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  • 1
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The increasing requirements in wastewater treatment have led to the development of new wastewater treatment processes based on the know-how and experience in reaction and process engineering of the chemical industry. Due to their compactness, closed operation and high flexibility, these new processes show a large potential for process integration and significant cost reduction in particular for highly polluted industrial wastewaters.This paper discusses the HCR (high-performance compact reactor) - process, developed at the Mass Transfer Laboratory of the Technical University of Clausthal within the last decade. This process has been realized in more than 30 technical applications with a volume loading of up to 70 kg COD/m3 d and an energy consumption of about 0.4 kWh per kg CODelim.
    Additional Material: 10 Ill.
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  • 2
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 169-174 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nitrogen fixing Anabaena azollae strains isolated from four different Azolla cultures were characterized based on their total protein profile and RAPD profile to study the existing variation among them. As expected, the isolates showed almost similar protein banding patterns, but exhibited differences in 40-70 KDa protein subunits. Polymerase chain reaction of the DNA of the isolates, using four different primers, amplified specific sequences of DNA and showed clear polymorphism among the isolates. The RAPD profile generated the fingerprinting pattern characteristic of each strain based on the sequence of the primers used. Common band sharing observed between the strains A. azollae-RS-KK-SK-AM and A. azollae-RS-KK-SK-RP probably represents maternal inheritance of DNA to the progeny. The polymorphic bands were generated specifically for the isolates A. azollae-RS-KK-SK-RP and A. azollae-RS-KK-SK-AM with primers numbered 2 and 4, respectively, which could be developed as possible markers for these isolates.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 175-183 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mature seed-derived callus from an elite Chinese japonica rice cv. Eyl 105 was transformed with a plasmid containing the selectable marker hygromycin phosphotransferase (hpt) and the reporter β-glucuronidase (gusA) genes via particle bombardment. After two rounds of selection on hygromycin (30 mg/l)-containing medium, resistant callus was transferred to hygromycin (30 mg/l)-containing regeneration medium for plant regeneration. Twenty-three independent transgenic rice plants were regenerated from 127 bombarded callus with a transformation frequency of 18.1%. All the transgenic plants contained both gusA and hpt genes, revealed by PCR/Southern blot analysis. GUS assay revealed 18 out of 23 plants (78.3%) proliferated on hygromycin-containing medium had GUS expression at various levels. Genetic analysis confirmed Mendelian segregation of transgenes in progeny. From R2 generations with their R1 parent plants showing 3:1 Mendelian segregation, we identified three independent homozygous transgenic rice lines. The homozygous lines were phenotypically normal and fertile compared to the control plants. We demonstrate that homozygous transgenic rice lines can be obtained via particle bombardment-mediated transformation and through genetic analysis-based selection.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 202-202 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 219-233 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The GRAM-positive bacterium Rhodococcus erythropolis K2-3 and the GRAM-negative Ochrobactrum anthropi K2-14 are capable of synergistically degrading 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB). The two strais execute this task in a symbiotic manner, but the nature of the interaction involved in the degradation is only partially understood as yet. An essential first step in elucidating the interaction is to be able to monitor the two strans separately, at the cellular level, within mixed populations. Therefore a method exploiting fluorescently labelled lectin probes was developed. Since Concanavalin A (Con A) binds specifically to R. erythropolis K2-3, it was selected and linked to the fluoresent dye Bodipy 630/650, which has an excitation maximum in the red part of the visible light spectrum. Forward light scatter (FSC) and DNA fluorescence from both strains were also measured to obtain simultaneous information about their physiological states. The three parameters were conveniently monitored by dual and triple excitation flow cytometry in conjunction with double fluorescent staining techniques. In addition, the strains were identified using an epifluorescence microscope. These techniques were found powerful tools for the population analysis of this mixed bacterial system.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 235-274 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A quite unconventional, innovative scientific methodology called “macroscopic pattern analysis” is presented in this paper. This approach is more adequate in the case of complex systems than the well-known microscopic, mechanistic approach. Complex systems are not only attracting more engineering interest, but their scientific treatment is increasingly wanted by society due to the manifold problems in Earth's ecosphere. The macroscopic pattern approach will be explained in depth and illustrated in some case studies from the ecosphere (sustainability, hurricanes and avalanches), where nature serves as a teacher for the solution of the sustainability problem. Then, a series of case studies on macropatterns are described showing the problem-solving capacity for anthropo- and technosphere: sustainability in society with an index of sustainability, the eco-social market economy with eco-tech as an instrument, biokinetics, bioreactor mixing and integrated bioprocessing with models, design of cars and houses and even quality of life as an attempt to quantify macropatterns.The innovations are briefly compared in their problem-solving capacity with known approaches such as the microscopic method in science, technology and society (free market economy), including the evaluation of other indices and cleaner production, industrial ecology and zero emission initiative. Finally, a deeper integration of sciences, ethics, arts and nature will be introduced based on the vision with macroscopic pattern analysis, where the different domains of human life are integratable to effect a reconciliation.
    Additional Material: 22 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 17-29 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behaviour of biofilters intended to remove toluene and xylene from air was studied during transient states. Laboratory scale biofilters were filled with a mixture of peat, bark and wood and inoculated with a mixed microbial population. Toluene and xylene were applied both as single pollutants and as mixtures. Attention was focused on the evaluation of the following transients: the response of biofilters to step changes and peaks in pollutant concentrations, the effect of changes between single and multiple pollutant loadings and the response to shutdown periods.The biofilters demonstrated a good dynamic stability during transient states induced by change in inlet pollutant concentrations. Their time periods did not exceed three hours. No interaction between xylene and toluene degradation was observed during changes in loading with single pollutants or their mixture. The performance interruptions lasting less than 24 hours were found to have no significant influence on the removal efficiency of biofilters. When the biofilters were reacclimated after longer starvation periods, a short temporary decrease in efficiency whose minimum and duration were proportional to the length of a preceding shutdown period was observed. The longest starvation period (7 days) resulted in a reacclimation lasting 7 hours only. Adaptations of a microbial population to new operating conditions as well as sorption/desorption processes were suggested as the main factors influencing the dynamic reponse characteristics.
    Additional Material: 10 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 31-38 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this paper, the in vivo decolourization of the polymeric dye Poly R-478 by semi-solid-state cultures of Phanerochaete chrysosporium BKM-F-1767 (ATCC 24725) was investigated, employing corncob as a support. In order to stimulate the ligninolytic system of the fungus, the cultures were supplemented with veratryl alcohol (2 mM) or manganese (IV) oxide (1 g/l).Maximum manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of around 2,000 U/l and 400 U/l were attained by the former, whereas the activities reached by the latter were of about 1,500 U/l and 200 U/l, respectively. Furthermore, laccase activity (around 150 U/l) was only detected in manganese (IV) oxide supplemented cultures.The polymeric dye Poly R-478 (0.02 w/v) was added to three-day-old cultures. A percentage of biological decolourization of about 85% was achieved using cultures supplemented with veratryl alcohol, whereas MnO2 cultures showed a rather lower percentage of around 58% after nine days of dye incubation. Moreover, a correlation between MnP activity and Poly R-478 decolourization could be observed, indicating that this enzyme is mainly responsible for dye degradation.In the present work, the in vivo decolourizing capability of the ligninolytic complex secreted by P. chrysosporium was investigated under the above-mentioned cultivation conditions, employing a model compound, such as the polymeric dye Poly R-478.
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 187-187 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 189-201 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Desulfovibrio vulgaris strain PY1 was isolated from a 3-chlorobenzoic acid (3CBA) degrading anaerobic enrichment culture, using anaerobic Percoll density centrifugation. When grown on pyruvate (20 mM), in the absence of sulphate and under strict anaerobic conditions, this organism converted not only the co-substrates benzoate (BA), 3-amino-BA and 3CBA to the corresponding alcohols but also ten other different halogenated benzoic acids, viz., 4-Cl-, 3-Br-, 4-Br-, 3-I-, 3-F-, 4-F-, 2,4-di-Cl-, 2,5-di-Cl-, 3,4-di-Cl- and 3,5-di-Cl-BA. This was verfied with HPLC and GC/MS spectrometric analyses. The yields of the co-substrate converted after 30 days of growth were between 20% and 88%, depending on the compounds which had been added at initial concentrations of 500 μM. Sulphate, sulphite, thiosulphate and disulphite inhibited the formation of 3-Cl-benzyl alcohol (3CBOH), i.e. a 97 to 99% inhibition, and nitrate and sulphur had no effect (a 7-10% inhibition). In cell-free extracts, the reduction of 3CBA to 3CBOH required strict anaerobic conditions, pyruvate or H2 as electron donors and the addition of methylviologen (MV), FAD, FMN or ferredoxin as electron carriers. The specific activity of the reduction of 3CBA to 3CBOH in crude extract was 5.3 nmol/(mg protein min). The reaction was not inhibited by additions of sulphate or sulphite (5 mM), but was completely inhibited at concentrations of 10 mM 3CBA or 50 mM BA. A carboxylic acid reductase (aldehyde dehydrogenase), which acted on non-activated 3CBA and was responsible for the reduction of 3CBA to 3-Cl-benzaldehyde, was found in the solube fraction (94% of the total activity). These results demonstrate that strain PY1 was able to effectively reduce a wide range of halogenated benzoic acids to the corresponding alcohols.
    Additional Material: 3 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 203-218 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The recent upsurge in information technology has provided the international community with an easy access to professional journals (e.g. Electronic Journal of Biotechnology at http://www.ejb.org; etc.), discussion groups (e.g. bioenergy@cret.org; digestion@crest.org; etc.) and recently to electronic international conferences (e.g. ICIBS; http://www.cid.harvard.edu/cidbiotech, etc.) as well as a series of biotechnological information material (e.g. http://www.psrast.org, etc.) to stay in contact and receive up-to-date information in biotechnology. There is no doubt that this new technology will be more cost effective in future and reach more people in communities around the globe.This review reports on one such an electronic conference aiming at bridging the communication gap between developed and developing countries. This conference dealt with integrated biosystems and has provided an excellent forum for more than 100 active participants from all regions of the world. As has been demonstrated in this review, the conference was able to show the very different approaches towards the use of biotechnology in developed and developing countries, cold and tropical climate regions owing to their different ecological, economical and societal problems. It also demonstrated very clearly that the field of molecular genetics and/or genetic engineering is not a priority issue in developing countries, but rather the need for clean technologies, multiproduct formation through socio-economic integrated biosystems, e.g. incorporating microbial waste management into agro-industries, in human activities and their roles in creating better health conditions, a better environment and sustain development.It is hoped that this review will lead to a greater use of the electronic facilities available to inform and educate both the northern and the southern communities more readily of their needs and requirements to improve understanding and efforts for a sustainable future.
    Additional Material: 4 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 275-288 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The purpose and scope of this article is to introduce capable zeolites into downstream processing of natural compounds, especially flavour compounds like 2,5-dimethyl-4-hydroxy-3(2H)-furan-3-one (Furaneol®Furaeol is a registered trademark of FIRMENICH, Ch). The synthesis and the recovery of Furaneol from L-rhamnose are presented. Therefore adsorption isotherms of the zeolites ZSM5 and DAY with varying modules have been determined and adsorption experiments using model and reaction mixtures of Furaneol synthesis were performed and will be discussed.
    Additional Material: 11 Ill.
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  • 16
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fermentation process for manufacturing 1,4-piperazinium-(L,L)-dilactate from renewable raw materials and a method for processing this product into L,L-dilactide are described. Lactic acid fermentation with Lactobacillus paracasei was modified in such a way that pH control occurred by using an aqueous solution of piperazine as a correcting agent instead of sodium hydroxide solution. The production of a stoichiometrically composed piperazinium lactate was possible when the pH was 5.0. From 5.0 kg of glucose and 2.15 kg of piperazine, 6.65 kg of 1,4-piperazinium-(L,L)-dilactate were formed in the fermentation process. Separation from fermentation broth, purification and concentration of the product in aqueous solutions were carried out by means of ultrafiltration, nanofiltration and electrodialysis. Total product retention by the membranes used was about 33%. The crystalline salt was obtained by vacuum evaporation. Processing of the 1,4-piperazinium-(L,L)-dilactate into L,L-dilactide was performed in a special glass reactor. A product yield of 70% was achieved. The purified product was characterized by elementary analysis, as well as solubility behaviour, polarity and spectroscopic data. An overall process consisting of the stages fermentation, purification and concentration of piperazinium dilactate as well as cyclization of the latter to dilactide is described.
    Additional Material: 9 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 161-168 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Five different chemical reagents and γ-rays were tested for the sanitization of immobilized biocatalysts with high penicillin G acylase (PGA) activity. The most effective chemical reagents were N-cetyl-N,N,N-trimethylammonium bromide (CTAB) and 2-isopropyl-5-methylphenol (thymol). The optimum concentration of CTAB for the treatment of the immobilized enzyme was 0.25% [w/v] and 1 h, for immobilized cells 0. [w/v] and 3 h. The optimum concentration of thymol for the immobilized enzyme was found to be 0.1% [w/v] and 1 h, for immobilized cells 0.27% [w/v] and 2 h. The optimum dose of γ-rays for the sanitization of the immobilized enzyme was established as 3.2 kGy, for immobilized cells as 4.5 kGy.
    Additional Material: 5 Tab.
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  • 18
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 53-64 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: An advanced primary treatment process for a municipal waste water was systematically studied, using a bio-flocculation-adsorption, sedimentation and stabilzation process (BSS). It was shown that the organic removal efficiency was higher than that of the traditional primary treatment processes but lower than that of the traditional secondary treatment processes. Both adsorption and bio-flocculation played an important role in the removal of pollutants. The activated sludge within the bio-flocculation-adsorption tank could be considered a bio-flocculent which improved the quality of the effluent from the primary treatment process. As the effluent of the BSS process did not meet the requirements for a typical secondary effluent, the process may be regarded as an advanced (or enhanced) primary treatment process, suitable for waste water containing a high concentration of suspended solids and colloidal particles.
    Additional Material: 7 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 67-73 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The concentration of airborne fungal spores and bacteria as related to room temperature, humidity and occupancy levels within a library building in Singapore was determined. Measurement of indoor air quality with respect to microorganisms is of particular importance in tropical environments due to the extensive use of air-conditioning systems and the potential implications for human health. This study has revealed a number of interesting relationships between the concentrations of fungal spores and bacteria in relation to both environmental and human factors. The levels of fungal spores measured in the indoor environment were approximately fifty times lower than those measured outside, probably because of the lowered humidity caused by air-conditioning in the indoor environment. The variation in fungal spore concentration in the outdoor environment is likely to be due to the diurnal periodicity of spore release and the response to environmental factors such as light temperature and humidity. The indoor concentration of fungal spores in air was not clearly correlated to concentrations measured in air outside of the library building and remained relatively constant, unaffected by the difference in the numbers of occupants in the library. In contrast, the indoor concentrations of bacteria in air were approximately ten times higher than those measured outdoors, indicating a signficant internal source of bacteria. The elevated levels of indoor bacteria were primarily attributed to the number of library occupants. Increased human shedding of skin cells, ejection of microorganisms and particulates from the respiratory tract, and the transport of bacteria on suspended dust particles from floor surfaces probably accounts for the strong positive correlation between occupancy levels and the concentration of bacteria in internal air.
    Additional Material: 2 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 22
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 96-96 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 87-96 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Preliminary results on the novel use of the bacterium Thiobacillus ferrooxidans (ATCCJ 3598 and ATCC33020) for the micro-machining (or biomachinig) of metals are reported. Biomachning is a controlled microbiological process to selectively form microstrucutures on a metal work-piece by metal removal (or dissolution) using microorganisms. Applying copper and mild steel as work-pieces, it was shown that the mass removed increased proportionately with machining time. In another experiment, the work-pieces were coated with organic photo-resistive materials to mask (i.e. protect) certain regions of the metlas, thereby defining the microstructure to be formed. The unmasked regions were successfully biomachined; the final machined profile was shown to be similar to the coating image on the original metal. Although biomachining proceeded at a slower rate than chemical machining, the undesired leaching of the metal in the region under the masked area (termed undercutting) was not as severely encountered when compared with the latter. This work demonstrates the potential use of microorganisms for the biomachining of metals. As a “green process”, the innovative use of T. ferrooxidans for the micro-machining of metals opens up the possibility of biomachining as an alternative to conventional metal processing.
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  • 24
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the microbial treatment of a sandy model soil artificially contaminated with polycyclic aromatic hydrocarbons (PAHs), a large residual pollution was found. The remainig PAHs were sorbed into the micropores of the soil and were therefore not bioavailable. Using a lab-scale precolator, the microbially pretreated soil was subjected to aftertreatment with surfactants with the aim of further degradation of its pollution. Two commercial nonionic surfatants of the polyethoxylate type, Präwozell F1214/5 N and Sapogenat T-300, were used. The surfactants differ both in their physicochemical properties (CMC value, PAH solubilization capacity, adsorption onto soil) and in their microbial degradability. During aftertreatment under permanently aerobic conditions, only a weak PAH accumulation in the liquid phase was observed, which was due to a low solubilization rate as well as to simultaneous microbial degradation of the dissolved PAHs. Temporary anaerobiosis successfully suppressed the microbial degradation of both the surfactant and the solubilized PAHs, resulting in a more intensive PAH accumulation. But the PAH content of the soil - the essential criterion for evaluating the efficiency of surfactant application - was not decreased to a larger extent with surfactants than without them. To find out why the surfactants failed to act, the surfactant and hydrocarbon distribution among the liquid and solid phases was studied in mixtures of phenantherne-spiked solis and Präwozell-containig liquids; at heavy phenanthrene loading, the aqueous phase was saturated with PAH; at weak loading, it was unsaturated. Model-aided data analysis showed that the soil may contain PAH in two fractions: strongly sorbed into soil pores and, in the case of heavy loading, also weakly attached to the soil surface. The latter is easily extractable, resulting in a PAH-saturated liquid, while strongly adsorbed PAH is only partially dissolved due to competition between the micelles and the soil pores for the PAH. The microbially pretreated soil contains only strongly bound PAHs, which are as difficult to extract by surfactants as they are poorly accessible for microbes.
    Additional Material: 8 Ill.
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  • 25
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Autochthonous bacteriocenoses in semiarid soils in Patagonia were found to be capable of rapidly adapting to high contamination with crude oil. This adaptation at community level is due to the selective enrichment of hydrocarbon-utilizing bacteria always present in these soils. Immediately after a heavy contamination with crude oil, the authochthonous bacteriocenosis contained about 28% hydrocarbon-utilizing bacteria which could be classified into eight ecotypes with characteristic metabolic profiles. Mainly n-alkanes were used as growth substrates of representative strains. After seven months' exposure to crude oil, the bacteriocenosis consisted almost entirely of hydrocarbon-utilizing bacteria. At least fourteen ecotypes were distinguishable, and the majority of representative strains were able to metabolize a broad spectrum of aliphatic and aromatic hydrocarbons. Corresponding to the significant alteration of the physiological diversity, drastic changes to the taxonomic diversity were also found. Whereas at the beginning of the study the autochthonous bacteriocenoses were dominated by GRAM-positive genera of the Actinomycetales (Dietzia, Gordona, Nocardia, Rhodococcus, Streptomyces) with high ecological potency, after just two months' exposure to crude oil, GRAM- negative bacteria (especially Pseudomonas stutzeri) became predominant within the hydrocarbon-utilizing bacteriocenoses accompanied by some GRAM-positive genera of the Actinomycetales with a significantly lower abundance. These findings underline the importance of Pseudomonas and some genera of Actinomycetales for processes of natural attenuation and the technically supported in situ bioremediation of soil polluted by crude oil in Patagonia.
    Additional Material: 2 Ill.
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  • 26
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    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 149-159 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Some parameters of the production of an alkaline protease by Rhizopus oryzae in the solid state fermentation of wheat bran were optimized. Using the optimum parameters of an inoculum age of 7 days, an incubation time of 9 days, an amount of CZAPEK-DOX (liquid medium) of 6 ml/g bran and an incubation temperature of 33°C, an activity of 50 U/g bran was achieved. The initial pH of the CZAPEK-DOX medium had little effect. Re-incubation of mouldy bran with only fresh CZAPEK-DOX yielded 3 times total activity compared to single-cycle fermentation. As for the effect of the amount CZAPEK-DOX medium, the water constituent contributed more to activity increase than did the salt component. The ARRHENIUS activation energies were 23 and 7.9 kcal/mole below and above the optimum of 33°C, respectively. In all the studies, along with protease production, variation of protein content and specific activity were also observed. Attempts were made to explain the effects and also gauge their implications for large-scale production.
    Additional Material: 4 Ill.
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  • 27
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 28
    Electronic Resource
    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 29
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Because of the growing utilization of renewable raw materials, the technical use of lignocellulosic fibres from wood and other annual plant materials is becoming increasingly important. The conventional production process of fibreboards is characterized by high-energy consumption and use of ecologically insecure synthetic lesins. Approximately 40 to 45% of the total energy expenditure are used for the thermo-mechanical pulping. Because of high plastication temperatures, an inactive lignin crust on the fibre surface is formed. For that reason, for glueing of the fibres, urea formaldehyde and melamin resins are usually used. The costs for the resin amount to approximately 50% of the entire material costs. In addition, environmental problems are caused. The aim of our investigation is the reduction of energy and resin consumption by enzymatic modification of wood chips and the enzymatic activation of the inherent bonding strength of the material. The first industrial use of fungi for the modification of wood was in the production of “Myco wood”. Pleurothus ostreatus and Trametes versicolor were applied for nonsterile delignification of beech wood. The present investigation of the authors deals with the mycological pre-treatment of wood chips in order to reduce the energy consumption during wood pulping. The screening results favour the brown rotter Gleophyllum trabeum for pinewood (Pinus silvestris) and the white rotter Trametes hirsuta for beech (Fagus silvatica). Both species show resistance against mould fungi. The use of submerged inoculum of these fungi has the advantage over wheat inoculum that the lag phase is less than 12 hours and that the addition of nutrients or fungicides is not necessary. Short-time wood chip incubation results in a 40% decrease of energy consumption during thermo-mechanical pulping and in improved fibreboard properties. Lignin reduction could not be determined by gravimetrical and x-ray microanalysis.Comparative investigations of fibre incubation using laccase, a submerged culture of Trametes versicolor and rape straw fibres show a high increase in bending and tensile strength and an improvement in the hygroscopic properties of glue-free fibre boards for the last two incubation kinds. Similar effects have been obtained incubating pine wood fibres for the production of fibre sheets with enzyme medium of Trichoderma reseei.
    Additional Material: 4 Ill.
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  • 30
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    Electronic Resource
    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 335-350 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the 20th century, important relationships developed between the oil industry and both microbiological and biotechnological research. Basic microbiological research has played an important role in both the exploration and production sectors of the oil industry, but as the maturity of the industry has progressed, such contributions have been relegated with respect to their importance. With respect to refining and petrochemicals manufacture, process routes have been extensively researched, but only rarely have the biotechnological solutions developed satisfied the economic criteria that resulted in major investment. In fact, situations exist where investment has occurred, but project life was unrealistically short, suggesting a need for extreme caution when evaluating biotechnological processes for the oil industry. However, as far as engineered processes for both biotreatment and bioremediation are concerned, the fundamental research that has underpinned other areas of hydrocarbon microbiology will finally prove to be of both technical and economic value, in ensuring that the essential needs of treatment, rather than disposal, and restoration, rather than environmental destruction, can be satisfied by the oil and other industries involved in both geochemical manipulation and natural resource exploitation.
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  • 31
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of different growth-limiting factors - namely the sources of carbon, nitrogen and phosphorus and the dilution (growth) rate - on the ice-nucleation activity of Pseudomonas syringe CCM 4073 was studied. A higher ice-nucleation activity was observed at a lower dilution (growth) rate (D = 0.1 h-1) than at a higher dilution (growth) rate (D = 0.3 h-1). Remarkable differences in ice-nucleation activity were found in its dependence on the growth-limiting factor. The highest ice-nucleation activity was observed under carbon limitation (T90 = -2.7°C), a medium activity under nitrogen limitation (T90 = -5°C) and lowest activity under phosphorus limitation (T90 = -12.3°C). After the addition of excess nitrogen or phosphorus to steady-state cultures, the ice-nucleation activity was restored.
    Additional Material: 1 Tab.
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  • 32
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 33
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 65-65 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 34
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 35
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 41-52 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies were carried out to evaluate the feasibility of using coffee industry residues, viz. coffee husk, coffee leaves and spent coffee ground as substrates in solid state fermentation (SSF) to cultivate edible mushrooms Pleurotus. Eight strains of Pleurotus ostreatus and two strains of Pleurotus sajor-caju were screened on a medium prepared from aqueous extract of coffee husk and agar. Based on best mycelial growth (9.68 mm/day) and biomass production (43.4 mg/plate in 9 days at 24°C), the strain P. ostreatus LPB 09 was selected for detailed studies. SSF was carried out using these substrates under different moisture conditions (45-75%) and spawn rates (2.5-25%). In general, although a 25% spawn rate appeared superior, the 10% spawn rate was recommended for all the three substrates in view of the process economics, as there was not any significant difference in the increase with 10 to 15%. The ideal moisture content for mycelial growth was 60-65% for coffee husk and spent coffee ground, and 60-70% for coffee leaves. The biological efficiency (BE), which is defined as the ratio of the weight of fresh fruiting bodies to the weight of dry substrate, multiplied by 100, and which indicates the fructification ability of the fungus for utilizing the substrate, was best with coffee husk. With coffee husk as the substrate, the first fructification occurred after 20 days of inoculation, and the biological efficiency reached about 97% after 60 days. When coffee leaves were used as the substrate, no fructification was observed even upon prolonged cultivation. With spent ground as the substrate, the first fructification occurred 23 days after inoculation and the biological efficiency reached about 90% in 50 days. There was a significant decrease in the caffeine and tannin contents (61 and 79%, respectively) of coffee husk after 60 days. It was remarkable to observe that caffeine was adsorbed onto the fruiting body (0.157%), indicating that it was not completely degraded by the fungal culture. However, no tannins were found in the fruiting body, indicating that the fungal strain was capable of degrading them. The results showed the feasibility of using coffee husk and spent coffee ground as substrates without any pre-treatment for the cultivation of edible fungi in SSF, and provided one of the first steps towards an economical utilization of these otherwise unutilized or poorly utilized residues.
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  • 36
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 75-81 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Serratia marcescens biovar A2/A6 is able to produce a red pigment as a secondary metabolite which has antimicrobial activity. This paper describes its growth and biopigment formation in batch cultures, in media containing different concentrations of lactic acid and beef extract as carbon and nitrogen sources, respectively. An unstructured model has also been developed to describe its growth, lactic acid uptake and biopigment formation. The comparison of simulated and experimental data shows that the proposed model predicts reasonably well the system behaviour over a range of conditions.
    Additional Material: 2 Ill.
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  • 37
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 97-98 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 38
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000) 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 39
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 334-334 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 40
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The impact of hydrocarbon remediation on several enzyme activities (catalase, dehydrogenase, lipase, protease, urease, alkaline phosphomonoesterase, fluorescein diacetate hydrolysis) and microbial properties (biomass-C, respiration, N-mineralization, qCO2, microbial counts) was evaluated in a laboratory study over a period of 10 weeks. A pristine soil was contaminated with diesel oil (10 mg/g soil) or with a mixture of phenanthrene and naphthalene (total amount 1 mg/g soil) and supplemented with inorganic nutrients to give a C:N ratio of 20:1. The corresponding controls consisted of uncontaminated nutrient-supplemented soil. Oil contamination caused a significant initial increase of all biological parameters measured. In the presence of PAHs, biomass-C, respiration, protease activity and heterotrophic counts were significantly enhanced, while urease activity was depressed. N-mineralization was initially, however, reversibly inhibited in the presence of oil and PAHs.The measured parameters behaved differently over time: Biomass-C, respiration and alkaline phosphomonoesterase activity reached a maximum activity after about 2-5 weeks, corresponding to the period during which the majority of hydrocarbons disappeared, and declined thereafter to the background level. Activities of catalase and dehydrogenase also followed this pattern, however, were characterized by fluctuations. Activities of lipase, protease, urease and fluorescein diacetate hydrolysis increased and remained almost constant throughout the incubation period.
    Additional Material: 10 Ill.
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  • 41
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    Berlin : Wiley-Blackwell
    Acta Biotechnologica 20 (2000), S. 351-368 
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: The action resonance theory (ART), a hypothesis based on a logical extension of EINSTEIN's theory of Brownian movement, suggests that the genotype × environment interaction can be modelled as forceful encounters of the gene-products of an organism with its environment. This model has implications for molecular and cell biology, morphogenesis, evolutionary development via mutation, the mechanism of natural selection and overall function of ecosystems, extending SCHRÖDINGER's programme for molecular biology. Action, a thermodynamic property with the same physical dimensions as angular momentum and PLANCK's quantum of action, is proposed to be reversibly generated as a result of the molecular exchange of quanta, which become resonant at equilibrium, corresponding to an optimum degree of entropy and action for living systems. Because the theory can potentially predict solutions to unsolved problems such as the folding of proteins it has strong implications for successful genetic modification of organisms and for biotechnology in general; the design of a programme of research to test this theory is proposed. A key element in this research programme, improving productivity and sustainability, would be the need to select genetically modified strains in the ecological environment or niche in which they are required to function.
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  • 42
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
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  • 43
    ISSN: 0138-4988
    Keywords: Life Sciences ; Life Sciences (general)
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuous counter-current chromatographic processes have been successfully used in the petrochemical and sugar industry over the last 30 years. Only recently has simulated moving bed (SMB)-technology attracted widespread interest in the pharmaceutical industry, mainly as a very efficient system for chromatographic enantioseparation. The application of this technique to the downstream processing of biotechnological products requires some specific changes to meet the special demands of bioproduct isolation. Production processes are set up on an multi-ton scale, for example, for the purification of fructose with both yield and purity higher than 90%. Examples for other mono- and oligosaccharides are reported. In the purification of fatty acids or fat soluble vitamins, SMB technology under supercritical fluid conditions gives additional benefits and increases the productivity by a factor of four when a pressure gradient is applied. Another field of operation is the isolation of drug compounds from natural sources where different batch- and SMB-chromatographic steps could be successfully combined. First examples are reported for cyclosporine A and paclitaxel isolation. Finally, step-gradient elution modes can be used continuously, as demonstrated for the isolation of monoclonal antibodies.
    Additional Material: 6 Ill.
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  • 44
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 68-77 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoelectron Spectra and Molecular Properties, XXVI. The Delocalisation of Sulfur Electron Pairs in Sulfides and DisulfidesThe photoelectron (PE) spectra of sulfides R—S—R (R=H, CH3, C2H5, n- und i-C3H7, n- and tert-C4H9) and disulfides R—S—S—R (R=H, CH3, C2H5, n- and i-C3H7, tert-C4H9, —[CH2]4—) are comparatively discussed. For sulfides the first ionization energy, which decreases as expected with increasing degree of alkylation, can also be obtained from the charge transfer excitation energies of their σ-complexes with tetracyanoethylene (TCNE). Disulfides show a splitting of the first PE-band in a clear dependence on the dihedral angle of the sulfur electron pairs. All observations can be rationalised within MO models as interactions of the sulfur electron pairs with the σ-skeleton and/or with each other.
    Notes: Die Photoelektronen(PE)-Spektren von Sulfiden R—S—R (R=H, CH3, C2H5, n- und i-C3H7, n- und tert-C4H9) und Disulfiden R—S—S—R (R=H, CH3, C2H5, n- und i-C3H7, tert-C4H9, —[CH2]4—) werden vergleichend diskutiert. Bei den Sulfiden R—S—R kann die mit steigendem Alkylierungsgrad erwartungsgemäß abnehmende erste Ionisierungsenergie auch aus den Charge-transfer-Anregungsenergien ihrer σ-Komplexe mit Tetracyanäthylen (TCNE) abgelesen werden. Bei Disulfiden R—S—S—S—R wird eine Aufspaltung der ersten PE-Bande in deutlicher Abhängigkeit vom Diederwinkel zwischen den Schwefel-Elektronen-paaren beobachtet. Die Befunde lassen sich mit MO-Modellen als Wechselwirkungen der Schwefel-Elektronenpaare mit dem σ-Gerüst und/oder untereinander verstehen.
    Additional Material: 6 Ill.
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  • 45
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 93-101 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nickelalkyl Ylid ComplexesFrom reactions of [(CH3)3P]3 Ni(CH3)2 and [(CH3)3P]2Ni(CH3)Cl with the ylid (CH3)3PCH2, molecular (1) an ionic complexes (2) are obtained, containing three covalent Ni—C-σ-bonds of square planar nickel atoms. These bonds are strongly stabilized by the proximity of the ylid onium center. Excess ylid converts 2 into a binuclear complex 3, where the metal atoms are bridged by dimethylphosphonium-bismethylid units, with formation of [(CH3)4P]Cl as a byproduct. An isoelectronic dimethylphosphinate complex, 4, containing a similar eight-membered ring structure, has also been prepared.
    Notes: Durch die Reaktion von Dimethyltris(trimethylphosphin)nickel und Methylbis(trimethyl-phosphin)nickel-chlorid mit Trimethylmethylenphosphoran werden molekulare (1) bzw. ionische (2) Ylid-Komplexe erhalten, in denen das quadratisch-planar konfigurierte Nickel-atom jeweils drei kovalente Ni—C-σ-Bindungen ausbildet. Diese Bindungen werden durch das Onium-Zentrum der Ylide erheblich stabilisiert. 2 liefert mit überschüssigem Ylid unter Abspaltung von [(CH3)4P]Cl einen zweikernigen Komplex 3, dessen Metallatome durch Dimethylphosphonium-bis-methylid-Brücken verbunden sind. Hierzu existiert ein isoelektronischer Dimethylphosphinat-Komplex 4, der ebenfalls Achtringstruktur besitzt.
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  • 46
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 123-127 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of carbonyl-stabilized Sulfonium-ylides of 1,3-Dithiolane with Acylating Reagents and Activated AcetylenesIn aqueous sodium hydroxide monophenacyl-1,3-dithiolanium bromides 3 form carbonylstabilized 1,3-dithiolanium-1-phenacylides 4. These yield with acylation reagents and activated acetylenes new resonance-stabilized sulfonium-ylides 6, 8, 10.
    Notes: Monophenacyl-1,3-dithiolanium-bromide 3 bilden in wäßriger Natronaluge carbonyl-stabilisierte 1,3-Dithiolanium-1-phenacylide 4. Diese reagieren mit Acylierungsmitteln und aktivierten Acetylenen zu neuen mesomeriestabilisierten Sulfonium-yliden 6, 8, 10.
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  • 47
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 145-151 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Amino Acids and Peptides, IX. On Pyruvoyl Amino AcidsAmino acid derivatives were tranformed to Pyruvoyl amino acid derivatives by use of pyruvoyl chlorid, p-nitrophenyl pyruvate, hydroxymaleic anhydride and the DCC-procedure. The application range of the different acylations is discussed. A convenient method for the preparation of pyruvoyl chloride is given.
    Notes: Aminosäurederivate werden mit Brenztraubensäurechlorid, Brenztraubensäure-p-nitrophenylester, Hydroxymaleinsäureanhydrid und mit Hilfe des DCC-Verfahrens zu Pyruvoylaminosäurederivaten umgesetzt. Die Anwendungsbreite der verschiedenen Acylierungen wird verglichen. Ein Weg zur praktischen Herstellung von Brenztraubensäurechlorid wird ausgearbeitet.
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  • 48
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 253-262 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of Hexakis(phenylthio)ethaneThe structure of hexakis(phenylthio)ethane has been determined by single crystal X-ray diffraction. The phase determination was carried out by means of the Symbolic Addition Method. The structure has been refined with 1780 observed reflections to an R-value of 10.9%. The pseudo bodycentered unit cell contains two molecules, which are situated at the center at 0, 0, 0 and 1/2, 1/2, 1/2, respectively. The bodycentering is almost perfect for the six sulfur atoms, but does not involve the central ethane bonding, which implies that the sulfur atoms, that are connected by the centering, are bonded to different carbon atoms. The six sulfur atoms are staggered around the ethane C—C bond. The S—C—S angles of 113° are larger than the ideal tetrahedrane angles by the same amount by which the S—C—C angles of 105° are smaller. The ethane C—C distances are 1.59 and 1.56 Å respectively.
    Notes: Die Struktur des Hexakis(phenylthio)äthans wurde mit Röntgenmethoden bestimmt. Die Phasenbestimmung wurde mit der symbolischen Additionsmethode durchgeführt. Die Struktur wurde unter Benutzung von 1780 beobachteten Reflexen bis auf einen R-Wert von 10.9% verfeinert. Die pseudoinnenzentrierte Elementarzelle enthält zwei Moleküle, die um die Symmetriezentren in 0, 0, 0 bzw. 1/2, 1/2, 1/2 gelagert sind. Die Innenzentrierung ist nahezu genau für die sechs Schwefelatome, aber gilt nicht für die zentrale Äthanbindung, was zur Folge hat, daß die durch Zentrierung verbundenen Schwefelatome an verschiedene Kohlenstoffatome gebunden sind. Die sechs Schwefelatome sind gestaffelt um die Äthan-C—C-Bindung angeordnet. Die S—C—S-Winkel sind mit 113° etwas größer, die S—C—C-Winkel mit 105° um denselben Betrag kleiner als der Tetraederwinkel. Die Äthan-C—C-Abstände betragen 1.59 bzw. 1.56 Å.
    Additional Material: 5 Ill.
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  • 49
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 305-316 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Benzothiazole N-Oxides, II. New Synthesis of Substituted 2-BenzothiazolonesIn the presence of phosphoryl chloride, 2-carbamoylbenzothiazole N-oxides undergo a new intramolecular redox reaction to give 2-benzothiazolones. In two cases investigated, also 2-ethoxycarbonylbenzothiazole N-oxides undergo this rearrangement. The spectroscopic data are discussed.
    Notes: 2-Carbamoylbenzothiazol-N-oxide gehen in Gegenwart von Phosphoroxychlorid eine neuartige intramolekulare Redoxreaktion unter Bildung von 2-Benzothiazolonen ein. In zwei untersuchten Fällen unterliegen unterliegen auch 2-Äthoxycarbonylbenzothiazol-N-oxide dieser Umlagerung. Spektroskopische Daten werden diskutiert.
    Additional Material: 7 Tab.
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  • 50
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aromatic Sulfenyl Chlorides, IX. Preparation, Oxidation, and Spectroscopic Investigation of 1-Substituted 5-Tetrazolyl Aryl Disulfides1-Substituted 5-tetrazolyl mesityl disulfides were synthesized which on oxidation with hydrogen peroxide gave disulfide S2, S2-dioxides (thiolsulfonates). The structure of these as well as that of the 1-substituted 5-tetrazolyl p-tolyl disulfide S2, S2-dioxides synthesized earlier was elucidated by means of their i. r. and n. m. r. spectra. The supposed structures have been established by synthesis.
    Notes: Es wurden 1-substituierte (5-Tetrazolyl)mesityldisulfide hergestellt, welche zu Disulfid-S2, S2-dioxiden (Thiosulfonate) oxidiert wurden. Deren Struktur und die der früher hergestellten 1-substituierten (5-Tetrazolyl)p-tolyldisulfid-S2, S2-dioxide wurde anhand ihrer IR- und NMR-Spektren wahrscheinlich gemacht. Die angenommenen Strukturen wurden durch Synthese bewiesen.
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  • 51
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 367-379 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Lithio-1,3,5-trithianes Generation in Solution, Reactions with Electrophiles, and Use in Nucleophilic Acylation1,3,5-Trithiane and 2-mono- as well as 2,4,6-trisubstituted trithianes are shown to be metallated by n-butyllithium in THF. Reaction of the lithio derivatives thus obtained with electrophiles leads to more highly substituted trithianes which in some cases can be isolated in a pure form. The n.m.r. spectra of the products at room temperature are described. Mercury(II)-assisted solvolysis of alkyltrithianes „liberates“ the most highly substituted carbon with formation of carbonyl compounds or their O-acetals. This completes a sequence of reactions which suggests use of lithiotrithianes as reagents for nucleophilic acylation. Advantages and disadvantages of this procedure compared to the dithiane method are discussed.
    Notes: 1,3,5-Trithian selbst sowie 2-mono- und 2,4,6- trisubstituierte Trithiane lassen sich mit n-Butyllithium in Tetrahydrofuran metallieren. Umsetzung der Lithiumderivate mit Elektrophilen führt zu höher substituierten Trithianen, die teilweise in reiner Form isoliert werden können. Die NMR-Spektren der erhaltenen Produkte bei Raumtemperatur werden beschrieben. Quecksilber(II)-assistierte Solvolyse von alkylierten Trithianen führt zu Carbonyl-verbindungen oder deren O-Acetalen unter „Herauslösung“ des höchstsubstituierten C-Atoms, was die Verwendung von Lithiotrithianen als nucleophile Acylierungsmittel ermöglicht. Vor- und Nachteile gegenüber der Dithian-Methode werden diskutiert.
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  • 52
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Dependence of the Bond-length in some N,O-Dibenzoylhydroxylamines on the Torsion of the Carboxylic and Hydroxamic Groups against the Benzene Nuclei. The Crystal Structures of N,O-Dibenzoyl-(C14H11NO3), N,O-Bis(2-chlorobenzoyl)-(C14H9Cl2NO3), N-BenzoylO-p-toluoyl- (C15H13NO3), and N-Benzoyl-O-o-toluoylhydroxylamines (C15H13NO3)The crystal structures of four N,O- dibenzoylhydroxylamines - 1: N,O-dibenzoylhydroxylamine (C14H11NO3), 2: N,O- bis(2-chlorobenzoyl)hydroxylamine (C14H9Cl2NO3), 3: N-Benzoyl-O-p toluoylhydroxylamine (C15H13NO3), 4: N-benzoyl-O-o- toluoylhydroxylamine (C15H13NO3) - have been determined by X-ray techniques, using direct methods for phase determination. The torsion angles ϕ of the C—C- bonds between the phenyl groups and the hydroxamic acid groups or the carboxylic groups, respectively, have been calculated. The values of the intramolecular distances of these bonds, plotted versus cos2 ϕ, can be approximated by a straight line. Extrapolating to ϕ = 90°, the pure sp2-sp2-C—C-single-bond is found to be 1.513 Å.
    Notes: Die Kristallstrukturen von vier N,O- Dibenzoylhydroxylaminen - 1: N,O-Dibenzoylhydroxylamin (C14H11NO3), 2: N,O -Bis(2-chlorbenzoyl)hyroxylamin (C14H9Cl2NO3), 3: N-Benzoyl-O-p-toluoylhydroxylamin (C15H13NO3), 4: N- Benzoyl-O-o-toluoylhydroxylamin (C15H13NO3) - wurden röntgenographisch unter Anwendung direkter Methoden zur Lösung des Phasenproblems bestimmt. Die C—C- Bindungslängen zwischen den Phenylgruppen einerseits und den Hydroxamsäure- bzw. Carboxylatgruppen andererseits lassen sich als Funktion der Verdrillungswinkel ϕ dieser Bindung durch eine Gerade darstellen, wenn man die Bindungslängen gegen cos2 ϕ aufträgt. Der reine sp2-sp2-C—C- Einfachbindungsabstand (ϕ = 90°) ist danach 1.513 Å.
    Additional Material: 10 Ill.
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  • 53
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 680-685 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Synthesis of Tetracyclo[3.3.0.02.8.04.6]octan-3-ones by Intramolecular Thermal [2π + 2σ]-CycloadditionThe synthesis of the tetracyclooctanone 19 by thermolysis of the tricyclic acetal 15 and subsequent removal of the acetal group is described. Thus, a third synthetic access to this system is now available. The reaction involves the cycloaddition of a thermally ring-opened cyclopropane to a double bond.
    Notes: Die Synthese des Tetracyclooctanons 19 durch Thermolyse des tricyclischen Acetals 15 und anschließende Entacetalisierung wird beschrieben. Damit bietet sich ein dritter synthetischer Zugang zu diesem System an. Die Reaktion beinhaltet die Cycloaddition eines thermisch ringgeöffneten Cyclopropans an eine Doppelbindung.
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  • 54
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 717-720 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 731-734 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 56
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 785-795 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pteridines, LX. Synthesis and Autoxidation of 7, 8-DihydroxanthopterinsThe synthesis of 7,8-dihydroxanthopterin (18) and of various N- and C-methyl derivatives (19-27, 30) is described. Their pKa values and u.v. spectra have been determined and the behaviour during autoxidation has been investigated. The monoanions are subject to autoxidation which is catalysed strongly by ammonia and primary amines. A mechanism for the autoxidation is discussed in which the existence of various intermediates is based on the oxidative behaviour of differently blocked N- und C-methyl derivatives.
    Notes: Die Synthese des 7,8-Dihydroxanthopterins (18) und verschiedener N- und C-Methyl-Derivate (19-27, 30) wird beschrieben. Ihre pKa-Werte und UV-Spektren werden bestimmt und ihr Autoxidationsverhalten untersucht. Die Monoanionen unterliegen der Autoxidation, welche durch Ammoniak und primäre Amine stark katalysiert wird. Ein Mechanismus wird diskutiert und verschiedene Zwischenprodukte anhand von blockierten N- und C-Methyl-Derivaten wahrscheinlich gemacht.
    Additional Material: 4 Ill.
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  • 57
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 832-837 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of 6,6-Bis(dimethylamino)fulvene6,6-Bis(dimethylamino)fulvene crystallizes in the space group Pn21a, the lattice constants being ao = 13.344 Å, bo = 7.844 Å and co = 9.438 Å. The structure has been solved by superposition and by direct methods in the space group Pnma. The structure was refined by block-diagonal-least-squares to R = 0.037.
    Notes: Das 6,6-Bis(dimethylamino)fulven kristallisiert in der Raumgruppe Pn21a mit den Gitter-konstanten ao = 13.344 Å, bo = 7.844 Å und co = 9.438 Å. Die Struktur wurde durch Superposition und anschließende Resymmetrisierung der Patterson-Funktion und mit direkten Methoden in der zentrosymmetrischen Obergruppe Pnma gelöst.
    Additional Material: 2 Ill.
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  • 58
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 847-853 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bromine/Lithium Exchange in Vinyl and Aryl Bromides with tert-Butyl Lithium. On the Ring Enlargement via Dibromocarbene AdductsTwofold molar excess of tert-butyl lithium replaces vinylic and arylic bromine by lithium. The tert-butyl bromide formed is dehydrohalogenated rapidly to isobutene by tert-butyl lithium even at very low temperatures. Transformation of 1-bromo-1-cyclooctene and - cyclononene via the lithium derivatives to vinyl thioethers 1d, e, and i in high yields opens up a simple alternative route from olefin dibromocarbene adducts to ring enlarged ketones. The bromobenzenes 2a and 3a reveal that the Br/Li-exchange described here is not accompanied by arine formation; it is feasible even in the presence of sensitive benzylic CH2-groups as present in 3.
    Notes: Vinylisch und an Aromaten gebundenes Brom läßt sich quantitativ mit zweifachem molarem Überschuß an tert-Butyllithium gegen Lithium austauschen. Das entstehende tert-Butylbromid wird selbst bei tiefen Temperaturen von tert-Butyllithium rasch zu Isobuten dehydrohalogeniert. Die Überführung von 1-Brom-1-cycloocten und -1-cycloneone in Vinylthioäther 1d, e und i über die Lithiumderivate ist in hoher Ausbeute möglich und eröffnet einen einfachen Weg von Dibromcarbenaddukten an Olefine zu ringerweiterten Ketonen. Am Beispiel der Brombenzole 2a und 3a wird gezeigt, daß der hier beschriebene Br/Li-Austausch nicht von Arin-Bildung begleitet und auch in Gegenwart der empfindlichen benzylischen CH2-Gruppe von 3 durchführbar ist.
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  • 59
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 892-897 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N-VinylimidazolecarboxylatesN-Vinylation of imidazolecarboxylates with vinyl acetate leads to the formation of the N-vinylimidazoles 3a, 3b, 6, 8a, 8b und 9a. The structures are determined by mass and n.m.r. spectra. 3a, 6, 8a are polymerizable.
    Notes: Durch N-Vinylierung von Imidazolcarbonsäureestern mit Vinylacetat werden die N-Vinylimidazole 3a, 3b, 6, 8a, 8b und 9a, erhalten. Die Strukturen werden mit Hilfe von NMR-und Massen-Spektren gesichert. 3a, 6, 8a und 8bsing polymerisationsfähig.
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  • 60
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 929-936 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclizations, XIII. New Polycyclic Pyrimidines with Bridge-Head NitrogenThe base-catalized condensation of 2,3,3-trimethyl-3H-benz[f]indole (9) with dielectrophilic iso(thio)cyanates to polycyclic pyrimidines with bridge-head nitrogen (11, 15, 16) in most cases involves preliminary formation of 1: 2 adducts followed by elimination of diacylamides. Contrary to this the less nucleophilic 2,3,3-trimethyl-3H-pyrrolo [2,3-b]pyridine (20) affords the analogue pyrimidines by intermediacy of 1:1 adducts and elimination of water or ethanol solely.
    Notes: Die basenkatalysierte Kondensation von 2,3,3-Trimethyl-3H-benz[f] indol (9) mit dielektrophilen Iso(thio)cyanaten zu polycyclischen Pyrimidinen mit Brückenkopf-Stickstoff (11, 15, 16) verläft meist über die Bildung von 1:2-Addukten als Zwischenstufe und Eliminierung von Diacylamiden. Dagegen liefert das weniger nucleophile 2,3,3-Trimethyl-3 H-pyrrolo[2.3-b]-pyridin (20) analoge Systeme (22, 23) ausschließlich über 1: 1-Addukte und Eliminierung von Wasser bzw. Äthanol.
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  • 61
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 686-697 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkaloids from Rhamnaceae, XVIII. Amphibine-F, -G and -H, further Peptide Alkaloids from Ziziphus amphibia A. Cheval.From the complex mixture of crude alkaloids from Ziziphus amphibia A. Cheval., in addition to the already described Amphibines-A, -B, -C, -D and -E, three further peptide alkaloids Amphibine-F, -G and -H have been isolated and their structures elucidated (1-3). Amphibine-F and -G (1, 2) belong to the class of cyclic peptide alkaloides having a fourteen-membered ring system made up from trans-3-hydroxyproline, p-hydroxystyrylamine and an α-aminoacid. Amphibine-H (3) has a thirteen-membered ring system formed from 5-hydroxy-2-methoxystyrylamine and the aminoacids trans-3-hydroxyproline and phenylalanine.
    Notes: Aus dem komplexen Rohbasengemisch von Ziziphus amphibia A. Cheval. wurden neben den bereits beschriebenen Amphibinen-A, -B, -C, -D und -E drei weitere Peptidalkaloide Amphibin-F, -G und -H isoliert und in der Struktur geklärt (1-3). Die Amphibine-F und -G (1, 2) zählen zu den Cyclopeptidalkaloiden mit 14 gliedrigem Ringsystem aus trans-3-Hydroxyprolin, p-Hydroxystyrylamin und einer α-Aminosäure. Das Amphibin-H (3) weist ein 13 gliedriges Ringsystem auf, das aus den Aminosäuren trans-3-Hydroxyprolin und Phenylatanin sowie aus 5-Hydroxy-2-methoxystyrylamin gebildet wird5).
    Additional Material: 3 Ill.
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  • 62
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 698-705 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Preparation of New ChloroformamidinesAction of phosphine/carbon tetrachloride or dichlorotriphenylphosphorane on N,N,N′-trisubstituted ureas leads to the formation of even such chloroformamidines which are not or only difficultly obtainable by the conventional methods. The spectroscopic and analytic data of the new compounds are given.
    Notes: Durch Einwirkung von Phosphin/Tetrachlorkohlenstoff oder von Dichlortriphenylphos-phoran auf N,N,N′-trisubstituierte Harnstoffe können auch solche Chlorformamidine dargestellt werden, die nach den bisherigen Methoden nicht oder nur schwer zugänglich sind. Die spektroskopischen und analytischen Daten der neuen Verbindungen sind angegeben.
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  • 63
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 721-724 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 725-726 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 65
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 739-744 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Fulvenes, VIII. Indeno[2,1-c]-1,2-dithioles, a Group of New PseudoazulenesAcylation of 2-pyrrolidinoindene (4) with carboxylic acid chlorides and subsequent hydrolysis leads to the 1-acyl-2-indanones 6, which have been condensed with diacetyl disulfide in aequous perchloric acid/acetic acid to afford the 8H-indeno[2,1-c]-1,2-dithiolium-perchlorates 7. These are deprotonated with N-ethyldiisopropylamine to yield the indeno[2,1-c]-1,2-dithioles 10, a group of new pseudoazulenes.
    Notes: Acylierung von 2-Pyrrolidinoinden (4) mit Carbonsäurechloriden und nachfolgende Verseifung liefert die 1-Acyl-2-indanone 6, die mit Diacetyldisulfid in wäßriger Perchlorsäure, Eisessig zu den 8H-Indeno[2,1-c]-1,2-dithiolium-perchloraten 7 kondensieren. Letztere lassen sich durch N-Äthyldiisopropylamin zu den Indeno[2,1-c]-1,2-dithiolen 10, einer Gruppe neuer Pseudoazulene, deprotonieren.
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  • 66
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 759-770 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereochemistry and Reactivity of Tetrahalogenated 2,3-Diazabicyclo[3.2.0]hept-2-enes and Bicyclo [2.1.0] pentanesThe addition of diazoalkanes to tetrahalogenated cyclobutenes 1-3 leads to 6,6,7,7-tetrahalo-2,3-diazabicyclo[3.2.0]hept-2-enes 4-8, the structure and stereochemistry of which are determined by means of n. m. r. spectroscopy. Thermal decomposition of 4, 5, and 8 in boiling toluene affords the tetrahalobicyclo[2.1.0]pentanes 9, 10, and 12 in good yields. Under the same conditions 7 decomposes in a stereospecific manner to form 11 and small amounts of 13. Sodium methoxide converts 9-11 into the cyclobutenes 14 and 15. Under the influence of sulfuric acid 10 forms the cyclobutenedione 16 or a mixture of cyclopentenones 18, 19 depending on the reaction conditions.
    Notes: Addition von Diazoalkanen an die tetrahalogenierten Cyclobutene 1-3, führt zu 6,6,7,7-Tetrahalogeno-2,3-diazabicyclo[3.2.0]hept-2-enen 4-8, deren Konstitution und Stereochemie auf NMR-spektroskopischem Weg ermittelt wurde. Durch thermische Zersetzung der Bicyclen 4,5 und 8 in siedendem Toluol erhält man in guten Ausbeuten Tetrahalogenobicyclo-[2.1.0]pentane 9,10 und 12. Unter gleichen Bedingungen entstehen aus 7 in stereospezifischer Reaktion 11 sowie geringe Mengen des Cyclobutens 13. Mittels Natriummethylat werden die Bicyclen 9-11 zu den Cyclobutenen 14, 15 abgebaut; unter dem Einfluß von konz. Schwefelsäure entsteht aus 10 je nach Reaktionsbedingungen das Cyclobutendion 16 bzw. ein Gemisch der Cyclopentenone 18 und 19.
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1221-1227 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conversion of Aldehydes into Nitriles without Isolation of IntermediatesAldehydes are converted into nitriles without isolation of the intermediates by treating their oximes with carbodiimides in the presence of copper(II)ions and triethylamine. The entire process requires 3 hours at room temperature; it is unsuccessful if the oxime does not form or is consumed by competition reactions.
    Notes: Aldehyde können ohne Isolierung von Zwischenprodukten in Nitrile übergeführt werden, indem ihre Oxime in Gegenwart von Kupfer(II)-Ionen und Triäthylamin mit Hilfe von Carbodiimiden dehydratisiert werden. Der gesamte Prozeß erfordert bei Raumtemperatur durchweg 3 Stunden. Das Verfahren versagt, wenn die Oximbildung gestört ist oder das Oxim Konkurrenzreaktionen eingeht.
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  • 68
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Reactivity of Silicon Transition Metal Complexes, V. The Modified Alkali Salt Elimination Method  -  a General Procedure for the Synthesis of Silicon Transition Metal CompoundsThe heterogeneous reaction of the sodium carbonylmetallates Na[Fe(CO)2π-C5H5], Na[M(CO)3π-C5H5] (M=Mo, W), and Na[Mn(CO)5] with various halo- and organohalosilanes leads to the formation of the corresponding silyl complexes. The new compounds are characterized by spectroscopy and the chemical properties are described. The results of a decomposition study of the trimethylsilyl-VIB transition metal complexes are discussed in connection with former synthetic experiments. Exchange reactions of these species with heterosiloxanes can be used for a qualitative estimation of relative metal-metalloid bond reactivity.
    Notes: Die Umsetzung der komplexen Metallate Na[Fe(CO)2π-C5H5], Na[M(CO)3π-C5H5] (M=Mo, W) und Na[Mn(CO)5] mit verschiedenen Halogen- und Organohalogensilanen führt in heterogener Reaktion zu den Silylkomplexen dieser Metalle. Die neuen Verbindungen werden spektroskopisch charakterisiert und ihre chemischen Eigenschaften beschrieben. Die Ergebnisse einer Zerfallsstudie der Trimethylsilyl-VIB-Übergangsmetallkomplexe werden im Zusammenhang mit früheren Syntheseversuchen diskutiert. Der Verlauf von Austauschreaktionen der gleichen Verbindungen mit Heterosiloxanen (Ge, Sn) ermöglicht eine qualitative Abschätzung der Reaktivität der Metall- Metalloideinheit.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1057-1065 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on 4-Pyrones, 51. Aminoalkylation of ChromonesThe aminoalkylation of 2-methylchromones (1b, e and 2b, c) leads to the formation of benzopyrano[3.2-c]pyridinium chlorides (9a-d and 11a-e).
    Notes: Die Aminoalkylierung von 2-Methylchromonen (1b, e sowie 2b, c) führt zu Benzopyrano-[3.2-c]pyridinium-chloriden (9a-d sowie 11a-e).
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1069-1069 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 71
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mass Spectrometric Investigation of Amides, VII. Intramolecular Interactions of Bifunctional Groups in the electron Impact Induced Fragmentation of Piperidides and PiperideidesThe activation energy ∊ for the electron impact induced splitting of the N-carbonyl bond in bifunctional amides is estimated. A clear correlation is shown of ∊ with the ring size of the transition state and the nucleofuge or nucleophilic properties of the nitrogen groups. Furtheron by means of [D]-labelled model compounds selective hydrogen migrations have been established.
    Notes: Die Aktivierungsenergie ∊ für die elektronenstoßinduzierte Spaltung der N-Carbonylbindung bifunktioneller Amide wird bestimmt. Es ergibt sich ein klarer Zusammenhang von ∊ mit der Ringgröße des Übergangszustandes und den nucleofugen bzw. nucleophilen Eigenschaften der Stickstoffgruppen. Ferner werden mit Hilfe [D]-markierter Modellverbindungen selektive Wasserstoffübertragungen nachgewiesen.
    Additional Material: 3 Tab.
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  • 72
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1126-1135 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Nature of Benzonorbornen-2-yl Cations, II. Solvolysis of Isopropylidene-substituted benzonorbornen-2yl EstersThe 2-epimeric at C-7 and C-3 substituted benzonorbornenols 4a, 6a, 7a and 8a are synthesized. The rate of solvolysis of the tosylates 4b and 6b is measured in acetic acid, that of the 3,5-dinitrobenzoates 7b and 8b in 90% dioxane. The solvolysis products are determined in 80% acetone puffered with 2,6-lutidine. The epimeric 7-isopropylidene derivatives 4b and 6b solvolyse by a different mechanism; the exo derivative 4b reacts exclusively with assistance of the benzene ring, the endo compound by participation of the homoallylic double bond. The epimeric 3-isopropylidene derivatives 7b and 8b solvolyse to a common intermediate allylic ion 10. The kexo/kendo ratio is reduced to 9 due to the presence of this neighbouring group, which is a measure of the steric factor in the secondary benzonorbornen-2-yl system.
    Notes: Die epimeren Benzonorborneole 4a und 6a sowie 7a und 8a werden synthetisiert. Die Solvolysegeschwindigkeit der Tosylate 4b und 6b wird in Eisessig, die der 3,5-Dinitrobenzoate 7b und 8b in 90 proz. Dioxan gemessen. Die Reaktionsprodukte werden in 80 proz., mit 2,6-Lutidin gepuffertem Aceton bestimmt. Die epimeren 7-Isopropyliden-Verbindungen 4b und 6b solvolysieren nach einem unterschiedlichen Mechanismus; die exo-Verbindung 4b reagiert ausschließlich mit Beteiligung des Aromaten, die endo-Verbindung 6b mit der der Isopropyliden-Doppelbindung. Die epimeren 3-Isopropyliden-Verbindungen 7b und 8b solvolysieren zu einem gemeinsamen Allyl-Ion 10 als produktbestimmende Zwischenstufe. Das Verhältnis kexo/kendo wird durch diese Nachbargruppe auf 9 herabgesetzt, welches ein Maß für den sterischen Anteil des sekundären Benzonorbornen-2-yl-Systems ist.
    Additional Material: 1 Ill.
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  • 73
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXXII. Cleavage of the Double Bond of 1-vinyl-2-pyrrolidone and β-Substituted 1-Vinylpyrrolidones by Reaction with Pentacarbonyl(methoxyphenylcarbene)chromium(0)Pentacarbonyl(methoxyphenylcarbene)chromium(0) reacts with 1-vinyl-2-pyrrolidone to form α-methoxystyrene by transfer of a methylene group to the carbene moiety. The origin of the transfered methylene group is proved by using methylsubstituted 1-vinylpyrrolidones. The reaction products are identified by their i.r., 1H n.m.r., and mass spectra. As reaction mechanism a cyclic transition state is proposed, which explains the breaking and following formation of a double bond analogously to the heterolytic fragmentation according to Grob.
    Notes: Bei der Umsetzung von Pentacarbonyl(methoxyphenylcarben)chrom(0) mit 1-Vinyl-2-pyrrolidon entsteht durch Übertragung einer Methylengruppe auf den Carben-Rest α-Meth-oxystyrol. Durch Einsetzen methylsubstituierter 1-Vinylpyrrolidone wird die Herkunft der übertragenen Methylengruppe bewiesen. Die Produkte werden anhand ihrer IR-, 1H-NMR- und Massenspektren identifiziert. Als Reaktionsmechanismus wird ein cyclischer Übergangszustand vorgeschlagen, der - in Analogie zur heterolytischen Fragmentierung nach Grob - die Spaltung und Neuknüpfung einer Doppelbindung erklärt.
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  • 74
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1207-1212 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemical Reactions, XXIII. The Photocyclisation of 9-Benzylidenexanthenes and 9-BenzylidenethioxanthenesDehydrocyclisations of the 9-benzylidenexanthenes in u.v. or sunlight (6a-6d→7a-7d) were realized. 6 may be considered as derived from stilbene, and 7 as derived from phenanthrene. Therefore the photoprocess 6→7 is analogue to the photoprocess cis-stilbene → phenanthrene.
    Notes: Dehydrocyclisierungen der Benzylidenxanthene im UV-oder Sonnenlicht (6a-6b→7a-7d) wurden durchgeführt. Da 6 als substituierte cis-Stilbene und 7 als substituierte Phenanthrene aufgefaßt werden können, liegen Analogiereaktionen zu dem Photoprozeß cis-Stilben → Phenanthren vor.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1228-1234 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Dynamic Behaviour of Mono-cyclopentadienylarsinesMono-cyclopentadienylarsines (3a-e) are synthesized by the reaction of cyclopentadienyl-trimethylsilane (1) or cyclopentadienyllithium (5) with the halogenoarsines 2a-e. They are very sensitive against air and moisture and thermally unstable. The cp-ligands are σ-bonded; the molecules have a fluxional structure. The rapidity of the degenerate metallotropic rearrangements is influenced by the other ligands on the arsenic atom.
    Notes: Mono-cyclopentadienylarsine (3a-e) werden durch Umsetzung von Cyclopentadienyl-trimethylsilan (1) oder Cyclopentadienyllithium (5) mit den Halogenarsinen 2a-e dargestellt. Sie sind äußerst luft- und feuchtigkeitsempfindlich und thermisch instabil. Es liegen σ-gebundene Cp-Liganden und Moleküle mit fluktuierender Struktur vor. Die Geschwindigkeit der entarteten metallotropen Umlagerungen wird durch die anderen Liganden am Arsenatom beeinflußt.
    Additional Material: 3 Tab.
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  • 76
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1318-1328 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enehydrazines, 9. 1-Alkyl-3-hydroxypyrazoles from Hydrazones or HydrazinesReaction of dimethyl acetylendicarboxylate with hydrazinen oder Alkyl hydrazonen gives the methyl 1-alkyl-3-hydroxy-5-pyrazolecarboxylats 9 and 13a-e, subsequent saponification and decarboxylation gives the 1-alkyl-3-hydroxypyrazoles 11 and 15a-e. The cyclization of 13f to lactone 19a is a structure proff. Starting from benzaldehyde hydrazones, 2-pyrazoline-4,5-dicarboxylic esters are the main products.
    Notes: Durch Umsetzung von Acetylendicarbonsäure- dimethylester mit Hydrazinen oder Alkyl-hydrazonen erhält man die 1-Alkyl-3-hydroxy-5-pyrazolcarbonsäure-methylester 9 und 13a-e, durch Verseifung und Decarboxylierung hieraus die 1-Alkyl-3-hydroxypyrazole 11 und 15a-e. Die Cyclisierung von 13f zum Lacton 19a ist strukturbeweisend. Bei Verwendung von Benzaldehyd-hydrazonen entstehen hauptsächlich 2-Pyrazolin-4,5- dicarbonsäureester.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1334-1343 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrophilic Addition of Disulfur Dichloride to Alkynes, 3. Reaction of Asymmetric of Asymmetric Substituted Alkynes with Disulfur DichlorideDisulfur dichloride adds to the triple bond of asymmetric substituted alkynes to afford vinyl sulfides, which are constitution isomers. Substituents R with a negative I-effect yield „Markownikof“ products whereas a positive I-effect leads to the formation of „anti-Markownikoff“ products. The addition is always trans. The obtained sulfides are oxidized with H2O2 in glacial acetic acid to yield the corresponding sulfones.
    Notes: Die bei der elektrophilen Addition von Dischwefeldichlorid an asymmetrische Alkine gebildeten Vinylsulfide sind Konstitutions -Isomere. Substituenten R mit negativem Induktionseffekt führen zu „Markownikoff“-Produkten, während ein positiver I-Effekt „anti-Markownikoff“-Orientierungen liefert. In allen Fällen erfolgt eine trans-Addition. Die erhaltenen Sulfide werden nach der Oxidation mit Wasserstoffperoxid/Eisessig als Sulfone isoliert.
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  • 78
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1371-1379 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Oxidative Addition Reactions of Nitroalkanes to Tetrakis(triphenylphoshine)platinum(0)The oxidative addition of nitromethane to Pt(PPh3)4 in polar protic solution provides a convenient and safe method for the preparation of trans-(Ph3P) 2Pt(CNO)2 Pt(CNO2)(3). From Pt(PPh3)4 and nitromethane or 2-nitropropane cis-(Ph3P) 2Pt(NO2)2 (2) is obtained. The reactions of Pd(PPh3)4 or Rh(PPh3)2CO)Cl with CH3NO2 or some of its derivatives afford isocyanato compounds. Formaidoxime hydrochloride reacts with Pt(PPh3)4 to give trans-(Ph3P)2Pt-(CN)Cl (4).
    Notes: Die oxidative Addition von Nitromethan an Pt(PPH3)4 in polarem, protischem Medium liefert gefahrlos und in guter Ausbeute trans-(Ph 3P)2Pt(CNO)2 (3). Aus Pt(PPh3)4 und Nitromethan bzw. 2-Nitropropan wird cis-(Ph3P)2Pt(NO2)2 (2) erhalten. Die Umsetzungen von Pd(PPh 3)4 oder Rh(PPh3)2(CO)Cl mit Nitromethan oder Methylnitrolsäure führen zu Isocyanatoverbindungen. Formaldoxim-hydrochlorid reagiert mit Pt(PPh 3)4 zu trans-(Ph3P)2Pt(CN)Cl (4).
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1720-1730 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Botrydial, a Sesquiterpene Antibiotic from the Culture Solution of the Fungus Botrytis cinereaThe antibiotic botrydial (3) and its dihydro derivative (1) were isolated from the culture solution of the fungus Botrytis cinerea. Their structural formulas were elucidated by means of a series of chemical transformations together with the application of spectroscopic methods, especially a detailed analysis of the n.m.r. spectra. The basic skeleton of botrydial is a bicyclic, non-isoprenoid sesquiterpene system.
    Notes: Aus der Nährlösung des Pilzes Botrytis cinerea wurden das antibiotisch wirksame Botrydial (3) und sein Dihydroderivat (1) isoliert. Durch eine Folge chemischer Umwandlungen, verbunden mit der Anwendung spektroskopischer Methoden, insbesondere einer detaillierten Analyse der NMR-Spektren, wurden ihre Konstitutionsformeln abgeleitet. Botrydial liegt ein bicyclisch nicht-isoprenoides Sesquiterpenskelett zugrunde.
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  • 80
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1767-1768 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 81
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1773-1776 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occuring Terpene Derivatives, XXXVI. Synthesis of 8-Hydroxybrickellol and Dehydronerol isovalerateThe sesquiterpene 7 named 8-hydroxybrickellol as well as the isovalerate of dehydronerol (14) have been synthesized.
    Notes: Das 8-Hydroxybrickellol benannte Sesquiterpen 7 sowie der Isovaleriansäureester des Dehydronerols (14) werden synthetisch dargestellt.
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  • 82
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1420-1427 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reactions of Phosphorus Ylids with Excess Alkohol and AlkanethiolThe alkoxytetraalkylphosphoranes of the formula R4POR′, obtained from equimolar amounts of ylid and alkohol, which contain pentacoordinate phosphorus atoms, are converted into ionic products (1 - 7) by addition of excess alkohol. In these compounds phosphonium cations R4P⊕ are accompanied by hydrogen-bonded hydrogenalkoholate anions of the types [R′O…H…OR′]⊖, [H2(OR′)3]⊖, and [H3(OR′)4]⊖. This structure is proposed on the basis of n.m.r., i.r., and Raman-spectroscopic data. With ylids and alkanethiols only salt-like products R4P⊕RS⊖ are formed.
    Notes: Die aus äquimolaren Mengen von Yliden und Alkoholen zugänglichen, kovalent gebauten Alkoxytetraalkylphosphorane R4POR′ mit pentakoordinierten Phosphoratomen werden durch Addition von überschüssigem Alkohol in die Produkte 1 - 7 verwandelt, in welchen Phosphonium-Kationen R4P⊕ den wasserstoffbrückenverknüpften Hydrogenalkoholat-Anionen vom Typ [R′O…H…OR′]⊖, [H2(OR′)3]⊖ und [H3(OR′)4]⊖ gegenüberstehen. Der Strukturvorschlag stützt sich auf NMR-, IR- und Raman-spektroskopische Untersuchungen. Aus Yliden und Alkanthiolen entstehen nur die salzartigen Phosphonium-alkanthiolate R4 P⊕RS⊖.
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  • 83
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1472-1482 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangements of 3-Substituted Norbornanediazonium Ions3-Oxonorbornane-2-endo-diazonium ions (1), generated by acid-catalyzed decomposition of 3-diazonorcamphor (5) in alcoholic solutions, produce derivatives of endo-bicyclo[2.2.1]heptane 3 and bicyclo [3.1.1]heptane derivatives 4, varying with the nucleophilicity of the solvent. This suggests the 7-bridged ion 2 as intermediate, which plays also an important part in the deamination of 3,3-dimethoxynorcamphor tosylhydrazone (16) in alkaline solutions as shown by the formation of 3 and 4. In the alkaline deamination of 3,3- dimethoxy-5-norbornen-2-on tosylhydrazone (32) in methanol the homoallylic ion 34 is dominating.
    Notes: 3-Oxonorbornan-2-endo-diazonium-Ionen (1), erzeugt durch sauer katalysierte Zersetzung von 3-Diazonorcampher (5) in alkoholischen Lösungen, ergaben endo-Bicyclo[2.2.1]heptan-3 und Bicyclo[3.1.1]heptan-Derivate 4, deren Menge von der Nucleophilie des eingesetzten Lösungsmittels abhängig ist. Dies läßt das 7-verbrückte Ion 2 als Zwischenstufe vermuten, welches auch bei der Desaminierung des 3,3-Dimethoxynorcampher-tosylhydrazons (16) in alkalischen Lösungen eine entscheidende Rolle spielt, wie die Bildung der Produkte 3 und 4 beweist. Bei der alkalischen Desaminierung des 3,3-Dimethoxy-5-norbornen-2-on-tosylhydrazons (32) in Methanol ist jedoch die Homoallylumlagerung zum Kation 34 produkt-bestimmend.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1536-1544 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Derivatives of Guanidines Containing Phosphorus and SulfurN-Chloroguanidines 1 react with tervalent phosphorous compounds or with sulfides to yield N-guanylphosphine imidium (3) or sulfimidium salts (9). Dehydrohalogenation gives the respective N-guanyl phosphine imides and sulfimides. The structure and reactions of these compounds are discussed.
    Notes: Die Umsetzung von N-Chlorguanidinen 1 mit tervalenten Phosphorverbindungen sowie Sulfiden führt zu N-Guanylphosphinimidium- (3) bzw. -sulfimidium-Salzen (9). Durch Dehydrohalogenierung werden die entsprechenden Phosphinimide und Sulfimide erhalten. Die Eigenschaften dieser Verbindungen - insbesondere die Struktur-und Bindungsverhältnisse-sowie ihre Reaktionen werden untersucht.
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  • 85
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1568-1578 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conformational Analysis, III. exo-Anomeric Effect and Circular Dichroism of Glycopyranosyl AzidesTetra-O-acetyl-aldopentopyranoses and penta-O-acetyl-aldohexopyranoses react readily with trimethylsilyl azide in the presence of BF3 or SnCl4 to afford the corresponding glycosyl azides 1a - 11 (table 1). Only the anomeric glycosyl azide having the azido group „trans“ to the 2-acetoxy group is obtained in each case. The polarization of the Cl—Nx and Nx—Nz bonds in glycosyl azides is such that in both cases the dipole is directed toward Nx. It can be deduced that glycosyl azides, like methyl glycopyranosides, should exhibit an exo-anomeric effect which strongly favors the conformers 9 and 12. The application of the azide-octant rule predicts a negative Cotton effect for the α-D-glycosyl azide 12 and a positive effect for the β-D-glycosyl azide 9. Circular dichroism measurements are in good agreement with these predictions, indicating the operation of an exo-anomeric effect in the glycosyl azides.
    Notes: Tetra-O-acetyl-pentopyranosen und Penta-O-acetyl-hexopyranosen setzen sich mit Trimethylsilylazid bei Gegenwart von BF3 oder SnCl4 leicht zu den entsprechenden Glycosylaziden 1a bis 11 um (Tab. 1). Es entsteht stets nur das anomere Glycosylazid, in dem die Azidogruppe und 2-OAc „trans“ zueinander angeordnet sind. In Glycosylaziden sind die Bindungen Cl—Nx und Nx—Nz in der Weise polarisiert, daß der Dipol in beiden Fällen zum Nx weist. Hieraus wird abgeleitet, daß bei Glycosylaziden wie bei Methylglycosiden ein exo-anomerer Effekt wirksam sein sollte, der die Konformeren 9 und 12 stark bevorzugt. Die Anwendung der Azid-Oktantenregel sagt für das α-D-Glycosylazid 12 einen negativen, für das β-D-Glycosylazid 9 einen positiven Cotton-Effekt voraus. Messungen des Circular-dichroismus stimmen mit diesen Voraussagen gut überein, was für einen exo-anomeren Effekt bei Glycosylaziden spricht.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1645-1648 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermally Induced Reactions of Imidazole Derivatives, IV. Kinetics of the Thermal Rearrangement of 2,4,4-Triaryl-5-methylthio-4H-imidazolesThe thermal rearrangements of the title compounds 1a - d into the 2,4,5-triarylimidazoles 2 in different solvents and at different temperatures are first order reactions. No linear relation exists between the effect of the p-substituents of the migrating aryl groups on the reaction rates and their Hammett-Brown σ+ values. The solvent has practically no effect on the rearrangement rate of 1c. The activation parameters of the rearrangement 1c → 2c are given.
    Notes: Die thermische Umlagerung der Titelsubstanzen 1a - d in die 2,4,5-Triarylimidazole 2 in verschiedenen Lösungsmitteln und bei verschiedenen Temperaturen folgt einem Geschwindigkeitsgesetz 1. Ordnung. Der Einfluß des p-Substituenten der wandernden Arylgruppe ändert sich nicht linear mit den Hammett-Brownschen σ+-Werten. Das Lösungsmittel hat praktisch keinen Einfluß auf die Umlagerungsgeschwindigkeit von 1c. Die Aktivierungsparameter der Umlagerung 1c → 2c werden angegeben.
    Additional Material: 1 Ill.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1676-1683 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vinyl Cations, 15. Preparation and Solvolysis of the Stereoisomeric 1-Bromomethylene-2-methylcyclopropanesThe stereoisomeric 1-bromomethylene-2-methylcyclopropanes (6Z and 6E) are synthesized and their solvolysis rates and products in ethanol/Water mixtures are determined. 6Z and 6E solvolyse at approximately the same rates. Both isomers yield only the rearranged products 12, 14, 16 and 18, which are formed from both isomers in the same ratio. The products as well as the kinetic data are explained by assuming the formation of the stabilized cyclopropylidenemethyl cation 7.
    Notes: Die stereoisomeren 1-Brommethylen-2-methylcyclopropane (6Z und 6E) wurden dargestellt und die Solvolysegeschwindigkeiten sowie die Produkte in Äthanol/Wasser-Gemischen bestimmt. 6Z und 6E solvolysieren dabei etwa mit gleicher Geschwindigkeit. Aus beiden Isomeren entstehen ausschließlich die umgelagerten Produkte 12, 14, 16 und 18 im gleichen Mengenverhältnis. Produktanalyse und Kinetik werden mit der Bildung des stabilisierten Cyclopropylidenmethylkations 7 erklärt.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1684-1701 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dispiro[2.0.2.4]deca-7,9-diene and Related Model Compounds: Synthesis, U.V, N.M.R, and Photoelectron-Spectroscopic InvestigationsDispiro[2.0.2.4]deca-7,9-diene (4) and spiro[2.5]octa-4,6-diene (5 can be obtained from the corresponding monoolefins 6 and 10, respectively, by bromine addition and subsequent dehydrobromination. The u. v. spectra of 5 and 4 with λmax = 269 nm (log ε = 3.4) and 284 nm (3.7), respectively, show bathochromic shifts of their longest wavelength bands as compared to 1,3-cyclohexadiene. An analysis of the 1H n. m. r. chemical shifts and H, H-coupling constants for the olefinic protons in 4 indicates that there is no cyclic electron delocalization in this ring system. The six-membered ring in 4 is only slightly flatter than the one in 1,3- cyclohexadiene. The photoelectron spectroscopic data of 4, 5, spiro[2.5]octane (13), spiro[2.5]oct-4-ene (15), dispiro[2.0.2.4]decane (14), and dispiro[2.0.2.4]dec-7-ene (16) demonstrate the effect of the interaction between π-orbitals and cyclopropyl Walsh-orbitals; an assignment for the first bands in the p. e. spectra of these compounds is proposed.
    Notes: Dispiro[2.0.2.4] deca-7,9-dien (4) und Spiro[2.5]octa-4,6-dien (5) lassen sich aus den entsprechenden Monoolefinen 6 bzw. 10 durch Bromierung und anschließende Dehydrobromierung gewinnen. Die UV-Absorptionen von 5 und 4 mit λmax = 269 nm (log ε = 3.4) bzw. 284 nm (3.7) sind bathochrom verschoben gegenüber denjenigen des 1,3-Cyclohexadiens. Aus einer Analyse der Chemischen Verschiebungen und H,H-Kopplungskonstanten der olefinischen Protonen im 1H-NMR-Spektrum von 4 ist zu schließen, daß 4 kein cyclisch delokalisiertes Elektronensystem enthält. Der Sechsring in 4 ist nur wenig stärker eingeebnet als derjenige im 1,3-Cyclohexadien. Anhand der Photoelektronen-Spektren von 4, 5 sowie Spiro[2.5]octan (13), Spiro[2.5]oct-4-en (15), Dispiro[2.0.2.4]decan (14) und Dispiro[2.0.2.4]dec-7-en (16) wird der Effekt der Wechselwirkung zwischen π-Orbitalen und Cyclopropyl-Walsh-Orbitalen aufgezeigt; für die jeweils ersten Banden in den PE-Spektren dieser Verbindungen wird eine Zuordnung vorgeschlagen.
    Additional Material: 4 Ill.
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  • 89
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1748-1763 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Asymmetric Hydrogenation with 1,4-Bis(dimethylamino)-(2S,3S)- and -(2R,3R)-butane-2,3-dio(DBD)/Lithium Aluminium HydrideThe diaminodiol 6 (DBD) mentioned inthe in the title is readily available in two steps from commercial diethyl tartrate. It reacts with lithium aluminium hydride (LAH) or deuteride to give chirally modified 1:1-complexes which reduce aldehydes, ketones, and ozonides to optically active carbinols in optical yields of up to 75%. Since both enantiomers of DBD are to accessible, both dextro- and levo-rotatory products may be prepared at will. DBD is easily separated from products and recovered without loss of activity. The (-)- DBD-LAH-complex reduces both dialkyl and aryl alkyl ketones to give samples enantiomerically enriched with carbinols of (S)- configuration, while the (+)-DBD-complex acts the other way around. This result is independent of the mode of preparation of the complex, of the ratio of reducing reagent over substrate, of addition of alcohols or water, of reaction temperature, or solvent. The effects of some of these influences upon the optical yields are large. Optimum conditions are given; the efficiency of the DBD-LAH-complex is compared with similar chirally modified LAH derivatives already known. A mechanism explaining the stereochemical results is proposed.
    Notes: Das aus Weinsäureester in zwei Stufen leicht zugängliche, im Titel genannte Diaminodiol 6 (DBD) setzt sich mit Lithiumaluminiumhydrid (LAH) und -deuterid zu chiral modifizierten 1: 1-Komplexen um. Diese reduzieren Aldehyde, Ketone und Ozonide zu opt. aktiven Carbinolen in optischen Ausbeuten bis zu 75%. Da beide Enantiomeren von DBD zugänglich sind, lassen sich gezielt (+)- oder (-)-drehende Produkte darstellen. DBD ist von den Produkten bequem abtrennbar und ohne opt. Verluste zurückgewinnbar. Mit (-)-DBD-LAH- Komplex entstehen Dialkyl- und Alkyl-aryl- carbinole mit (S)-, aus dem enantiomeren Komplex mit (R)-Konfiguration des Überschußenantiomeren. Dies ist völlig unabhängig von Darstellungsmodus des Komplexes, molarem Verhältnis von Reduktionsmittel und Substrat, Zusätzen von Alkoholen oder Wasser, Reaktionstemperatur oder -lösungsmittel. Die Einflüsse dieser Faktoren auf die opt. Ausbeuten, für die optimale Bedingungen angegeben werden, sind indessen zum Teil groß. Vergleiche mit bekannten Komplexen aus LAH und anderen chiralen Liganden werden gezogen. Es wird ein Vorschlag zur Erklärung der stereochemischen Befunde gemacht.
    Additional Material: 1 Tab.
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  • 90
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1777-1779 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occurring Terpene Derivatives, XXXVII. Synthesis of the Sesquiterpene from Elvira biflora DCThe aromatic sesquiterpene 11 isolated from Elvira biflora DC has been synthesized starting with the p-cresol 2-butenyl ether (1).
    Notes: Das aus Elvira biflora DC isolierte aromatische Sesquiterpen 11 wird ausgehend vom p-Cresol-2-butenyläther (1) synthetisiert.
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  • 91
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1823-1834 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactivity of Nitrile Ylides of Different OriginThermolysis and photolysis of 2,3-dihydro- 1,4,2λ5-oxazaphospholes 2, photolysis of 1- azetines 3 as well as 1,3-elimination of hydrogen chloride from imidoyl chlorides 4 proceeds via the nitrile ylide intermediate 1. This is deduced from the same product ratio of the isomeric cycloadducts 5:6 on trapping with acrylic acid esters.
    Notes: Die Thermolyse und Photolyse von 2,3-Dihydro-1,4,2λ5-oxazaphospholen 2, die Photolyse von 1-azetine 3 wie auch die 1,3-Eliminierung von Chlorwasserstoff aus Imidoylchloriden 4 verläuft über die Nitril-ylid-Zwischenstufe 1. Dies wird aus dem jeweils gleichen Produkt-verhältnis der isomeren Cycloaddukte 5:6 bei der Abfangreaktion mit Acrylsäureestern abgeleitet.
    Additional Material: 9 Tab.
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  • 92
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1903-1914 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,8-Di-tert-butyl-[9-13C]-9-fluorenyl, Bis(2-tert-butylphenyl)[α-13C]methyl and their DimersThe preparation of the title compounds is reported. The 1H n. m. r. spectra of the dimers of 1 and [9-13C]-1, respectively, yield the cyclohexadiene structure 12 for the dimer. The 1H n. m. r. spectrum of [α-13C]-2 dimer confirms structure 1411). The e. s. r. results of 1 and 2 are discussed.
    Notes: Die Darstellung der Titelverbindungen wird beschrieben. Die 1H-NMR-Spektren der Dimeren von 1 bzw. [9-13C]- 1 ergeben die Cyclohexadien-Struktur 12 für das Dimere. das 1H-NMR-Spektrum des [α-13C]- 2-Dimeren bestätigt die Struktur 14 11). Die ESR-Ergebnisse (a(H) und a(13C)) von 1 und 2 werden diskutiert.
    Additional Material: 3 Ill.
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  • 93
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemistry of Small Rings, 30. Photochemistry of β,γ-Unsaturated Aldehydes.  -  Mechanism of the Photofragmentation of Phenyl-substituted CyclopentenecarbaldehydesA new synthesis of β,γ-unsaturated cyclopentenecarbaldehydes 1 by thermolysis of bicyclo-[3.1.0]hexenols 13 is described. Photolysis of the aldehydes 1 in benzene solution affords the cis-configurated cyclopentenes 2 in good yields. Cyclopentaphenanthrenes 16 are isolated as byproducts. 2 undergoes an electrocyclic reaction to form 17, which is then dehydrogenated to 16. The quantum yields of the photofragmentation and -cyclization are Φ2 = 0.23 and Φ16 = 0.07, respectively. From the emission spectra of 1a the energy of the singlet and triplet state is calculated to ES1 = 84.1 and ET1 = 62.2 kcal/mole. The kinetics of photoreactions 1 → 2 → 16 are studied using ED- and EDQ-diagrams. Sensitization studies demonstrate that the photoreaction 1 → 2 can also occur via a triplet state, but with reduced effectivity. Since quenching with piperylene is ineffective the reaction 1 → 2 very probably involves predominantly an n-π-singlet state. The mechanism proposed for the stereospecific, intramolecular reaction 1 → 2 involves the formation of a formyl allyl radical as a main intermediate.
    Notes: Eine neue Synthese von β,γ-ungesättigten Cyclopentencarbaldehyden 1 durch Thermolyse von Bicyclo [3.1.0]hexenolen 13 wird beschrieben. Die Photolyse der Aldehyde 1 in Benzol ergibt in guten ausbeuten die cis-konfigurierten Cyclopentene 2 und als Nebenprodukte die Cyclopentaphenanthrene 16.2 geht durch elektrocyclischen Ringschluß in 17 über, das unter Dehydrierung in 16 umgewandelt wird. Die Quantenausbeuten der photofragmentierung bzw. -cyclisierung betragen Φ2 = 0.23 bzw. Φ16 = 0.07. aus den Emissionsspektren von 1a wird die Energie von singulett- und Triplett-Zustand zu ES1 = 84.1 bzw. ET1 = 62.2 kcal/mol errechnet. Die Kinetik der Photoreaktionen 1 → 2 → 16 wird mit Hilfe von Ed- und EDQ-Diagrammen näher studiert. Wie Sensibilisierungsstudien zeigen, kann die Photoreaktion 1 → 2, wenn auch mit geringerer Effektivität, über einen Triplett-Zustand verlaufen. Sie läßt sich mit Piperylen nicht löschen, weshalb die Reaktion 1 → 2 weitgehend über einen angeregten n-π-S1-Zustand formuliert wird. Für den Mechanismus der stereospezifischen, intramolekularen (D-Markierung) Reaktion 1 → 2 wird ein Formyl-Allyl-Radikalpaar als Wesentliche Zwischenstufe vorgeschlagen.
    Additional Material: 7 Ill.
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  • 94
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1882-1890 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoelectron Spectra and Molecular Properties, XXXIV. CyanamideThe PE spectrum of cyanamide is easily assigned by comparison with that of the isoelectronic acetonitrile. The orbital sequence obtained is supported by vibrational fine structures, by the PE spectrum of dimethylcyanamide, and by CNDO calculations. Furthermore, the calculated charge densities render possible an appreciation of properties of cyanamide and its alkyl derivatives.
    Notes: Das PE-Spektrum von Cyanamid läßt sich durch Vergleich mit dem des isoelektronischen Acetonitrils zwanglos zuordnen. Die so abgeleitete Orbitalreihenfolge wird durch Schwingungsfeinstrukturen, das PE-Spektrum von Dimethylcyanamid sowie durch CNDO-Rechnungen gestützt. Die berechneten Ladungsdichten erlauben darüber hinaus. Eigenschaften von Cyanamid und seinen Alkylderivaten zu verstehen.
    Additional Material: 2 Ill.
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  • 95
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1915-1924 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensed Ring Systems, VI. Synthesis of [4.2.2]Propella-7,9-diene, a Dewar Benzene Bridged in 1,4-PositionThe reaction of 8,11-dithia [4.3.3] propellane (1, n = 4) with N-chlorosuccinimide and monoperphthalic acid yields a mixture of four isomeric dichlorinated disulfones (2, n = 4). The major isomer 7 is formed in 40% yield. Upon treatment of 2 (n = 4) with potassium tert-butoxide at low temperatures [4.2.2] propella-7,9-diene2) (3, n = 4) is obtained. The constitution of 3 (n = 4) is deduced by 1H and 13C n. m. r as well as mass spectrometry.
    Notes: Die Umsetzung des 8,11-Dithia [4.3.3] propellans (1, n = 4) mit N-Chlorsuccinimid und Monoperphthalsäure führt zu einem Gemisch von vier isomeren dichlorierten Disulfonen (2, n = 4), von denen das Hauptprodukt 7 in 40proz. Ausbeute entsteht. 2 (n = 4) läßt sich mit Kalium-tert-butylat bei tiefen Temperaturen in das [4.2.2]Propella-7,9-dien2)(3, n = 4) überführen, dessen Konstitution durch die 1H-, 13C-NMR- und Massenspektren bewiesen wird.
    Additional Material: 6 Ill.
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  • 96
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1988-1997 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoisomerisation Reactions in Bicyclo[3.2.2]nona-6,8-diene DerivativesFrom the photochemical behavior of suitably substituted derivatives (dicarboxylic ester 3a, dicarboxylic acid 3b, bis(trifluoromethyl)-derivative 3c) it is concluded, that in the bicyclo-[3.2.2]nona-6,8-diene skeleton 1 (n = 3) the [2π + 2π]-Cycloaddition to 2 (n = 3) neither by direct nor by sensitized excitation takes place. Instead 1,3-alkyl shift (3a → 6a) and di-π-methane-rearrangement 3a → 7a, 3c → 8c) are observed. Arguments for this behavior differing from the lower homologues 1 (n = 0, 1, 2) are discussed.
    Notes: Aus dem photochemischen Verhalten geeignet substituierter Derivate (Diester 3a, Dicarbonsäure 3b, Bis-trifluormethyl-Derivat 3c) wird geschlossen, daß im Bicyclo[3.2.2]nona-6,8-dien-Gerüst 1 (n = 3) die [2π + 2π]-Cycloaddition zu 2 (n = 3) weder bei direkter noch bei sensibilisierter Lichtanregung stattfindet. Als Ersatzreaktionen werden 1,3-Alkylverschiebung (3a → 6a) und Di-π-Methanumlagerung (3a → 7a, 3c → 8c) beobachtet. Gründe für dieses von den niedrigeren Homologen 1 (n = 0, 1, 2) abweichende Verhalten werden diskutiert.
    Additional Material: 1 Ill.
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  • 97
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: PFT-13C-N.M.R. and Mass Spectra of Heterocycles.  -  1,2-Diazaspiro[4.4]nonatetraenesl Azaindolizines, and 3aH-Indazoles13C n.m.r. spectra obtained by the pulse Fourier transform method of 1,2-diazaspiro[4.4]-nonatetraenes 1, azaindolizines 2, and 3aH-indazoles 3 are described. A combination of highest and lowest field resonances allows an unambigous distinction between 1 and 2. A similiar approach is suggested for 3. Estimated increments from model compounds agree well with the c.m.r. spectra. „Strickspektren“ demonstrate the effect of the substituents on the chemical shift of 1 - 3. The mass spectra of 1 - 3 are discussed briefly.
    Notes: Die mit der Puls-Fourier-Transform-Methode erhaltenen 13C-NMR-Spektren von 1,2- Diazaspiro[4.4]nonatetraenene 1, Azaindolizinen 2 und 3aH-Indazolen 3 werden beschrieben. aus einer Kombination von Höchst-und Tiefstfeld-Resonanzfrequenzen konnten die Strukturen 1 und 2 eindeutig unterschieden werden. Eine entsprechende Analyse wurde für 3 vorgenommen. Inkrementabschätzungen führten zu meist guter Übereinstimmung mit den gemessenen Spektren. Aus den Strichspektren kann der durch die verschiedenen Substituenten hervorgerufene Einfluß auf die chemischen Verschiebung von 1 - 3 werden kurz diskutiert.
    Additional Material: 3 Ill.
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  • 98
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2120-2122 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2095-2114 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Substituenteffects in Pericyclic Reactions: The Cycloheptatriene-Norcaradiene-Problem, investigated in C-7-Monosubstituted CompoundsCharacteristic features of the cycloheptatriene-norcaradiene potential curves can be simulated by using methyl cations, which are stabilized by heterofunctional groups and bound to C-7: 1. The potential curve corresponding to low energy cycloheptatriene is realized for the 7-bis(alkylamino)methyl cation 9a 2. Cycloheptatriene and norcaradiene are energetically comparable in the case of the 7-alkoxy(amino)methyl cations. At room temperature 9b - e and 10b - e form a fast dynamic equilibrating system. 3. Norcaradiene 10f comprises the lower minimum of the potential curve for the 7-(1,3-dioxolan-2-ylium) cation. In 10f the substituent is in the exo-position. Using variable temperature 1H-n.m.r., thermodynamic parameters are determined for the equilibria 9b - e ⇋ 10b - e. The influence of C-7-substituents on the cycloheptatriene-norcaradiene equilibrium is discussed and visualized using the MO-model.
    Notes: Methylkationen, stabilisiert durch nachbarständige Alkoxy-oder Alkylaminogruppen und gebunden an C-7, ermöglichen es, drei charakteristische Lagen des Cycloheptatrien-Norcaradien-Gleichgewichtes zu simulieren: 1Mit energieniedrigem Cycloheptatrien-Niveau im 7-Bis(alkylamino)methyl-Kation 9a.2Mit nahezu energiegleichen Cycloheptatrien- und Norcaradien-Grundzuständen in den 7-Alkoxy(amino)methyl-Kationen 9b-e ⇋ 10b - e. 3. Mit energieniedrigem Norcaradien-Grundzustand in der 7-(1,3-Dioxolan-2-ylium)-Verbindung 10f. In 10f ist der Substituent exo-ständig. Thermodynamische Daten der schnellen und reversiblen Gleichgewichte 9b - e ⇋ 10b - e werden bestimmt. Die C-7-Substituentenbeeinflussung des Cycloheptatrien-Norcaradien-Gleichgewichtes wird diskutiert und durch das MO-Modell beschrieben.
    Additional Material: 7 Ill.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2169-2175 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Easy Way for the Preparation of Organylfluorophosphoranes RnPF5-nOrganylfluorophosphoranes can easily be synthesized by reaction of phosphines or chlorophosphines with CCl4 and HF-donors, especially phenylcarbamoyl fluoride.
    Notes: Eine einfache Synthese der Organylfluorphosphorane beruht auf der Umsetzung von Phosphinen und Chlorphosphinen mit CCl4 und HF-Donatoren, vorzugsweise Phenylcarbamoyl-fluorid.
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