, 14 and 16 served in vain for ring closure reactions. Finally, 20 yields the tricyclus 21, which upon Baeyer-Villiger oxidation surprisingly leads to the carboxylic acid 25 and to 22 as well. 25 yields 2 on oxidative decarboxylation. The synthesis is used to determine the absolute configuration of the natural compound 2 and furthermore proves an uncommon endo - selectivity for the Nametkin rearrangement.
    Notes: Unterschiedliche Wege zur Synthese von (-)-„Alben“ (2) werden untersucht. Über 2-Norbornanon (5) wird stereospezifisch das tert. Carbinol 8 gewonnen, dessen ionische Cyclisierung zu einem Chlorolefin der mutmaßlichen Struktur 11 führt. Ausgehend von Camphenilon wurden 14 und 16 vergeblich in eine Ringschlußreaktion eingesetzt. Schließlich liefert 20 den erwünschten Tricyclus 21. Baeyer-Villiger-Oxidation hieran ergibt neben 22 überraschenderweise die Carbonsäure 25, die bei der oxidativen Decarboxylierung 2 erbringt. Gleichzeitig führt die Synthese zur Aufklärung der absoluten Konfiguration des Naturstoffs 2 sowie zur Beobachtung einer ungewöhnlichen endo -Selektivität für die Nametkin - Umlagerung.
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  • 52
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 445-461 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Triazenium Salts  -  A New Class of CompoundsTriazenium ions (azaallyl ions) of type 5 are obtained by alkylation, especially in an intramolecular reaction, of triazenes trisubstituted by alkyl and/or aryl groups. The cations 5 are isolated as stable tetrafluoroborates, perchlorates or iodides. The salts are decomposed by bases whereby the cyclic typ 20 (n = 2) forms triazolium salts. The UV spectra of 5 exhibit strong influences of substituents and geometry. Triazenium salts are the simplest azacyanines and they absorb at longer wave lengths (50-80 nm) than the corresponding amidinium salts.
    Notes: Durch Alkyl- und/oder Arylreste trisubstituierte Triazene lassen sich, insbesonders intramolekular, zu Triazenium-Ionen (Triazaallyl-Kationen) vom Typ 5 alkylieren, die als stabile Tetrafluoroborate, Perchlorate oder Iodide isoliert werden. Basen zersetzen die Salze, wobei aus dem cyclischen Typ 20 (n = 2) Triazoliumsalze entstehen. Die UV-Spektren der Triazeniumsalze zeigen starke Einflüsse von Substituenten und Geometrie. Als einfachste Azacyanine absorbieren sie 50 - 80 nm längerwellig als die entsprechenden Amidiniumsalze.
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  • 53
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 468-479 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Azidocobalt(III) Chelate Complexes with IsocyanidesAzidochelatecobalt(III) complexes N3Co(chelate)B (la-e) [chelate = e. g. dianion of N,N′-o-phenylenebis(salicylidenimine), B = PPh3] react with organic isocyanides to give metal-carbon bonded tetrazolate complexes 3, 4. 2-Isocyanoethanol affords tetrazolato- (9, 10) or azido-oxazolidin-2-ylidene complexes (11), depending on the nature of the solvent, the trans-base B, and the chelate ligand. The mechanism of formation of C-coordinated tetrazoles from azido complexes and isonitriles is discussed.
    Notes: Azidochelatcobalt(III)-Verbindungen N3Co(chelat)B(la-e) [chelat = z. B. Dianion von N,N′-o-Phenylenbis(salicylidenimin), B = PPh3] setzen sich mit organischen Isocyaniden zu Tetrazolatokomplexen 3, 4 mit Cobalt-Kohlenstoff-Bindung um. Mit 2-Isocyanethanol entstehen in Abhängigkeit vom Lösungsmittel, der trans-ständigen Base B und dem Chelatliganden Tetrazolato-(9, 10) oder Azido-oxazolidin-2-yliden-Komplexe (11). Der Mechanismus der Bildung C-koordinierter Tetrazole aus Azidokomplexen und Isonitrilen wird diskutiert.
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  • 54
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 567-576 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enantiomeric Pentatetraenes and their Thermic Racemization EnergiesPartial hydroboration of the racemic pentatetraene 4 with chiral di(3-pinanyl)borane (6) gives the olefins 7 and 8, and starting material with about 5% enrichment of one enantiomer of 4. Complete separation of the enantiomers of 4 is achieved by chromatography on microcrystalline peracetylated cellulose. ( + )-4 with [α]D22 = + 336.6° (c = 0.8; CHC1,3) most likely has (S)-configuration. The enantiomers 4 racemize thermally at 358 K with activation parameters of ΔH≠ = 109.4 ± 1 kJmol-1, ΔS≠ = -18 ± 5JK-1 mol-1. and ΔG≠ = 115.8 ± 0.1 kJmol-1, independent of the polarity of the solvent.
    Notes: Die partielle Hydroborierung des racemischen Pentatetraens 4 mit chiralem Di(3-pinanyl)boran (6) führt zu den Olefinen 7 und 8, wobei im zurückgewonnenen Ausgangsmaterial 5% eines Enantiomeren von 4 angereichert werden. Die vollständige Enantiomerentrennung von 4 gelingt durch Chromatographie an mikrokristalliner peracetylierter Cellulose. (+)-4, [α]D22 = + 336.6° (c = 0.8; CHC13), besitzt wahrscheinlich (S)-Konfiguration. Die thermische Racemisierung von 4 ist bei 358 K von der Polarität des Mediums unabhängig und ergibt ΔH≠ = 109.4 ± l kJmoI-1, ΔS≠ = -18 ± 5JK-1mol-1 und ΔG≠ = 115.8 ± 0.1 kJmol-1.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1923-1925 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pheromones, XXIV. Synthesis of the Sex Attractants (Z)-7-Dodecenyl Acetate and (Z)-7-Tetradecenyl Acetate(Z)-7-Dodecenyl acetate, the female sex pheromone of the Noctuid moth Trichoplusia ni, and (Z)-7-tetradecenyl acetate, the sex attractant of Amathes c-nigrum (Lepidoptera), are prepared by stereoselective Wittig olefination using the „silazide“ -technique.
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  • 56
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1948-1955 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of α-BromoisothiocyanatesSecondary isothiocyanates (1j-q) and primary isothiocyanates R—CH2 - NCS with an activating group R (1f, g) react with N-bromosuccinimide (NBS) to form α-bromoisothiocyanates 2 in high yields. The not activated primary isothiocyanate 1c slowly forms the stable α,α-dibromoisothiocyanate 10. In the presence of β-hydrogens some of the α-bromoisothiocyanates 2 eliminate HBr spontaneously, and secondary products may be formed. The α-bromination of isothiocyanates is a radical reaction following a Goldfinger mechanism.
    Notes: Sekundäre Isothiocyanate (1j-q) und primäre Isothiocyanate R-CH2 - NCS mit einer aktivierenden Gruppe R (1f, g) lassen sich mit N-Bromsuccinimid (NBS) in hohen Ausbeuten zu den α-Bromisothiocyanaten 2 bromieren. Das nicht aktivierte Isothiocyanat 1c reagiert langsam zum stabilen α,α-Dibromisothiocyanat 10. Bei Anwesenheit von β-Wasserstoffatomen spalten die α-Bromisothiocyanate 2 zum Teil spontan HBr ab, und es entstehen Folgeprodukte. Die α-Bromierung der Isothiocyanate erfolgt radikalisch nach einem Goldfinger-Mechanismus.
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  • 57
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1956-1972 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of α-Bromoisothiocyanatesα-Bromoisothiocyanates 11.2) with a hydrogen in β-position eliminate HBr to form vinyl isothiocyanates (products 2, 3, 5). Water hydrolyzes 1 to carbonyl compounds (7a). Hard nucleophiles attack 1 at the α-C-atom with substitution of bromine (products 8-12), but soft nucleophiles add to the C-atom of the isothiocyanato group (products 14, 19). Compounds 1 react with bifunctional nucleophiles to heterocycles (e. g. products 16, 21). The chemical properties of the classes of compounds, part of which are new, e. g. the geminal diisothiocyanates 12, are examined. The alkylidene thiourea 14f shows hindered rotation around the amide-CS—N bond (ΔG≠394 = 82.8 kJmol-1) and around the C=N double bond (ΔG≠244 = 52.9 kJmol-1).
    Notes: α-Bromisothiocyanate 1 mit einem β-Wasserstoff spalten HBr zu Vinylisothiocyanaten ab (Produkte 2, 3, 5). Wasser hydrolysiert 1 zu Carbonylverbindungen (7a). Harte Nucleophile greifen 1 am α-C-Atom unter Substitution des Broms an (Produkte 8-12), weiche Nucleophile lagern sich dagegen an das C-Atom der Isothiocyanatgruppe an (Produkte 14, 19). Verbindungen 1 reagieren mit bifunktionellen Nucleophilen zu Heterocyclen (z. B. Produkte 16, 21). Die chemischen Eigenschaften der z. T. neuen Verbindungsklassen, z. B. der geminalen Diisothiocyanate 12, werden untersucht. Der Alkylidenthioharnstoff 14f zeigt behinderte Rotation um die Amid Cs—N-Bindung (ΔG≠394 = 82.8 kJmol-1) und um die C=N-Doppelbindung (ΔG≠244 = 52.9 kJmol-1).
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1981-1990 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrazidines, III. Synthesis of 1,2,4,5-Tetrazino[3,2-a]isoindolesReaction of acetohydrazide hydrazone hydrochloride (1) with phthalaldehydic acid (5) yields 3-methyl-1,10b-dihydro-1,2,4,5-tetrazino[3,2-a]isoindol-6(4H)-one (8), which affords 1,2,4,5-tetrazino[3,2-a]isoindol-6(4H)-one (9a) by mild oxidation. 9a is also obtained by the reaction of 1 with the phthalic acid derivatives 6a, 7a, and 7b. Starting with 9a, the 1,2,4,5-tetrazino[3,2-a]isoindoles 12-15 are synthesized. Interaction of 1 and 3-nitrophthalic anhydride (6b) yields two isomeric nitro-1,2,4,5-tetrazino[3,2-a]isoindol-6(4H)-ones (9b,c). Oxidation of 9a or b with KMnO4 in methanol affords the 1,2,4,5-tetrazino 17a, b. Mild Oxidation of 9a with KMnO4 in water/trichloromethane yields a dimer (20), which dissociates in nitromethane into the radical 19.
    Notes: Durch Reaktion von Acetohydrazid-hydrazon-hydrochlorid (1) mit Phthaladehydsäure (5) wird 3-Methyl-1, 10b-dihydro-1,2,4,5-tetrazino[3,2-a]isoindol-6(4H)-on (8) erhalten das durch milde Oxidation in 3-Methyl-1,2,4,5-tetrazino[3,2-a]isoindol-6(4H)-on (9a) übergeführt wird. 9a entsteht auch aus 1 und den Phthalsäurederivaten 6a, 7a und 7b. Ausgehend von 9a werden die 1,2,4,5-Tetrazino[3,2-a]isoindole 12-15 synthetisiert. Aus 1 und 3-Nitrophthalsäureanhydrid (6b) werden zwei isomere Nitro-1,2,4,5-tetrazino[3,2-a]isoindol-6(4H)-one (9b, c) erhalten. Oxidation von 9a oder b mit KMnO 4 in Methanol ergibt die 1,2,4,5-Tetrazine 17a, b. Vorsichtige Oxidation von 9a mit KmnO4 in Wasser/Chloroform ergibt ein Dimeres (20), das in Nitromethan in das Radikal 19 dissoziiert.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2012-2021 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bicyclo[2.1.1]hexanes from Tricyclo[3.1.0.02,6]hexanesThe novel tricyclo[3.1.0.02,6]hexane derivatives 3 and 4, being fused with a fife- and a sixmembered ring respectively, are prepared from benzvalene in several steps. They and their lower homologues 1 and 2, having a three- and fourmembered ring respectively, add thiophenol under conditions of a radical reaction to form smoothly one cyclobutylphenyl thioether (16-19) in each case. Therefrom the parent hydrocarbons (5-8) which contain the bicyclo[2.1.1]hexane skeleton, are obtained by means of reduction with lithium in ethylamine.
    Notes: Ausgehend von Benzvalen werden in mehreren Stufen die neuen Tricyclo[3.1.0.02,6]hexan-Derivate 3 und 4 mit anelliertem Fünf- bzw. Sechsring dargestellt. Sie und ihre niedrigeren Homologen 1 und 2 mit Drei- bzw. Vierring nehmen unter Bedingungen einer Radikalreaktion Thiophenol auf, wobei glatt jeweils ein Cyclobutylphenylthioether (16-19) gebildet wird. Mit Lithium in Ethylamin sind aus 16-19 die tricyclischen Stammkohlenwasserstoffe mit dem Bicyclo[2.1.1 ]hexan-Gerüst (5-8) erhältlich.
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Protonenresonanz-Untersuchugen zur Inversion am dreibindigen Stickstoffatom, 6. Präparative Trennungen enantiomerer Diaziridine durch Flüssigkeits-Chromatographie an Triacetylcellulose. Verfolgung der Racemisierungen mittels Polarimetrie und 1H-NMREnantiomere Diaziridine ließen sich durch Chromatographie an Triacetylcellulose anreichern. (-)-2, (+)-4 und (-)-4 wurden fast rein erhalten, wobei die enantiomeren Reinheiten (Tab. 1) mittels 1H-NMR in Gegenwart optisch aktiver Zusätze bestimmt wurden. Dasselbe Verfahren wurde im Hinblick auf die Verfolgung von Racemisierungen (Tab.2) erprobt, welche mit höherer Genauigkeit außerdem mittels Polarimetrie studiert wurden. Die Schwellen der Stickstoff-Inversion, welche die trans-Diaziridine 2 und 4 in cis-Zwischenstufen überführt, werden mit bekannten ΔG≠-Werten verglichen.
    Notes: Enantiomeric diaziridines have been partially separated by chromatography on triacetlycellulose. (-)-2, (+)-4, and (-)-4 were obtained almost pure, enantiomeric purities (Table 1) being measured by 1H NMR in the presence of optically active additives. The same procedure was tested for monitoring racemizations (Table 2) which were also studied, with higher accuracy, by polarimetry. The barriers to nitrogen inversion, converting the trans-diaziridines 2and4into cis-intermediates, are compared with known ΔG≠ values.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2062-2067 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Trimethylsilyl Cyanide  -  A Reagent for Umpolung, II. Nucleophilic Acylation of Aldehydes and Ketones with Anionic 1,4-O,O-Silyl ShiftThe anion 9, derived from O-(trimethylsilyl) benzaldehyde-cyanohydrin (8), adds quantitatively to aldehydes and ketones. The primary adduct 11, which can be trapped as 12 after short reaction times, rearranges with 1,4-0,0-silyl shift. By subsequent cyanide elimination acyloin silyl ethers 14 are formed. Hydrolysis of 14 yields 80-90% of acyloins 15.
    Notes: Das Anion 9 des O-(Trimethylsilyl)benzaldehyd-cyanhydrins (8) addiert sich quantitativ an Aldehyde und Ketone. Das Primäraddukt 11, nach kurzer Reaktionszeit als 12 faßbar, lagert sich unter 1,4-0,0-Silylgruppenwanderung und Cyanidabspaltung zu den Acyloin - trimethylsilylethern 14 um, aus denen durch Hydrolyse die Acyloine 15 mit 80-90% Ausbeute entstehen.
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  • 62
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,6-Anhydrofuranoses, IX. Selective Monotosylation of 1,6-Anhydro-α-D-galactofuranose. Synthesis and Structure Determination of 1,6: 3,5-Dianhydro-α-D-gulofuranoseReaction of 1,6-anhydro-α-D-galactofuranose (1a) with 1.7 mol ρ-toluenesulfonyl chloride gives a mixture of all possible tosylates, the 3-0-derivative 1f with than 40% isolated yield predominating. Cyclization of 1f yields 1,6:3,5-dianhydro-α-D-gulofuranose (2a) with 2,5,7-trioxatricyclo[4.2.1.03.8]nonane skeleton. the structure of it being determined by X-ray crystallography and discussed in comparison to the equally determind structure of 1,6-anhydro-α-L-gulofuranose (3a).
    Notes: Umsetzung von 1,6-Anhydro-α-D-galactofuranose (1a) mit 1.7 mol ρ-Toluolsulfonylchlorid liefert ein Gemisch aller denkbaren Tosylate, in dem das 3-0-Derivat 1fmit über 40% isolierter Ausbeute überwiegt. Dieses läßt sich zur 1,6:3,5-Dianhydro-α-D-gulofuranose (2a) mit 2,5,7-Trioxatricyclo[4.2.1.03.8] nonan-Gerüst cyclisieren, deren Struktur wie die der 1,6-Anhydro-α-L-gulofuranose (3a) durch Röntgenstrukturanalyse bestimmt und diskutiert wird.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2087-2094 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclopentadienylidenes, XV. Cyclohepta[c]pyrrole-6(2H)-thione, a Stable TropothioneCyclohepta[c]pyrrole-6(2H)-thiones (5) are synthesized in two ways from cyclohepta[c]pyrrole-6[2H]-ones (2). The thiones are characterized by reaction with methyl iodide, 9-diazo-1,8-diaza-fluorene (8), and diphenyldiazomethane (11), respectively. Dipole moments of 2 and 5 are reported, spectroscopic data of 5 and of some reaction products are discussed.
    Notes: Cyclohepta[c]pyrrol-6(2H)-one (2) lassen sich nach zwei Methoden in stabile Thioanaloge 5 überführen, die chemisch als Methoiodide 6 und durch Reaktion mit 9-Diazo-1,8-diazafluoren (8) bzw. Diphenyldiazomethan (11) charakterisiert werden können. Dipolmomente von 2 und 5 werden mitgeteilt, spektroskopische Daten von 5 und deren Folgeprodukte diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2120-2144 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Deamination Reactions, 33. Reactions of Aliphatic Diazonium Ions with Lithium AzideThe reactions of aliphatic diazonium ions with lithium azide in methanol to give organic azides proceed by a variety of mechanisms. Azo coupling has been definitely established by means of 15N labels in the case of cyclopropane and alkenediazonium ions. The contribution of a pentazole to the coupling pathway is ca. 40% with cyclopropanediazonium ions, but less than 20% with alkenediazonium ions, as shown by a comparison of α- and β- 15N labeled diazonium ions. No coupling occurs with diazonium groups at sp3 hybridized carbons, including bicyclo[2.2.1]heptane-1-diazonium ions (2). Most of them produce alkyl azides by SN1 mechanisms; selectivities indicate some participation of azide ion in the extrusion of nitrogen from primary alkanediazonium ions. Whenever the diazo compounds generated by deprotonation of the diazonium ions are thermally labile, the carbenes thus produced also contribute to the formation of organic azides. Variations in product distribution, 15N content, and deuterium incorporation served to identify this novel mechanism.
    Notes: Die Reaktionen aliphatischer Diazonium-Ionen mit Lithiumazid in Methanol zu organischen Aziden verlaufen nach unterschiedlichen Mechanismen. Für Cyclopropan- und Alkendiazonium-Ionen wurde Azokupplung mit Hilfe von 15N-Markierung eindeutig nachgewiesen. Der Pentazol-Anteil an der Kupplungsreaktion beträgt ca. 40% bei Cyclopropandiazonium-Ionen, dagegen ≤ 20% bei Alkendiazonium-Ionen, wie aus dem Vergleich α- und β-15N-markierter Diazonium-Ionen hervorgeht. Diazoniumgruppen an sp3-hybridisiertem Kohlenstoff zeigen keine Kupplung, auch nicht Bicyclo[2.2.1]heptan-1-diazonium-Ionen (2). Aus ihnen entstehen Alkylazide meist nach einem SN1-Mechanismus; Selektivitätsuntersuchungen weisen auf die Beteiligung des Azid-Ions an der Stickstoffabspaltung aus primären Alkandiazonium-Ionen hin. Wenn die Deprotonierung der Diazonium-Ionen zu thermisch labilen Diazoverbindungen führt, tragen die so erzeugten Carbene ebenfalls zur Bildung organischer Azide bei. Veränderungen in der Produkt-verteilung, im 15N-Gehalt und im Deuterium-Einbau dienten zum Nachweis dieses neuartigen Mechanismus.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2190-2196 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Bifunctional Mercaptanes and Selenomercaptanes with Phosphine-coordinated d8-Metal DichloridesPhosphine-coordinated d8-metal dichlorides (7, 8, and 9) react with bifunctional mercaptanes (1 and 2) and selenomercaptanes (3 and 4) in benzene to form airstabel phosphine-coordinated six-membered ring molecules (10-21). IR, Raman, and 1H-NMR spectra as well as physical and chemical properties of the new coordination compounds are reported. Bis(selenylmethyl) sulfide (4) is described for the first time.
    Notes: Phosphan-komplexiete d8-Metallchloride (7, 8 und 9) reagieren mit bifunktionellen Mercaptanen (1 und 2) und Selenomercaptanen (3 und 4) in Benzol unter Bildung luftstabiler phosphan-komplexierter Sechsringe (10-21). IR-, Raman- und 1H-NRM-Daten sowie physikalische und chemische Eigenschaften der neuen Komplexe werden mitgeteilt. Bis (selenylmethyl)sulfid (4) wird erstmals beschrieben.
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2197-2208 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Synthesis of Fluoranthenes and Related Aromatic Polycycles by Means of Pyridinium SaltsBenzyl-and fluorenylpyridinium- and isoquinolinium salts 1, 7, 8 react with activated alkenes (2) to yield tetrahydroindolizines (3, 9, 10), which easily undergo ring-opening with acids forming cyclimonium salts (4, 11, 12). These salts, which may be isolated in some cases, may be regarded as masked β,γ-unsaturated ketones. The tetrahydroindolizines and their subsequent products are cyclised with zinc chloride to compounds like substituted naphthalenes, fluoranthenes, and higher aromatic polycycles 15 not described before.
    Notes: Benzyl- und Fluorenylpyridinium- sowie -isochinoliniumsalze 1, 7, 8 geben mit Verbindungen mit aktivierter Doppelbindung (2) Tetrahydroindolizine (3, 9, 10), die mit Säuren leicht den Fünfring zu Pyridinium-(Isochinlinium-)-Salzen (4, 11, 12) öffnen. Diese Salze, die sich in bestimmten Fällen isolieren lassen, kann man als verkappte β, γ-ungesättigte Ketone auffassen, in die sie in der Fluorenreihe auch übergehen. Die Tetrahydroindolizine und ihre Folgeprodukte können mit Zinkchlorid, meistens glatt, zu substituierten Naphthalinen, Fluoranthenen und höheren, bisher nicht bekannten, aromatischen Polycylen 15 ringgeschlossen werden.
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2209-2219 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diels-Alder Reactions of 2,3-Bis(trimethylsilyloxy)1,3-dienesDiels-Alder reactions of 2,3-bis(trimethylsilyloxy)-1,3-dienes 2, 3 and 4 with a number of dienophiles afford the desired cycloadducts 7-11, 13-16, and 20-23 containing a 1,2-bis(trimethylsilyloxy)-alkene function which can be transformed in a variety of ways. For example, they react with bromine under mild conditions to form 1,2-diketones. The method is complementary to Scharf's cycloadditions of dichlorovinylene carbonate.
    Notes: Diels-Alder-Reaktionen von 2,3-Bis (trimethylsilyloxy)-1,3-dienen 2, 3 und 4 mit einer Reihe von Dienophilen liefern die gewünschten Cycloaddukte 7-11, 13-16 und 20-23, die eine abwandelbare 1,2-Bis(trimethylsilyloxy) ethylen-Funktion enthalten. Sie lassen sich z. B. unter milden Bedingungen mit Brom glatt in 1,2-Diketoverbindungen überführen. Die Methode ist komplementär zu den von Scharf beschriebenen Cycloadditionen mit Dichlorvinylencarbonat.
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 890-898 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structure and Internal Flexibility of Sterically Fixed s-cis-ButadienesForce Field Calculations yield a coplanar arrangement of the π systems of the vicinal exo-methylene derivatives 1 and 2 of cyclobutane and cyclopentane and of the corresponding derivatives 4-7 of norbornane, bicyclooctane, bicyclononane and bicyclooctene. The detailed geometry of the cis-butadiene unit is essentially determined by the ring system. For the cyclohexane derivative 3 on the other hand a chair conformation is obtained. 2,5 and 6 are rather flexible molecules for which torsions of the π system up to 20° require energies less than 5 kJ/mol, whereas for the more rigid systems 1, 4 and 7 approximately 10 kJ/mol are necessary for twisting the π system by 10°.
    Notes: Kraftfeldrechnungen ergeben für die vicinalen exo-Methylenderivate 1 und 2 des Cyclobutans und des Cyclopentans sowie für die entsprechenden Derivate 4-7 des Norbornans, Bicyclooctans, Bicyclononans und des Bicyclooctens eine planare Anordnung des π-Systems. Dessen genaue Geometrie im wesentlichen durch das cyclische Gerüst bestimmt wird. Das Cyclohexanderivat 3 dagegen liegt in einer Sesselform vor. Die Moleküle 2, 5 und 6 zeichnen sich durch große Flexibilität aus, Torsionen des π-Systems bis etwa 20° erfordern Energien von weniger als 5 kJ/mol, während für die starreren Systeme 1,4 und 7 bereits bei Verdrillungen um 10° etwa 10 kJ/mol erforderlich sind.
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  • 69
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 899-907 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ligand Structure and Complexation, XLIV. Synthesis and Selectivity of New Four-Armed Noncyclic Neutral LigandsNew, noncyclic neutral ligand systems 4-6 and 8-11 of the tetrapode type 3, equipped with various end groups, were synthesized. The cation selectivity depends on the structure of the end groups. The potentiometrically determined values of the complex stability constants as a rule lie between those of the analogous tripode (2) and dipode ligands (1). Numerous complexes between the four-armed complexing agents and several dipodands (14-16) and alkali and alkaline earth metal salts are reported.
    Notes: Neue nichtcyclische Neutralligandsysteme 4-6 und 8-11 vom Tetrapodentyp 3 mit verschiedenen Endgruppen wurden synthetisiert. Die Kation-Selektivität hängt von der Endgruppenstruktur ab. Die potentiometrisch bestimmten Komplexstabilitätskonstanten liegen i. a. zwischen denjenigen der Tripoden- (2) und Dipoden-Liganden (1). Zahlreiche kristalline Komplexe der vierarmigen Komplexbildner sowie einiger zum Vergleich synthetisierter neuer Dipodanden (14-16) mit Alkali- und Erdalkalimetallsalzen wurden erhalten.
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  • 70
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 950-956 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Mechanism of the Photolytic Reaction of Pyridine with Bis(trimethylsilyl)mercury, a Contribution to the Photochemistry with Metal AlkylsThe photolytic generation of N-(trimethylsilyl)pyridinyls 2 or. resp., their 4,4′-dimers from pyridine or its alkyl derivatives and bis(trimethylsilyl)mercury (1) involves surprisingly no free silyl radicals, but passes a long-lived, photoexcited, polar state 1a of the molecule 1. The latter is described more closely. It is complexed stepwise by two molecules of pyridine, and only in the last step free radicals are formed. The possibly more general importance of these findings for photolytic reactions with metal alkyls is pointed out.
    Notes: Die photolytische Bildung von W-(Trimethylsilyl)pyridinylen 2 bzw. ihren 4.4′-Dimeren. aus Pyridin bzw. seinen Alkylverbindungen und Bis(trimethylsilyl)quecksilber (1) verläuft überraschenderweise nicht über freie Silyl-Radikale, sondern über einen längerlebigen, photoangeregten, polaren Zustand la des Moleküls 1, über den nähere Aussagen gemacht werden. Er wird schrittweise durch zwei Moleküle Pyridin komplexiert, worauf erst im letzten Schritt freie Radikale entstehen. Auf die mögliche Bedeutung der Befunde für andere photolytische Reaktionen mit Metallalkylen wird hingewiesen.
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  • 71
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metabolic Products of Microorganism, 172. Isolation of the Antibiotic semi-Vioxanthin from Penicillium citreo-viride and Synthesis of XanthomegninBesides xanthomegnin (16 b), 3,4-dehydroxanthomegnin (29a), viomellein (23) and vioxanthin (3) from Penicillium citreo-viride under different culture conditions semi-vioxanthin (7) was isolated. Structure 7 has been established by its spectra and the fact that oxidation with Fremy's salt gives 3,4,6,9-tetrahydro-10-hydroxy-7-methoxy-3-methyl-1,6,9-trioxo-1H-naphtho[2,3-c]pyran (9a = semi-xanthomegnin). -9c, prepared by demethylation of 9a, was dimerized by potassium peroxydisulfate/sodium hydroxide and methylated, giving 16b. Synthetic 16b and authentic xanthomegnin were identical, which verifies the structure revised by Höfle and Röser9) and shows, that the dyes of the xanthomegnin series are biogenetically homogenous. - The metabolic products of the strain inhibit the growth of bacteria. 16b and 26 furthermore have an effect against insects.
    Notes: Neben Xanthomegnin (16b), 3,4-Dehydroxanthomegnin (29 a), Viomellein (23) und Vioxanthin (3) wurde aus Penicillium citreo-viride unter veränderten Kulturbedingungen semi-Vioxanthin (7) isoliert. Konstitution 7 folgt aus den Spektren und dem Befund, daß mit Fremy-Salz 3,4,6,9-Tetrahydro-10-hydroxy-7-methoxy-3-methyl-1,6,9-trioxo-1H-naphtho[2.3-c]pyran (9a = semi-Xanthomegnin) entsteht. - Das durch Entmethylierung von 9a zugängliche 9c ließ sich mit Kaliumpersulfat/Natriumhydroxid zu 16a dimerisieren, das zu 16b methyliert wurde. Synthetisches 16b war mit nativem Xanthomegnin identisch, was die von Höfle und Röser9) revidierte Konstitution bestätigt und beweist, daß die Farbstoffe der Xanthomegnin-Reihe biogenetisch einheitlich sind. - Die Stoffwechselprodukte des Stammes hemmen das Wachstum von Bakterien, 16b und 23 wirken ferner gegen Insekten.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 979-989 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Microbial Transformations of Steroids XVI. Synthesis of 11β,21-Dihydroxy-6, 16α-dimethyl-1,4,6-pregnatriene-3,20-dione and of its 11-Keto Compound21-Acetoxy-5α,6α-epoxy-3β-hydroxy-6β16α-dimethyl-20-pregnanone (3a), prepared from 3β-hydroxy-6, 16α-dimethyl-5-pregnen-20-one (1) by epoxidation and chemical introduction of the 21-acetoxy group, was oxidized to 6α,21-dihydroxy-6β,16α-dimethyl-4-pregnene-3,20-dione (4) by Flavobacterium dehydrogenans and dehydrated to the 3-keto-4,6-diene 5. The 11β-hydroxy group was introduced by Curvularia lunata to give 6, and the 11α-hydroxy group by Aspergillus ochraceus to yield 8. Both compounds were dehydrogenated with Bacillus lentus to from 7 and 9. The 11α-hydroxy compound 9 was selectively acetylated to 10, which was oxidize to 11. This on saponification yielded 12.
    Notes: 21-Acetoxy-5α,6α-epoxy-3β-hydroxy-6β,16α-dimethyl-20-pregnanon (3a), dargestellt aus 3β-Hydroxy-6, 16α-dimethyl-5-pregnen-20-on (1) durch Epoxidierung und 21-Acetoxylierung, wurde mit Flavobacterium dehydrogenans zu 6α,21-Dihydroxy-6β, 16α, -dimethyl-4-pregnen-3,20-dion (4) oxidiert und zu 21-Hydroxy-6, 16α-dimethyl-4,6-pregnadien-3,20-dion (5) dehydratisiert. Mit Curvularia lunata wurde die 11β-Hydroxygruppe eingeführt zu 6, während Aspergillus ochraceus die entsprechende 11α-Hydroxyverbindung 8 ergab. Beide Verbindungen wurden mit Bacillus lentus zu 7 bzw. 9 dehydriert. Die 11α-Hydroxyverbindung 9 wurde nach selektiver Acetylierung der 21-Hydroxygruppe zu 10 zum 11-Keton 11 oxidiert, dessen Verseifung 12 ergab.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2380-2388 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On 2-tert-Butyl-l,3,2λ5-dioxaphospholanes and 2-tert-Butyl-1,2λ5-oxaphosphetanesOxidative addition of hexafluoroacetone to the phosphorus(III) compounds 1c-g furnished the 1,3,2λ5-dioxaphospholanes 2c, 2d, 2f, 2g, and the 1,2λ5-oxaphosphetane 3, respectively; 2d undergoes thermal rearrangement to the corresponding l,2λ5-oxaphosphetane 4. The phospholes 5 and 6 are formed from hexafluorobiacetyl with phosphinous acid esters. 19F NMR spectroscopy was employed to investigate dynamic effects in the compounds obtained. For the phosphorane 2 c magnetic nonequivalence of the CF3 groups of the dioxaphospholane ring system as well as of those of the (CF3)2CHO group was observed. The related compounds 7-9 were studied for comparison, and the influence of the bulky tert-butyl groups at phosphorus was investigated.
    Notes: Durch oxidative Addition von Hexafluoraceton an die Phosphor(III)-Verbindungen 1c-g werden die 1,3,2λ5-Dioxaphospholane 2c, 2d, 2f und 2g bzw. das 1,2λ5-Oxaphosphetan 3 gebildet; 2d lagert sich thermisch in das entsprechende 1,2λ5-Oxaphosphetan 4 um. Die Phosphole 5 und 6 entstehen aus Hexafluorbiacetyl und Phosphinigsäureestern. Mit Hilfe der 19 F-NMR-Spektroskopie wurden dynamische Effekte untersucht. Bei dem Phosphoran 2c tritt magnetische Nichtäquivalenz sowohl der CF3-Gruppen des Dioxaphospholan-Ringsystems als auch der des (CF3)2CHO-Restes auf. Die analogen Verbindungen 7-9 wurden zur vergleichenden Betrachtung herangezogen und der Einfluß der raumerfüllenden tert-Butylgruppe am Phosphor studiert.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2402-2412 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Applications of Phase Transfer Catalysis, II. Synthesis of 2-Dihalogenomethyl-1,3-dioxolanes and 2-Dihalogenomethyl-1,3-dioxanes2-Substituted 1,3-dioxolanes 1a-35a react with dichlorocarbene generated by phase transfer catalysis via selective C(2)-H-insertion giving the 2-dichloromethyl-1,3-dioxolanes 1b-24b. and 26b-35b. In the same way the 2-dichloromethyl-1,3-dioxanes le, 2e, 4e-6e,12e, 26e, and 30e and the 2-dibromomethyl-1,3-dioxolanes 1c, 2c, 4c-6c, 12c, 26c, 28c, and 30c are prepared.
    Notes: 2-Substituierte 1,3-Dioxolane 1a-35a reagieren mit durch Phasentransfer-Katalyse erzeugtem Dichlorcarben unter selektiver C(2)-H-Insertion zu den 2-Dichlormethyl-1,3-dioxolanen 1b-24b und 26b-35b. Ebenso entstehen die 2-Dichlormethyl-1,3-dioxane 1e, 2e, 4e-6e, 12e, 26e und 30e und die 2-Dibrommethyl-1,3-dioxolane lc, 2c, 4c-6c, 12c, 26c, 28c und 30c.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2413-2418 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Molecular Structure of a Metal Cluster with Cubane Structure, [η5-C5H5Mo(CO)3HgMo]4(4)The compound [η5-C5H5Mo(CO)3HgMo]4 has been isolated as an additional product of the reaction between [η5-C5H5Mo(CO)3]2, 2-butenyl chloride, and sodium amalgam. The X-ray structure (R = 0·050) analysis of this novel species revealed that the compound has a slightly distorted cubane structure, for the first time the cubane unit being built up by two different metal atoms (Mo and Hg).
    Notes: Die Verbindung [η5-C5H5Mo(CO)3HgMo]4 (4) wurde als weiteres Produkt der Reaktion zwischen [η5-C5H5Mo(CO)3]2, 2-Butenylchlorid und Natriumamalgam isoliert. Die Röntgenstrukturanalyse dieser neuartigen Spezies zeigt eine leicht verzerrte Cubanstruktur, bei der das Cubangerüst erstmals aus zwei verschiedenen Metallatomen (Mo und Hg) aufgebaut ist. Der R-Wert beträgt 0·050.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2436-2443 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of α-Halogen Sulfides with Antimony PentachlorideContrary to reports in the literature 5-7), the carbenium salts 2 and 3 are not obtained from antimony pentachloride and chloromethyl methyl sulfide or dichloromethyl methyl sulfide; instead, the reaction leads to the chlorosulfonium salts 8 and 11. On the other hand trichloromethyl methyl sulfide is indeed converted into the carbenium salt 4 by treatment with antimony pentachloride 7). The structures of 8, 11, and 4 are confirmed by analytical and spectroscopic data as well as by the reaction of the isolated compounds with dimethyl sulfide and triphenylphosphane. The carbenium ion 3 may be generated in solution around - 30°C and characterized as a mixture of E/Z isomers by 13C NMR spectroscopy.
    Notes: Die Reaktion von Antimonpentachlorid mit (Chlormethyl)methylsulfid und (Dichlormethyl)-methylsulfid führt entgegen den Literaturangaben5-7) nicht zu den Carbeniumsalzen 2 und 3, sondern zu den Chlorsulfoniumsalzen 8 und 11. Die analoge Umsetzung von Antimonpentachlorid mit (Trichlormethyl)methylsulfid liefert hingegen das Carbeniumsalz 47). Reaktionen mit Dimethylsulfid und Triphenylphosphan stützen die analytisch und spektroskopisch abgeleiteten Konstitutionen von 8,11 und 4. Das Carbenium-Ion 3 läßt sich in Lösung bei etwa - 30°C erzeugen und im 13C-NMR-Spektrum als Gemisch von E/Z-Isomeren charakterisieren.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2444-2452 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Investigation of the Magnetic Properties of 2,6-Bis(triphenylphosphoranylidenamino)phenols and the Corresponding AroxylsThe synthesis of the 4-alkyl-2.6-bis(phosphoranylidenamino)phenols 1-3 from 4-alkyl-2.6-diaminophenols and dibromotriphenylphosphorane is described. The 31P NMR spectra of the compounds investigated show three different phosphorus nuclei. The intensities of these signals are temperature-dependent, and therefore an iminophosphorane-benzoxazaphospholine equilibrium is indicated. The oxidation of the phenols 1-3 in solution leads to the corresponding phenoxyls 1a-3a. The ESR and ENDOR spectra are interpreted in terms of an interaction of the free electron with two equivalent phosphorus nuclei. From the temperature dependence of the phosphorus coupling constants a planar low temperature conformation for the o-(phosphoranylidenamino)-phenoxyls is concluded.
    Notes: De Synthese der 4-Alkyl-2,6-bis (phosphoranylidenamino)phenole 1-3 aus 4-Alkyl-2,6-diamino-phenolen und Dibromtriphenylphosphoran wird beschrieben. Die 31P-NMR-Spektren von 1-3 zeigen jeweils drei nichtäquivalente Phosphorkerne. Die Intensitäten der Signale sind temperatur-abhängig, so daß auch für diese Verbindungen ein Iminophosphoran-Benzoxazaphospholin-Gleichgewicht nachgewiesen wird. Die Phenole 1-3 lassen sich in Lösung zu den entsprechenden Phenoxylen 1a-3a oxidieren. Die ESR- und ENDOR-Spektren zeigen Kopplungen mit jeweils zwei äquivalenten Phosphorkernen. Aus den Temperaturgradienten dieser Phosphoraufspaltungen wird auf eine planare Tieftemperaturkonformation für o-(Phosphoranylidenamino)phenoxyle geschlossen.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2472-2480 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Reversible Rearrangement of the trans-Erythrinane Ring System, I. First Observation and Attempt of an InterpretationThe „diolA“ (1) with trans-erythrinane structure has an unusual reactivity, compared with „diol B“ (3) which belongs to the cis- series. On acetylation, 1 yields the diacetate 17 due to a rearrangement. Hydrolysis of 17 regenerates the starting material 1. Structures 1a and 17a illustrate the stereochemistry of the reversible rearrangement. The ring-enlargement of 1 to 17 is seen in the 1 H-NMR spectra by a characteristic high-field shift of the signal of the aromatic proton at C-14.
    Notes: „Diol A“ 1 der trans-Erythrinan-Reihe zeigt im Gegensatz zu „Diol B“ 3 der cis-Reihe ein ungewöhnliches Verhalten. Durch Acetylierung entsteht unter Umlagerung des Ringsystems das Diacetat 17, dessen Verseifung wieder zum Ausgangsmaterial 1 zurückführt. Die Stereochemie der umkehrbaren Gerüstumlagerung zeigen die Formeln 1a und 17a. Die Ringerweiterung zu 17 erkennt man im 1 H-NMR-Spektrum an der charakteristischen Hochfeldverschiebung des Signals für das aromatische Proton an C-14.
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  • 79
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    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, C Radical Ions, XXXI. NMR and ESR Spectroscopic Investigations on Five- and Six-membered B/N-Heterocycles3)B/N-Heterocycles with a B2N3, ring skeleton contain 6 π electrons, form preferentially on reaction of bifunctional boron compounds RBX2 with monoalkylhydrazines, and possess planar structures according to NMR spectroscopic investigations. In contrast, tetraazadiboracyclohexane derivatives RB(NR-NR)2BR with 8 π electrons exhibit a twist conformation. - One-electron oxidation of the isomeric five- and six-membered B/N-heterocycles R2N-N(BR-NR-)2 and RB(NR-NR)2, BR using A1C13 in H2CCl2 yield each the dark-blue, thermodynamically favored radical cation RB(NR-NR)2BR⊕, which as a presumably planar 7 π-electron system is iso-π-electronic to benzene radical anions. Its high-resolution ESR spectrum has been assigned by simulation as well as ENDOR measurements, and shows as sets of equivalent nuclei 4N, 12H, and 2 B. In accord with MO arguments the spin density concentrates predominantly on the nitrogen atoms, while the boron atoms are located in π-nodal planes and the NR-NR⊕-bridges have been levelled.
    Notes: B/N-Heterocyclen mit B2N3-Fünfring-Gerüst enthalten 6 π-Elektronen, entstehen bei Umsetzung bifunktioneller Borverbindungen RBX2 mit Monoalkylhydrazinen bevorzugt und sind nach NMR-Untersuchungen planar. Demgegenüber weisen Tetraaza-dibora-cyclohexan-Derivate RB(NR-NR)2BR mit 8 πN-Elektronen eine „Twist“-Konformation auf. - Einelektronen-Oxidation der isomeren Fünfring- und Sechsring-B/N-Heterocyclen R2N-N(BR-NR-)2 und RB(NR-NR)2BR mit A1C13 in H2CC12 führt jeweils zum dunkelblauen, bei Raumtemperatur stabilen Radikalkation RB(NR-NR)2BR⊕, das als vermutlich planares 7 π-Elektronensystem mit Benzol-Radikalanionen iso-π-elektronisch ist. Sein hochaufgelöstes und durch Simulation sowie ENDOR-Messungen zugeordnetes ESR-Spektrum zeigt als Sätze äquivalenter Kerne 4N, 12H und 2B. Im Einklang mit MO-Argumenten konzentriert sich die Spindichte überwiegend an den N-Atomen, die B-Atome liegen in π-Knotenflächen, und die NR-NR⊕-Brücken sind eingeebnet.
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  • 80
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2539-2551 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 14-Alkyl-substituted Morphine DerivativesClaisen-Eschenmoser rearrangement of 1 resulted in the generation of the amide 2b, which is reduced by LiAlH4 to 14-[2-(dimethylamino)ethyl]codeinone acetal 2d. Treatment with CH3I leads to 14,17-ethanonorcodeinone acetal methoiodide 4a, which undergoes LiBEt3H-reduction to give 14-ethylcodeinone acetal 2g. This is transformed into a number of derivatives of pharmacological interest. Moreover the absolute configuration at C-14 of the known 14-methyldihydrocodeinone as well as of its precursors and derivatives is proved.
    Notes: Durch Claisen-Eschenmoser-Umlagerung von 1 erhält man 2b, das mit LiAlH4 in das 14-[2-(Dimethylamino)ethyl]codeinon-acetal 2d übergeführt werden kann. Daraus entsteht mit CH3I das 14,17-Ethanonorcodeinon-acetal-methoiodid 4a, das durch Reduktion mit LiBEt3H in sehr guter Ausbeute das 14-Ethylcodeinon-acetal 2g liefert, von dem eine Anzahl von Derivaten mit pharmakologischer Bedeutung synthetisiert wurden. Darüber hinaus wird der Beweis für die Absolutkonfiguration an C-14 des schon früher beschriebenen 14-Methyldihydrocodeinons sowie von dessen Vorstufen und Derivaten erbracht.
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  • 81
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbyne Complexes, XLVII. IR and Raman Spectroscopic Investigations of trans-Halogenotetracarbonyl(methylcarbyne)tungsten ComplexesIR spectra in the range from 2200 to 300 cm -1and Raman spectra in the range of 2200 to 50 cm -1of the carbyne complexes trans-Cl(CO)4W ≡ C-CH3 (1), trans-Br(CO)4W ≡ C-CH3 (2), trans-I(CO)4W ≡ C-CH3 (3) and of the deuterated compound trans-Br(CO)4 W ≡ C-CD3(2a) have been investigated and the bands have been assigned. The attribution is proved by a preliminary normal coordinate analysis.
    Notes: Die IR-Spektren im Bereich von 2200 bis 300 cm -1und Ramanspektren im Bereich von 2200 bis 50 cm-1wurden von den Carbinkomplexen trans-Cl(CO)4W ≡C-CH3 (1), trans-Br(CO)4W ≡ C-CH3 (2), trans-I(CO)4W≡C-CH3 (3) sowie der deuterierten Verbindung trans-Br(CO)4W≡C-CD3 (2a) untersucht und die Banden zugeordnet. Die Zuordnung konnte durch eine vorläufige Normalkoordinatenanalyse in wichtigen Punkten bestätigt werden.
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  • 82
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2680-2691 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Partial Synthesis of (25R)-26-Aminocholesterol and (25R)-26-Amino-5-cholestene-3β,16β -diol from DiosgeninDiosgenin acetate (1b) was converted via (25R)-5-cholestene-3β, 16β,26-triol (2a) to (25R)-5-cholestene-3β,26-diol (4a). From 4a and 2a (25R)-26-aminocholesterol (5d) and (25R)-26-amino-5-cholestene-3β,16β-diol (6e) were prepared via the tosyl-, iodo-, and phthalimido derivatives. Selective acetylation of 5d and 6e yielded the 26-(acetylamino)cholesterols 5e and 6f. The mass spectra of the amino- and (acetylamino)cholesterols are discussed.
    Notes: Diosgenin-acetat (1 b) wurde über (25R)-5-Cholesten-3β,16β,26-triol (2a) zu (25R)-5-Cholesten-3β,26-diol (4a) umgesetzt. Aus 4a und 2a wurden (25R)-26-Aminocholesterol (5d) und (25R)-26-Amino-5-cholesten-3β,16β-diol (6e) über die Tosyl-, Iod- und Phthalimido-Derivate dargestellt. Selektive Acetylierung von 5d und 6e ergab die 26-(Acetylamino)cholesterole 5e und 6f. Die Massenspektren der Amino- und (Acetylamino)cholesterole werden diskutiert.
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  • 83
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2709-2717 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Phosphorus Ylides with Transition Metal Compounds, VII. Nitrile Complexes of the Type (CO)5CrL, Synthesis and Reaction with MethylenetriphenylphosphoranePentacarbonyl(tetrahydrofuran)chromium(0) reacts with nitriles to yield the stable (CO)5CrNCR complexes 1 -12. Depending on the substituent R, their reactions with (C6H5)3P=CH2 lead to substitution of the nitrile ligand with formation of the known complex (CO)5C̄r-CH2=(C6H5)3 or to nucleophilic attack on the nitrile carbon to yield the new ketimine complexes (CO)5CrNH = CR=CH = P(C6H5)3 (14-21) which exist as cis and trans isomers. All complexes are characterized by their IR and NMR spectra. The reaction of the ketimine complex 14 (R = CH3) with HBF4 yields cis- and trans=[(C6H5)3P=CH = C(NH2)CH3]BF4 (22).
    Notes: Pentacarbonyl(tetrahydrofuran)chrom(0) reagiert mit Nitrilen zu den stabilen (CO)5CrNCR-Komplexen 1-12. Ihre Reaktion mit (C6H5)3P = CH2 führt in Abhängigkeit von dem Substituenten R entweder zu einer Verdrängung des Nitrilliganden unter Bildung von (CO)5C̄r-CH2=(C6H5)3 oder zu einem nucleophilen Angriff am Nitrilkohlenstoff unter Bildung der neu-artigen Ketiminkomplexe (CO)5CrNH = CR=CH = P(C6H5)3 (14-21), die jeweils als cis- und trans-Isomere auftreten. Alle Komplexe werden anhand ihrer Spektren sowie analytisch charakterisiert. Die Reaktion des Ketiminkomplexes 14 (R = CH3) mit HBF4 führt zu cis- und trans-[(C6H5)3P=CH = C(NH2)CH3]BF4 (22).
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3293-3301 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Lewis Acids, 331) The Photochemistry of Cyclic Acylals of Alkylidene-, Alkenylidene-, and Benzylidenemalonic AcidsThe photochemistry of the title compounds 1 resembles that of α,β-unsaturated esters. Observed reactions include deconjugation (→ 2), β, δ-cyclopropane ring closure(→ 4), and [2 + 2]-cycloaddition (→ 5, 7, 8) as well as ene-type addition to olefins (→ 9). Reaction mechanism and preparative aspects are discussed.
    Notes: Die Photochemie der Titelverbindungen 1 entspricht der von α,β-ungesättigten Estern: Dekonjugation zu 2, β,δ-Cyclopropanbildung (→ 4) und [2 + 2]-Cycloaddition (→ 5, 7, 8) sowie substituierende Addition an Olefine (→ 9) Reaktionsmechanismus und präparative Aspekte werden diskutiert.
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  • 85
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3390-3412 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactivity of Metal-Metal Bonds. Repeated Formation and Cleavage of a Fe - Co Bond by Elimination and AdditionIn arsenic-bridged dinuclear metal carbonyl complexes the sequence of formation and cleavage of the metal-metal bond by elimination of CO and addition of a phosphine ligand is repeatable. Starting from (CO)4Fe -AsMe2 - Co(CO)4 it can be performed four times in a row. The ligand which in each case is introduced at the cobalt atom can be transferred to the iron atom by isomerisation in complexes with and without metal-metal bonds. With Pme3 and P(OMe)3 as phosphines and up to the introduction of three ligands thus 44 different complexes are possible of which 35 were isolated (scheme 1). By side reactions or for the purpose of comparisons further complexes with chain-like arrangements of metal and P or As atoms were obtained. When four ligands are introduced the elimination/addition scheme reaches a natural limit since then phosphine elimination is preferred to CO elimination. The described sequences can be understood as basic patterns of catalytic activity by opening of metal-metal bonds.
    Notes: In arsenverbrückten Metallcarbonyl-Zweikernkomplexen ist die Sequenz von Bildung und Lösung der Metall-Metall-Bindung durch Eliminierung von CO und Addition eines Phosphanliganden wiederholbar. Ausgehend von (CO)4Fe-AsMe2-Co(CO)4 läßt sie sich viermal hintereinander durchführen. Der jeweils am Cobaltatom eingeführte Ligand kann in Komplexen mit und ohne Metall-Metall-Bindung durch Isomerisierung auch auf das Eisenatom übertragen werden. Mit PME3 und P(OMe)3 als Phosphanen sind so bis zur Einführung von drei Liganden 44 verschiedene Komplexe denkbar, von denen 35 isoliert wurden (Schema 1). Durch Nebenreaktionen bzw. zu Vergleichszwecken wurden weitere Komplexe mit kettenförmiger Anordnung von Metall- und P- bzw. As-Atomen erhalten. Nach der Einführung von vier Liganden findet das Eliminierungs/ Additions-Schema eine natürliche Grenze, da dann Phosphan-Eliminierung gegenüber der CO-Eliminierung bevorzugt wird. Die beschriebenen Sequenzen lassen sich als Grundmuster katalytischer Aktivität durch Öffnung von Metall-Metall-Bindungen verstehen.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3413-3423 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Carbamoyliron Complexes;. Crystal Structure of Nickelbis[tetracarbonyi-μ-(dimethylcarbamoyl-O)-iron](2M-Fe)The carbamoyl complex 1 can be transaminated with piperidine and pyrrolidine to give 2 and 3. 1-3 react with anhydrous nickel bromide to yield the nickelbis[tetracarbonyl-μ-(carbamoyl-O)-iron] (2 Ni-Fe) complexes 4-6, which are studied by spectroscopic methods. The X-ray analysis proves a linear iron nickel iron spine in 4. The crystals are triclinic, space group PT, with one molecule in the unit cell.
    Notes: Der Carbamoylkomplex 1 läßt sich mit Pyrrolidin und Piperidin zu 2 und 3 umaminieren. 1-3 reagieren mit wasserfreiem Nickelbromid zu den Nickelbis[tetracarbonyl-μ-(carbamoyl-0)-eisen](2N - Fei)-Komplexen 4-6, die spektroskopisch untersucht werden. Die Röntgenstrukturanalyse von 4 beweist das Vorliegen einer linearen Eisen-Nickel-Eisen-Anordnung. Die Kristalle sind triklin, Raumgruppe PT, mit einem Molekül in der Elementarzelle.
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  • 87
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complex Chemistry of Polyfunctional Ligands, 511) About Halogeno- and Pseudohalogeno-manganese(I)-carbonyl Complexes of the TritertiaryPhosphane 1,1,1 -Tris[(diphenylphosphino)methyl]ethane [Mn+1(CO)3(R2PCH2)3CCH3][Mn-1(CO)5] (R = C6H5) (2) reacts with aqueous HX (X = Cl, Br, I) to give [Mn(CO)3(R2PCH2)3CCH3]X (4a-c). 4a undergoes metathesis with NaN3 to yield 4d (X = N3). On ultraviolet irradiation the ionic 4a-d rearrange to the nonionic, monomeric complexes XMn(CO)3(R2PCH2)2C(CH3)CH2PR2 (5a-d). 5e (X = NCO) is obtained from the reaction of [Mn(CO)3(R2PCH2)3CCH3]Y (Y = Clo4, BR4) (3a, b) with KOCN under UV irradiation. The potentially tridentate ligand CH3C(CH2PR2)3 (1) serves in 5 as a bidentate monometallic ligand. Boiling of 5a-e in acetone leads to CO elimination and formation of XMn(CO)2(R2PCH2)3CCH3 (6a-e). These compounds arc more easily obtained by the direct reaction of 3a, b with alkali metal halides and pseudohalides MX (M = Na, K, X = Cl, Br, I, N3, NCO) on ultraviolet irradiation in methyl alcohol. The new complexes have been characterized by conductimetry and spectroscopy.
    Notes: [Mn+1(CO)3(R2PCH2)3CCH3][Mn-1(CO)5] (R = C6H5) (2) setzt sich mit HX in wäßriger Lösung (X = Cl, Br, I) zu [Mn(CO)3(R2PCH2)3CCH3]X (4a-c) um. 4a reagiert mit NaN3 unter Metathese zu 4d (X = N3). Bei der Bestrahlung mit UV-Licht lagern sich die ionischen Komplexe 4a - d in die nicht ionischen, monomeren Komplexe XMn(CO)3(R2PCH2)2C(CH3)CH2PR2 (5a-d) um. 5e (X = NCO) erhält man durch Umsetzung von [Mn(CO)3,(R2PCH2)3CCH3,]Y (Y = C1O4, BR4) (3a, b) mit KOCN bei UV-Bestrahlung. Der potentiell dreizahnige Ligand CH3C(CH2PR2)3 (1) wirkt in 5 lediglich zweifachkoordinierend monometallisch. Erhitzt man 5a-c in Aceton, so entstehen unter Eliminierung von CO XMn(CO)2(R2PCH2)3CCH3 (6a-v). Diese sind einfacher durch direkte Reaktion von 3a, b mit Alkalimetallhalogeniden und -pseudohalogeniden MX (M = Na, K, X = Cl, Br, I, N3. NCO) bei gleichzeitiger UV-Bestrahlung; in Methanol zugänglich. Die Verbindungen wurden durch Leitfähigkeitsmessungen und spektroskopisch charakterisiert.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3480-3485 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,3-Butadiene-2-carboxylic Acids Starting from the Wittig Salt of 2-(Bromomethyl)acrylic AcidThe phosphonium salt 1b from 2-(bromomethyl)acrylic acid (1a) reacts after deprotonation with the aldehydes 3 to give the 4-substituted 1,3-butadiene-2-carboxylic acids, isolated as Z-configurated methyl esters 4.
    Notes: Das Phosphoniumsalz 1b aus 2-(Brommethyl)acrylsäure (1a) reagiert nach Deprotonierung mit den Aldehyden 3 zu 4-substituierten 1,3-Butadien-2-carbonsäuren, die als Z-konfigurierte Methylester 4 isoliert werden.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3490-3514 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1H NMR Shifts in the Molecular Planes of Anisotropic CO, CN, and CC Double BondsSynthetic procedures are given for fluorenes with 2,7- and 1,8-dimethyl as well as 2-fluoro and 2,7-difluoro substituents. Analysis and comparison of the NMR spectra provides evidence of downfield shifts for protons situated in the planes of doubly bonded moieties with reference to compounds devoid of such double bonds. Tetralin and indan derivatives lead to corresponding conclusions. The importance of conjugation and of electric field effects is assessed by protonation studies.
    Notes: Die Synthese von Fluorenderivaten mit 2,7- und 1,8-Dimethyl- sowie 2-Fluor- und 2,7-Difluor-Substituenten wird beschrieben. Durch Analyse und Vergleich ihrer NMR-Spektren zeigt sich, daß 1H-Atomkerne in Doppelbindungsebenen bei geringeren Magnetfeldstärken absorbieren als in Vergleichsverbindungen ohne entsprechende Doppelbindung. Modellverbindungen mit Tetralin- und Indan-Struktur führen zum gleichen Schluß. Die Bedeutung konjugativer Substituenteneinflüsse und elektrischer Feldeffekte wird anhand von Verschiebungsänderungen bei der Protonierung beurteilt.
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  • 90
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3531-3537 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Sulfur-Nitrogen Compounds with Basket StructuresThe reaction of S3N3Cl3(1) with (CH3)2S[NSi(CH3)3]2(2) or N[Sn(CH3)3]3yield the bicyclic compounds 3-6. 6 crystallizes in the monoclinic space group C2/c and has a basket structure with a transannular S - S distance of 242.5 pm. On the basis of the very similar IR spectra we assume the same structure for 5. S4N4Cl2 reacts with 2 to give 5 in a good yield.
    Notes: Die Reaktion von S3N3Cl3(1) mit (CH3)2S[NSi(CH3)3]2(2) oder N[Sn(CH3)3]3ergibt die bicyclischen Verbindungen 3-6. 6 kristallisiert in der monoklinen Raumgruppe C2/c und hat eine korbartige Struktur mit einem transannularen S-S-Abstand von 242.5 pm. Aufgrund der sehr ähnlichen IR-Spektren nehmen wir für 5 die gleiche Struktur an. S4N4CI2reagiert mit 2 in guter Ausbeute zu 5.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3538-3551 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conformation of Peptides, VI. Determination of Intramolecular Hydrogen Bonds in cyclo(-Phe-Gly-Xxx-Val-Ala-) by 1H NMR Spectroscopy.The title compounds with Xxx = Aib (1) and Leu (2) were synthesized and their structures in DMSO were investigated by 1H NMR spectroscopy. From the temperature dependence of the NH proton signals and the changes of chemical shifts on titration with chloroform or trifluoroethanol, we conclude the dominance of a single conformation with two internal oriented NH groups. The evaluation of the NH-CαH coupling constants, combined with model building leads to a conformation with a ßIγ↑ or a γ↑γ↑ structure. The results are compared with the conformation of other cyclic pentapeptides and some general rules are deduced. The structure of a ß-turn (ßI or ßII) is found to be determined by certain amino acids. Amino acids with bulky side chains are mainly to be found in the central position (j + 1) of a γ-turn.
    Notes: Die Titelverbindungen mit Xxx = Aib (1) und Leu (2) wurden synthetisiert und 1H-NMR-Spektroskopisch in DMSO untersucht. Aus der Temperaturabhängigkeit der chemischen Verschiebung der NH-Signale und deren Veränderung bei Zugabe von Chloroform bzw. Trifluorethanol wird auf das Dominieren einer Konformation geschlossen, die zwei interne NH-Orientierungen aufweist. Die Interpretation der NH-C2H-Kopplungen läßt im Zusammenhang mit Modellbetrachtungen nur eine βIγ↑- oder eine γ↑γ↑-Struktur zu. Die Ergebnisse werden den Konformationen anderer Cyclopentapeptide gegenübergestellt und gewisse allgemeine Regeln daraus abgeleitet. So wird die Struktur der β-Schleife (βI oder βII) durch bestimmte Aminosäuren determiniert. Sterisch anspruchsvolle Aminosäuren sind vorwiegend in der mittleren Position (j + 1) einer γ-Schleife zu finden.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1743-1750 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reactivity-Selectivity Principle, 4. Selectivity of Alkyl Radicals in Competition System BrCCl3/CCl4Alkyl radicals were generated from alkylmercuric salts 1 and peresters 4. Their reactions in competition system BrCCl3/CCl4 show that at 273 and 403 K the sequences of radical selectivities are completely reversed. At 273 K the methyl radical is the least selective but at 403 K it is the most selective alkyl radical of table 1. The isoselective temperature lies in the region of 340 K. The reason of this is the opposing influence on activation enthalpies and activation entropies. With increasing alkylation of the radicals, activation enthalpies enlarge but activation entropies reduce the selectivities (table 2). The differences of radical selectivities are governed below the isoselective temperature by variation of activation enthalpies and above the isoselective temperature by variation of activation entropies.
    Notes: Alkyl-Radikale wurden aus Alkylquecksilbersalzen 1 und Perestern 4 erzeugt. Ihre Reaktionen im BrCCl3/CCl4-Konkurrenzsystem zeigen, daß bei 273 und 403 K die Selektivitätsreihenfolge der Radikale einander genau entgegengesetzt ist. Während bei 273 K das Methyl-Radikal das am wenigsten selektive Radikal ist, besitzt es bei 403 K die größte Selektivität aller Alkyl-Radikale der Tab. 1. Die isoselektive Temperatur liegt im Bereich von 340 K Ursache für dieses Verhalten ist der gegenläufige Einfluß auf die Aktivierungsenthalpien und Aktivierungsentropien. Mit zunehmender Alkylierung der Radikale führen die Aktivierungsenthalpien. Zu einer Vergrößerung, die Aktivierungsentropien jedoch zu einer Verkleinerung der Radikalselektivitäten (s. Tab. 2). Unterhalb der isoselektiven Temperatur werden die Unterschiede der Radikalselektivitäten von den Änderungen der Aktivierungsenthalpien, oberhalb der isoselektiven Temperatur von den Änderungen der Aktivierungsentropien bestimmt.
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    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1763-1768 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions involving Hydrogen Transfer, III. Hydrogen-Transfer Between o,o′-Bridged Tetraarylethylenes and DiarylmethanesThermal hydrogen transfer between o,o′-bridged diarylmethanes and o,o′-bridged tetraarylethylenes leads to reduction of the ethylenes and to dimerization and dehydrogenation of the diarylmethanes (equ. (1)-(5)). The ethylene 1 reacts with 9,10-dihydroanthracene (15) to form 3 and anthracene (16)[equ. (6)]. The principles of these reaction are discussed.
    Notes: Bei der thermischen Wasserstoffübertragung zwischen o,o′-überbrückten Diarylmethanen und o,o′-überbrückten Tetraarylethylenen werden die eingesetzten Ethylene hydriert und die Diarylmethane dehydrierend dimerisiert (Gleichungen (1)-(5)). Das Ethylen 1 und 9, 10-Dihydroanthracen (15) liefern nach (6) 3 und Anthracen (16) Die Grundlagen dieser Reaktion werden diskutiert.
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  • 94
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1779-1784 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organometalphosphine-substituted Transition Metal Complexes, XXIV. Organoelement(IVb)-phosphine Derivatives of OctacarbonyldicobaltOctacarbonyldicobalt (1) reacts with (t-C4H9)3P (2), (t-C4H9)2PH (3), [(CH3)3Si]3P (4),[(CH3)3Ge]3P (5) [(CH3)3Sn]3P (6) and (t-C4H9)2[(CH3)3Si]P (7) with displacement of two CO ligands and formation of corresponding hexacarbonyldi(organoelement)IVb)-phosphine)-cobalt complexes. The vibrational and NMR spectra of the new compounds are discussed.
    Notes: Octacarbonyldicobalt (1) reagiert mit (t-C4H9)3P (2), (t-C4H9)2PH (3), [(CH3)3Si]3P (4), [(CH3)3 Ge]3P (5), [(CH3)3Sn]3P (6) und (t-C4H9)2[(CH3)3Si]P (7) unter Abspaltung von zwei CO-Liganden und Bildung entsprechender Hexacarbonyldi(organoelement(IVb)-phosphan)-cobalt-Komplexe. Die Schwingungs- und Kernresonanzspektren der neuen Verbindungen werden diskutiert.
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  • 95
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1769-1778 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thiirenes as Intermediates in the Thermolysis of 1,2,3-ThiadiazolesThermolysis of the isomeric thiadiazoles 1a or 1b in moist 2,2′-oxydiethanol (3) yields the ketone 6, the thiophene 7, the alkyne 8, and the disulfide 11, the structure of which was determined by an X-ray analysis. In the presence of diphenylacetylene (15) 1a and 1b react to give the thiophenes 16a and 16b in the same ratio. This implies that the primary products of thermolysis, the 1,3-diradicals 13, can be trapped by alkynes. The formation of identical thiophenes from isomeric thiadiazoles 1 can be understood in terms of an equilibrium between the primary fragments 13 via the thiirene 14. Similarly, the ketone 6 seems not to result from 8 but from 14.
    Notes: Bei der Thermolyse der stellungsisomeren Thiadiazole 1a oder 1b in feuchtem 2,2′-Oxydiethanol (3) entstehen das Keton 6, das Thiophen 7, das Alkin 8 und das durch eine Röntgenstrukturanalyse eindeutig aufgeklärte dimere Disulfid 11. In Gegenwart von Diphenylacetylen (15) bilden sich aus 1a und 1b die Thiophene 16a und 16b im selben Verhältnis. Die bei der Thermolyse zunächst entstehenden 1,3-Diradikale 13 können demnach durch Alkine abgefangen werden. Die Bildung identischer Thiophene aus isomeren Thiadiazolen 1 läß sich durch ein Gleichgewicht der Primärfragmente 13 verstehen, das sich über das Thiiren 14 einstellt. Auch das Keton 6 scheint nicht aus 8, sondern aus 14 zu entstehen.
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  • 96
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1835-1840 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aromatic Diazonium Salts, IX. The Nα, Nβ-Interchange in Aromatic Diazonium Salts during SolvolysisThe Nα, Nβ-interchange during the solvolysis of [β-15N]benzenediazonium tetrafluoroborate in 2,2,2-trifluoroethanol under N2 was inhibited by less than 4% when the free radical inhibitors bromotrichloromethane, 1,1-diphenylethylene or methyl acrylate were added. Under an air atmosphere the N-inversion was increased by 8%. The main part of the N-inversion under solvolysis conditions is therefore not occurring via reversible addition of phenyl radicals to the diazonium salt.
    Notes: Der Nα, Nβ-Austausch in [β-15N] Benzoldiazonium-tetrafluoroborat bei der Solvolyse in 2,2,2-Trifluorethanol unter N2 wurde durch Zusatz der Radikalinhibitoren Bromtrichlormethan, 1,1-Diphenylethylen und Acrylsäure-methylester nur um maximal 4% erniedrigt. Unter Luftatmosphäre stieg die N-Inversion um 8% an. Eine umkehrbare Addition von Phenyl-Radikalen an das Diazoniumsalz ist daher als Hauptweg der N-Inversion unter Solvolysebedingungen ausgeschlossen.
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  • 97
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1808-1834 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermolabile Hydrocarbons, VIII. Thermolyses of 1,2-Dialkyl,2-diphenylethanesA series of 1,2-dialkyl-1,2-diphenylethanes 3 was prepared by dimerisation procedures. In several cases pure diastereomers were isolated and their configuration was determined. The analyses of the thermolysis products show that bond cleavage occurs primarily at the central C—C-bond. The rates of thermolysis increase parallel with the steric substituent constants ESC and Sf of the halves of the molecules. An even better correlation is observed between rates and strain enthalpies of 3 as obtained from combustion experiments or force field calculations. A comparison of this correlation with a similar one of aliphatic hydrocarbons published recently 4) allows the separation of steric and resonance effects on the thermal stabilities of 3. It is concluded that the position of the transition state on the reaction coordinate depends strongly on group sizes.
    Notes: Eine Reihe 1,2-Dialkyl-1,2-diphenylethane 3 wurde durch Dimerisationsreaktionen dargestellt. Teilweise wurden die reinen Diastereomeren isoliert und ihre Konfigurationen aufgeklärt. Der thermische Zerfall der Kohlenwasserstoffe 3 wurde präparativ und kinetisch untersucht, er erfolgt fast ausschließlich durch primäre Spaltung der zentralen C—C-Bindung. Die Zerfallskonstanten steigen semiquantitativ parallel mit den sterischen Substitutionskonstanten ESC und Sf der Molekülhälften an. Eine bessere Korrelation geben die experimentell bzw. Durch Kraftfeldrechnungen ermittelten Spannungsenthalpien. Der Vergleich dieser Korrelation mit der entsprechenden früher4) für reine Alkane ermittelten gestattet eine Separierung von sterischen und Resonanzeffekten auf die thermische Stabilität von 3. Es wird gefolgert, daß die Lage der Übergangszustände der Thermolysen auf der Reaktionskoordinate mit der Gruppengröße stark variiert.
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1849-1858 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Biologically Important Carbohydrates, 18. The vic. cis-Oxyamination as the Key Reaction for Amino Sugar Syntheses: Methyl N-Acetyl-4-epi-α-garosamindeMethyl 2-O-benzyl-3,4-dideoxy-α-D-glycerol-pent-3-enopyranoside (11), easily available by Corey-Winter olefination of the 3,4-thionocarbonate 10, reacts with chloramines-T/cat. OsO4 to give the 2:1-mixture of methyl 2-O-benzyl-4-deoxy-4-tosylamino- (12) and methyl 2-O-benzyl-3-deoxy-3-tosylamino-β-L-arabinoside (15). With diazomethane 15 yields with N-methyl derivative 16 which is oxidized with cat. RuOO2/KIO4 TO FORM METHYL 2-O-BENZYL-3-DEOXY-3-(N-methyl-tosylamino)-β-L-threo-pentopyranos-4-uloside (17). Grignard reaction of 17 gives stereospecifically methyl 2-O-benzyl-3-deoxy-4-C-methyl-3-(N-methyltosyamino)-α-D-xylopyranoside (19) from which the N-tosyl group and the benzyl substituent at 2-O are split off with sodium in liquid ammonia. N-Acetylation yields methyl 3-deoxy-4-C-methyl-3-(N-methylacetylamino)-α-D-xylopyranoside (methyl N-acetyl-4-epi-α-garosaminide) (21).
    Notes: Methyl-2-O-benzyl-3,4-didesoxy-α-Dglycero-pent-3-enopyranosid (11), das gut durch Corey-Winter-Olefinierung des 3,4-Thionocarbonats 10 zugänglich ist, reagiert mit Chloramin-T/kat. OsO4 zum 2:1-Gemisch des Methyl-2-O-benzyl-4-desoxy-4-tosyalmino- (12) und Methyl-2-O-benzyl-3-desoxy-3tosylamino-β-L-arabinosids (15). 15 wird mit Diazomethan zum N-Methyl-Derivat 16 umgesetzt, das mit kat. RuO2/KIO4 zu Methyl-2-O-benzyl-3-desoxy-3-(N-methyltosylamino)-β-L-threo-pentopyranos-4-ulosid (17)oxidiert wird. Grignard-Reaktion von 17 liefert stereospezifisch Methyl-2-O-benzyl-3-desoxy-4-C-N-methyl-3-(methyltosylamino)-α-D-xylopyranosid (19), aus dem die N-Tosylgruppe und der 2-O-Benzylrest mit Natrium in flüss. Ammoniak abgespalten werden. N-Acetylierung führt zu Methyl-3-desoxy-4-C-methyl-3-(N-methylacetylamino)-α-D-xylopyranosid (Methyl-N-acetyl-4-epi-α-garosaminid) (21).
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  • 99
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Biologically Important Carbohydrates, 19. On the Regioselectivity of the vic. cis-Oxyamination of 3,4-Unsaturated Carbohydrates: Directed Syntheses of 4-Amino-4-deoxy- and of 3-Amino-3-deoxyaldosidesThe oxyamination of methyl 2-O-benzyl-3,4-dideoxy-α-D-glycero-pent-3-enopyranoside (1) with chloramine-T/[OsO4] yields a 2:1 mixture of methyl 2-O-benzyl-4-deoxy-4-tosylamino- (2) and of methyl 2-O-benzyl-3-deoxy-3-tosylamino-β-L-arabinoside (3). In the presence of a phase transfer catalyst the ratio is 4.5:1. In contrast benzyl 2-O-acetyl-3.4-dideoxy-α-D-glycero-pent-3-enopyrano-side (13) reacts with formation of the corresponding 4-deoxy-4-tosylamino- (14) and 3-deoxy-3-tosylamino-arabinoside 15 in the ratio 1:2. With reference to the preparative importance of this „reversal“ a hypothesis is given for the reasons of the observed regio orientation: in the reaction 1→2 + 3 through space interactions are supposed.
    Notes: Methyl-2-O-benzyl-3,4-didesoxy-α-D-glycero-pent-3-enopyranosid (1) reagiert mit (Chloramin-T/[OsO4 ] zu Methyl-2-O-benzyl-4-desoxy-4-tosylamino- (2) und Methyl-2-O-benzyl-3-desoxy-3-tosylamino-β-L-arabinosid (3) im Verhältnis 2:1. In Gegenwart eines Phasentransfer-Katalysators entstehen die isomeren im Verhältnis 4.5:1. Dagegen führt das Benzyl-2-O-acetyl-3,4-didesoxy-α-D-glycero-pent-3-cyanopyranosid (13) zum entsprechenden 4-Desoxy-4-tosylamino- (14) und 3-Desoxy-3-tosylamino-arabinosid 15 im Verhältnis 1:2. Auf die präparative Bedeutung dieser Umkehrung wird hingewiesen. Für ihre Ursachen wird eine Hypothese entwickelt: als Grund für die Regioorientierung bei 1→ 2 + 3 werden „through space“-Wechselwirkungen angenommen.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1889-1901 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Indole Derivatives, XXXVIII. Cyclopropane Reactions in the Indole SeriesThe acid-catalyzed and the nucleophilic ring-opening of the cyclopropanelactams 1 and 2 studied and their stereospecifity is reported. The ketolactams 22 and 23 obtained via this route represent important intermediates.
    Notes: Die protonenkatalysierte und die nucleophile Ringöffnung der Cyclopropanlactame 1 und 2 werden studiert und die Stereospezifität beschrieben. Die auf diese Weise erhaltenen Ketolactame 22 und 23 sind wichtige Zwischenprodukte.
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