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  • Wiley-Blackwell
  • 2010-2014  (18)
  • 1980-1984
  • 1960-1964  (4,682)
  • 1925-1929  (4,339)
  • 2014  (18)
  • 1963  (4,682)
  • 1929  (2,236)
  • 1926  (2,103)
Collection
Years
  • 2010-2014  (18)
  • 1980-1984
  • 1960-1964  (4,682)
  • 1925-1929  (4,339)
Year
  • 1
    Publication Date: 2020-12-15
    Description: We present a time-independent gridded earthquake rate forecast for the European region including Turkey. The spatial component of our model is based on kernel density estimation techniques, which we applied to both past earthquake locations and fault moment release on mapped crustal faults and subduction zone interfaces with assigned slip rates. Our forecast relies on the assumption that the locations of past seismicity is a good guide to future seismicity, and that future large-magnitude events occur more likely in the vicinity of known faults. We show that the optimal weighted sum of the corresponding two spatial densities depends on the magnitude range considered. The kernel bandwidths and density weighting function are optimized using retrospective likelihood-based forecast experiments. We computed earthquake activity rates (a- and b-value) of the truncated Gutenberg–Richter distribution separately for crustal and subduction seismicity based on a maximum likelihood approach that considers the spatial and temporal completeness history of the catalogue. The final annual rate of our forecast is purely driven by the maximum likelihood fit of activity rates to the catalogue data, whereas its spatial component incorporates contributions from both earthquake and fault moment-rate densities. Our model constitutes one branch of the earthquake source model logic tree of the 2013 European seismic hazard model released by the EU-FP7 project ‘Seismic HAzard haRmonization in Europe’ (SHARE) and contributes to the assessment of epistemic uncertainties in earthquake activity rates. We performed retrospective and pseudo-prospective likelihood consistency tests to underline the reliability of our model and SHARE’s area source model (ASM) using the testing algorithms applied in the collaboratory for the study of earthquake predictability (CSEP). We comparatively tested our model’s forecasting skill against the ASM and find a statistically significant better performance for testing periods of 10–20 yr. The testing results suggest that our model is a viable candidate model to serve for long-term forecasting on timescales of years to decades for the European region.
    Description: EC-Research FP7-projects, SHARE, under grant agreement No. 226967 and NERA, under grant agreement No. 262330
    Description: Published
    Description: 1159-1172
    Description: 2T. Tettonica attiva
    Description: 3T. Pericolosità sismica e contributo alla definizione del rischio
    Description: JCR Journal
    Description: restricted
    Keywords: Probabilistic forecasting ; Statistical seismology ; Europe ; 04. Solid Earth::04.06. Seismology::04.06.02. Earthquake interactions and probability ; 04. Solid Earth::04.06. Seismology::04.06.11. Seismic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 2
    Publication Date: 2017-04-04
    Description: This paper describes an application of artificial neural networks for the recognition of volcanic lava flow hot spots using remote sensing data. Satellite remote sensing is a very effective and safe way to monitor volcanic eruptions in order to safeguard the environment and the people affected by such natural hazards. Neural networks are an effective and well-established technique for the classification of satellite images. In addition, once well trained, they prove to be very fast in the application stage. In our study a back propagation neural network was used for the recognition of thermal anomalies affecting hot lava pixels. The network was trained using the three thermal channels of the Advanced Very High Resolution Radiometer (AVHRR) sensor as inputs and the corre- sponding values of heat flux, estimated using a two thermal component model, as reference outputs. As a case study the volcano Etna (Eastern Sicily, Italy) was chosen, and in particular the effusive eruption which took place during the month of 2006 July. The neural network was trained with a time-series of 15 images (12 nighttime images and 3 daytime images) and validated on three independent data sets of AVHRR images of the same eruption and on two relative to an eruption occurred the following month. While for both nighttime and daytime validation images the neural network identified the image pixels affected by hot lava with a 100 per cent success rate, for the daytime images also adjacent pixels were included, apparently not interested by lava flow. Despite these performance differences under different illumination conditions, the proposed method can be considered effective both in terms of classification accuracy and generalization capability. In particular our approach proved to be robust in the rejection of false positives, often corresponding to noisy or cloudy pixels, whose presence in multispectral images can often undermine the performance of traditional classification algorithms. Future work shall address application of the proposed method to data acquired with a high temporal resolution, such as those provided by the spinning enhanced visible and infrared imager sensor on board the Meteosat second generation geostationary satellite.
    Description: Published
    Description: 1525-1535
    Description: 5V. Sorveglianza vulcanica ed emergenze
    Description: JCR Journal
    Description: restricted
    Keywords: Image processing ; Neural networks ; fuzzy logic ; Remote sensing of volcanoes ; Hot-spot detection ; Mt. Etna ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
    Publication Date: 2017-04-04
    Description: We present a systematic study on the influence of pressure (0.1–600 MPa), temperature (750– 1200 ◦C), carbon dioxide fugacity (logfCO2 = −4.41 to 3.60) and time (2–12 hr) on the chemical and physical properties of carbonate rock. Our experiments aim to reproduce the conditions at the periphery of magma chamber where carbonate host rock is influenced by, but not readily assimilated by, magma. This permits the investigation of the natural conditions at which circulating fluids/gases promote infiltration reactions typical of metasomatic skarns that can involve large volumes of subvolcanic carbonate basements. Results show that, providing that carbon dioxide is retained in the pore space, decarbonation does not proceed at any magmatic pressure and temperature. However, when the carbon dioxide is free to escape, decarbonation can occur rapidly and is not hindered by a low initial porosity or permeability. Together with carbon dioxide and lime, portlandite, a mineral commonly found in voluminous metasomatic skarns, readily forms during carbonate decomposition. Post-experimental analyses highlight that thermal microcracking, a result of the highly anisotropic thermal expansion of calcite, exerts a greater influence on rock physical properties (porosity, ultrasonic wave velocities and elastic moduli) than decarbonation. Our data suggest that this will be especially true at the margins of dykes or magma bodies, where temperatures can reach up to 1200 ◦C. However, rock compressive strength is significantly reduced by both thermal cracking and decarbonation, explained by the relative weakness of lime + portlandite compared to calcite, and an increase in grain size with increasing temperature. Metasomatic skarns, whose petrogenetic reactions may involve a few tens of cubic kilometres, could therefore represent an important source of volcanic instability.
    Description: Published
    Description: 369-380
    Description: 2R. Laboratori sperimentali e analitici
    Description: JCR Journal
    Description: restricted
    Keywords: Volcanic hazards and risks ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
    Publication Date: 2017-04-04
    Description: Interactions of conduit geometry with gas–liquid flows control volcanic activity, implying that the evaluation of volcanic hazards requires quantitative understanding of the inner structure of the volcano. The more established geophysical imaging techniques suffer from inherent ambiguity, may require spatially dense measurements in active areas and may not provide sufficient spatial resolution in the uppermost part of the conduit system. It is thus desirable to develop new imaging techniques allowing a better spatial resolution of a volcano's upper feeding system, with reduced ambiguity and a low level of risk for operators. Muon particles can be utilized to image the internal density distribution of volcanic structures. The principle of muon radiography is essentially the same as X-ray radiography, except for substituting penetrating particles in place of photons. Muons are more attenuated by higher density parts inside the target and thus information about its inner structure are obtained from the differential muon absorption. We report on a muon-imaging experiment that was conducted at Mt Etna in 2010. The target structure was one of the summit craters of the volcano. This experiment was performed using a muon telescope suitably designed to withstand the harsh conditions in the summit zone of a high volcano. We found a marked difference between synthetic and observed attenuation of muons through the target. This discrepancy is likely due to the bias on the observed flux, arising from false muon tracks. They are caused by low-energy particles that, by chance, hit simultaneously the two matrixes of the telescope, leading to detection of a false positive. We separated the useful from the unwanted signal through a first-order model of the background noise. The resulting signal is compared with the corresponding synthetic flux. Eventually, we found regions of higher- and lower-than-expected muon flux, that are possibly related to inner features of the target crater.
    Description: Published
    Description: 633-643
    Description: 2V. Dinamiche di unrest e scenari pre-eruttivi
    Description: JCR Journal
    Description: restricted
    Keywords: Tomography; Volcano monitoring; Volcanic hazards and risks ; 04. Solid Earth::04.03. Geodesy::04.03.06. Measurements and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
    Publication Date: 2017-04-04
    Description: The identification of a source model for the catastrophic 1908 December 28 Messina earth- quake (Mw = 7.2) has been the subject of many papers in the last decades. Several authors proposed different models on the basis of seismological, macroseismic and geodetic data sets; among these models, remarkable differences exist with regard to almost all parameters. We selected a subset of six models among those most cited in literature and used them to model the post-seismic sea level variation recorded at the tide gauge station of Messina (until 1923), to attempt an independent discrimination among them. For each model, we assumed a simple rheological structure and carried out a direct-search inversion of upper crust thickness and lower crust viscosity to fit the post-seismic sea level signal. This approach enabled us to iden- tify a class of fault geometries which is consistent with the post-seismic signal at the Messina tide gauge and with the known structural and rheological features of the Messina strait
    Description: Published
    Description: 611-622
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: open
    Keywords: Sea level change ; Earthquake source observations ; Rheology: crust and lithosphere ; 04. Solid Earth::04.07. Tectonophysics::04.07.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
    Publication Date: 2017-04-04
    Description: When remote sensing users are asked to define their requirements for a new sensor, the big question that always arises is: will the technical specifications meet the scientific requirements? Herein, we discuss quantitative relationships between instrumental spectral and radiometric characteristics and data exploitable for lava flow subpixel temperature analysis. This study was funded within the framework of ESA activities for the IR GMES (Global Monitoring for Environment and Security) element mission requirements in 2005. Subpixel temperature retrieval from satellite infrared data is a well-established method that is well documented in the remote sensing literature. However there is little attention paid to the error analysis on estimated parameters due to atmospheric correction and radiometric accuracy of the sensor. In this study, we suggest the best spectral bands combination to estimate subpixel temperature parameters. We also demonstrate that poor atmospheric corrections may vanish the effectiveness of the most radiometrically accurate instrument.
    Description: Published
    Description: 112-125
    Description: 3V. Dinamiche e scenari eruttivi
    Description: JCR Journal
    Description: restricted
    Keywords: Remote sensing, error analysis, IR sensors, sub-pixel temperature, Numerical solutions; Non-linear differential equations; Effusive volcanism; Eruption mechanisms and flow emplacement; Remote sensing of volcanoes; Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
    Publication Date: 2021-11-25
    Description: Here we inverted the GPS data to infer the coseismic slip of the Tohoku-Oki earthquake and the time-dependent afterslip distribution in the 4 months following the main shock. The Tohoku-Oki earthquake showed an unexpected magnitude and a characteristic depth-dependent differentiation of seismic energy radiation. In this context the estimation and comparison of the distribution of the fault portions that slip coseismically and post-seismically contribute to a better understanding of the variation of frictional characteristics of the plate interface. The inferred coseismic slip extends in a relatively compact region located updip from the hypocentre and reaches its highest value (about 60 m) near the trench. Afterslip occurs mostly outside the coseismic rupture and is distributed in two main modal centres. It reaches its largest values in an area located downdip of the coseismic slip and extends to a depth of 80 km. In the depth range between 30 and 50 km afterslip overlaps the portion of the fault that experienced historical moderate earthquakes, high-frequency seismic radiation and thrust-type aftershocks. The behaviour of this area can be explained by a rheologically heterogeneous region made of a ductile fault matrix interspersed with compact brittle asperities. On the contrary, the region beneath 50–60 km depth is probably characterized by a fully velocity strengthening behaviour. Southern afterslip, located off-Chiba Prefecture, is probably related to the Mw 7.9 Ibaraki-Oki aftershock. The northward extension of the afterslip stops at a latitude of about 40◦ N, just south of the off-Aomori region. This may be related to three large events occurred in this area during the last century and the consequent strong coupling or complete depletion of the accumulated strain that characterize this region.
    Description: Published
    Description: 580-596
    Description: 2T. Tettonica attiva
    Description: JCR Journal
    Description: restricted
    Keywords: Satellite geodesy; Seismic cycle; Earthquake source observations; Subduction zone processes ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.04. Plate boundaries, motion, and tectonics ; 04. Solid Earth::04.07. Tectonophysics::04.07.06. Subduction related processes
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  • 8
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    Wiley-Blackwell
    In:  EPIC3Functional Ecology, Wiley-Blackwell, 28, pp. 1482-1493, ISSN: 0269-8463
    Publication Date: 2023-09-15
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 9
    Publication Date: 2024-05-09
    Description: Episodic gas seepage occurs at the seafloor in the Gulf of Izmit (Sea of Marmara, NW Turkey) along the submerged segment of the North Anatolian Fault (NAF), which ruptured during the 1999 Mw7.4 Izmit earthquake, and caused tectonic loading of the fault segment in front of the Istanbul metropolitan area. In order to study gas seepage and seismic energy release along the NAF, a multiparametric benthic observatory (SN-4) was deployed in the gulf at the western end of the 1999 Izmit earthquake rupture, and operated for about 1 yr at 166 m water depth. The SN-4 payload included a three-component broad-band seismometer, as well as gas and oceanographic sensors. We analysed data collected continuously for 161 d in the first part of the experiment, from 2009 October to 2010 March. The main objective of our work was to verify whether tectonic deformation along the NAF could trigger methane seepage. For this reason, we considered only local seismicity, that is, within 100 km from the station. No significant (ML ≥ 3.6) local earthquakes occurred during this period; on the other hand, the seismometer recorded high-frequency SDEs (short duration events), which are not related to seismicity but to abrupt increases of dissolved methane concentration in the sea water that we called MPEs (methane peak events). Acquisition of current velocity, dissolved oxygen, turbidity, temperature and salinity, allowed us to analyse the local oceanographic setting during each event, and correlate SDEs to episodic gas discharges from the seabed. We noted that MPEs are the result of such gas releases, but are detected only under favourable oceanographic conditions. This stresses the importance of collecting long-term multiparametric time-series to address complex phenomena such as gas and seismic energy release at the seafloor. Results from the SN-4 experiment in the Sea of Marmara suggest that neither low-magnitude local seismicity, nor regional events affect intensity and frequency of gas flows from the seafloor.
    Description: Published
    Description: 850-866
    Description: 1T. Geodinamica e interno della Terra
    Description: 3A. Ambiente Marino
    Description: 7A. Geofisica di esplorazione
    Description: JCR Journal
    Description: restricted
    Keywords: Time-series analysis ; Seismicity and tectonics ; Broad-band seismometers ; multiparametric seafloor observatory ; Izmit Gulf ; Sea of Marmara ; gas seepage ; 03. Hydrosphere::03.04. Chemical and biological::03.04.05. Gases ; 04. Solid Earth::04.04. Geology::04.04.04. Marine geology ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry
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  • 10
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-L-proline in the molecular weight range 50,000-90,000 has been synthesized from L-proline-N-carboxyanhydride. The molecular weight obtained is dependent on the initiator concentration. The rate constants for the polymerization have been determined by measuring the CO2 evolution. By observation of rotation during the polymerization, it is possible to deduce the conformation of the polymer in the polymerization solution. It is concluded that the immediate product of the polymerization is neither pure form I nor pure form II. The differences between form I and form II of poly-L-proline have been further characterized by measurements of their ultraviolet rotatory dispersion and their ultraviolet spectra.
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  • 11
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The base-catalyzed hydrolysis rate of the cationic esters obtained by quaternization of N,N,N′,N′-tetramethylethylenediamine with phenylbromoacetate was studied in buffers and in solutions of partially neutralized polymeric acids. The polyanions were found to be powerful inhibitors of the reaction. This effect was interpreted as due to the association of the ester with the polyanion, from which the catalytically active hydroxyl groups are repelled. It is shown that kinetic data may be interpreted by a procedure similar to the Lineweaver-Burk plot to yield the reactivity of the bound ester and the dissociation constant of the polymer-ester complex.
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  • 12
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of high molecular weight copolypeptides of L-proline and sarcosine have been synthesized. Experimental evidence is presented which indicates that the products are true copolymers rather than mixtures of homopolymers. In contrast to poly-L-proline I, a copolymer of L-proline-sarcosine I containing approximately 50% sarcosine is soluble in water. Two molecular conformations of the copolymers, similar to those found for polyproline, have been characterized by means of infrared spectroscopy and optical rotatory dispersion. The residue rotation of L-proline has been obtained from the copolymers and is -250°.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 1-1 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 14
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 25-32 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grand-partition-function theory of the preceding paper is used to derive expressions for the number of base pairs bonded in DNA with explicit consideration of the copolymeric nature of the DNA. The following features of the DNA molecule are taken into account: (1) the DNA's from different sources have different ratios of a-t and g-c pairs; (2) the a-t pair is weaker than the g-c pair; (3) the nearest-neighbor frequencies of the two kinds of base pairs are nonrandom; (4) the stacking energies (nearest-neighbor energies) of the various combinations of pairs may be different. An ensemble is constructed in which the features (1) through (4) are introduced by means of statistical weights on the various pairs and combinations of pairs, and an expression for the corresponding partition function is written. Expressions are derived for the number of bonded base pairs and the number of helical sequences.
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  • 15
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 1 (1963) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 16
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for formation of hydroxamic acids by direct coupling, in aqueous medium, of hydroxylamine hydrochloride and the sodium salt of a carboxylic acid. The reaction is mediated by a water-soluble carbodiimide, 1-cyclohexyl-3-[2-morpholinyl-(4)-ethyl]-carbodiimide metho-p-toluene sulfonate. Using model compounds, the production of α-, β- and γ-acyl hydroxamic acids was studied. Hydroxamic acid derivatives of α-polyglutamic and γ-polyglutamic acids were also prepared. Dinitro-phenylhydroxamate derivatives were prepared and subjected to Lossen rearrangement, and the reaction mixtures hydrolyzed. Analysis showed that α-polyglutamic acid yielded as many molecules of α,γ-diaminobutyric acid as there had been glutamic acid residues in the form of the dinitrophenylhydroxamate, and gave rise to no ammonia and succinic semialdehyde. In contrast, γ-polyglutamic acid yielded exactly twice the molar quantity of ammonia as there had been glutamic acid residues in the form of dinitrophenylhydroxamate, and also gave rise to significant quantity of succinic semi-aldehyde but no α,γ-diaminobutyric acid. Since production of the latter is characteristic of α-glutamyl hydroxamates and production of the former is associated with γ-glutamyl hydroxamates, the results indicated that the side-chain carboxyl groups of either polymer retained their identities during formation of the hydroxamic acid derivative, and no interchange had occurred between α- and γ-carboxyl groups. These methods were then used to establish that gelatin of ichthyocol contains (per 1000 total residues) at least 20 residues of glutamic acid in γ-peptide linkage. Due to the incomplete dinitrophenylation of the hydroxamic acid derivative of the protein, gelatin of calf skin collagen gave a lower figure of 10 such linkages per 1000 total amino acid residues-a value which must be considered a minimum value. These results show that γ-glutamyl peptide bonds exist in collagen.
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  • 17
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A statistical thermodynamic treatment of thermally induced helix-coil transitions is formulated with the matrix method for an (ensemble) of system(s) in which one strand of a double helix consists of a homopolymeric polynucleotide and the other strand comprises a number of complementary oligonucleotides. Each oligonucleotide is considered to be completely bound to the longer chain when in the helical configuration and completely free from it when in the randomly coiled configuration. The case of partial binding; i.e., “dangling,” is treated in a later paper. Taken into account in both cases are intrachain “stacking” interactions between nearest neighbor residues and interchain hydrogen bonding.An approximate treatment of the characteristic equation of the formulation indicates that the reciprocal of the transition temperature (1/T0) is a linear function of the reciprocal of the degree of polymerization (D.P.) of the oligonucleotides. In the same approximation, 1/T0 is also a linear function of the negative logarithm of the absolute activity of the oligonucleotides. Transition curves obtained by exact calculation on a computer are presented for various degrees of polymerization of both the oligo- and polynucleotides. These curves show a sharpening of the transition with increasing D.P. of the long chain and the aforementioned reciprocal D.P. dependence of 1/T0.
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  • 18
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 171-182 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric dispersion of polyglutamic acid (PGA) was studied in the pH range of 4-9.8. Three different dispersion curves were obtained. Above pH 6.0, where PGA has a random coil configuration, the dielectric dispersion is characterized by a large dielectric increment (ca. 450) and a relaxation time of 10-12.7 × 10-6 sec. Between pH 6.0 and 5.0, where PGA is in a transitional state with small viscosity, a dispersion curve with very small dielectric increment and also small relaxation time was observed. Below pH 5.0, where PGA has a helical configuration, the dispersion is characterized by a relaxation time of 10-12 × 10-6 sec. and a dielectric increment of about 120. The dipole moment of coil and helical forms of PGA were calculated by using Allgen's equation, and qualitative discussions of these dielectric properties are presented.
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  • 19
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 193-208 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ultaviolet absorption spectra down to 185 mμ are presented for a number of nucleic acids and synthetic polynucleotides in the helical and random forms, and of their constituent mononucleotides, as well as the corresponding nucleosides and free bases. A short wavelength absorption band is in all cases observed with a maximum varying between about 187 and 201 mμ. These bands are more intense than those near 260 mμ. The helical polymers show a hypochromic effect in this region of a somewhat similar magnitude to that in the 260 mμ region. Other spectral phenomena accompanying denaturation and degradation are described.
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  • 20
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 209-229 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The inactivation of sRNA by reaction with formaldehyde has been reported as it occurs under various conditions giving differing amounts of secondary structure. The theory of inactivation of an active macromolecule by a chemical reaction is developed. Results obtained with a partially melted out secondary structure show that formaldehyde inactivates sRNA by a single reaction at any one of about ten sites, while reaction at other sites does not affect the activity of the sRNA. In the presence of Mg++ at neutral pH, a large proportion of the active molecules are completely protected against inactivation. From the correlation between the amount of secondary structure and the difficulty of inactivation, it is shown that at least a portion of the secondary structure of sRNA is essential to its amino acid acceptor ability. A comparison of results of various workers shows that formaldehyde does not alter RNA as drastically as other reagents and thus enables more discrimination between sites of reaction which are essential and those which are not essential to biochemical activity.
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  • 21
    Electronic Resource
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    Biopolymers 1 (1963), S. 295-295 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 22
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared absorption and x-ray diffraction measurements have been made of D,L-copoly-γ-benzylglutamate fibers (cast from dioxane solutions) with various D/L ratios and with various degrees of polymerization. It was found that each chain of these copolymers consists of a random coil portion and an α-helix portion and that the conformation of the latter is similar to the α-helix of pure poly-γ-benzyl-L-glutamate. It was also found that the fraction of the α-helix portion increases with the degree of polymerization of the copolymer. A simplified polymerization mechanism has been proposed for mixtures of D- and L-amino acid N-carboxyanhydrides. A model of the molecular conformation of the D,L-copolypeptide chains derived from this proposed polymerization mechanism is in good agreement with infrared, x-ray, and other measurements. Based on the results of these observations, we discuss the number of L- or D-residues linked in succession that is required for initiating the formation of an α-helix during the course of polymerization.
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  • 23
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-L-proline I and II, polyphydroxy-L-proline II, polysarcosine, and collagen, as well as two model amides have been examined by far ultraviolet spectrophotometry. Absorption spectral data are presented. Neither in solution nor in oriented films of poly-L-proline I and II is there any indication of excition resonance splitting of the peptide absorption band. In collagen there is some, in the poly-L-prolines only minimal, hypochromicity. These observations, at least in poly-L-proline II, run counter to theory. Optical rotatory dispersion measurements in the ultraviolet indicate simple dispersion in collagen and poly-L-proline II down to at least 232 mμ. The Cotton effect (trough at 233 mμ) observed in α-helical polypeptides and proteins is absent. The implications of these findings are discussed.
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  • 24
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix - coil transition of poly-L-glutamic acid (PGA) in aqueous solutions was followed by volume changes, ΔV, and also differential refractive indices, Δn. The increase in ΔV or decrease in Δn upon mixing the sodium salt of PGA with dilute HCl gave three straight lines between pH 7 and 4, the two breaks corresponding to the transition zone observed by other physical methods. For the reaction: —COO- + H+ → —CO-OH, ΔV per mole of H+ bound was 11.4 and 11.1 ml. in 0.01 and 0.2M NaCl solutions, respectively. An additional conformational change of about 0.5-1 ml. per amino acid residue was observed for the reaction: coil → helix, after taking electrostatic interaction into consideration. This was probably due to the release of the water of hydration at the amide linkages when the polypeptide coil is converted into the α-helix, or even the occurrence of voids in the polypeptide chain as a result of imperfect packing of the atoms, although the origin of this volume change is still not fully understood at the present time. The volume changes as calculated from Δn by assuming a constant polarizability of the polymer was found to be higher for the association reaction than those mentioned above. On the other hand, the calculated ΔV for the transition was in fair agreement with those by direct measurements.
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  • 25
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dye-macromolecule complexes provide good models for the study of the effects of coupling between chromophores. In addition to modifications of the visible and UV absorption spectra of the dyes at small interchromophore distances, very efficient energy transfer has been demonstrated at longer distances. The probability of nonradiative transition increases with the number of excitation transfers so that an array of oscillators close to one another becomes nonfluorescent. The insertion of a dye molecule, acting as a trap for the excitation energy, in the highly ordered system of chromophores constituted by the purine and pyrimidine bases of native DNA has given results supporting the intercalation model of Lerman and providing an experimental approach to the problem of the path length of energy migration in the DNA molecule. The average excitation path length seems to be of the order of only ten base pairs, a result which can explain the lack of fluorescence of the DNA.
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  • 26
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    Biopolymers 1 (1963), S. 473-495 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sedimentation, diffusion, and osmotic behavior of poly-L-lysine hydrochloride is examined over a wide range of ionic strengths and in solutions which range in relative composition from a swamping excess of added salt (suppression of charge effect) to salt-free solutions (maximum effect). The charge effect is found to essentially obey the theoretical treatment proposed in Part I of this work. The frictional coefficient of the macroion in salt-free solutions is comparable to that of the fully stretched chain. In excess of salt the friction is appreciably smaller, its magnitude not varying greatly with ionic strength. The molecular weight is determined osmotically and also from diffusion-sedimentation, with the charge effect suppressed by addition of salt or eliminated through the use of non-ionized forms of the polymer; a reasonable agreement is obtained between the methods. The influence of small ions on sedimentation is also examined. The secondary salt effect is found to be much smaller than that predicted theoretically; on the other hand, the substitution of different counterions in the absence of secondary salt effect gives rise to changes of the expected magnitude.
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  • 27
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    Biopolymers 1 (1963), S. 500-502 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 28
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-β-hydroxybutyric acid has been isolated from two bacterial sources by two different procedures. Molecular weight and intrinsic viscosity for the two samples were vastly different. This was blamed on degradation occurring during polymer isolation. An optical rotatory dispersion curve for the high molecular weight sample showed a sharp increase in specific rotation at wavelengths less than 450mμ. From this fact and the reported optical activity of the monomer it is concluded that the polymer is stereo-regular. X-ray examination of the “native” and “regenerated” polymer yielded the same crystalline pattern. Electron diffraction and x-ray data on single crystals of the polymer indicate a fiber repeat of 5.9 A. The value can only be reconciled with some kind of helical conformation in the solid state.
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  • 29
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been suggested previously that water is a nearly indifferent solvent for amylose on the basis that the exponent a of the Mark-Houwink equation is very nearly 0.50 and the second virial coefficient A2 is extremely small. It is shown that such solutions do not show the expected precipitation on cooling and the temperature coefficient of the intrinsic viscosity is small and negative. It is suggested that water is both an indifferent and a nearly athermal solvent for this polymer. Various lines of evidence suggest the polymer to exist as a very stiff coil in this and in other solvents. Variations in the intrinsic viscosity and radius of gyration in various solvents show the importance of skeletal effects in addition to the usual osmotic effects. Application of the Porod-Kratky wormlike coil model leads to unreasonably short persistence lengths if the contour length is based on a fully extended conformation but large and reasonable values of the order 40-70 A. if it is assumed that the basic conformation is the helical one observed in various amylose complexes in the crystalline state. As was previously known, the specific optical rotation decreases sharply in aqueous solutions above approximately pH 12. Accompanying this change in rotation there is first a decrease, then an increase in intrinsic viscosity. This later behavior is strikingly reminiscent of the known behavior of polyglutamic acid in the pH-dependent transition from helix to coil. It is concluded that the conformation is that of a stiff coil with essentially helical backbone contour in neutral solution, and the decrease in rotation and in intrinsic viscosity at high pH results from a partial breakdown of the helical structure with a concomitant increase in backbone flexibility. The increase in viscosity and radius of gyration in extreme alkaline solution is probably due to a polyelectrolyte expansion of the polymer coil. Some other miscellaneous observations which are in accord with this model are also pointed out.
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  • 30
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    Biopolymers 1 (1963) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 31
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    Biopolymers 1 (1963), S. 419-429 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Lifson-Roig theory for the helix-random coil transition in polyglycine has been modified to take side-chain interactions into account. The modified theory is developed specifically for poly-L-alanine which probably contains a β1-α4 hydrophobic bond. A conditional probability, expressing the strength of such a hydrophobic bond, is evaluated from the Nemethy-Scheraga data for the free energy of formation of the bond. This, together with the conditional probabilities for the states of the backbone chain, permit an evaluation of the partition function and properties of the helix-random coil transition. It is seen that the hydrophobic bond renders the poly-L-alanine helix much more stable than the corresponding polyglycine one, in agreement with data obtained by Gratzer and Doty.
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  • 32
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical, hydrodynamic, and titration properties of polyribouridylic acid (poly U) were investigated in 0.2M Na+, pH 6. Above 15°C., poly U was shown to be a randomly coiled single chain, devoid of secondary structure. There is no shear rate dependence of viscosity; molecular weight is independent of ionic strength; there is virtually no conformationally dependent hypochromicity; no anomalous optical rotatory dispersion; and no anomalous titration behavior. The dependence of the sedimentation constant and intrinsic viscosity on molecular weight was determined. Poly U was shown to be the most highly expanded of all synthetic and naturally occurring randomly coiled polynucleotides.
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  • 33
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    Biopolymers 1 (1963) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 34
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free poly-L-lysine base has been synthesized from ∊,N-trifluoroacetyl-α,N-carboxy-L-lysine anhydride via poly-∊,N-trifluoroacetyl-L-lysine (IV). No racemization occurred during the removal of trifluoroacetyl groups from IV with 1M piperidine. Measurements of optical rotatory dispersion suggest that IV exists in methanol in a helical form. The synthesis of poly-L-lysyl rabbit serum albumin is also described.
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  • 35
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 168-173 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die basenkatalysierte Kondensation von Benzil mit Guanidin oder n-Butyl-guanidin führt nebeneinander zu 55-Diphenyl-glykocyamidin (Ic) und 7.8-Diphenyl-glykoluril-2.5-diimid (IIc) bzw. 3-(IIIc), sowie N2-[n-Butyl]-5.5-diphenyl-glykocyamidin (IVc) und 7.8-Diphenyl-glykoluril-2.5-bis-n-butylimid (Vb). Wie schon bei der früher untersuchten Kondensation mit Benzylguanidin, begünstigt Temperaturerhöhung die Bildung der Glykocyamidine, Temperaturerniedrigung die der Glykoluril-diimide, Erhöhung des pH im Medium die Bildung der N2-substituierten Glykocyamidine (bzw. mit Guanidin die des N-unsubstituierten Glykocyamidins), Erniedringung des pH die der 3-substituierten Glykocyamidine und Glykoluril-diimide.
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  • 36
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 253-259 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nach der Reissert'schen Methode wurden 4-, 5-, 6- und 7-Methoxy-oxindol synthetisiert und im UV-Spektrum verglichen. Drei dieser Oxindole wurden mit Propionaldehyd zu den 3-Propylidenverbindungen kondensiert, die durch katalytische Hydrierung in die 3-Propylderivate verwandelt wurden. Die Anlagerung von Butylmercaptan oder Thiophenol an die exocyclische Doppelbindung führt zu 31-Thioäthern. Das 4- und 6-Methoxy-oxindol wurde nach SUGASAWA u. a. zum entsprechenden Indolin reduziert. N-Acetyl-6-methoxy-indolin zeigt ein den Amanitinen sehr ähnliches UV-Spektrum.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 279-283 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus NaPHC6H5 und 1.2-Dichlor-äthan entsteht Äthylen- 1.2-bis-monophenyl-phosphin (I). Es wird durch Phenyllithium zu C6H5(Li)P -CH2·CH2-P(Li)C6H5 (V) metalliert, das mit ClCH2.CH2Cl bzw. CH3J das 1.4-Diphenyl- 1.4-diphospha-cyclohexan (VI) bzw. Äthylen- 1.2-bis-methyl-phenylphosphin (III) bildet. III ist auch aus Äthylen- 1.2-bis-[hydrogen-methyl- phenylphosphoniumjodid] und Natriummethylat zugänglich. VI gibt mit Schwefel ein Bis-P-Sulfid, das in einer cis- und trans-Form existiert.
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  • 38
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Äthylester von Fluoro-mono- und -diphosphorsäuren erweisen sich als starke Alkylierungsmittel. So werden Carbonsäuren in ihre Äthylester, Chlor- und Jodwasserstoff in die Äthylhalogenide übergeführt. Nach Entfernen der Alkylierungsprodukte können die den eingesetzten Estern zugrunde liegenden Fluorophosphorsäuren papierchromatographisch und durch Derivate in den Reaktionsrückständen nachgewiesen werden, besonders die noch nicht beschriebene symm. Difluoro-diphosphorsäuren. - Weiterhin werden geeignete organische und anorganische Salze durch Fluorophosphorsäureester alkyliert, wobei neben den Alkylierungsprodukten die entsprechenden Salze der eingesetzten Fluoro-phosphorsäure, u. a. die ebenfalls noch nicht beschriebenen symm. Difluoro-diphosphate, in z. T. guten Ausbeuten und großer Reinheit entstehen. - Das Difluoro-diphosphation P2O5F22⊖ ist in neutraler wäßriger Lösung relativ stabil.
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  • 39
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 342-348 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Strukturen und Bildungsweisen der über 1-Halogen-2-Metall-cyclcohexen entstehenden Kohlenwasserstoffe C18H24 und C24H34 werden diskutiert. Herkunft und Konstitution zeigen auf, daß sich intermediär auftretendes Cyclohexin zum Octahydrobiphenylen III dimerisiert, das in Diels-Alder-Reaktionen Cyclohexin zu V und II zu IV addiert.
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  • 40
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 143-151 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch eine röntgenographische Strukturuntersuchung wird bewiesen, daß dem Samandaridin, einem Nebenalkaloid aus dem Gift des Feuer-und Alpensalamanders, die Konstitution und Konfiguration IIa zukommt.
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  • 41
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 152-156 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Methanolyse des 5-Hydroxy-3-acetoxy-B-norcholestan-säure-(6)-lactons (VII) führt in normaler Reaktion zu X und nicht zu einem Umlagerungsprodukt, entsprechend III (OH statt OAc), wie von DAUBEN und Mitarbb.1,2) angegeben. Ähnlich liefert Hydrolyse bzw. Äthanolyse die entsprechenden B-Norcholestan- Derivate VIII bzw. VI.
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  • 42
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 157-159 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman- und IR-Spektren primärer und sekundärer Propyl-und Butyl-natrium-thiosulfate werden aufgenommen und ihre Frequenzen zugeordnet. Die unterschiedliche chemische Stabilität dieser Stoffe steht in keinem direkten Zusammenhang mit ihren Schwingungsspektren.
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  • 43
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 329-341 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 12-Dibrom-cyclohexen sowie 1-Fluor-2-brom-cyclohexen und 1-Fluor-cyclohexen, deren Synthesen beschrieben werden, führte man auf metallorganischer Basis in 2-metalliertes 1-Halogen-cyclohexen über, das sich als zu kurzlebiges Gebilde in allen Fällen dem Nachweis entzog. Das sofort entstehende Cyclohexin erwies sich als sehr additionsbereit, wie die Folgeprodukte bei Einwirkung von Butyllithium einerseits und von Diphenyl-isobenzofuran andererseits aufzeigten. Der Chemismus der Abwandlung des Diels-Alder-Adduktes VII zu VIII und IX unter den herrschenden Versuchsbedingungen wird geklärt.
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  • 44
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 363-373 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus 2-Isothioureido-tetronsäure (V) entsteht durch alkalische Hydrolyse 2-Mercapto-tetronsäure (VI), die sich unter intermolekularer Schwefelwasserstoff-abspaltung leicht zu 22′-Bis-tetronsäure-sulfid (VII) umsetzt. Aus den Alkalisalzen der 2-Mercapto-tetronsäure (VI) lassen sich stabile Acyl- und Alkyl-derivate darstellen. Die Oxydation von VI führt zum 22′-Bis-tetronsäure-disulfid (IXa). Die IR-Spektren stabiler 2-Mercapto-tetraonsäure-Derivate deuten -übereinstimmend mit dem chemischen Verhalten  -  auf die Enolform dieser Verbindungen hin.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 385-387 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eine brauchbare Synthese der 1.3.6.2′.3′.4′.6′-Heptaacetyl-α-D-cellobiose mit freiem 2-OH wird beschrieben. Die Struktur wird durch Mesylierung gesichert.
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  • 46
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    Keywords: Chemistry ; Inorganic Chemistry
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    Topics: Chemistry and Pharmacology
    Notes: Die Synthese von 2-Chlor-bzw. 2-Brom-2-desoxy-D-arabinose und -ribose aus Diacetyl-D-arabinal über die Halogenadditionsprodukte wird beschrieben. Ausgehend von diesen Verbindungen wird eine neue praktische Darstellungsweise der 2-Desoxy-D-ribose ausgearbeitet.
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  • 47
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 432-437 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Halogen-acyl-aldosen ergeben bei der Reaktion mit Bis-[benzoxazolthionyl]-quecksilber in Dimethylformamid N-[Acyl-glykosyl]-benzoxazolthione, mit Benzoxazolthion-natrium in Äthanol S-[Acyl-glykosyl]-benzoxazolthione. Durch Entacylieren erhält man freie N-bzw. S-Glykosyl-benzoxazolthione. Die Struktur der Verbindungen geht aus den UV-Absorptionssspektren hervor.
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  • 48
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 462-464 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zinntetraphenyl reagiert zwischen 190° und 210° mit mehr als zwei Äquivv. Schwefel unter Bildung von Diphenylsulfid und polymeren Phenylzinnsulfiden, die umso weniger Phenylgruppen am Zinn enthalten, je mehr Schwefel eingesetzt wird. Oberhalb von 220° entsteht quantitativ Zinnsulfid.
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  • 49
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 486-493 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Unter Verbesserung eines bisher nicht beachteten Verfahrens von F. SACHS, für dessen Verlauf ein Reaktionsmechanismus vorgeschlagen wird, werden 16 Amidine, darunter 7 noch nicht bekannte, dargestellt.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 509-516 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die durch Benzophenon primär dehydrierend photosensibilisiterte Autoxydation von sek. Alkoholen führt durch R-H-substituierende Addition von O2 glatt zu den bisher unbekannten α-verzweigten [α-Hydroxy-alkyl]-hydroperoxyden 2). Die Reaktion wurde auf die Darstellung von Ätherhydroperoxyden ausgedehnt. - Der Bäckströmsche Reaktionsmechanismus wird unter Berücksichtigung der bisher übersehenen Reaktionen modifiziert.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 442-447 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1.4.5-Trimethyl-napthalin wird durch Natrium in flüssigem Ammoniak zu einen Gemisch von 1.4.5-Trimethyl-Δ6- und -Δ7-dihydronaphthalin reduziert. Die reduzierende Methylierung, d. h. die Umsetzung seiner Natriumverbindung mit Methylbromid, läßt nur ein Methyl unter Bildung von 1.4.5.8-Tetramethyl-Δ2-dihydronaphthalin in das Molekül eintreten. 1.4.5.8-Tetramethyl-naphthalin wird auf die gleiche Weise nur zu einem Gemisch ungefähr gleicher Teile von Δ1- und Δ2- Dihydroisomerem und ebensoviel von einem leicht veränderlichen Kohlenwasserstoff, vielleicht 1.4.5.8-Tetramethyl-isotetralin, reduziert; Methyl tritt nicht in das Molekül ein.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 494-497 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wie aus methylenaktiven Pyridiniumsalzen kann man auch aus vergleichbaren aliphatischen und ar-aliphatischen Nitroverbindungen Nitrone und cyanierte Anile gewinnen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 526-533 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition von Alkyl-, und Acylsenfölen an β-Iminoketone bzw. β-Iminonitrile führte zu α-Acyl- (bzw. Cyan)-β-amino-thiocrotonamiden, die durch Dehydrierung zu 5-Amino-4-acyl(bzw. cyan)-isothiazolen cyclisiert wurden. - Aus einigen der genannten Thiocrotonamide ließen sich durch intramolekulare Kondensation auch 4-Mercapto-5-acyl-pyrimidine in guter Ausbeute darstellen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 556-569 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Leitfähigkeitstitrationen wird gezeigt, daß das Decavanadation, V10O286⊖, Komplexe mit Kationen bildet. Die Komplexbeständigkeit hängt dabei wesentlich vom Ionenradius des Kations ab. Es wird angenommen, daß das Decavanadation etwa kugelförmigen Bau hat und einen Hohlraum besitzt, in den ein hydratisiertes Kation unter Bildung eines Einschlußkomplexes eindringen kann. Durch die Feldwirkung des Hydratwassers an Kation acid. Dadurch wird das Decavanadation zur Bildung höherbasischer Salze befähigt.  - Für die Decavanadinsäure wird ein Strukturmodell vorgeschlagen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 765-770 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diazotiertes 2-Amino-diphenylmethan und dessen 4′-Methyl-, 4′-Methoxy- und 4′-Chlor-Abkömmlinge werden in wäßriger Schwefelsäure thermische mit und ohne Kupfer zersetzt sowie photolysiert. Die mageren Ausbeuten an Fluoren und Abkömmlingen weisen nicht auf einen starken Substituenteneinfluß bei der Cyclisierung.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 798-801 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Chinolinaldehyd wird durch Diazomethan in 3-Acetonyl-chinolin umgewandelt.  -  Bei der Einwirkung von Diazomethan auf 6-Methyl-pyridin-aldehyd-(2)] entsteht in Gegenwart von Methanol [6-Methyl-pyridyl-(2)-äthylenoxyd. In Abwesenheit von Methanol dagegen bildet sich ausschließlich 6-Methyl-;2-acetyl-pyridin. setzt man 2 Mol 6-Methyl-pyridin-aldehyd-(2) mit nur 1 Mol Diazomethan um, so entsteht 1.3-Bis-[6-methyl-pyridyl-(2)]-propanol-(3)-on-(1).
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    Berichte der deutschen chemischen Gesellschaft 96 (1963) 
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    Keywords: Chemistry ; Inorganic Chemistry
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1221-1228 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Umsetzung von Alkinolen mit Ketonen in flüssigem Ammoniak oder Dioxan werden Alkindiole, bei der oxydativen Kupplung von Alkinolen mit Kupfer(I)-chlorid und Sauerstoff werden Butadiin- bzw. Hexadiindiole erhalten, deren monovalente Reduktion zu Kumulenen führt.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1259-1264 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Methyl-dicyclopropylcarbinol (I) reagiert mit Bromwasserstoffsäure praktisch ausschließlich zum 4-Brom-1-cyclopropyl-penten-(1) (II). Mit feuchtem Silberoxid wird quantitativ der Cyclopropanring zurückgebildet. Die Methanolyse von 1-Cyclopropyl-buten-(1)-ol-(4)-p-toluolsulfonat ergab zu 93% Dicyclopropylcarbinyl-methyläther.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1281-1284 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus N.N′-Thionyl-bzw. N.N′-Carbonyl-di-imidazol, Carbonsäuren und tert.-Butylhydroperoxyd wurden Percarbonsäure-tert.-butylester in 50-80% Ausbeute dargestellt. Dies ist die erste Synthese von Perestern, welche die Stufe der Carbonsäure-halogenide umgeht.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1293-1297 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Darstellung der Reihe der Organoazidosilane RxSi(N3)4-x(R = CH3, C6H5; x = 3, 2, 1) gelang auf zwei Wegen: 1. Umsetzung der entsprechenden Methylchlorsilane mit Natriumazid in geschmolzenen Salzen als Lösungsmittel; 2. Umsetzung von solchermaßen dargestelltem Trimethylazidosilan mit Organochlorsilanen in Gegenwart von Aluminiumchlorid als Katalysator (Substituentenaustausch). Weiterhin konnten erstmals gemischt halogen-pseudohalogen-substituierte Organosilane, CH3SiCl2N3, CH3SiCl(N3)2 und (CH3)2SiClN3 (?) erhalten werden.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1285-1288 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch die stereospezifische Reaktion der Glucose-6-phosphat-isomerase werden die zwei möglichen Fructosen-[1-T] dargestellt. Die damit unter verschiedenen Bedingungen durchgeführten Osazondarstellungen zeigen: Die Spaltung der C—H-Bindung ist reaktionsgeschwindigkeitsbestimmend, die beiden Wasserstoffe an C-1 der Fructose sind bei der Osazonbildung nicht gleichwertig. Daraus lassen sich Folgerungen für den Ablauf der Reaktion ziehen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1308-1315 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: P(NMe2)3 reagiert mit Sauerstoff, Schwefel, Phenylazid und Schwefelkohlenstoff zu den Verbindungen (Me2N)3PO, (Me2N)3PS, (Me2N)3PNPh, Me2NP(SC(S)NMe2)2 und P(SC(S)NMe2)3. Die ME2N-Liganden von P(NMe2)3 werden mittels ÄtOH, MeCO2H und PhNH2 substituiert.
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    Notes: Das üblicherweise monoklin nach P21/c kristallisierende V(C6H6)2 wurde durch Umkristallisieren in organischen Medien unterhalb + 18° in einer kubischen Modifikation mit der auch bei Cr(C6H6)2 auftretenden Raumgruppe Pa3 erhalten. Kristallographische Daten des kubischen und des monoklinen V(C6H6)2 werden gegeben und denen der isomorphen Verbindungen Cr(C6H6)2 und Fe(C5H5)2 gegenübergestellt.  - Spektroskopische Untersuchungen zeigen, daß nicht nur im monoklinen, sondern im Gegensatz zu Cr(C6H6)2 auch im neuen kubischen V(C6H6)2 die D6h-Symmetrie der Benzolliganden erhalten bleibt. Angesichts der identischen Raumgruppe beider Aromatenkomplexe des Cr0 und V0 kann daher ein Gittereffekt nicht Ursache der Verformung der C6H6-Liganden im Cr(C6H6)2 zur C3v-Symmetrie sein.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1428-1435 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aktive Methylenverbindungen kondensieren in Gegenwart von Triäthylamin leicht mit 4-Äthoxymethylen-2-phenyl-oxazolon-(5) (I, R = C2H5O). Besitzen erstere eine zum Methylenkohlenstoff benachbarte, hinreichend nucleophile CO-Gruppe, so entstehen unter Ringisomerisierung 3-Benzoylamino-α-pyrone, z. B. XII. Fehlt eine solche, so bilden sich die entsprechenden aliphatisch substituierten Alkyliden-2-phenyl- oxazolone-(5).  -  Oxazolon-Struktur besitzen auch die Kondensationsprodukte von I (R = C2H5O) mit Enaminen des Typs IX (Formeln X und XI), und mit dem Phosphoran XV (Formel XVI).  -  4-[o-Hydroxy-aryliden]-oxazolone-(5) isomerisieren, wie Beispiel XIII zeigt, unter der Einwirkung tertiärer Basen zu 3-Acylamino-cumarinen XIV.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1454-1464 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus Trimethylthionophosphat und Antimon(V)-chlorid entsteht über ein 1 : 1-Addukt quantitative Tetramethylthiophosphatacidium-hexachloroantimonat, das auch durch Methylierung des Trimethylesters mit Oxoniumsalzen erhalten werden kann. Die Eigenschaften der neuartigen Phosphonium- Verbindung sowie weitere Versuche über die Einwirkung von Alkylierungsmitteln auf tertiäre Thionophosphate werden beschrieben.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1485-1494 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Untersuchung von ca. 30 Arten der Gattung Anthemis L. ergibt, daß im Hinblick auf die Inhaltsstoffe verschiedene Gruppen vorliegen In einigen Arten sind nur bereits bekannte, für den Tribus Anthemideae typische Inhaltsstoffe zu finden, während etwa die Hälfte der untersuchten Arten verschiedene Methyl-mercapto-Polyinester enthalten. Die Strukturen wurden vor allem durch ihre spektralen Daten geklärt. Die enge biogenetische Beziehung der Schwefelverbindungen zum weitverbreiteten Dehydromatricariaester wird aufgezeigt. Ein isoliertes Benzoesäureesterderivat steht offensichtlich in enger Beziehung zu den Polyinestern.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1520-1528 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eine neue Synthese der Homoisovanillinsäure, die vom Isovanillin ausgeht, benötigt nur 2 Stufen und ergibt eine über 80-Proz. Ausbeute. Von hier aus kommt man nach den in der Isochinolin-Chemie üblichen Methoden leicht in die Klasse der 6-Methoxy-isochinoline.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1551-1560 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxydation der Anlagerungsverbindungen aus Carbophenoxysenföl und einigen anderen Senfölen an β-Amino-crotonester führe zu Isohizolen vom Typus der Anthranilsäure. Insbesondere erwies sich das 3-Methyl-4-carbäthoxy-5-[carbophenoxy-amino]-isohiazol als eine vielseitig abwandelbare Verbindung, die u. a. zur Synthese von Bicyclen verwendet wurde.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1395-1405 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch chromatographische Trennung an phosphorylierter Cellulose wurden Biopterin und 7-Biopterin erstmals in reiner Form erhalten. Im Gegensatz zum Biopterin ist 7-Biopterin im Wachstumstest bei Crithidia fasciculata inaktiv. Die Ausbeute ist bei der Biopterinsynthese stark von den Reaktionsbedingungen abhängig und liefert unter optimalen Bedingungen 7% Biopterin und 26% 7-Biopterin, bezogen auf eingesetztes 2.4.5-Triamino-6-hydroxy-pyrimidin. Die Radiosynthese der beiden pterine, ausgehend von K14CN, wird beschrieben. Ferner werden die Eigenschaften des 2-Amino-4-hydroxy-6-bzw. 7-[L-erythro-1.2.3-trihydroxy-propyl]-pteridins mitgeteilt.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 1535-1543 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die aus Ketenen und Triphenylphosphin-isopropyliden erhaltenen Betaine III und IX zerfielen beim Erhitzen zu Triphenylphosphinoxyd und den zu erwartenden Allenen. Die thermischen Zersetzungen analog präparierter Phosphoniumbetaine X und XI hingegen verliefen unübersichtlich. Unstimmigkeiten früherer Literaturangaben werden berichtigt.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 38-47 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Herstellung von 2-Amono-äthylthioschwefelsäure (III) aus Chloräthylamin-hydrochlorid und Natriumthiosulfat wird verbessert. Eine Reihe von III-Derivaten wurde durch Acylierung und Alkylierung gewonnen. Durch Behandlung mit Natriumsulfid gehen diese über Trisulfide in Disulfide über. Einige Disulfide wurden durch elektrolytische Reduktion in die Mercaptane übergeführt. Dieses Verfahren eignet sich besonders für die Herstellung von 2-Mercaptoäthyl-harnstoff. Enthalten die Acylierungsmittel aromatisch gebundene Nitrogruppen, so lassen sich die Kondensationsprodukte zu den entsprechenden aromatischen Aminen reduzieren. 2-Amino-äthylthioschwefelsäure und ihre Derivate setzen sich mit Formaldehyd zu Thiazolidinen um.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 93-113 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ein neues Darstellungsverfahren für 2-Aryl-Δ1- payrroline bzw. 2-Aryl-Δ1-piperideine durch Umsetzung von γ- bzw. δ-Aminosäuren mit aliphatischen Phenol- oder Thiophenol-äthern oder mit Phenolen in Polyphosphorsäure wird beschrieben.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 88-92 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Siebengliedrige Thia-lactame bilden sich bei der Umsetzung von α.β-ungesättigten Carbonsäureestern mit β-Amino-mercaptanen unter milden Reaktionsbedingungen. Diese Reaktion wird stark durch Basen katalysiert. - β-Mercaptocarbonsäureester lassen sich mit Äthylenimin ebenfalls zu Thia-lactamen umsetzen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 130-135 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden Kondensationen von 2-Aminomethyl-benzimidazol mit 1.3-Dicarbonylverbindungen und mit α.β-ungesättigten Ketonen beschrieben.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 174-178 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Einwirkung von Arylsulfenylchoriden auf heterocyclische Methylenbasen entstehen, je nach den Eigenschaften des betreffenden Heterocyclus Mono-bzw. Bis-ω -arylmercapto-methylenderivate oder beide zusammen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 204-212 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Synthese monoaktivierter Diester der Glutaminsäure wird beschrieben; diese erwiesen sich als günstige Ausgangsstoffe für den selektiven Aufbau von α- und γ-Peptiden dieser Aminodicarbonsäure. Die aktivierten Verbindungen entstehen durch Veresterung der freien Carboxylgruppe N-geschützter Glutaminsäuremonoalkyl- bzw. -monobenzylester mit Chloracetonitril, Nitrophenol, Thiophenol und anderen Phenolderivaten. - Zur Gewinnung der sterisch reinen Cbo-Monobenzylester wird ein einfaches Verfahren beschrieben, welches auf der quantitativen Trennung des bei der Alkoholyse von Cbo-Glutaminsäureanhydrid entstehenden α-γ-Estergemisches beruht.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 247-248 
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    Keywords: Chemistry ; Inorganic Chemistry
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 260-265 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus verschiedenen Phenylhydrazonen von Acetonyl- und Acetaldehyd-thioäthern wurden durch Umlagerung mit äthanolischem Chlorwasserstoff mehrere Indolyl-(3)-thioäther hergestellt. Durch hydrogenolytische Entschwefelung der vom Mercaptoacetaldehyd abgeleiteten Indolyl-(3)-thioäther mit Raney-Nickel erhält man daraus im Pyrrolkern unsubstituierte Indole, die sonst nur aus den α -Carbonsäuren durch Decarboxylierung zugänglich sind.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 284-287 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei Methylierungen in Dimethylformamid ist es vielfach von Vorteil, Dimethylsulfat an stelle von Methyljodid zu verwenden. Substanzen, die in Dimethylformamid zu wenig löslich sind, methyliert man in Dimethylsulfoxyd bzw. in Dimethylformamid/Dimethylsulfoxyd-Gemischen. Auf diese Art wurde Mesoinosit-hexamethyläther kristallisiert (Schmp. 18°) erhalten.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 320-328 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 3α-Oxido-3-benzyl-chromanonen-(4) wird der Epoxydring mit Pd(OH)2)/BaSO4- Katalysator selektiv hydriert zu 3-Hydroxy-3-benzyl-chromanonen-(4), während die Carbonylgruppe mit NaBH4 selektiv zu 4-Hydroxy- 3α-oxido-3-benzyl-chromanen reduziert wird. Die weitere Reduktion der Produkte mit LiAlH4 ergibt 34-Dihydroxy-3-benzyl-chromane.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 349-356 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Brommethyl-dimethyl-silyl-Gruppe reagiert in Gegenwart stöchiometrischer Mengen tert. Amine mit Alkoholen und Mercaptanen zu β-Sila-äthyl-äthern bzw. -thioäthern. In Modellreaktionen wurde die Übertragung dieses Reaktions-prinzips zur Synthese von ringförmigen Derivaten untersucht und gleichzeitig die Anwendbarkeit für die schon auf anderem Wege dargestellten SiN-Hetero-cyclen geprüft.  -  So entstanden durch Umsetzung von Brommethyl-dimethyl-silanen mit 12-Diolen, Mercaptoäthanol, Äthanolaminen und 1 2-Diaminen 6 gliedrige Heterocyclen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 374-374 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: HgBr2 ergibt in indifferenten Lösungsmitteln mit Acetohalogenzuckern reaktionsfähige Komplexverbindungen1). Bei Verwendung von Tetrahydrofuran als Lösungsmittel tritt schon bei Raumtemperatur, auch ohne Zusatz einer Hydroxylverbindung ROH, eine Reaktion ein: Es läßt sich, wenn auch zunächst nur in einer Ausbeute von etwa 25%, das Tetraacetyl-[4-brom-n-butyl]-β-D-glucoside, Br-[CH2]4-O-C6H7O5(CH3.CO)4, isolieren. Demnach lagert sich im Endeffekt die Acetobromglucose unter Aufspaltung des Furanringes an -[CH2]4-O-an. Sicher geht die Reaktion über eine Reihe von Zwischenstufen, auf deren Diskussion aber vorerst verzichtet wird.Im Anschluß an diesen Befund soll untersucht werden, ob auch andere, Katalysatoren als HgBr2 und ob auch andere sauerstoffhaltige Ringe, auch der Kohlenhydrate selbst, analoge Reaktionen mit Acetohalogenosen ermöglichen.Dem Verband der CHEMISCHEN INDUSTRIE, FONDS DER CHEMIE, sind wir für Unterstützung dieser Arbeit zu Dank verpflichtet.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 388-398 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sulfoxyde und Thioäther fangen die bei der Photolyse und Thermolyse von Sulfonylaziden entstehenden Arylsulfonylimene unter Bildung von N-Sulfonyl-sulfoximinen bzw. N-Sulfonyl-sulfiminen ab. Bei der Photolyse von p-Toluolsulfazid in Methanol entsteht neben anderen Produkten N-[p-Toluolsulfonyl]-O-methyl-hydroxylamin (I). Benzazid, in Dimethylsulfoxyd mit UV-Licht bestrahlt, liefert als Hauptprodukt N-Benzoyl-dimethylsulfoximin (III). Bei allen untersuchten Beispielen stabilisieren nucleophile Molekeln aus dem Solvatbereich die Primärfragmente mit Elektronensextett unter Bildung der oben angegebenen Reaktionsprodukte.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 420-425 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus den Haloformen entstehen in flüssigem Ammoniak mit Amiden über Haloformcarbanionen die Dihalocarbene und daraus mit Ammoniak Ammoniumcyanid. Chloroform- und Bromoformcarbanionen lassen sich leicht in zumeist hoher Ausbeute durch die präparativ interessanten Kondensations-reaktionen mit Carbonylverbindungen oder Michael-artig mit α.β-ungesättigten Carbonsäurederivaten abfangen. Demgegenüber ist die Stabilität fluorierter Haloformcarbanionen offenbar so gering, daß diese Abfangreaktion nicht mehr präparativ gelingt.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 448-452 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Chlor-2.4-dinitro-benzol läßt sich mit Natriumborydrid zu 1-Chlor-2.4-dinitro-cyclohexen-(6) reduzieren. Analog reagieren andere 1-subst. 2.4-Dinitro-benzolderivate. Aus Pikrinsäure wurde 1.3.5-Trinitro-pentan erhalten.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 470-477 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mit Hilfe von Fluoreszenzspektren ausgeführte Untersuchungen über den Einfluß von Substituenten an Siloxen lassen den Schluß zu, daß der für die Farbe wesentliche Teil der Si6-Ring ist, in dem über d-Bahnen ein zusätzliches Elektronensystem aufgebaut wird. Die dazu notwendigen Elektronen stammen aus den Substitutenten und aus den die Ringe verknüpfenden Sauerstoffatomen.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 465-469 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Umsetzung von Triphenylphosphin-carbomethoxymethylen (I) mit α-Bromketonen entstehen in guten Ausbeuten β-Acyl-acrylsäure-methylester (VII) neben Triphenylphosphin und Triphenyl-carbomethoxymethyl -phosphoniumbromid (IV). Die Reaktion verläuft über ein Phosphoniumsalz VI, das durch Einwirkung eines Mol. I als Base dem Hofmannschen Abbau unterliegt.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 498-508 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die durch Benzoophenon photosensibilisierte Cycloaddition von Dimethyl-maleinsäureanhydrid an Thiophen und sieben Olefine verschiedener Typen führt glatt zu Cyclobutanderivaten. Das Trichloräthylen- Dimethylmaleinsäureanhydrid-Addukt geht durch HCl-Abspaltung in ein Cyclobutenderivat über, dessen Isomerisierung α.α′-Dimethyl-β.β′- dichlor-muconsäure liefert.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 520-525 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehydronorcampher (I) wird photochemisch quantitativ nach Art einer Retrodienspaltung in Cyclopendadien und Keten zerlegt. endo-Dicyclopentadien (IX) zeigt keine photochemische Retrodienspaltung. IX wird nach dem Prinzip der durch Carbonylverbindungen photosensibilisierten Cycloaddition durch intramolekulare Vierringsynthese isomerisiert. Die rein biradikalischen Reaktions- mechanismen beider Photoreaktionen werden diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 570-583 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei geeigneter Arbeitsweise erhält man durch Einwirkung von Nitrosylchlorid auf aromatische Amine die primären Nitrosamine. Durch Umsetzung mit Kaliumäthylat können diese in die entsprechenden Diazotate übergeführt werden, wobei je nach Charakter des Kernsubstituenten die n- oder iso- Verbindungen anfallen. Ihre Eigenschaften, der Einfluß der Versuchsbedingungen auf ihre Bildung, der Substituenteneinfluß im aromatischen Kern sowie einige Reaktionen werden besprochen. - Die instabilen primären aromatischen Nitrosamine selbst sind nur bei tiefen Temperaturen haltbar und werden bei -70° UV-spektrographisch identifiziert.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 600-603 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von Carbonsäurechloriden und Benzyliden- methylamin werden N-α-Halogenalkyl-carbonsäureamide gewonnen, die durch Alkoholyse bei Gegenwart tertiärer Amine in N-α-Alkoxyalkyl-carbonsäureamide über geführt werden. - Die aus Benzyliden-methylamin und Carbonsäurebromiden entstehenden Additionsprodukte reagieren hingegen mit einer zweiten Molekel Schiffscher Base unter Bildung leicht hydrolysierbarer, mesomeriestabilisierter Immonium-Oxonium-Salze.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 609-618 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Synthese des partiell durch tert.-Butyloxycarbonyl-Gruppen (Abk. BOC) geschützten Tetradecapeptidamids N∊-BOC-Lysyl-prolyl-valyl-glycyl-N∊-BOC-lysyl-valyl-tyrosly-prolinamid (sämtlich L-Konfiguration) nach dem Schema (4+2) + (3+5) wird beschrieben. Die Verbindung ist ein geeignetes Zwischenprodukt für die Darstellung ACTH-wirksamer Tetracosapeptidamide.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 634-635 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 636-637 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 658-669 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Bedingungen zur Gewinnung von Zucker-tolyl-und-methyltolyl-hydrazonen werden untersucht. In essigsaurer Lösung bilden die primären Hydrazine je nach Art des eingesetzten Zuckers Hydrazone oder Osazone. Erstere lassen sich in saurem Milieu ohne weiteren Hydrazinzusatz in Osazone überführen. Die UV-Absorptionsspektren eignen sich gut zur Identifizierung der nicht kristallisierenden Reaktionsprodukte, nicht jedoch zur Klärung von Strukturfragen. Dagegen können aus der Formazanreaktion der Zucker-tolylhydrazone Hinweise für das überwiegende Auftreten der cyclischen oder acyclischen Form erhalten werden. Die möglichen Zusammenhänge zwischen Konstitution und Löslichkeit der Hydrazone werden diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 694-698 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Brom-adamantan-carbonsäure-(1) wurde über das Säurechlorid in das Amid übergeführt, das durch Hofmann-Abbau N-[3-Brom-adamantyl-(1)]-methylurethan lieferte. Bei der Alkalibehandlung erleidet dieses eine Fragmentierung, wobei in hoher Ausbeute 3-Methylen-bicyclo-[1.3.3]-nonanon-(7) gebildet wird. Ozonolyse gibt das bisher unbekannte Bicyclo-[1.3.3]-nonan-dion-(3.7), das bei der Aldolkondensation mit Nitromethan in 1.3-Dihydroxy-;2-nitro-adamantan übergeht. Durch Lithiumalanat-Reduktion des Diketons wurde Bicyclo-[1.3.3]- nonan-diol-(3.7) erhalten, aus dem durch intramolekulare Wasserabspaltung das bisher unbekannte 2-Oxa-adamantan zugänglich ist.
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    Berichte der deutschen chemischen Gesellschaft 96 (1963), S. 736-746 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Diazoverbindung aus 2-[o-Amino-benzoyl]-napthalin (IV) schließt unter Stickstoffabgabe den Ring zum angularen und lineraren Benzofluorenon (XIII und XIV). Auf dem vom Diazoniumion ausgehenden polaren Reaktionsweg entstehen XIII und XIV im Verhältnis 2.4: 1 bei einer Gesamtausb. von 50 bis 78%. Der Zerfall der kovalenten Diazoverbindungen liefert dagegen über das Arylradikal die Cyclisierungsprodukte im Verhälthnis 9.5 : 1; daneben tritt die Arylierung des als Lösungsmittel dienenden Benzols Konkurrierend auf.
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