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  • 1970-1974  (836)
  • 1940-1944
  • 1970  (836)
  • Inorganic Chemistry  (809)
  • Electron microscopy
  • Nuclear reactions
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 132 (1970), S. 107-157 
    ISSN: 1432-0568
    Keywords: Differentiation ; Down feathers ; Electron microscopy ; Keratinization ; Keratohyalin granules ; Periderm granules
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The morphology of the developing chick feather germ (down feather) was studied at the ultrastructural level from 8 to 18 days of incubation. The process of keratinization in the developing feather germ was described, discussed and compared to keratinization in mammalian skin and hair. This study has shown that: 1. Apico-basal gradients of differentiation and different cell types are recognizable at the ultrastructural level in the developing feather germ. 2. The hypothesis that keratin is synthesized de novo by ribosomes is probably correct, because the largest number of these organelles is present at the time when keratin formation is most prominent. 3. Intercellular gaps in the developing feather germs facilitate the reorientation and rearrangement of different cell types into definitive feather structures. 4. The sources of nutrition and energy for the completion of keratinization during later developmental stages of feather germs are the supportive and the barb medullary cells and large stores of glycogen. 5. Keratohyalin granules are not precursors of feather keratin, since no such structures were observed in feather germs. 6. Two distinct modes of keratinization occur in feather germs. Keratinization in sheath cells is similar to that which occurs in mammalian epidermal cells. Barb and barbule cell keratinization resembles that of hair. 7. The basal lamina is probably involved in transport of synthetic material from the pulp cavity to the epidermal cells. The lamina may also provide mechanically strong connections between the feather germ and the dermis. It is suggested that desmosomal tonofilaments provide a framework which orients the synthesis of keratin. It is also suggested that the periderm granules provide mechanically weak areas in the sheath and facilitate the fragmentation of this structure.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 130 (1970), S. 216-233 
    ISSN: 1432-0568
    Keywords: Guinea-pig ; Placenta ; Syncytiotrophoblast ; Fetal capillaries ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wurde elektronenmikroskopisch die reife Hauptplacenta von 31 Meerschweinchen untersucht. Die Ergebnisse zeigen, daß das Organ aus, drei morphologisch unterscheidbaren Gebieten aufgebaut ist: Interlobär- und, Randsyncytium, Läppchenperipherie und Läppchenzentrum. Zwischen diesen Zonen befinden sich noch zwei Übergangszonen, die die Eigenschaften der angrenzenden Hauptgebiete haben. Das Interlobär- und Randsyncytium enthält keine fetalen Capillaren, besitzt, aber teilweise ein sehr gut entwickeltes endoplasmatisches Reticulum mit zum Teil parallel angeordneten Zisternen sowie vielen Einschlüssen und verschiedenartigen vacuolären Gebilden. Nach dem Vorkommen dieser Bestandteile unterscheiden wir vier unregelmäßig verteilte Syncytioplasmazonen: a) mit vielen Vacuolen, b) mit vielen Filamenten, c) mit Vacuolen und Filamenten und d)— am häufigsten — Gebiete, die fast frei von derartigen Strukturen sind. Der Trophoblast besitzt an der den mütterlichen Lacunen zugewandten Oberfläche viele Mikrovilli und unterschiedliche polypartige Gebilde. Die Läppchenperipherie ist reich an fetalen Capillaren. Die Trophoblastbalken sind dünn und zeigen unterschiedlichen Organellengehalt. Oft kommen viele Vesikel vor. Das endoplasmatische Reticulum ist um die mitochondrien angeordnet. Das Läppchenzentrum zeigt häufig eine vacuolisierte, netzartige Struktur. Im Syncytiotrophoblast sowie in den Endothelzellen werden ausgedehnte endoplasmatische Zisternen gesehen. Die Oberfläche der fetalen Capillaren besitzt viele polypartige Gebilde. In funktioneller Hinsicht wird das Rand- und Interlobärsyncytium mit der Proteinsynthese in Zusammenhang gebracht. Trotz des Fehlens embryonaler Gefäße können sich hier Resorptionsvorgänge abspielen (positive ATP'ase-Reaktion). In der Läppchenperipherie überwiegt möglicherweise der Austausch der Atemgase und niedermolekularer Substanzen. Das Läppchenzentrum scheint wieder in Beziehung zum Proteinaustausch und zum Lipidumsatz zu stehen. Es gibt Hinweise, daß über alle Placentazonen hinweg eine lebhafte Cytoplasmaströmung erfolgt.
    Notes: Summary The mature main placenta of 31 guinea-pigs was investigated by means of electron microscopy. It is shown that the organ consists of 3 morphologically different regions, i.e. interlobar and marginal syncytium, lobular periphery and lobular centre. Between these regions there are 2 transitional zones having the morphological characteristics of both adjacent main regions. The interlobar and marginal syncytium is devoid of fetal capillaries However, in some parts it has an extremely developed endoplasmic reticulum, in parts of which the cisternae are arranged in parallel. In addition it has many inclusions and various vacuolated structures. According to the presence or absence of these structures four irregularly distributed syncytioplasma zones can be distinguished: a) containing large numbers of vacuoles, b) containing large numbers of filaments, c) containing vacuoles and filaments and d)— the main group —regions which are almost entirely free from these structures. On the surface facing the maternal lacunae the trophoblast has an abundance of microvilli as well as various polypoid structures. The lobular periphery is rich in fetal capilaries. The trabeculae of the trophoblast are thin and show a varying of organelles. Frequently large numbers of vesicles are observed. The endoplasmic reticulum is arranged around the mitochondria. The lobular centre frequently shows a vacuolized net-like structure. Extensive endoplasmic cisternae are observed in the syncytiotrophoblast as well as in the endothelial cells. The surface of the fetal capillaries shows an abundance of polypoid structures. From a functional point of view it seems likely that the interlobar and marginal syncytium is involved in protein synthesis. Despite the lack of fetal capillaries, absorptive processes can take place in this region. It is suggested that the main function of the lobular periphery is exchange of the respiratory gases and of substances of low molecular weight. The lobular centre seems to be associated with protein synthesis and lipid turnover.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 10 (1970), S. 276-282 
    ISSN: 1432-1106
    Keywords: Chlorpromazine ; Rabbit hypothalamus ; Glycogen ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The tuber cinereum of hypothalamus, cerebral cortex, cerebellar cortex and caudate nucleus of rabbits were examined under the electron microscope following intramuscular administration of chlorpromazine with special consideration of ultrastructural changes in amount and distribution of glycogen granules in their hypothalamus. In these regions, normal astrocytes and their processes contain glycogen granules diffusely scattered in the cytoplasm. In the neurons of the normal hypothalamus and cerebellar cortex, glycogen granules are seen in some presynaptic endings and distal parts of dendrites but not in the perikaryal cytoplasm. In the tuber cinereum of the hypothalamus, after chlorpromazine administration, abundant glycogen granules accumulate at the postsynaptic sites, especially in peripheric parts of dendrites, and clusters of glycogen granules appear in the perikaryal cytoplasm of the nerve cells. These findings are interpreted as an increase of glycogen in these cellular regions and the suggestion is made that chlorpromazine inhibits the glycolytic metabolism in the distal parts of dendrites, particularly at postsynaptic sites and in the perikarya of nerve cells of the hypothalamus.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 11 (1970), S. 387-391 
    ISSN: 1432-1106
    Keywords: Trifluoperazine ; Rabbit pallidum ; Glycogen ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Following administration of trifluoperazine (a psychotropic drug of the phenothiazine group), the brains of rabbits were examined by electron microscopy, with special reference to the glycogen changes in the globus pallidus, and were compared with the normal materials. After seven days' intramuscular injections of trifluoperazine (10 mg/kg/day), abundant glycogen granules were accumulated in dendrites of pallidum. Those animals showed extrapyramidal symptoms throughout the period. The administration of the drug might inhibit either neural activity or the glycolytic metabolism in dendrites of the pallidum.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 10 (1970), S. 1-16 
    ISSN: 1432-1106
    Keywords: Cerebral cortex ; Laminar lesions ; Degeneration ; Dendrites ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The morphological characteristics of dendrites in layers of the cerebral cortex above laminar lesions induced by ionizing particle irradiation have been studied in the striate field of rat at various survival times. Within two weeks following irradiation an increasing number of dendrites display unusual alterations inferred to be signs of degeneration. Degenerating dendrites can be characterized by a dense cytoplasmic matrix, disruption of mitochondria, presence of dense bodies, irregular outline and a marked alteration of the plasmalemma in its dimensions and staining properties. Some degenerating dendrites possess a large accumulation of dense subsynaptic material and are contacted by synapses with enlarged and altered synaptic clefts. A few dendrites contain extensive membranous whorls. Engulfment by reactive astrocyte processes is a common feature and often includes the presynaptic axonal knob, but only the degenerating dendrite has been observed within glial cytoplasm. The inference that the majority of degenerating dendrites in this material are apical dendrites of pyramidal cells suggests that either shaft synapses are common for these cells, protuberances may retract during degeneration, or spines are lost due to loss of afferent terminals.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 11 (1970), S. 528-538 
    ISSN: 1432-1106
    Keywords: Visual pathway ; Hypothalamus ; Arcuate nucleus ; Rat ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Degenerating nerve fibres and boutons were searched with the aid of the electron microscope in the arcuate nucleus of rats 2–7 days after bilateral destruction of the retina. In the arcuate nucleus of the control animals as well as in the operated animals, 4 types of boutons were distinguished on the basis of vesicular contents and glial ensheathment. In the operated animals changes interpreted as degenerating were found in small myelinated axons and boutons of type II (boutons containing both synaptic and granular vesicles). The changes were similar to those described in the literature as the “dark” type of degeneration in experimentally interrupted axons and boutons. Similar changes were not found in the unoperated animals. The conclusion is reached, that a small number of fibres of the optic tract reach the arcuate nucleus to terminate here.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 111 (1970), S. 316-345 
    ISSN: 1432-0878
    Keywords: Electron microscopy ; Histophysiology of median eminence ; Avian neurohypophysis ; Neurosecretion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Résumé Les effets de l'adénohypophysectomie et de diverses sollicitations de l'axe hypothalamo-hypophysio-corticosurrénalien sur l'ultrastructure de l'Eminence Médiane (E.M.) ont été étudiés chez le Pigeon. 1. Chez le Pigeon entier, l'Eminence Médiane Caudale (E.M.C.) se distingue de l'Eminence Médiane Rostrale (E.M.R.) essentiellement par l'absence dans les deux couches les plus externes (couches palissadique et superficielle) de l'E.M.C. de granules de gros calibres (1600 à 1900 Å), la rareté de granules de diamètre moyen (1200–1400 Å) et la prédominance de petites vésicules à cœur dense de 600–800 Å. 2. La préhypophysectomie entraine: a) dans l'E.M.R. la quasi disparition de granulations dans les deux couches externes; b) dans l'E.M.C. la ≪vidange≫ de nombreux axones, mais un enrichissement relatif, parmi les granulations restantes, des granulations de gros calibre (1600–1900 Å) aux dépens des granules de plus petit calibre. 3. Un shock insulinique entraine des modifications du même ordre: a) déplétion des granules denses, limitée dans ce cas à la portion la plus antérieure des deux couches externes de l'E.M.R.; b) enrichissement relatif des granulations de moyen (1200–1400 Å) et de gros (1600–1900 Å) calibre dans l'E.M.C. avec, en plus dans l'E.M.C., un enrichissement en vésicules de type synaptique. 4. Un traitement à la métopirone produit un accroissement du nombre des granulations de moyen (1200–1400 Å) calibre dans les couches externes de l'E.M.R. et de l'E.M.C., et un enrichissement important de l'E.M.C. en vésicules de type synaptique. 5. Le traitement à la prednisolone conduit à un enrichissement très marqué des couches externes de l'E.M.R. en grains de 1200–1400 Å, et à un enrichissement des couches externes de l'E.M.C. en granulations de 1000 Å. Ces résultats sont discutés dans la perspective des régulations hypothalamo-corticotropes, particulièrement en ce qui concerne les granules de 1200–1400 Å.
    Notes: Summary The effects of adenohypophysectomy, and of several experimental interventions on the hypothalamo-pituitary-adrenal cortical axis have been studied in relation to the fine structure of the median eminence in the pigeon. 1. In control animals, the following morphological features of the caudal median eminence (C.M.E.) distinguish it from the rostral median eminence (R.M.E.): a) the absence in both external layers of the C.M.E. of large (1,600–1,900 Å) electron-dense granules, b) the presence in the C.M.E. of a small number of medium-size (1,200–1,400 Å) granules, and c) the predominance in the C.M.E. of small (600–800 Å) dense-core vesicles. 2. Adenohypophysectomy leads to: a) almost complete disappearance of electron-dense granules in both external layers of the R.M.E., and b) “emptying” of numerous axons and a relative increase in the number of large (1,600–1,900 Å) granules in the C.M.E. 3. Insulin shock produces modifications similar to those of adenohypophysectomy. The depletion of electron-dense granules from the axons is, however, restricted to the most anterior part of the R.M.E., and, in the C.M.E., the relative increase in the number of larger granules affects the 1,200–1,400 Å and the 1,600–1,900 Å size granules. 4. Metopirone enhances the number of medium-size (1,200–1,400 Å) granules in the external layers of both the R.M.E. and the C.M.E. and causes a significant increase in the number of synaptic-like vesicles in the C.M.E. 5. Prednisolone treatment leads to a marked enrichment of the external layers of the R.M.E. with 1,200–1,400 Å granules, and of the external layers of the C.M.E. with 1,000 Å granules. These results have been discussed with special reference to the hypothalamic control of the adrenocorticotropic function, especially reviewing the role of the 1,200–1,400 Å granules.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 106 (1970), S. 451-472 
    ISSN: 1432-0878
    Keywords: Hemocytopoiesis ; Insects ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Mikroskopische Beobachtungen an normalen „phagozytären Geweben“ (im Sinne der älteren Autoren) entlang des dorsalen Diaphragmas der beiden Orthopteren-Arten Gryllus bimaculatus und Locusta migratoria zeigen übereinstimmend, daß diese Bildungen eine hematopoietische Struktur haben. Bei beiden Arten entwickeln sich die blutbildenden Stammzellen aus einer großen Anzahl sog. Retikularzellen mesodermalen Ursprungs, die den Retikularzellen der blutbildenden Gewebe der Vertebrata sehr stark ähneln. Wie bei den Vertebrata differenzieren sich bei den Insekten die Blutzellen in sog. isogenen Zellgruppen von gleichem Typus und gleichem Entwicklungsstadium. Die starke phagozytäre Neigung der Retikularzellen erklärt, warum die blutbildenden Gewebe der Orthoptera von den älteren Autoren als phagozytäre Organe angesprochen wurden. Die hämatopoietische Differenzierung der Retikularzellen in reife Blutzellen (Haemozyten) findet entweder in einem lockeren Gewebe entlang des dorsalen Blutgefäßes, wie bei Locusta, statt, oder im inneren mehrerer, an das Herz gebundener, hoch organisierter blutbildender Organe, wie bei Gryllus, die noch stärker an die klassischen Strukturen der Vertebrata erinnern. Wir beschreiben im einzelnen beide Strukturtypen, insbesondere bei Gryllus die Einteilung der Organe in einen Cortex, in dem sich die Blutzellen bilden, und eine Medulla, in welcher sich die reifen Haemozyten ansammeln können. Nach starken Blutverlusten zeigen besonders die blutbildenden Gewebe von Gryllus eine dramatische Stimulierung der Hämatopoiese an; die Punktion der hämatopoietischen Organe kann also ebenfalls experimentell nachgewiesen werden.
    Notes: Summary Microscopic observations of the normal “phagocytic tissues” (in the sense of the classic authors) of the dorsal diaphragm in the two Orthopterans Gryllus bimaculatus and Locusta migratoria unequivocally demonstrate the hematopoietic nature of these cellular accumulations. In the two species, the hematopoietic elements develop from a large number of so-called reticular cells of mesodermic origin, which resemble closely the reticular cells of the hematopoietic organs of Vertebrates. As it is the case in Vertebrates, the differentiation of the hematopoietic elements into mature blood cells occurs in the two Orthopterans also in isogenic cell islets. The phagocytic activity of the reticular cells explains the fact that these organs were classically considered in the Orthopterans as simple phagocytic organs. The hematopoietic differentiation of the reticular cells can occur either in a poorly organized, loose tissue located along the dorsal vessel, as is the case in Locusta, or in a group of highly organized hematopoietic organs, as in Gryllus, which resemble far more the classical hematopoietic structures of Vertebrates. We give a detailed description of both types of organization, especially of the subdivision in Gryllus, of the hematopoietic organs into a cortex, where the haemocytes differentiate, and a medulla, where they can accumulate. After severe hemorrhages, the hematopoietic organs of Gryllus show all the features of a dramatic stimulation of hematopoiesis; their function can thus be experimentally demonstrated.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 106 (1970), S. 523-538 
    ISSN: 1432-0878
    Keywords: Ependyma ; Intracytoplasmic lipid bodies ; Histochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Bei erwachsenen Feuersalamandern und bei Salamanderlarven konnten in Ependymzellen sowie in subependymären Zellelementen des Gehirns und Rückenmarks zahlreiche rundliche intrazytoplasmatische Körper von starker Osmiophilie beobachtet werden, deren Durchmesser bis zu 12 μ betrug. Vereinzelt fanden sich diese voluminösen Gebilde auch im Cytoplasma von Satellitenzellen der Hirnnerven- und Spinalganglien. Das histochemische Verhalten und das Ultrastrukturbild der intrazytoplasmatischen Körper sprechen dafür, daß sie hauptsächlich aus Lipiden bestehen. Ihre funktionelle Bedeutung konnte bisher nicht eindeutig geklärt werden.
    Notes: Summary The ependymal and subependymal cells of the ventricular system and the central canal in adult und larval salamanders contain numerous unusually large intracytoplasmic osmiophilic spherical bodies with a diameter of up to 12 μ. Sporadically the bodies are found within satellite cells of peripheral ganglia. Histochemical and ultrastructural examination suggests that the bodies consist mainly of lipids. Their functional significance is unknown.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 109 (1970), S. 384-397 
    ISSN: 1432-0878
    Keywords: Heart muscle cells ; Electron microscopy ; Quantitative ; Asphyxia ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Normale und hypoxische Herzmuskelzellen aus der Wand des linken Ventrikels der Ratte wurden quantitativ-morphologisch anhand von elektronenmikroskopischen Längsschnitten nach Perfusionsfixierung untersucht. In normalen Zellen waren alle Myofibrillen relaxiert, die mittlere Sarcomerlänge betrug 2,2 μm. Die Schnittfläche wurde zu 55% von Myofibrillen, zu 27% von Mitochondrien und zu 18% von Grundplasma und Reticulum eingenommen. Die zwischen den Myofibrillen liegenden Mitochondrien waren längsoval und im Mittel 2,3mal so lang wie breit. Es bestand kein Unterschied zwischen subendokardial und subepikardial gelegenen Zellen. 10 min nach Erstickung der Tiere waren in den sonst unauffälligen Muskelzellen die Glycogengranula vermindert. Nach 20 min führte die Hypoxie zu einer Zunahme der relativen Schnittfläche der Mitochondrien um etwa 16% und zu einer beginnenden Kontraktur der Myofibrillen (Sarcomerlänge 2,0 μm). 20 min Hypoxie in Hypothermie (25–30°C intrathorakal) veränderte die normale Zellstruktur dagegen kaum. Wenn die Herzen während der 20 min dauernden Hypoxie in Normothermie mit einer procainhaltigen sauerstoff- und glucosefreien Blutersatzlösung durchspült wurden, waren die Myofibrillen relaxiert, die Schwellung der Mitochondrien dagegen wurde nicht reduziert. 30 min nach Erstickung wurde die Kontraktur stärker (Sarcomerlänge 1,7 μm). Nach 60 min bildeten sich Superkontraktionsknoten, einzelne Myofibrillen waren in Höhe der I-Bänder unterbrochen. Die Cristae der Mitochondrien wichen auseinander, die Schnittfläche der Mitochondrien hatte um 27% zugenommen. Während in Normotherapie eine Asphyxie des Tieres bereits nach 10 min die Herzmuskelzellen funktionell schwer schädigt, ist die Schädigung morphologisch erst nach 20 min eindeutig. Das bedeutet, daß für die elektronenmikroskopische Präparation eine Hypoxie von unter 10 min bedeutungslos ist. Hinsichtlich der morphologischen Manifestationszeit für die Unterbrechung der Sauerstoffversorgung stimmen unsere Befunde an Herzmuskelzellen gut mit vergleichbaren Angaben an Leberzellen überein.
    Notes: Summary In heart muscle cells of the left ventricle of rats the distribution of cell organelles and their reaction to hypoxia were investigated by electron microscopy. In normal hearts fixed by perfusion with aldehydes, the mean sarcomere length was 2.2 μm. 27% of the longitudinal sectional area was occupied by mitochondria, 55% by myofibrils and 18% by sarcoplasmic reticulum and ground plasm. The mitochondria situated in rows between the fibrils were oval and measured 2.3 times more in length than in width. There was no difference between cells from subendocardial and subepicardial regions. 10 min hypoxia (complete occlusion of the trachea) did not affect the appearance of muscle cells but diminished the number of glycogen granules. After 20 minutes the area occupied by mitochondria was increased by 16%, the mitochondria between the myofibrils were more spherical and only 1.5 times longer than wide. The sarcomeres shortened to 2.0 μm. With hypothermia (25–30°C) hypoxia of 20 minutes duration did not affect the cell structure. Perfusion of the heart by a saline solution, which contained procaine but neither oxygen nor glucose, for 20 minutes prevented shortening of the sarcomeres but not swelling of the mitochondria. 30 minutes after occlusion of the trachea the myofibrils shortened to a sarcomere length of 1.7 μm. After 60 minutes irregularly and excessively contracted myofibrils appeared and some sarcomeres were interrupted at the level of the I-bands. In some of the swollen mitochondria the cristae were widely separated. The increase of the area occupied by mitochondria was 27%. Asphyxia affects heart muscle cells severely with respect to function within 10 min, but morphologically it takes 20 min before a definite effect can be noticed. As to the time after which lack of oxygen is manifested morphologically, our results are consistent with findings in liver cells.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 109 (1970), S. 431-449 
    ISSN: 1432-0878
    Keywords: Contractile ring ; Cytokinesis ; Cell division ; Cytochalasin B ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Techniques of individual cell selection and precise ultramicrotomy have been employed to demonstrate that the contractile ring of cleaving HeLa cells is a transitory cytoplasmic organelle of distinctive fine structure and location. The contractile ring is an uninterrupted annulus encircling the equator of dividing cells exactly where the cleavage furrow forms. It is about 10 microns wide, up to 0.2 microns in thickness, and is composed exclusively of circumferentially aligned thin filaments 40–70 Å in diameter. Contractile ring filaments appear to be associated with the overlying plasma membrane. Controlled experiments with a mold metabolite (cytochalasin B) reveals that within a few minutes the drug abolishes the ability of HeLa cells to undergo cytokinesis. Cytochalasin B seems to decompose the contractile ring. It has no other clearly identifiable effects on other cell structures, notably the mitotic apparatus. Cytochalasin B is the only drug known which selectively inhibits cytokinesis in animal cells. In conclusion, the contractile ring is the most likely organelle responsible for cytokinesis in HeLa cells. Similar organelles probably occur in all cleaving animal cells. Successful cleavage depends upon the structural and functional integrity of the contractile ring.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 110 (1970), S. 153-165 
    ISSN: 1432-0878
    Keywords: Reptiles ; Skin ; Keratin ; Electron microscopy ; Evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The different patterns of keratin formation that have evolved in the class Reptilia are all variations of a common process. In Squamata (snakes and lizards), a sequence of layers composed of α or β keratin is formed periodically, after which the old epidermal generation is shed. In Chelonia (turtles and tortoises), the epidermis of the shell is composed of only β keratin, whereas the skin of the neck and leg is composed exclusively of α keratin. Molting in toto does not occur and shedding is a continuous process comparable to that in avian and mammalian epidermis. In Crocodilia (crocodiles, caimans, alligators) there is only a single layer of cornified cells, but the composition of the layer varies in different parts of the scale. The hinge regions have many of the morphological characteristics of α and β keratin whereas the center resembles β keratin. The living cells beneath contain accumulations of keratohyalin. There are four ultrastructural characteristics of a keratinized α layer: 1) cellular outlines remain distinct, 2) a thickened plasma membrane forms during keratinization, 3) 80 Å filaments embedded in an amorphous matrix can be seen, and 4) PAS-positive material accumulates in extracellular spaces between the desmosomes. The β layer exhibits none of these features. Instead the cells more or less (depending on species) coalesce into a compact layer which becomes attenuated in the hinge regions. A 30 Å filament pattern can be seen. The mesos layer of squamates resembles the hinge region of crocodilians, exhibiting a combination of the characteristics of both α and β keratin.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 106 (1970), S. 309-321 
    ISSN: 1432-0878
    Keywords: Red nucleus ; Substantia nigra ; Neuroglia ; Pericytes ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The morphology of perivascular and perineuronal cells in the substantia nigra and red nucleus was studied in Nissl, silver carbonate, and electron microscopic preparations. In light microscopic preparations of the red nucleus and substantia nigra oligodendrocytes and astrocytes are located adjacent to blood vessels and nerve cells. Pericytes are also found adjacent to blood vessels. Scattered perineuronal oligodendrocytes and astrocytes are present in the magnocellular portion of the red nucleus and in the substantia nigra, whereas a distinguishing morphological feature of the parvocellular portion of the red nucleus is the clustering of perineuronal oligodendrocytes around a single neuron. In the present electron micrographs of the red nucleus and substantia nigra oligodendrocytes are separated from the vascular basement membrane (basal lamina) by astrocyte processes and therefore are not truly perivascular. Pericytes are easily identified by the basement membrane which encompasses their cell bodies and processes. Characteristic of the neuropil in the red nucleus are astrocytic processes that approximate dendrites. In contrast, astrocytic processes in the substantia nigra rarely contact dendrites which are covered by a mosaic of synaptic endings. A “third type of neuroglial element” is also present in the neuropil of the substantia nigra and the red nucleus.
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  • 14
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    Cell & tissue research 108 (1970), S. 324-338 
    ISSN: 1432-0878
    Keywords: Human myocardium ; Innervation ; Nerve endings ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Electron microscope studies of axons, distributing singly or in small bundles in the human ventricular and atrial myocardium, indicate a few per-cent of the axon profiles to be significantly large in diameter (1.5–3.0 μ). They are characteristically packed with a profuse number of mitochondria along with large granular vesicles, glycogen rosettes, lysosomic bodies; and some of them terminate on a “specific terminal cell” (Knoche and Schmitt). These mitochondria-rich, large axons are assumed to be terminal portions of the cardiac afferents. About half of the axons encountered in the ventricle and 2/3 in the atrium are non-vesiculated, usually less than 0.5 μ. in diameter. The varicosities containing numerous vesicles are mostly 0.5–1.5 μ in diameter and are assumed to be terminal portions of the cardiac efferents. The ratio between the number of axon profiles containing small granular vesicles and that of axon profiles containing agranular vesicles without small granular vesicles is 2∶1 in the ventricular myocardium and 1∶1.7 in the atrial myocardium.
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  • 15
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    Cell & tissue research 109 (1970), S. 33-45 
    ISSN: 1432-0878
    Keywords: Testis ; Interstitial cells ; Reptiles ; Hormone Production ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Résumé L'ultrastructure des cellules interstitielles du testicule de Lacerta vivipara a été étudiée entre le printemps et l'automne pendant deux années. Le retioulum endoplasmique lisse, et les mitochondries à crêtes tabulaires sont les organites les plus remarquables comme dans les autres cellules productrices de stéroïdes, mais les liposomes et l'appareil de Golgi sont bien représentés aussi. Les variations ultrastructurales les plus significatives apparaissent entre le printemps et le début de l'été. Au printemps, alors que les caractères sexuels secondaires sont hypertrophiés, un système remarquable de vésicules et de vacuoles se développe à partir du reticulum et probablement aussi du Golgi. Au début de l'été, lorsque les caractères sexuels secondaires sont atrophiés, les vacuoles sont moins nombreuses et le reticulum forme un réseau dense de tubules typiques, souvent étroitement associés aux liposomes; les crêtes mitochondriales sont gonflées. Ces images sont discutées en fonction de l'activité saisonnière d'élaboration d'hormones. L'hypertrophie des systèmes membranaires au printemps correspond probablement à la production ou (et) à l'excrétion des hormones androgènes. Au début de l'été, la cellule n'élabore pas d'androgènes, mais n'est peut-être pas complètement inactive: elle pourrait stocker des précurseurs hormonaux.
    Notes: Summary Interstitial cells of the testis of Lacerta vivipara have been studied electronmicroscopically in animals obtained between spring and autumn. Smooth endoplasmic reticulum and mitochondria with tubular cristae are the most prominent organels, lipid droplets and Golgi apparatus being also well developed. The most significant ultrastructural changes occur between spring and the beginning of summer. In spring, during the hypertrophy of secondary sexual characters, a conspicuous system of vesicles and vacuoles originates from the smooth endoplasmic reticulum and probably also from the Golgi apparatus. At the beginning of summer, when secondary sexual characters are atrophied, vacuoles are less prominent and the smooth endoplasmic reticulum consists of a dense network of typical tubules, often closely associated with the lipid droplets; the cristae of the mitochondria are swollen. These ultrastructural findings are discussed in relation to the production of hormones. The hypertrophy of membrane systems in spring corresponds presumably to production or (and) release of androgen hormones. In the beginning of summer the cell does not produce androgens, but probably is not completely inactive: it may store precursors of hormones.
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  • 16
    ISSN: 1432-0878
    Keywords: Neurosecretion ; Gastropoda ; Fluorescence ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Durch Vergleich fluoreszenz- und elektronenmikroskopischer Untersuchungen am zentralen Nervensystem von Planorbarius corneus L. wird nachgewiesen, daß in den Schlundringganglien Neurosekretzellen vorkommen (Nachweis mit Pseudoisocyaninchlorid), die mit Nervenzellen nicht identisch sind, die durch ihren hohen Gehalt an biogenen Aminen auffallen (Nachweis durch die Methode von Falck und Owman, 1965). Es können daher im Schlundring von Planorbarius corneus peptiderge und aminerge Neurosekretzellen unterschieden werden. Die PSC-positiven Neurosekretzellen enthalten elektronendichte Elementargrana und die aminergen Neurone „dense-core“ Vesikel. Der Nachweis biogener Amine in einigen Nervenzellen von Planorbarius corneus spicht für deren chemische Identität mit Transmittersubstanzen, ihre hohe Konzentration aber für eine Abgabe in die Körperflüssigkeit.
    Notes: Summary The neurosecretory system of the snail Planorbarius corneus has been investigated by fluorescence and electron microscopy. With the fluorochrome Pseudoisocyanin the established neurosecretory system in the cerebral ganglia and single neurosecretory cells in the other ganglia show an intensive yellow fluorescence. Electron micrographs reveal the presence of electron dense granules (elementary granules) in the pericarya and the axons of neurones which have the same localisation in the ganglia as the pseudoisocyanin-positive cells. The fluorescence technique for biogenic amines produces yellow and green fluorescence within neurons and in the neuropil and nerves. The fluorescence obtained in determinable areas and neurones correlates well with the electron microscopic location of “dense-core” vesicles within the pericarya and axons of cells in even the same areas. It is discussed, that in this animal both types of cells are so-called “neurosecretory cells”, because the high content of elementary granules in the “peptidergic neurosecretory cells” and of “dense-core” vesicles in the “aminergic neurosecretory cells” is an indication for secretion of these products in neurohaemal areas (circulatory channels).
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  • 17
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    Cell & tissue research 110 (1970), S. 321-335 
    ISSN: 1432-0878
    Keywords: Thymus ; Lymphocyte ; Analysis ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Thymic small lymphocytes of dd-mice were qualitatively and quantitatively studied by electron microscopy. Differences in fine structure were revealed between cortical and medullary small lymphocytes. Cortical small lymphocytes are rounded in cell outline with a round nucleus. The cytoplasm surrounding the nucleus as a narrow rim is scanty and appears relatively dense due to an abundance of free ribosomes. The cell organelles are not well developed. On the other hand, medullary small lymphocytes are more irregular in shape with uneven cell membranes. Their nuclei are also more irregular in outline with frequent infoldings of the nuclear membrane. The cytoplasm is more abundant and paler with less numerous ribosomes. The cell organelles are better developed. Quantitative analysis was made of both cortical and medullary small lymphocytes by means of the point counting method. The nuclei of both cortical and medullary small lymphocytes are almost the same in size (a diameter of 4.9 μ). The cell sizes are different between cortical and medullary lymphocytes: cortical small lymphocytes with a diameter of 5.5 μ were smaller than medullary ones with a diameter of 6.4 μ. Cortical small lymphocytes are very sensitive to the destructive effects of hydrocortisone, whereas the medullary ones are resistant. Periarteriolar lymphoid sheath in the splenic white pulp, which is known to be a thymus-dependent area, contains small lymphocytes that were similar in cytological details to medullary small lymphocytes of the thymus. In the light of the recent knowledge about a recirculating long-lived small lymphocyte pool, it appears probable that medullary small lymphocytes represent a contribution to the pool and that small lymphocytes with a long life span can be cytologically identified by electron microscopy.
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  • 18
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    Cell & tissue research 110 (1970), S. 386-400 
    ISSN: 1432-0878
    Keywords: Autonomic nerves ; Perineurial sheath ; Termination ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Das Perineurium kleiner Mesenterial- und Trachealnerven besteht aus einer Lage platter, beiderseits von einer Basalmembran umschlossener Zellen. Im Bereich von Abzweigungen kleiner Nerven bildet das Perineurium ein gekammertes, stark kollagenfibrillenhaltiges Hüllensystem. Die Endigung der einschichtigen Perineuralhülle hat die Form einer in das Interstitium geöffneten Röhre. Im ansatznahen Drittel des Mesenteriums und in der Schleimhaut der Trachea wurden ausschließlich perineuriumfreie Nerven gefunden. Es liegt nahe, diese perineuriumfreien Bezirke zu funktionellen Endräumen zusammenzufassen. In perineuriumfreien Bezirken wird das gehäufte Auftreten von Nervenauftreibungen mit Vesikeln, die Transmittersubstanz enthalten, und Mitochondrion beobachtet. Die erhobenen Befunde werden mit den an dickem Perineurium gewonnenen Ergebnissen verglichen und diskutiert.
    Notes: Summary The perineurial sheath of small tracheal and mesenteric nerves consists of a layer of flat, basement membrane coated cells. Its ramifications form a complicated layered system, interspersed with collagen fibrils. The tube formed by the thin perineurial sheath ends openly, which affords communication between the respective interstitial spaces. The mesenteric nerves close to the duodenum as well as the nerves in the vicinity of the tracheal epithelium show no perineurial sheath. Peripheral nerves lacking a perineurial layer seem to be close to their terminations. Their fibers show varicosities containing transmitter vesicles and mitochondria with longitudinally orientated cristae. Our results are compared with those found in thick, multilayered perineurial sheaths and functional differences are discussed.
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  • 19
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    Cell & tissue research 111 (1970), S. 51-63 
    ISSN: 1432-0878
    Keywords: Purkinje cell ; Golgi apparatus ; Dendrites ; Differentiation ; Histochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The morphology of postnatal differentiation of the Golgi apparatus, the nucleus, the perikaryon, and the dendrites was studied in Purkinje cells of the rat cerebellum for 30 days after birth using histochemical, histological, and electron microscopic methods. The Golgi apparatus during differentiation undergoes morphological and positional changes. From the 1st to 7th postnatal day, the Golgi apparatus is found in a supranuclear position, and is connected with the axes of differentiating primary dendrites by beam-like processes. From days 8 to 11 this connection disappears, and most of the Golgi apparatus assumes a lateronuclear and infranuclear position. After the 11th or 12th day, the Golgi apparatus is found in perinuclear and peripheral cytoplasmic positions. The formation of granular endoplasmic reticulum occurs in the vicinity of the perinuclear Golgi apparatus. The differentiation of cell and nuclear forms requires approximately 20 days. The morphological changes of differentiation are discussed in relation to the participation of the Golgi apparatus in the differentiation of dendrites and in the formation of the granular endoplasmic reticulum.
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  • 20
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    Cell & tissue research 111 (1970), S. 149-159 
    ISSN: 1432-0878
    Keywords: Rabbit ovum ; Fertilization ; Pronucleus ; Cleavage ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Fertilized ova were flushed from the Fallopian tubes of New Zealand White rabbits at 15 to 30 hours after mating and examined with the electron microscope. Between 21 and 22 hours intact pronuclei with extensive interdigitation of apposing surfaces were found in most ova. In some, an appearance suggesting internuclear communication was observed. In other ova disrupted pronuclear membranes surrounded centrally placed chromosome aggregates. In still others an advanced cleavage furrow was already present. By 23 hours all ova were in the two-cell stage.
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  • 21
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    Cell & tissue research 103 (1970), S. 382-397 
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Newborn rat ; Stereology ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The structure of the zona glomerulosa and the zona fasciculata of the newborn rat adrenal cortex has been studied by the light and the electron microscope. The ultrastructural features of the cells of both zones are described. By morphometric methods the relative volumes occupied by mitochondria and by lipid droplets have been evaluated. The “membrane profile concentration” (i.e. the average number of microns of smooth reticulum profiles per square micron of cytoplasm) has been also measured. The most significant ultrastructural differences between the cells of the two zones concern the mitochondria, the lipid droplets, and the smooth endoplasmic reticulum. The mitochondria show typical lamellar cristae in the elements of the zona glomerulosa, and vesicular cristae in the cells of the zona fasciculata. They occupy the same relative volume in both elements. The lipid droplets and the smooth reticulum show no qualitative differences in the two cell types, but they are found in a larger amount in the cells of the zona fasciculata. These ultrastructural findings are discussed in relation to the numerous biochemical data, suggesting that the cells of the zona glomerulosa are resting elements at birth, while the cells of the zona fasciculata are active steroid-secreting elements already in late gestation.
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  • 22
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    Cell & tissue research 103 (1970), S. 398-409 
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Newborn rat ; Electron microscopy ; Lysosomes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The structural changes of the zona juxtamedullaris of the rat adrenal cortex at birth, have been examined by the light and the electron microscope. In this zone clusters of medullary cells lying among the strands of cortical tissue were observed. In the inner portion of the zona juxtamedullaris two types of adrenocortical cells were found: light and very-dark cells. The latter are smaller than the light cells and are always in close connection with the medullary tissue. The ultrastructural features of the very-dark cells suggest that these elements are in degeneration. This finding supports the hypothesis that at birth there is a partial degeneration of the rat zona juxtamedullaris, i.e. the zone corresponding to the “fetal zone” of some mammalian species. It is proposed that in all mammalian species at birth there is a partial regression of the zona juxtamedullaris and that the regression of the “fetal zone” is only the quantitative increase of this phenomenon. This hypothesis is discussed in relation to numerous data demonstrating that there are enzymatic conditions in the rat during fetal life, which permit a discrete hypertrophy of the adrenal cortex.
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  • 23
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    Cell & tissue research 103 (1970), S. 341-350 
    ISSN: 1432-0878
    Keywords: Catecholamines ; Brain ; Insects ; Electron microscopy ; Cytochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In the brain of the cockroach Periplaneta americana, the beta lobes of the corpora pedunculata respond with an intense positive reaction to a specific fluorescence histochemical method for catecholamines. The fluorescence reaction disappears completely after prolonged treatment of the cockroaches with reserpine. An ultrastructural examination of the beta lobes in formaldehyde-glutaraldehyde-osmium fixed preparations reveals the presence of two types of fibres: 1) Fibres and nerve endings containing small clear vesicles and sligthly larger vesicles with a semi-dense content. The appearance and size distribution of these vesicles ist not affected by treatment with reserpine. 2) Fibres containing larger and denser vesicles, but practically no clear vesicles. The size distribution of these dense vesicles is only slightly affected by treatment of the cockroaches with reserpine. If brain slices are incubated in a medium containing noradrenaline or α-methyl-noradrenaline and fixed in permanganate, small vesicles with electron-dense central cores show up, similar to those which have been described in vertebrate adrenergic nerve fibres (“small granular vesicles”). They are confined to one of the two types of fibres (a and b) visible in these preparations, namely to type b, whose correspondence with type 2 fibres of formaldehyde-glutaraldehyde-osmium fixed preparations is discussed.
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  • 24
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    Cell & tissue research 104 (1970), S. 345-357 
    ISSN: 1432-0878
    Keywords: Photoreceptor ; Lumbricus ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die Feinstruktur der Photorezeptorzellen in der Epidermis, in kleineren Nervenästen und im Zerebralganglion von Lumbricus terrestris wurde untersucht. Das Vorhandensein eines zentralen, intrazellulären Lumens (Phaosom), das mit Mikrozotten gefüllt ist, erinnert in der Struktur der Photorezeptorzelle des Regenwurms an Lichtsinneszellen von Hirudo. Außer Mikrozotten findet man im Phaosom einige Zilien vom Typ 9×2+0; solche Zilien sind von den Mikrozotten strukturell unabhängig. Durch eine Aufzweigung des Phaosoms in kleinere Buchten, die tief in das umgebende Zytoplasma eindringen, erhält es ein labyrinthartiges Aussehen. Glatte Zisternen in Gruppen von 2 bis 5 wurden oft um das Phaosom im Zytoplasma beobachtet. Charakteristische Bestandteile der Zelle sind noch Vesikel und Vakuolen, die mit einer Substanz von wechselnder Elektronendichte gefüllt sind. Die Photorezeptorzellen werden von Gliazellen und Gliafortsätzen umgeben, die an vielen Stellen die Zelloberfläche tief einstülpen (Trophospongium).
    Notes: Summary Photoreceptor cells in the epidermis and nerve branches of the prostomium and in the cerebral ganglion of Lumbricus terrestris were investigated with the electron microscope. The photoreceptor cell is similar to the visual cell of Hirudo by having a central intracellular cavity (phaosome) filled with microvilli. Besides microvilli, several sensory cilia can also be found in the phaosome but they are structurally independent of the microvilli. A gradual branching of the phaosome cavity into smaller cavities makes its sectional profile extremely labyrinthic. Flattened smooth-surfaced cisternae in stacks of 2 to 5 are frequently observed around the phaosome. Characteristic constituents of the cytoplasm are vesicles and vacuoles filled with a substance of varying density. The photoreceptor cell is covered by glial cells or by their processes which at many places deeply invaginate the cell surface (trophospongium).
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  • 25
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    Cell & tissue research 105 (1970), S. 176-187 
    ISSN: 1432-0878
    Keywords: Ependyma ; Salamandra maculosa ; Neuronal elements ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Zwischen den eigentlichen Ependymzellen des Zentralkanals adulter Feuersalamander kommen amphorenartig gestaltete Elemente vor, die sich aufgrund ihrer synaptischen Kontakte mit Axonendigungen als Neurone identifizieren lassen. Diese intraependymalen Nervenzellen weisen einen apikalen Fortsatz auf, der sich mit einer warzen- oder knotenförmigen Protrusion in das Lumen des Zentralkanals erstreckt. Die Protrusion ist gewöhnlich mit stereozilienartigen Ausläufern besetzt. Die funktionelle Bedeutung der beschriebenen neuronalen Elemente konnte bisher nicht geklärt werden.
    Notes: Summary The ependyma of the canalis centralis of adult salamanders was examined by electron microscopy. Between the ependymal cells occur amphora-like elements identifiable as neurons by their synaptic contacts with axon terminals. These intraependymal nerve cells exhibit an apical outgrowth extending into the lumen of the canalis centralis with a wart-like or knob-like protrusion. The latter usually bears extensions resembling stereocilia. The functional significance of the neuronal elements is still unknown.
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  • 26
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    Cell & tissue research 105 (1970), S. 515-525 
    ISSN: 1432-0878
    Keywords: Cuticle ; Rotifer ; Development ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Ultrastructural studies of developing Asplanchna brightwelli embryos support the following hypothetical scheme of cuticle formation. First the external hypodermal membrane invaginates, and deposition of a dense intracellular layer commences next to this membrane. Then the rough endoplasmic reticulum synthesizes fibrous protein which is transferred to the Golgi complex. Here polysaccharide is synthesized and added to the protein, and the resulting filamentous complex is enclosed in large irregularly shaped vesicles which bud off from the Golgi elements. Maturation of the filamentous material to condensed cuticle material occurs as the vesicles move to the invaginations. Each vesicle fuses with an invagination, thus forming a hypodermal bulb; then the cuticle material is discharged through the neck of the bulb to its extracellular location. After the bulbs are formed, new, smaller, spherical vesicles begin to bud off from the Golgi elements. They too contain the filamentous complex which is refined to condensed cuticle material as the vesicles near the bulb. These vesicles fuse with the hypodermal bulbs contributing the cuticle and membrane necessary for the growth of the hypodermis of the embryo and newborn animal. Ruthenium red staining has confirmed that the cuticle consists of glycoprotein.
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  • 27
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    Documenta ophthalmologica 28 (1970), S. 191-200 
    ISSN: 1573-2622
    Keywords: Acomys Cahirinus ; Retinal capillary basement membrane width ; Age modifications ; Electron microscopy ; Morphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L étude morphométrique des capillaires rétiniens de souris à piquants de différents âges (3, 6, 12 et 36 mois) a démontré un épaississement des membranes basales et un élargissement des diamètres capillaires en fonction de l'âge et, en outre, l'existence d'une corrélation positive entre ces deux paramètres.
    Abstract: zusammenfassung Die morphometrische Untersuchung von Retinakapillaren verschieden Alter (3, 6, 12 und 36 Monate) Stachelmäuse (Acomys cahirinus) ergab eine altersabhängige Zunahme sowohl der Basalmembrandicke als auch des Kapillardurchmessers. Zudem wurde eine positive Korrelation zwischen diesen beiden Parametern gefunden.
    Notes: Abstract Specimens of four age groups of non-diabetic, non-obese spiny mice (Acomys Cahirinus), 3, 6, 12, 36 months old respectively, were examined for changes in retinal capillaries. Morphometrical evaluation of electron-micrographs allowed to conclude that capillary basement membrane width, as well as capillary diameter, increase during ageing: the values in the four different age groups were found to be 656, 925, 1098, 1772 Ångström units for the average basement membrane width, and 3,72, 4,08, 4,58, 5,60 microns for average capillary diameter. The differences between the age groups proved to be significant at a p 〈 0,01. Furthermore, a positive correlation between capillary diameter and capillary basement membrane width seems to be highly probable.
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  • 28
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 104-111 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of FluoromethyldialkylaminesFluoromethyldialkylamines (3a-f) are prepared from N,N-acetals (aminals) by cleavage with carboxylic acid fluorides or l-fluoro-2,4-dinitrobenzene. They are low-boiling liquids and are characterized by a covalent carbon-halogen bond. Their reactivity is similar to that of the analogous carbimonium chlorides, bromides and iodides.
    Notes: Fluormethyl-dialkyl-amine (3a-f) werden durch Spaltung von Aminalen mit Carbonsäurefluoriden oder l-Fluor-2.4-dinitro-benzol gewonnen. Sie sind niedrigsiedende, durch eine kovalente Kohlenstoff-Halogen-Bindung charakterisierte Flüssigkeiten und zeigen ähnliche Reaktionsfähigkeit wie die analogen Carbimoniumchloride, -bromide oder -jodide.
    Additional Material: 3 Ill.
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  • 29
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 133-146 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Fulvenes, IV In the 5-Membered Ring Unsubstituted 6,6-DiaminofulvenesAlkylation of tetrasubstituted thioureas with methyl iodide leads to S-methyl isothiuronium iodides 3, which have been transformed to 6,6-diaminofulvenes 1 by condensation with cyclopentadienyl sodium. Some compounds of type 1 are also obtainable from the reaction between cyclopentadiene and chloroformamidinium chlorides 4 in the presence of triethylamine. I.r., u.v., and n.m.r. spectra of 1 and 3 are discussed.
    Notes: Tetrasubstituierte Thioharnstoffe lassen sich mit Methyljodid in die S-Methyl-isothiuroniumjodide 3 überführen, die ihrerseits mit Cyclopentadienylnatrium die 6.6-Diamino-fulvene 1 bilden. Einzelne Vertreter von 1 sind auch aus Cyclopentadien und Chlorformamidinium-chloriden 4 in Gegenwart von Triäthylamin zugänglich. Die IR-, UV- und NMR-Spektren von 1 und 3 werden diskutiert.
    Additional Material: 3 Tab.
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  • 30
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 183-192 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: VinylsulfonylmethylidsThe preparation of dimethylsulfonio-(vinylsulfonylphenylsulfonylmethanide) (5), triphenyl-phosphonio-(vinylsulfonylphenylsulfonylmethanide) (6) and triphenylphosphonio-(vinyl-sulfonylbenzoylmethanide) (8) is described. The u. v. spectra of 5 and 6 are similar to the u.v. spectrum of the bis(phenylsulfonyl)methane anion (9). Because of the interaction of the SO2-groups with the ylide carbanions, the SO2-stretching frequencies compared to those of vinylsulfonylphenylsulfonylmethane (4) are shifted 20 -30/cm to lower wave numbers. This interaction causes a higher electron density in the vinyl groups of the ylids compared to 4, as shown by n. m. r. measurements. The mass spectra of 5, 6 and 8 are discussed.
    Notes: Die Synthese von Dimethylsulfonio-[vinylsulfonyl-phenylsulfonyl-methanid] (5), Triphenyl-phosphonio-[vinylsulfonyl-phenylsulfonyl-methanid] (6)undTriphenylphosphonio-[vinyl-sulfonyl-benzoyl-methanid] (8) wird beschrieben. Die Elektronenspektren von 5 und 6 sind mit dem UV-Spektrum des Bis-phenylsulfonyl-methan-Anions (9) vergleichbar. Durch Wechselwirkung der SO2Gruppen mit den Ylidcarbanionen werden die SO2-Valenzschwingungsfrequenzen im Vergleich zu Vinylsulfonyl-phenylsulfonyl-methan (4) um 20 - 30/cm zu kleineren Wellenzahlen verschoben. Diese Wechselwirkung bedingt eine höhere Elektronendichte in den Vinylgruppen der Ylide als bei 4, was NMR-spektroskopisch nachweisbar ist. Die Massenspektren von 5, 6 und 8 werden diskutiert.
    Additional Material: 6 Ill.
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  • 31
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 173-182 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Cyclopentadienones with Aliphatic Diazo Compounds, 6 Experiments with „Indanocyclone“„Indanocyclone“ 3, prepared from ninhydrin (1) and dibenzylketone (2), reacts with an ethereal diazomethane solution to form an 1 :1-adduct 4a and two isomeric 1 : 2-adducts, presumably 12 and 13. Elimination of N2 from 4a leads to the formation of the cyclopropane 7, the fluorenone 6 and, by way of phenyl migration, the new cyclone 8a; elimination of N2 from 12 and 13 leads to undefined products. 5 is converted via its hydrazone into the diazo compound 10. Ring enlargement of 6 with diazomethane produces the phenanthrene 9.Reaction of diazoethane with 3 gives the instable 1 :1-adduct 4b, which yields the new cyclone 8b by N2-elimination and phenyl migration. 8b also forms an 1 :1-adduct (11?). Phenyl diazomethane adds to 3 giving a rather stable 1 :1-adduct 14, the isomeric 16 and the epoxide 15. Elimination of N2 from 14 yields the fluorenone derivative 17, which upon treatment with excess diazomethane undergoes ring enlargement to form the phenanthrene derivative 18.
    Notes: Das aus Ninhydrin(l)und Dibenzylketon(2) erhältliche, Indanocyclon‘ 3 gibt mit ätherischer Diazomethanlösung ein 1 :1-Addukt 4a und zwei isomere 1 : 2-Addukte, vermutlich 12 und 13. 4a zerfällt unter N2-Abspaltung zum Cyclopropanderivat 7, zum Fluorenonderivat 6 und unter Phenylwanderung zum neuen Cyclon 8a; 12 und 13 geben bei der N2-Abspaltung keine definierten Produkte. Aus 5 wird über sein Hydrazon die Diazoverbindung 10 und mit Diazomethan unter Ringerweiterung das Phenanthrenderivat 9 erhalten.Mit Diazoäthan entsteht aus 3 das instabile I :1-Addukt 4b, das bei der N2-Abspaltung unter Phenylwanderung das Cyclon 8b bildet; dieses gibt erneut ein Diazoathan-Addukt (11?).Mit Phenyldiazomethan liefert 3 ein ziemlich stabiles 1 :1-Addukt 14 und sein Isomeres 16 sowie das Epoxid 15. Bei der N2-Abspaltung entsteht aus 14 das Fluorenonderivat 17, das mit Diazomethan zum Phenanthrenderivat 18 ringerweitert wird.
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  • 32
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 222-235 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orthoamides, X: Reaction of Vinylogous Amide Acetals, Aminalesters and Amide AminalsDerivates of vinylogous orthoformic acid amides react with Grignard compounds to give l,3-bis(dimethylamino)-l-alkenes (4-7), with methylene active compounds to give derivates of N.N-disubstituted 4-amino-l,3-butadienes (17  - 29) and with primary aromatic amines to form vinylogous, N,N,N′-trisubstituted amidines (31-36, 38-40).
    Notes: Vinyloge Orthoameisensäureamid-Derivate geben mit Grignard-Verbindungen 1.3-Bis - dimethylamino-alkene-(l) (4-7), mit methylenaktiven Verbindungen N.N-disubstituierte 4 - Amino-butadien-(l.3)-Derivate (17-29) und mit primären aromatischen Aminen vinyloge N.N.N′-trisubstituierte Amidine (31-36, 38-40).
    Additional Material: 3 Tab.
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  • 33
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 34
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 17-22 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pyrimidines, VIII Synthesis and Properties of Uracil-4-carbaldehyde Hydrazone. The First Inner Orbital Complex of a Pyrimidine with CopperUracil-4-carbaldehyde (1) reacts with stoechiometric amounts of hydrazine to yield the azine 2. Under mild conditions (30 per cent hydrazine, room temperature) the azine is cleaved to uracil-4-carbaldehyde hydrazone (3). This cleavage by hydrazine is typical for the azomethine group in position 4 of the uracil ring. In aqueous or aqueous-alcoholic solution 3 reacts readily with aliphatic, aromatic and heterocyclic aldehydes to form mixed azines in good yield. With copper(II)-acetate 3 yields in aqueous solution a new type of symmetrical inner orbital complex in which the ratio of pyrimidine to copper is 2 :1. The crystalline and insoluble paramagnetic complex 13 presumably has a planar structure. Substitution of the amino group, even with a methyl group, prevents complex formation. 13 is decomposed by mineral acids to the respective copper salt and azine 2. In analogy to 1 2-thiouracil-4-carb-aldehyde forms the corresponding hydrazone 12.
    Notes: Uracil-carbaldehyd-(4) (1) liefert mit stöchiometrischer Menge Hydrazin das symmetrische Azin 2, welches unter milden Bedingungen (30proz. Hydrazin, Raumtemperatur) zum Uracil-carbaldehyd-(4)-hydrazon (3) gespalten wird. Die schonende Hydrazinolyse ist spezifisch für die Azomethingruppe in 4-Stellung des Uracilrings. 3 liefert in wäßriger bzw. Wäßrig-alkoholischer Lösung mit aliphatischen, aromatischen und heterocyclischen Aldehyden in guter Ausbeute gemischte Azine. Mit Kupfer(II)-acetat bildet 3 einen neuartigen symmetrischen Innerkomplex der Art Pyrimidin : Kupfer = 2:1. Analog zu Uracil-carb-aldehyd-(4) (1) erhält man aus 2-Thio-uracil-carbaldehyd-(4) mit Hydrazin das entsprechende Hydrazon 12.
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  • 35
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 46-49 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structure of l,2,3,4,4a,9a-hexahydro-4a,9-propanocarbazolium HydrobromideThe crystal structure of the title compound has been determined by X-ray structure analysis. From these results a twist angle of 64.5° of the orbital of the nitrogen is derived.
    Notes: Auf röntgenographischem Weg wurde die Kristallstruktur der Titel-Verbindung bestimmt. Aus den so erhaltenen Ergebnissen resultiert ein Verdrillungswinkel des Orbitals am Stickstoff von ϕpH = 64.5°.
    Additional Material: 3 Ill.
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  • 36
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 76-81 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Enthalpy of Formation of Tungsten Hexafluoride and Tungsten PentafluorideThe heat evolved on combustion of tungsten and tungsten pentafluorid in fluorine was measured in a bomb calorimeter. The enthalpies of formation calculated from these values were found to be ΔH°298(WF6, g) = -411.7 ± 0.5 kcal mol-1 and ΔH°298 (WF5, c) -346.1 ± 2.6 kcal mol-1.
    Notes: Die Verbrennungswärmen von Wolfram und Wolframpentafluorid in Fluor wurden in einem Bombenkalorimeter gemessen. Die aus den Meßdaten errechneten Bildungsenthalpien betragen ΔH°298(WF6, gas) -411.7 ± 0.5 kcal Mol-1 und ΔH°298(WF5, fest) -346.1 ± +2.6-1.0 kcal Mol1.
    Additional Material: 2 Ill.
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  • 37
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 97-103 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Inorganic Small Ring Compounds, III Cyclic Silyl-alkylidene PhosphoranesA simple method has been deviced for the synthesis of silyl-substituted alkylidene phosphoranes of the type F. Two members of this series, [(CH3)3PCSi(CH3)2]2 (1) and [( PCSi(CH3)2]2 (2), were prepared from methylene trimethyl and methylene tri-n-butyl phosphorane, resp., and dimethyl dichlorsilane and characterized by means of chemical analysis and n. m. r. spectroscopy. The pathway of the reactions is discussed and a possible mechanism confirmed by an independent preparation of the most likely intermediates. Among these the difunctional open-chain ylid 4, (CH3)3P= CH=Si(CH3)2=CH = P(CH3)3, is of special interest.
    Notes: Ein einfaches Darstellungsverfahren ermöglicht die Synthese von Silyl-alkylidenphosphoranen mit viergliedrigem Ringsystem des Typs F. Zwei Vertreter dieser Reihe, [(CH3)3PCSi(CH3)2]2 (1) und [(n-C4H9)3PCSi(CH3)2]2 (2), wurden aus Trimethyl-methylen- bzw. Tri-n-butyl-methylen-phosphoran und Dimethyldichlorsilan in guten Ausbeuten erstmals hergestellt und analytisch und NMR-spektroskopisch charakterisiert. Der Reaktionsablauf der Synthese wird diskutiert und durch die getrennte Darstellung möglicher Zwischenprodukte belegt. Unter letzteren ist das offenkettige difunktionelle Ylid 4, (CH3)3P=CH  -  Si(CH3)2  -  CH - P-(CH3)3, von Bedeutung.
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  • 38
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 147-155 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Fulvenes, V 6,6-Diaminofulvenes with Electronegative Substituents in the 5-Membered RingCondensation of tetramethyl chloroformamidinium chloride (5) with methoxycarbonyl-, bis(methoxycarbonyl)-, and cyanocyclopentadienyl salts leads to the correspondingly substituted 6,6-bis(dimethylamino)fulvenes 6, 7 and 8. Vilsmeier formylation of 6,6-bis(dimethyl-amino)fulvene yields the diformyl derivatives 9 and 11. Structure elucidation of the fulvenes obtained is based on spektroscopic data; the temperature dependence of the n.m.r. spectra is discussed.
    Notes: Tetramethyl-chlorformamidinium-chlorid (5) bildet mit Methoxycarbonyl-, Bis-methoxy-carbonyl- und Cyan-cyclopentadienylsalzen die im 5-Ring entsprechend substituierten 6.6-Bis-dimethylamino-fulvene 6, 7 und 8; Vilsmeier-Formylierung des 6.6-Bis-dimethylamino-fulvens liefert zwei Diformyl-Derivate 9 und 11. Die Strukturzuordnung der erhaltenen Fulvene erfolgt spektroskopisch; die Temperaturabhängigkeit der NMR-Spektren wird diskutiert.
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  • 39
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 205-209 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Compounds with Urotropin Structure, XLVI Synthesis of the 6-Thia-l,3-diazaadamantane Ring System.A synthesis of the hitherto unknown 6-thia-l,3-diazaadamantane ring system starting from N-benzenesulfonyl-diallylamine (1), is described. The first stage of the synthesis is the sulfurdichloride addition to 1, resulting in Nbenzenesulfonyl-2,6-bis(chloromethyl)thiomorpho-line (2).2 was converted with alkali into N-benzenesulfonyl-2,6-dimethylenethiomorpholine (6) and subsequently oxidized to the sulfone 7. Addition of benzylamine followed by removal of the benzyl and the benzenesulfonyl groups yielded 9-thia-3,7-diazabicyclo[3.3.l]nonane 9,9-dioxide (11), which reacted with formaldehyde to produce 6-thia-l,3-diazaadamantane 6,6-di-oxide (12).
    Notes: Ausgehend von Benzolsulfonsäure-diallylamid (1) wird das bisher noch unbekannte 6-Thia-1.3-diaza-adamantan-Ringsystem synthetisiert, wobei im ersten Schritt die Schwefeldichlorid-Addition an 1 zu 4-Benzolsulfonyl-2.6-bis-chlormethyl-thiomorpholin (2) erfolgt. 2 wurde mit Alkali in 4-Benzolsulfonyl-2.6-dimethylen-thiomorpholin (6) und durch anschließende Oxydation in das Sulfon 7 übergeführt. Benzylamin-Addition an 7 und anschließende Abspaltung des Benzyl- und Benzolsulfonyl-Restes führte zum 9-Thia-3.7-diaza-bicyclo[3.3.1]-nonan-9.9-dioxid (11), das mit Formaldehyd das 6-Thia-s-l.3-diaza-adamantan-6.6-dioxid (12) lieferte.
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  • 40
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orthoamides, XII: Synthesis of Acyl Isocyanate O,N- or -N,N-Acetals from Amide Acetals or from an Aminal tert-Butylester and N-Halogencarbonamides, Halogen Ureas and N-ChlorourethanesDimethylformamide dialkylacetals (2) and aminal-tert-butylester 5 [bis(dimethylamino)-tert-butoxymethane] react with N-halogen carboxylic acid amides, halogen ureas and N-chlorourethanes to give acyl isocyanate-O,N -or -N,N-acetals (isoureas 3 or guanidines 6, respectively).
    Notes: Dimethylformamid-dialkylacetale (2) und Aminal-tert.-butylester 5 (Bis-dimethylamino-tert.-butyloxy-methan) bilden mit N-Halogen-carbonsäureamiden, Halogenharnstoffen und N-Chlor-urethan Acylisocyanat-O.N- bzw. -N.N-acetale (Isoharnstoffe 3 bzw. Guanidine 6).
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  • 41
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 256-264 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orthoamides, XIII Studies on the Mechanism of Electrophilic Substitution of the Formyl-H Atom in Ortho Formic Acid AmidesOrtho formic acid amides and N-halogen carboxylic acid amides, halogen ureas or N-chloro urethanes primarily react to give adducts; these form ylides in the presence of bases. The ylides react by an intramolecular SE1- or SNi-mechanism to give O,N-acetals of the corresponding acyl isocyanates (isoureas).
    Notes: Bei der Umsetzung von Orthoamiden mit N-Halogen-carbonsäureamiden, -harnstoffen und N-Chlor-urethan wurden Primär-Addukte nachgewiesen. Diese bilden in Gegenwart von Basen Ylide, welche über einen intramolekularen SE1- oder SNi-Mechanismus C-N-Knüpfung eingehen unter Bildung von O.N-Acetalen der entsprechenden Acylisocyanate (Isoharnstoffe).
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  • 42
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 281-288 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Boron Azides, X Aminoazidoboranes and AlkoxyazidoboranesThe bis(dialkylamino)azidoboranes l a and 1b, the dialkylaminodiazidoboranes 2a and 2 b, diethylaminoazidophenylborane (3), and the dialkoxyazidoboranes 4 a and 4 b are formed from chloroboranes, chlorine being substituted by the N3-group with LiN3 or Bu3SiN3, respectively, as substitution agents. The monoazidoboranes 1, 3, and 4 are decomposed in a kinetically controlled manner at a noticeable rate only beyond 250° C; hydrolysis of the polymeric material gives the amines Et2NNH2 (from 1b), PhNH2 (from 3) and CH3ONH2 (from 4 a), respectively, indicating a rearrangement process during the thermolysis. The saltlike compounds (NH4N4 and (Et2NH2)N3, respectively, are the main products from the decomposition of the diazidoboranes 2a and 2b at 210°. The thermal decomposition of la in cyclohexene yields under participation of the solvent the diazadiborete derivative 6. From the photolytic decomposition of 1a and 1b, respectively, trisaminoboranes (as dismutation products) and the tetraaminodiazadiboretes 10 a and 10 b (as rearrangement products) are isolated.
    Notes: Die Bis(dialkylamino)azidoborane l a und l b, die Dialkylaminodiazidoborane 2 a und 2 b, Diäthylaminoazidophenylboran (3) und die Dialkoxyazidoborane 4 a und 4 b erhält man aus den entsprechenden Chlorboranen durch Azidierung mit LiN3 bzw. (im Falle von 4a) mit Bu3SiN3. Die Monoazidoborane 1, 3 und 4 zerfallen in kinetisch kontrollierbarer Weise mit nennenswerter Geschwindigkeit erst oberhalb 250°; neben N2 erhält man harzige Produkte, aus denen sich durch Verseifung die aus einer Umlagerungsreaktion hervorgegangenen Amine Ät2NNH2 (aus l b), PhNH2 (aus 3) bzw. CH3ONH2 (aus 4a) freimachen lassen. Der thermische Zerfall der Diazidoborane 2a und 2b bei 210° liefert neben N2 die salzartigen Azide (NH4)N3 bzw. (Nät2H2)N3. Der thermische Zerfall von l a in Cyclohexen führt unter Beteiligung des Lösungsmittels zum Diazadiboret-Derivat 6. Tetraaminodiazadiborete 10 a und 10 b sind neben Trisaminoboranen die Hauptprodukte des photolytischen Zerfalls von l a und l b.
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  • 43
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wir berichteten vor einiger Zeit über die Pyrolyse von Silbertetrafluorphthalat (1) und äußerten die Vermutung, daß als Hauptprodukt isolierte Octafluorbiphenylen seine Bildung dem intermediären Auftreten des Tetrafluorbenz-ins verdankte. Um diese Vermutung zu bestätigen, wurde die Pyrolyse von 1 in Gegenwart eines potentiellen Benz-in-Abfängers durchgeführt. In Anlehnung an McNelis setzten wir dafür Tetraphenylcyclopentadienon (Tetracyclon) (2) ein.
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  • 44
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 322-324 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 788-798 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Method for Synthesis of Peptides: Activation of the Carboxyl Group with Dicyclohexylcarbodiimide using 1-hydroxybenzotriazoles as Additives1-Hydroxybenzotriazole and a number of substituted 1-Hydroxybenzotriazoles are suitable additives in the synthesis of peptides using the dicyclohexylcarbodiimide method1). The glc-racemisation test described by Weygand and coworkers2) was used to determine the influence of these additives on the racemisation during peptide synthesis. The newly employed additives decrease racemisation, prohibit the formation of N-acylurea and afford peptides in excellent yield and a high state of purity.
    Notes: 1-Hydroxy-benzotriazol sowie verschiedene kernsubstituierte 1-Hydroxy-benzotriazole eignen sich als Zusätze bei der Dicyclohexylcarbodiimid-Methode zur Synthese von Peptiden. Ihr Einfluß auf die Racemisierung bei Peptidsynthesen wurde unter Anwendung des gaschromatographischen Racemisierungstests von Weygand u. Mitarbb.2) untersucht. Die neuen Zusätze senken die Racemisierung, verhindern die N-Acyl-harnstoffbildung und führen in hoher Ausbeute zu sehr reinen Peptiden.
    Additional Material: 9 Tab.
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  • 46
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 426-439 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Stereochemistry of Sigmatropic 1,5-Hydrogen ShiftsAt 250° (S)-cis,trans-3-methyl-7-deutero-octa-4,6-diene (5) rearranges by a non-catalysed first order reaction to a mixture of (R)-trans,cis-3-methyl-7-deutero-octa-3,5-diene (3) and (S)-cis,cis-3-methyl-7-deutero-octa-3,5-diene (4). Therefore the sigmatropic 1,5-hydrogen shift proceeds in this system preferentially by way of a suprafacial transition state, which is at least 8 kcal/mol lower in energy than the antarafacial one.
    Notes: (S)-cis,trans-3-Methyl-7-deutero-octadien-(4.6) (5) lagert sich bei 250° in einer nichtkatalysierten Reaktion erster Ordnung in ein Gemisch aus (R)-trans,cis-3-Methyl-7-deutero-octadien-(3.5) (3) und (S)-cis,cis-3-Methyl-7-deutero-octadien-(3.5) (4) um. In diesem System durchläuft die sigmatrope 1.5-Wasserstoffverschiebung damit bevorzugt einen suprafacialen Übergangszustand, der um mindestens 8 kcal/Mol gegenüber dem antarafacialen Übergangszustand begünstigt ist.
    Additional Material: 7 Ill.
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  • 47
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 855-862 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Catalytic Hydroalumination of 1,5-HexadieneThe hydroalumination of 1,5-hexadiene normally yields (cyclopentylmethyl)dialkylaluminium instead of the expected dimetallated hexane derivative. Titanium tetrabutoxide catalyses the reaction and favours the formation of the dimetallated product. - When the reaction is carried out in the absence of a catalyst but in the presence of electron donors such as ethers or tertiary amines, the two-fold hydroaluminated product is also formed exclusively. In such cases the reaction velocity is, however, drastically reduced. Titanium tetrabutoxide has now been found to act as an extraordinarily effective catalyst for this reaction, even in the presence of complex-forming agents. Certain amines or tetrahydrothiophene even intensify the catalytic activity of the titanium (IV) compound.
    Notes: Die Hydroaluminierung von Hexadien-(1.5) führt normalerweise nicht zu dem erwarteten dimetallierten Hexanderivat, sondern zum Cyclopentylmethyl-dialkyl-aluminium. Titantetrabutylat katalysiert die Reaktion und lenkt sie in Richtung des dimetallierten Produktes. Bei Durchführung der Reaktion ohne Katalysator, jedoch in Gegenwart von Elektronendonatoren wie Äthern oder tertiären Aminen wird ebenfalls ausschließlich das zweifach hydroaluminierte Reaktionsprodukt gebildet. Die Reaktionsgeschwindigkeit wird dabei allerdings drastisch vermindert. Titantetrabutylat katalysiert nun die Reaktion auch bei Anwesenheit der Komplexbildner außerordentlich wirksam. Durch einige tertiäre Amine oder auch durch Tetrahydrothiophen wird die katalytische Aktivität der Titan (IV)-Verbindung sogar noch verstärkt.
    Additional Material: 5 Tab.
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  • 48
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 486-495 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrazine Reactions, X Studies on Inversion-isomeric 1-Chloro-and 1-Aminoaziridines. Dependence of the 1H-C-14N-Coupling on the Konformation of the free Electron PairThe 1H-C-14N coupling depends on the conformation of the nitrogen lone-pair electrons. In 1-chloroaziridine for protons „cis“ to the nitrogen lone-pair electrons great values were found and for „trans“ protons smaller ones. The AA' BB'-system in the n.m.r. spectrum of 1-chloroaziridine is unsymmetrical. Irradiating of 14N frequency gives decoupling of 14N from other nuclei and the spectrum becomes symmetrical. In 1-amino-2-phenylaziridine the isomer with phenyl and amino group in „trans“ position is favoured. The variation of chemical shift in benzene solution of 1-amino- and 1-chloroaziridines are discussed.
    Notes: Die 1H-C-14N-Kopplung ist von der Konformation des freien Elektronenpaares abhängig und besitzt im 1-Chlor-aziridin für zum freien Elektronenpaar„cis“-ständige Protonen große, für „trans“-ständige kleine Werte. Das AA' BB'-System des NMR-Spektrums von 1-Chloraziridin ist daher unsymmetrisch und zeigt erst beim Einstrahlen der 14N-Frequenz infolge Spinentkopplung Symmetrie. 1-Amino-2-phenyl-aziridin liegt bevorzugt als das Inversionsisomere vor, in dem Phenyl- und Aminogruppe „trans“ zueinander stehen. Die Signalverschiebungen von 1-Amino-und 1-Chlor-aziridinen in Benzol werden diskutiert.
    Additional Material: 2 Tab.
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  • 49
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 534-538 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Structure of SphaerophysineSphaerophysine-formerly described as 1 or 2- is shown by n.m.r. and mass spectrometry to have structure 3 (N-(4-aminobutyl)-N-(3-methyl-2-butenyl)-guanidine). Dihydro-3 (7) has been synthesised.
    Notes: Sphaerophysin wurde bisher als 1-Isopentenylamino-4-guanidino-butan 1 oder 2 angesehen. Wir zeigen anhand von NMR- und Massenspektren sowie durch Synthese der Dihydro-verbindung, daß es die Struktur 3 eines N[4-Amino-butyl]-N-[3-methyl-buten-(2)-yl]-guanidins hat.
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  • 50
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 564-572 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Acetylenes, XXV Chain-Extension of Aldehydes and Ketones by two Carbon Atoms with Ynamines: Synthesis of Substituted AcrylamidesThe addition of ynamines to carbonyl groups, especially of aldehydes and ketones, leads to derivatives of acrylamides by reduction of which with lithiumaluminiumhydride and hydrogenation amines are available. The stereochemistry of the condensation has been investigated. cis- acrylamides are stereospecifically obtained by a kinetically controlled reaction from aldehydes.
    Notes: Die Addition von Inaminen an Carbonylverbindungen, insbesondere Aldehyde und Ketone. Führt zu Acrylamidderivaten, aus denen mit Lithiumaluminiumhydrid und durch Hydrierung Amine erhältlich sind. Die Stereochemie der Addition wurde untersucht: Aus Aldehyden entsteht kinetisch gesteuert und stereospezifisch das cis-Acrylamid.
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  • 51
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 648-651 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 52
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 659-662 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polycyclic Hydrocarbons by Cycli-alkylation, IV. Cycli-alkylations of Benzene and Partially Hydrogenated Polycyclic Aromatic Hydrocarbons with 1.2-Bis(bromomethyl)cyclohexaneThe reactions of benzene and partially hydrogenated aromatic hydrocarbons such as tetrahydronaphthalene and symm. octahydrophenanthrene with a mixture of cis- and trans 1.2-Bis (bromomethyl)cyclohexane in the presence of aluminiumchloride lead to the partially hydrogenated polycyclic hydrocarbons 2-6; the dehydrogenation with Pd/C yields the corresponding aromatic compounds.
    Notes: Die Reaktionen von Benzol and teilhydrierten Aromaten, wie Tetrahydronaphthalin und symm. Octahydrophenanthren, mit einem Gemisch aus cis- und trans-1.2-Bis-brommethyl-cyclohexan in Gegenwart von Aluminiumchlorid führen zu den partiell hydrierten polycyclischen Kohlenwasserstoffen 2-6, deren Dehydrierung mit Pd/C die entsprechenden Aromaten ergibt.
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  • 53
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 685-693 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Alkylidenetriphenylphosphoranes, XXV. A New Synthesis of α.β-Unsaturated Carboxylic AcidsThe reaction between alkylidenetriphenylphosphoranes (1) and α-bromo-or α-iodocarboxylic esters (2) (ratio 2:1) gives rise to the formation of α,β-unsaturated carboxylic esters (4), triphenylphosphine and phosphonium salts. The mechanism and the sterochemistry of this reaction are discussed.
    Notes: Triphenylphosphinalkylene (1) reagieren mit α-Brom-oder α-Jod-carbonsäureestern (2) im Molverhältnis 2:1 zu α.β-ungesättigten Carbonsäureestern (4), Triphenylphosphin und Phosphoniumsalzen. Der Mechanismus und die Stereochemie dieser Reaktion werden diskutiert.
    Additional Material: 2 Tab.
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  • 54
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1463-1476 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangement Reactions, V. A Kinetic Study on the Mechanism of the Wolff-RearrangementFor the thermal Wolff-rearrangement in the presence of nucleophiles such as alcohols or amines, the nitrogen evolution is measured as a function of the nucleophile concentration. With triphenylacetyldiazomethane and diacyldiazomethanes no influence of benzyl alcohol or aniline on the decomposition constants was found, whereas with phenylbenzoyldiazomethane, 2-oxo-1-diazocyclohexane and -dodecane a linear increase with the nucleophile concentration is observed. Benzyl alcohol, aniline and N-methylaniline are more active than pyridine, benzylamine or polar compounds such as nitrobenzene or bromobenzene. This acceleration is evidently a consequence of proton activity of the nucleophiles and not of an addition according to 2 → 3. The same effect is also observed with diazo compounds which cannot undergo the Wolff-rearrangement.
    Notes: Für die thermische Wolff-Umlagerung in Gegenwart von Nucleophilen (Alkohole, Amine) wird die Geschwindigkeit der Stickstoffentwicklung in Abhängigkeit von der Nucleophil-Konzentration gemessen. Bei Triphenylacetyl-diazomethan (7) sowie Diacyl-diazomethanen wird kein Einfluß von Benzylalkohol oder Anilin auf die Zersetzungskonstanten beobachtet, bei Phenyl-benzoyl-diazomethan, 2-Oxo-1-diazo-cyclohexan und -dodecan dagegen ein linearer Anstieg mit der Nucleophil-Konzentration. Benzylalkohol, Anilin und N-Methyl-anilin sind wirksamer als Pyridin, Benzylamin oder rein polare Zusätze wie Nitro- und Brombenzol. Diese Beschleunigung ist offenbar eine Folge der Protonaktivität der Nucleophile und nicht einer Einlagerung gemäß 2 → 3. Sie tritt auch bei Diazoverbindungen auf, die zur Wolff-Umlagerung nicht befähigt sind.
    Additional Material: 3 Ill.
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  • 55
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1512-1521 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Aromatic Erythrina-Alkaloids, XIII. A Direct Course to cis-15,16-Dimethoxyerythrinane-1,8-dioneThe enollactam 5 is obtained from ethyl dihydroresorcinol-2-acetate via the diketalamide 16. Cyclisation by heating with phosphoric acid yields the ketolactam 6; the overall yield of the five steps synthesis is 20%.
    Notes: Aus Dihydroresorcin-2-essigester wird über das Diketalamid 16 die Cyclisierungsvorstufe 5 gewonnen. Sie liefert beim Erhitzen mit Phosphorsäure das Ketolactam 6 mit einer Ausbeute von 20% über 5 Stufen.
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  • 56
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1168-1173 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Arylidene Isophorones Preparation and Properties of a Halochromic Polymethine SystemIsophorone (1) and araldehydes condense to give aryliden-isophorones 2-19. The yellow ary-dien-one systems of 2-19 form red polymethine cations like 21. Compounds of vinylogous carbonic acid structure yield red polymethine anions like 22. Differences between cation and anion are spectroscopically small with 6 relative to benzaurin (20).
    Notes: Aus Isophoron (1) und Araldehyden erhält man die Arylidenisophorone 2-19. Das gelbe Aryl-dien-on-System in 2-19 addiert leicht Protonen zu roten Polymethin-Kationen wie 21; vinyloge Carbonsäuren wie 6 bilden durch Dissoziation rote Polymethin-Anionen (22).Kation und Anion von z. B. 6 sind einander spektroskopisch ähnlicher als die analogen Salze des Benzaurins (20).
    Additional Material: 1 Ill.
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  • 57
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1216-1224 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Acetylenes, XXX1). A new Mechanism of Nucleophilic Halogen Substitution at Acetylene Triple BondsThe combination of nucleophilic and directiospecific addition in β-position to halogen 1) (except fluorine) with subsequent onium rearrangement is proposed as a new mechanism of nucleophilic halogen substitution at the acetylene triple bond. The reactions of chloro-tertbutyl-acetylene (1) with phenolate and thiophenolate are described as examples. The β-adducts 2,5 und 6 are formed directiospecifically. 5 and 6 give rise photochemically and thermally to the thermodynamically more stable isomer 8 in which the chlorine atom and the thioether residue have migrated and changed their C-atoms. All thioether isomers produce the tert-butylethinyl-thioether 10 upon elimination of HCl.
    Notes: Die Kombination von nucleophiler directiospezifischer Addition in β-Stellung zum Halogen1) (außer Fluor) mit anschließender Onium-Umlagerung 2) und Halogen-Anion-α-Eliminierung wird als neuer Mechanismus der nucleophilen Halogensubstitution an der Acetylendreifachbindung vorgeschlagen. Als Beispiel für diese Reaktionsschritte werden die Umsetzungen von Chlor-tert.-butyl-acetylen (1) mit Phenolat und mit Thiophenolat beschrieben. Directiospezifisch entstehen die β-Addukte 2,5 und 6. Thermisch und photochemisch bildet sich aus 5 und 6 das thermodynamisch stabilere Isomere 8, in welchem Chlor und der Thioätherrest unter Vertauschung der C-Atome gewandert sind. Alle Thioäther-Isomeren liefern bei der HCl-Abspaltung den tert.-Butyläthiny-thioäther 10.
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1273-1278 
    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, XIX. Synthesis of Cyclopropane Derivatives with Transition Metal Carbonyl Carbene ComplexesPhenyllmethoxycarbenepentacarbonylchromium(0) (1b) reacts on warming with trans-methyl crotonate (2) stereospecifically to give the isomeric methyl 2-methoxy-3-methyl-2-phenycyclopropane-1-carboxylates (3a, b) via transfer of the carbene ligand. The configuration of the isomers was determined by analysis of the 1H n.m.r. spectra.
    Notes: Phenylmethoxycarben-pentacarbonyl-chrom(0) (1b) reagiert bei erhöhter Temperatur unter Übertragung des Carbenrestes mit trans- Crotonsäure-methylester (2) stereospezifisch zu den isomeren 2-Methoxy-3-methyl-2-phenyl-cyclopropan-carbonsäure-(1)-methylestern (3a, b). Die Konfiguration der Isomeren wurde durch Analyse der 1H-NMR-Spektren bestimmt.
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  • 59
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1306-1306 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 60
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1334-1346 
    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, 19. Photolysis of Spiro-pyrazoles to Cyclopropabenzenes and their ReactionsPhotolysis of cyclopentadiene-spiro-pyrazoles (9) in benzene yields 1 H-cyclopropabenzenes (10) in a novel reaction. The latter compounds can be rearranged thermally to benzofuranes (11). Degradation reactions of diphenylcyclopropabenzene 10c to give 2′-p-terphenylylacetic acid (14c) together with the spectroscopic data prove the structure of the cyclopropabenzenes.  -  The formation of 10 from 9 involves n→π*-excitation, followed by ring enlargement to indazoles (24) which eliminate nitrogen in a familiar manner. The excited states of 9 and 24 are triplets.
    Notes: Die Photolyse von Cyclopentadien-spiro-pyrazolen (9) in Benzol liefert in einer neuartigen Reaktion 1 H-Cyclopropabenzole (10). Diese können thermisch in Benzofurane (11) umgelagert werden. Abbaureaktionen des Diphenyl-cyclopropabenzols 10c zu p-Terphenylyl-(2′)-essigsäure (14c) zusammen mit den spektroskopischen Daten beweisen die Struktur der Bicyclen 10.  -  Die Bildung von 10 aus 9 verläuft über eine n→π*-Anregung, gefolgt von einer Ringerweiterung zu Indazolen (24), die in bekannter Weise Stickstoff eliminieren. Die Anregungszustände von 9 und 24 sind Tripletts.
    Additional Material: 3 Tab.
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  • 62
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Short-Life Radicals, VII. The Stereochemical Route of Free-Radical Additions to Conjugated Dienes: Hydrostannation and Isomerization of Penta-1,3-dieneThe radical addition of Me3SnH and Et3SnH to both of the pure stereoisomers of penta-1,3-diene proceeds by a highly stereospecific mechanism, whereby an extremely high configurational stability of the intermediate allyl radicals 9 is indicated. Besides 1,2- and 1,4-adducts small amounts of 4,1-adducts are formed: altogether 6 of the 8 possible isomers 1-8 are obtained. At 80° the cis-diene reacts 2.6 or 2.9 times faster than the trans-isomer. At 20° and 40° only the transoid conformation is involved in the reaction of cis-isomer, whereas in the case of the trans-diene both cisoid and transoid configurations are involved. The attack of organotin radicals at C-4 (that is, at the internal C=C double bond) is much more readily reversible than that at C-l and leads (primarily) to cis-trans-isomerization of the diene; this is highly dependent on the molar ratio of diene to hydride. By means of capillary gas chromatography it was possible to observe each stage of the addition and isomerization processes.
    Notes: Die beiden Stereoisomeren von Pentadien-(1.3) addieren (CH3)3SnH und (C2H5)3SnH radikalisch hochgradig stereospezifisch, woraus eine beträchtliche Konfigurationsstabilität der intermediär auftretenden Allylradikale 9 folgt. Neben 1.2- und 1.4- entstehen wenig 4.1-Addukte, insgesamt 6 der 8 möglichen Isomeren 1-8. Das cis-Dien reagiert bei 80° 2.6 bzw. 2.9 mal schneller als das trans-Isomere. Bei 20° und 40° ist nur die transoide Konformation des cis-Isomeren beteiligt, beim trans-Dien dagegen sowohl cisoide als auch transoide. Der Angriff von Stannylradikalen an C-4, also an der mittelständigen C=C-Gruppe, ist weit stärker reversibel als derjenige am endständigen C-l und bedingt so (hauptsächlich) eine cis-trans-Isomerisierung des Diens. Diese hängt stark vom Molverhältnis Dien : Hydrid ab. Mittels Kapillar-GC konnten Additionen und Isomerisierung in jedem Stadium verfolgt werden.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1412-1419 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Identification and Preparation of Metalated NitroarenesPhenyllithium is unable to metalate nitrobenzene in THF, but instead is oxidized quantitatively to phenol at low temperatures. With 2-bromo-1-nitrobenzene and its methyl homologues a bromo-lithium exchange is effected to give high yields of the deeply coloured title compounds. They are stable only below -100° and are trapped as carboxylic acids with carbon dioxide. The halogen-metal exchange competes with the reduction of the nitro group, the latter reaction being favoured at higher temperatures and in solvents of low polarity. The redox reactions at the nitro group predominate with 3-and 4-bromo-1-nitrobenzene even under optimum conditions.
    Notes: Nitrobenzol wird durch Lithiumorganyle nicht metalliert. Dagegen oxydiert es Phenyllithium in Tetrahydrofuran(THF) schon bei tiefer Temperatur quantitativ zu Phenol. Der Brom-Lithium-Austausch an 2-Brom-1-intro-benzol und seinen Methylhomologen führt in hohen Ausbeuten zu den unterhalb von -100° stabilen, tieffarbigen Titelverbindungen, die man durch Carboxylierung nachweist. Die mit dem Halogen-Metall-Austausch konkurrierende Reduktion der Nitrogruppe tritt bei höherer Temperatur und in weniger polaren Lösungsmitteln stärker hervor; sie überwiegt bei 3- und 4-Brom-1-nitro-benzol auch unter optimalen Bedingungen.
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  • 64
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1477-1485 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on Diazo Compounds, VII. Comparative Kinetic Investigations on the Thermal Stability of Aliphatic Diazo CompoundsThe thermal stabilities of 16 aryl-, carbonyl-, sulfonyl-, phosphinyl- and phosphono-substituted diazomethanes are compared. From kinetic measurements on the decomposition of the diazo compounds in mesitylene the comparison values τ100, T 0.1 and k100 as well as the activation energy Ea of the N2-elimination were determined (see table 1). The following series of substituents with increasing stabilizing effect was derived:C6H5 〈 C6H5CO 〈 CH3CO 〈 Aryl-SO2 〈 (C6H5)2PO 〈 C2H5OCO 〈 (C2H5O)2PO 〈 H Carbonyl diazo compounds are thermally less stable than their PO-analogs (see figure 1), because of the mesomerism C ↔ D resulting from the interaction of the CO- and CN2-groups.
    Notes: Die thermischen Stabilitäten von 16 aryl-, carbonyl-, sulfonyl-, phosphinyl- und phosphono-substituierten Diazomethanen werden verglichen. Aus der Zersetzungskinetik in Mesitylen werden die Vergleichsgrößen τ100, T0.1 bzw. k100 sowie die Aktivierungsenergie Ea der N2-Abspaltung bestimmt. (s. Tab. 1). Eine Stabilisierungsreihe für die folgenden Substituenten wird abgeleitet: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 6} {\rm h}_{\rm 5} {\rm 〈 C}_{\rm 6} {\rm H}_{\rm 5}{\rm CO 〈 CH}_{\rm 3} {\rm CO 〈 Aryl - SO}_{\rm 2} {\rm 〈 (C}_{\rm 6} {\rm H}_{\rm 5} {\rm)}_{\rm 2} {\rm PO 〈 C}_{\rm 2} {\rm H}_{\rm 5} {\rm OCO 〈 (C}_{\rm 2} {\rm H}_{\rm 5} {\rm O)}_{\rm 2} {\rm PO 〈 H} $$\end{document}Carbonyl-diazoverbindungen sind thermisch instabiler als ihre PO-Analogen (s. Abbild.), bedingt durch mesomere Wechselwirkungen zwischen CO- und CN2-Gruppe gemäß C↔D.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1522-1535 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Aromatic Erythrina-Alkaloids, XIV. Application of the Glyoxylester Synthesis to DihydroresorcinolThe monocycloketal 7 of dihydroresorcinol yields, via glyoxylester synthesis, the condensation product 10. On treatment with dilute phosphoric acid, 10 hydrolyses to give the partially hydrogenated ketoisatin derivative 14a which is stabilised by conjugation and cannot be cyclised. In the presence of crystalline phosphoric acid 10 forms a violet cation, Pictet-Spengler cyclisation of which leads to a mixture of stereoisomeric spiroisoquinolines (22). From the mixture two racemates are isolated, the n. m. r. analysis of which permits the assignment of cis- and trans-configurations according to the formulae 22A and 22B.
    Notes: Aus dem Monocycloketal 7 des Dihydroresorcins wird auf dem Weg der Glyoxylestersynthese die Cyclisierungsvorstufe 10 gewonnen. Sie hydrolysiert unter der Einwirkung von verdünnter phosphorsäure zu dem Partiell hydrierten Ketoisatin-Derivat 14a, das durch Konjugation stabilisiert und nicht cyclisierbar ist. Mit kristalliner Phosphorsäure entsteht aus 10 ein violettes Kation, das durch Ringschluß nach Pictet-Spengler zu einem Gemisch stereoisomerer Spiroisochinoline 22 abreagiert. Nach Auftrennung in zwei Racemate wird durch NMR-Analyse die sterische Zuordnung zur cis- und trans-Reihe entsprechend den Formulierungen 22A und 22B ermittelt.
    Additional Material: 2 Tab.
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1572-1577 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of 2,2′-Bisoxazolyls and 2,2′ -Bisthiazolyls, of Arylene-bis-2-oxazolyl and Arylenebis-2-thiazolyl DerivativesThe reaction of desylamine hydrochloride with carboxylic acid chlorides and dicarboxylic acid chlorides yields ms- (acylamino) desoxybezoins (2a, b) and amides of N, N′ -bis-desyldicarboxylic acids (2c,-f), respectively. These compounds are converted by condensation with phosphorus pentachloride to derivatives of oxazole (3) and by condensation with phosphorus pentasulfide to derivatives of thaizole(4).
    Notes: Durch Umsetzung von Desylaminhydrochlorid mit Carbonsäurechloriden bzw. mit Dicarbonsäuredichloriden gelangt man zu ms-Acyalmino -desoxybenzoinen (2a, b) bzw. zu N. N′-Bis-desyl- dicarbonsäurediamiden (2c-f). Diese lassen sich mit Phosphorpentachlorid zu Oxazolderivaten 3, mit Phosphorpentasulfid zu Thiazolderivaten 4 kondensieren.
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1631-1636 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Monosaccharides Containing Nitrogen in the Ring, XXVIII. Synthesis and Dimerization of 5-Benzylamino-1,2-O-isopropylidene-5-deoxy-L-ido-hexodialdo-1,4(β)-3,6(α,β)-difuranoseSelective hemihydrogenation of 5-benzylamino-1,2-O-isopropylidene-5-deoxy-β-L-idofuranuronic acid nitrile (1) yields 5-benzylamino-1,2-O-isopropylidene-5-deoxy-L-ido-hexodialdo-1,4(β)-3,6(α,β)-difuranose (2), which can be dimerized to 5. 5 represents a symmetrical heptacyclic system of five- and six-membered rings containing a central piperazine ring.
    Notes: Selektive Halbhydrierung des 5-Benzylamino-1.2-O-isopropyliden-5-desoxy-β-L-idofuranuron-säurenitrils (1) liefert 5-Benzylamino-1.2-O-isopropyliden-5-desoxy-L-ido-hexodialdo-1.4(β)-3.6(α, β)-difuranose (2), die zu 5 dimerisiert werden kann. In 5 liegt ein symmetrisches heptacyclisches Ringsystem mit zentralem Piperazinring vor.
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1621-1630 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Monosaccharides Containing Nitrogen in the Ring, XXVII. Pyrolytic Rearrangement of 4-Amino-4-deoxy-L-xylose to 4-Amino-4-deoxy-L-lyxosePyrolysis of the periodate degradation product 2 results in the rearrangement of the L-xylo-to the L-lyxo-configuration and the formation of 4-amino-4-N, 5-O-carbonyl-2,3-O-isopropy-liden-4-deoxy-α-L-lyxofuranose (5). Free 4-amino-4-deoxy-L-lyxose is formed from 5 via the bisulfite adduct 13, which exists as an equilibrium mixture of the pyrrolidine-forms 14 ⇋ 15 ⇋ 18 The bis-pyrrolidine-form 18 predominates under anhydrous conditions. The dimeric structure of 18 is established by mass spectra of the pentaacetate 16 and the TMS-ether 17.
    Notes: Durch Pyrolyse des Perjodat-Spaltproduktes 2 erfolgt Umlagerung der L-xylo-in die L-lyxo-Konfiguration, und es wird 4-Amino-4-N.5-O-carbonyl-2.3-O-isopropyliden-4-desoxy-α-L-lyxofuranose (5) erhalten. Aus 5 ist über das Schwefligsäure-Addukt 13 freie 4-Amino-4-desoxy-L-lyxose darstellbar, die im Gleichgewicht der Pyrrolidin-Formen 14 ⇋ 15 ⇋ 18 vorliegt. Die Bis-Pyrrolidin-Form 18 überwiegt stark in der wasserfreien Substanz. Die dimere Struktur von 18 ergibt sich aus den Massenspektren des Pentaacetats 16 und des TMS-Äthers 17.
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  • 69
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 70
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1664-1673 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with N-Halogenphosphoranyliden-thiophosphoryldihalogenide AmidesThe reaction of S=PX2N=PF3 (X=F, Cl) with Si—N-compounds afforded the new compounds 1-11. It was proved that substitutions occurred only at the -N=PF3 group and that isomeric compounds were not formed. The reaction of S=PCl2N=PF3 and S=PFClN=PF3 with excess PF3Cl2 resulted in the formation of S=PCl2N=PFCl2 (12). The compounds 1, 2 are cleaved with water-free HBr at the P—N-bond to form the compounds 13, 14. The reaction of SPF2N=PF3 with amines yielded various products. The compounds 1-12 are much more stable towards hydrolysis than the starting compounds. 1H-, 19F-n.m.r., i.r., and mass spectra are reported and partially discussed.
    Notes: Durch Umsetzung von S=PX2N=PF3 (X=F, Cl) mit Si-N-Verbindungen erhielten wir die neuen Verbindungen 1-11. Wir konnten wahrscheinlich machen, daß die Substitutionen an der - N = PF3-Gruppe erfolgen und daß die isomeren Verbindungen dabei nicht ent-stehen. Die Reaktion von S=PCl2N=PF3 oder S=PFClN = PF3 mit überschüssigem PF3Cl2 führt zu S=PCl2N=PFCl2 (12). Die Verbindungen 1, 2 lassen sich mit wasserfreiem HBr an der P —N-Bindung spalten, wobei die Verbindungen 13, 14 entstehen. Die Umsetzung von S=PF2N=PF3 mit Aminen ergibt verschiedene Produkte. Die Verbindungen 1-12 sind gegen Hydrolyse stabiler als die Ausgangsverbindungen. 1H-, 19F-NMR-, IR- und Massenspektren werden mitgeteilt und teilweise diskutiert.
    Additional Material: 1 Ill.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1792-1796 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Glycosides of Amino Sugars, II. Synthesis of 2-amino-2-deoxy-α-D-glucopyranosidesThe synthesis of glycosides and disaccharides of 2-amino-2-deoxy-D-glucose has been explored using trifluoroacetyl as the N-blocking group. Because of its high tendency for neighboring group participation only β-D-glycosides were formed. The corresponding α-disaccharide could be obtained as the main product when employing 2.4-dinitrophenyl as the N-protecting group.
    Notes: Die N-Trifluoracetyl-Schutzgruppe wurde zur Synthese von Glykosiden und Disacchariden der 2-Amino-2-desoxy-D-glucose benutzt. Sie zeigte eine hohe Tendenz zur Nachbargruppen-beteiligung unter Bildung von -β-D-Glykosiden. Das entsprechende α-Disaccharid wurde als Hauptprodukt bei Verwendung der N-2.4-Dinitrophenyl-Schutzgruppe erhalten.
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  • 72
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Isolation, Structure, and Synthesis of 5,6,7,4′-Tetrahydroxy-3′-methoxyflavone (Batatifoline), a new Flavone from Mikania batatifolia D.C.The flavone batatifoline has been isolated from Mikania batatifolia D. C. (Compositae). Its structure has been confirmed as 5,6,7,4′-tetrahydroxy-3′-methoxyflavone (1) by synthesis of the isomers 1 and 5,6,3′,4′-tetrahydroxy-7-methoxyflavone (5, Pedalitine).
    Notes: Aus Mikania batatifolia D. C. (Compositae) wurde das Flavon Batatifolin isoliert und ihm durch Synthese der Isomeren 5.6.7.4′-Tetrahydroxy-3′-methoxy-flavon (1) und 5.6.3′.4′-Tetra-hydroxy-7-methoxy-flavon (5, Pedalitin) die Struktur 1 zugeordnet.
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  • 73
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1886-1893 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polyacetylenic Compounds, 175. Synthesis and Biogenesis of Anthemis-thioethersThe configurations of four isomeric naturally occuring thioethers are established by synthesis and a detailed analysis of the n. m. r. spectra. By feeding of 3H-labelled 1-4 the biogenesis of a phenylthioether is further confirmed.
    Notes: Die Konfigurationen von vier natürlich vorkommenden Thioäthern werden durch Synthese und eine eingehende Analyse der NMR-Spektren sichergestellt. Durch Verfütterung von 3H-markierten 1-4 wird die Biogenese eines Phenylderivates weiter gesichert.
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  • 74
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2024-2033 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Racemization in Peptide SynthesesVarious gaschromatographic racemization tests indicate, that 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine as additive to DCCD decreases racemization in the DCCD-method to a minimum, compared with a series of N-hydroxy-compounds. It is also possible to prepare the intermediate activated esters without racemization. Addition of weak tertiary bases has a favourable effect on the yield and racemization in the preparation of N-acylpeptide-N-hydroxysuccinimide esters by the DCCD-method.
    Notes: Durch Anwendung mehrerer gaschromatographischer Racemisierungstests wurde gefunden, daß bei der DCCD-Methode1) aus einer Reihe von N-Hydroxyverbindungen als Zusatz zum DCCD das 3-Hydroxy-4-oxo-3.4-dihydro-1.2.3-benzotriazin die Racemisierung am wirkungsvollsten senkt. Auch eine racemisierungsfreie Voraktivierung ist mit dieser Verbindung möglich. Bei der Herstellung von N-Acyl-peptid-[N-hydroxy-succinimidestern] nach der DCCD-Methode wirkt sich ein Zusatz schwacher tert. Basen günstig auf Ausbeute und Racemisierung aus.
    Additional Material: 8 Tab.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2077-2083 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ions, II. Wittig Olefination with Phosphonium FluoridesPhosphonium fluorides are available by ion exchange and can be used for the Wittig reaction without an auxiliary base.
    Notes: Phosphoniumfluoride sind durch Ionenaustausch zugänglich und gehen ohne Hilfsbase die Wittig-Reaktion ein.
    Additional Material: 2 Tab.
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  • 76
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Phosphorus Compounds, 65. The Selective Elimination of Allyl Groups from Allylphosphonium, -arsonium and -sulfonium Salts and from Allyl sulfones by CyanolysisKCN cleaves allylphosphonium, -arsonium, and -sulfonium salts to give methacrylonitrile and tertiary phosphines, tertiary arsines or thioethers, respectively. Phosphonium and arsonium salts with four different ligands can be built up by alternate cyanolysis and quaternization. Allylammonium salts do not undergo the reaction, nor do allylphosphine oxides and dialkyl allylphosphonates. On the other hand, ally sulfones react with KCN to afford good yields of methacrylonitrile and sulfinic acids.
    Notes: KCN spaltet Allylphosphonium-, -arsonium- und -sulfoniumsalze in Methacrylnitril und tertiäre Phosphine, tertiäre Arsine und Thioäther auf. Durch alternierende Cyanolyse und Quartärisierung können Phosphonium- und Arsoniumsalze mit vier verschiedenen Liganden aufgebaut werden. Allylammoniumsalze, Allylphosphinoxide und -phosphonsäureester können nicht gespalten werden. Dagegen liefern Allylsulfone mit KCN in guten Ausbeuten Methacrylnitril und Sulfinsäuren.
    Additional Material: 4 Tab.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2768-2774 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereochemistry and Solvolysis of some 3,4-Disubstituted ChromansReduction of 3-bromachromanone-(4) and of 3-bromo-2,6- dimethylchromanone-(4) yields the cis-3-bromo-4- hydroxychromans 1 and 2 which we converted to the trans-3,4-dihalogenochromans 8-11. Hydrolysis of 8-11 produces the trans-3-bromo-4-hydroxychromans 3 and 4; Solvolysis with alkohols yields the trans -3-bromo-4-alkoxychromans 5-7; by reaction with phenol we got the 3-bromo-4-arylchroman 12.
    Notes: Reduktion von 3-Brom-chromanon-(4) und 3-Brom-2.6 - dimethyl-chromanon-(4) liefert die 3c-Brom-4r -hydroxy-chromane 1 und 2, welche in die 3t.4r-Dihalogen-chromane 8-11 umgewandelt wurden. Die Hydrolyse von 8-11 ergibt die 3t-Brom- 4r-hydroxy-chromane 3 und 4; die Solvolyse mit Alkoholen führt zu den 3t- Brom-4r-alkoxy-chromanen 5-7; bei der Umsetzung mit Phenol haben wir dagegen das 3-Brom-4-aryl-chroman 12 erhalten.
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  • 78
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2784-2793 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hindered Rotation about the Arsenic and Antimony Nitrogen BondProton n. m. r. of aminoarsines and aminostibines of the type [(CH3)3C]2El-N[M(CH3)3]2 (El = As, Sb; M = Si, Ge) has been measured as a function of temperature. At 35° 4a, 4d, and 6c possess gauche-configuration with hindered rotation about the El—N bond. The corresponding ΔG≠ -values are 〉 23.2 kcal/Mol for 4a, 22.8 kcal/Mol for 4d and 19.6 kcal/ Mol for 6c. Comparison of 4a, 4d, and 6c with 6a, 6b, 7, and 8 supports the hypothesis that steric interactions and not (p→d)π-bonds between the El-N bond cause this hindered rotation. The proton n. m. r. spectra of 4b, 4c, 4e, and 5 give evidence that in the case of 4b, 4c, and 4e rotamers with different population are formed at 35°, whereas in the case of 5 only one rotamer is formed at 35°.
    Notes: Temperaturabhängige 1 H-NMR-Untersuchungen an Aminoarsinen und Aminostibinen des Typs [(CH3)3C]2El-N[M(CH3)3]2(El = As, Sb; M = Si, Ge) zeigen, daß 4a, 4d und 6c bei 35° in der gauche-Form mit rotationsgehinderter El-N-Bindung vorliegen. Die entsprechenden ΔG≠-Werte betragen für 4a 〉 23.2 kcal/Mol, für 4d 22.8 kcal/Mol und für 6c 19.6 kcal/Mol. Die Hypothese, daß diese Rotationsbehinderung auf sterische und nicht auf (p→d)π-Wechselwirkung zurückzuführen ist, wird durch die Vergleichssubstanzen 6a, 6b, 7 und 8 erhärtet. Für 4b, 4c, 4e und 5 geben die 1H-NMR-Spektren einen Hinweis darauf, daß 4b, 4c und 4e bei 35° Rotamere unterschiedlicher Population, 5 ausschließlich ein Rotameres bildet.
    Additional Material: 2 Ill.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2836-2844 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Substituted Rheniumcarbonyl Chlorides with Ligands Containing OxygenPolymeric [Re(CO)3Cl]x is extremely reactive even toward very weak ligands containing oxygen. Thus monomeric and dimeric compounds have been obtained with aliphatic alcohols. The resulting complexes contain sp3-hybridized oxygen-metal bonds. Compounds of the same type are also form ed with ethers such as diisopropylether and dioxane. With monodentate ketones predominantly complexes of the dimeric type [Re(CO)3LKetCl]2 have been obtained. Only with acetone has a monomeric compound Re(CO)3L2Cl been isolated. 1,2- and 1,3- diketones generally act as bidentate ligands yielding stable 5- or 6-membered ring complexes, which, however, are not innercomplexes, as they contain only Re-O-π-bonds. -The Structure of the compounds has been elucidated by i. r. and mass spectra as well as by molecular weight measurements.
    Notes: Polymeres [Re(CO)3Cl]x ist selbst gegenüber sehr schwachen sauerstoffhaltigen Liganden äußerst reaktiv. So wurden mit aliphatischen Alkoholen ein- und zweikernige Verbindungen, z. B. Re(CO)3L′AlCl (L′Al = HOC2H4OH) bzw. [Re(CO)3LAlCl]2 (LAl = i-C3H7OH, i-C4H9OH), erhalten. Die Bindung erfolgt über sp3-hybridisierten Sauerstoff an das Metall. Komplexe des gleichen Typs entstehen auch mit äthern, wie Diisopropyläther und Dioxan. Mit monofunktionellen Ketonen wurden vorwiegend Komplexe vom zweikernigen Typ [Re(CO)3LKetCl]2 mit „ylid“-artiger Bindung der Liganden an das Metallatom gebildet. Lediglich mit Aceton wurde eine einkernige Verbindung Re(CO)3L2Cl isoliert. 1.2- und 1.3- Diketone fungieren im allgemeinen als zweizählige Liganden unter Ausbildung stabiler Fünf-bzw. Sechsring-Chelatkomplexe, die jedoch nicht Innerkomplexe sind, d. h. nur Re-O-π-Bindungen enthalten. -Die Struktur der Verbindungen wurde durch IR-Spektren, Massenspektren und Molgewichtsbestimmungen sichergestellt.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2873-2876 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ketosylamine Rearrangement of D-threo-Pentulose (D-Xylulose) with α-Amino Acids1)D-threo-Pentulose (1) reacts with glycin (2a), L-α-alanine (2b) or L-valine (2c) to give mixtures of the D-xylose-and D-lycxose-amino acids, from which the D-xylose-amino acids (4a-c) can be obtained pure by chromatography. 2-L-α-alanino-2-desoxy-D-lyxose (5b) and 2-D-valino-2-deoxy-D-lyxose (5c) are obtained by crystallization. The reaction of D-xylulose and glycine is investigated quantitatively.
    Notes: D-threo-Pentulose (1) reagiert mit Glycin (2a), L-α-Alanin (2b) oder L-Valin (2c) zum Gemisch der D-Xylose-und D-Lycxose-Aminosäuren, aus dem sich durch Säulenchromatographie die D-Xylose-aminosäuren (4a-c) rein gewinnen lassen. 2-L-α-Alanino-2-desoxy-D-lyxose (5b) und 2-L-Valino-2-desoxy-D-lyxose (5c) werden durch Kristallisation erhalten. Die Reaktion der D-Xylulose (1) mit Glycin (2a) wird quantitativ verfolgt.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2894-2901 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Direct Photolysis of Carbonyl Sulfide in Alcohols and Acetonitrile in the Presence of Olefins. Reactions of Triplet Sulfur Atoms with Norbornene in Ethanol and 1, 4-DioxanePhotolysis of COS in methanol as well as in acetonitrile in the presence of cyclohexene or 1-octene gives rise to the formation of the corresponding episulfides due to the addition of triplet sulfur atoms, S(3P). With norbornene, however, episulfide formation ist not observed; only diastereomeric dinorbornyl sulfides 1a and 1b are obtained if the reaction is carried out in ethanol, whereas norbornyl 1,4-dioxanyl sulfide (5) is produced in addition to 1 a and 1 b, if 1,4-dioxane is used as solvent. The mode of formation of these compounds is discussed.
    Notes: Die COS-Photolyse führt in Methanol wie auch in Acetonitril in Gegenwart von Cyclohexen bzw. Octen-(1) zur Bildung der Episulfide durch Reaktion von S(3P)-Atomen mit den Olefinen. Mit Norbornen dagegen wird keine Episulfidbildung beobachtet; die COS-Photolyse in äthanol liefert ausschließlich die beiden diastereomeren Dinorbornylsulfide 1a und 1 b, während in 1.4-Dioxan außerdem noch [Norbornyl-(2)]-[1.4-dioxanyl]-sulfid (5) entsteht. Die Bildungsweisen dieser Verbindungen werden diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2984-2986 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Tab.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2245-2251 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polyacetylenic Compounds, 178. Constituents of Grindelia SpeciesThe investigation of further Grindelia species shows the presence of some new C10-acetylenic compounds (1-3, 8, 9, 13, 14, 22, 23) representing biogenetical relationships in this genus. Feeding experiments furnish more details of the biogenesis of the C10-compounds.
    Notes: In weiteren Grindelia-Arten werden einige neue C10-Acetylenverbindungen (1-3, 8, 9, 13, 14, 22, 23) nachgewiesen, die die biogenetische Beziehung in dieser Gattung aufzeigen. Fütterungsversuche zeigen weitere Einzelheiten über die Biogenese der C10-Verbindungen.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3028-3033 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on the Chemistry of Silicon and Germanium, XI. Preparation and Investigation of New Iodine Derivatives of Disilane, Trisilane, and n-TetrasilaneDisilane (Si2H6), trisilane (Si3H8), and n-tetrasilane (n-Si4H10) react with elementary iodine in solution to give partially iodated silanes. The isomer-free compounds have been isolated by gaschromatography in preparative amounts and have been examined by n.m.r. spectroscopy.
    Notes: Bei der Umsetzung von Disilan (Si2H6), Trisilan (Si3H8) und n-Tetrasilan (n-Si4H10) mit elementarem Jod in einem Lösungsmittel wurden teiljodierte Silane gewonnen. Isomerenreine Produkte wurden gaschromatographisch in präparativen Mengen isoliert und NMR-spektroskopisch untersucht.
    Additional Material: 6 Ill.
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  • 85
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3050-3057 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Synthesis of Belleau's TetrahydroerythrinaneCyclisation of Belleau's ketoamide 6 by polyphosphoric acid yields a mixture of the spiro-lactams 17 and 18, the ratio being 3:1 at 100° and 1 :3 at 150°. Lithium aluminium hydride reduction of the 3 :1 mixture affords the cis-base 12 as Mayn product which has previously been prepared by Boekelheide from the spirolactam 10. Correspondingly, from the 1:3 mixture the base is isolated which Belleau has described and characterized by its picrate (m. p. 178 to 179°). The base contains two more hydrogen atoms than so far assumed. It has, therefore, to be formulated as hexahydro-cis-erythrinane 20 and has to be eliminated from the series of trans-erythrinanes.
    Notes: Die Cyclisierung des Ketoamids 6 von Belleau mit Polyphosphorsäure liefert bei 100° ein Gemisch der Spirolactame 17 + 18 im Verhältnis 3 :1 und bei 150° im Verhältnis 1 :3. Durch Reduktion des 3 :1-Gemisches mit Lithiumalanat entsteht als Hauptprodukt die cis-Base 12, die Boekelheide auch aus dem Spirolactam 10 dargestellt hat. Entsprechend wird aus dem 1 :3-Gemisch die von Belleau beschriebene Base mit dem Pikrat vom Schmp. 178-179° isoliert, die entgegen der bisherigen Annahme 2 H-Atome mehr besitzt. Die Base ist als Hexahydro-cis-erythrinan 20 zu formulieren und scheidet damit aus der Reihe der trans-Erythrinane aus.
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  • 86
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2288-2301 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemical Transformations, 33Upon direct photoexcitation the three 7-azabenzonorbornadienes 12a, b, c are isomerized to the 3-benzazepines 22a, b, c. At temperatures above -40° the azaquadricyclanes 19a, b, c, postulated as intermediates, cannot be found. The sensitized reaction of 12a yields the 6-aminobenzofulvenes 23a and 24a preferentially.
    Notes: Durch direkte Lichtanregung werden die drei 7-Aza-benzonorbornadiene 12a, b, c in die 3-Benzazepine 22a, b, c isomerisiert. Oberhalb -40° lassen sich die als Zwischenprodukte postulierten Azaquadricyclane 19a, b, c nicht nachweisen. Bei der sensibilisierten Anregung von 12a werden die 6-Amino-2.3-benzo-fulvene 23a, 24a bevorzugt gebildet.
    Additional Material: 2 Ill.
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  • 87
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 88
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2336-2343 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Proanthocyanidins, XV. Rotational Hindrance at the C(sp2)—C(sp3) Linkage of the 4-Aryl-substituted PolymethoxyflavansThe 4-aryl-substituted polymethoxyflavans 2 and 3 are prepared as model substances for the natural C30H26O12-procyanidins 1. It is shown on the basis of the temperature dependence of the n. m. r. spectra that for the rotational hindrance at the C(sp2)—C(sp3) linkage of the ring C (attached at C-atom 4): 1. two substituents in the ortho-position of the joined nuclei C and 2. a substituent at C-3 or C-5 of the flavonoid unit are necessary. Both conditions are fulfilled by the natural procyanidins 1, so that, as a result of the large “lower” half of the molecule, conformational isomers of 1 may be found in nature.
    Notes: Als Modellsubstanzen für die natürlichen C30H26O12-Procyanidine 1 werden die 4-arylsubstituierten Polymethoxyflavane 2 und 3 hergestellt. Durch die Temperaturabhängigkeit ihrer NMR-Spektren wird bewiesen, daß für die Rotationsbehinderung an der C(sp2) — C(sp3)-Bindung des am C-Atom 4 stehenden Ringes C notwendig sind: 1. zwei Substituenten in ortho-Position des angegliederten Kerns C und 2. ein Substituent an C-3 oder C-5 der Flavonoid-Einheit. Beide Bedingungen sind bei den natürlichen Procyanidinen 1 erfüllt, so daß durch die große “unter” Molekülhälfte Konformationsisomere von 1 in der Natur auftreten können.
    Additional Material: 5 Ill.
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  • 89
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2424-2427 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Di- and Polyamino Sugars, XV. XIV. Mitteil.: W. Meyer zu Reckendorf, Tetrahedron Letters [London] 1970, 287. Synthese der 2.4-Diamino-1.6-anhydro-2.4-dideoxy-D-talose. Synthesis of 2,4-Diamino-1,6-anhydro-2,4-dideoxy-D-taloseDehydrogenation of the amino reductone 1 with iodine yields a triulose which is isolated as the phenylhydrazone-phenylazo derivative 2. Spontaneous cyclization of 2 forms the 1.6-anhydro compound 3. On hydrogenation 2as well as 3are transformed into the title compound.
    Notes: Die durch Dehydrierung des Aminoreduktons 1 mit Jod entstehende Triulose wird als Bis-phenylhydrazon 2 isoliert, das die Konstitution eines Phenylhydrazon-benzolazo-Derivates besitzt. 2 cyclisiert leicht zur 1.6-Anhydro-Verbindung 3, die, wie auch 2, bei der katalytischen Hydrierung die Titelverbindung liefert.
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  • 90
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3363-3369 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of Chloropentacyanobenzene1, 3, 5-Trichloro-2,4,6-tricyanobenzene (2a) reacts with the sodium salts of β-ketoesters by exchange of two chlorine atoms to give the compounds 6a-c. Of these 6c, by partial saponification and decarboxylation, yields diethyl 6-chloro-1,3,5-tricyanobenzene-2,4-diacetate (9), which reacts with ethyl nitrite in dimethylformamide to give the dioxime 10. By Beckmann fragmentation of 10 with phosphorus pentachloride chloropentacyanobenzene (5) is obtained.
    Notes: 1. 3. 5-Trichlor-2.4.6-tricyan-benzol (2a) reagiert mit den Natriumsalzen von β-Ketoestern unter Austausch von zwei Chloratomen, wobei die Verbindungen 6a-c entstehen. Von diesen ergibt, 6c durch partielle Verseifung und Decarboxylierung 6-Chlor-1.3.5-tricyan-benzoldiessigsäure-(2.4)-diäthylester (9), der mit Äthylnitrit in Dimethylformamid zum Dioxim 10 reagiert. Aus 10 wird mit Phosphorpentachlorid durch Beckmann-Fragmentierung das Chlorpentacyanbenzol (5) erhalten.
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  • 91
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3414-3418 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Synthesis of Quercetine-3-β-rutinoside-7-β-D-glucosidePartial benzylation of rutin-decaacetate (2) gave 7-O-benzylrutin nonaacetate (3). Catalytic debenzylation followed by coupling with acetobromoglucose afforded after saponification crystalline quercetine-3-β-rutinoside-7-β-D-glucoside (1), identical with a sample of 1 isolated from Evonymus lanceifolia.
    Notes: Partielle Benzylierung von Rutin-decaacetat (2) ergab 7-O-Benzyl-rutin-nonaacetat (3). Katalytisches Entbenzylieren und nachfolgende Kupplung mit Acetobromglucose führte nach Verseifung zu kristallinem Quercetin-3-β-rutinosid-7-β-D-glucosid (1), das mit dem aus Evonymus lanceifolia isolierten 1 identisch war.
    Additional Material: 1 Ill.
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  • 92
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2729-2743 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Revision of the Structure of NarciprimineNarciprimine is not identical with the synthetic phenanthridone derivative 2. It must, therefore, have the alternative structure 15.
    Notes: Narciprimin ist mit dem synthetisch dargestellten Phenanthridonderivat 2 nicht identisch, seine Struktur muß der alternativen Formulierung 15 entsprechen.
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  • 93
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2760-2767 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 3-Azapyrylium Salts, VI. Alkylidene-1.3-oxazines and AlkylidenepyrimidinesThe alkyl substituted 3-azapyrylium salts 3a-c and the pyrimidinium salt 9a are transformed into the iso-π-electronic heteroanalogues of heptafulvene 4a-c and 10 (alkylidene-1.3-oxazines and alkylidenepyrimidines) by treatment with bases. Benzo-substituted heteroanalogues of heptafulvene 19a-d (alkylidene-1.3-benzoxazines) are available by the reaction of the alkyl o-hydrophenyl ketimines 17a and b with orthoesters.
    Notes: Die alkylsubstituierten 3-Aza-pyryliumsalze 3a-c und das Pyrimidiniumsalz 9 a wurden durch Einwirkung von Basen in die iso-π-elektronischen Heteroanalogen des Heptafulvens 4a-c und 10 (Alkyliden-1.3-oxazine und Alkyliden-pyrimidine) übergeführt. Benzo-substituierte Heteroanaloge des Heptafulvens 19a-d (Alkyliden-1.3-benzoxazine) sind durch Umsetzung der Alkyl-[o-hydroxy-phenyl]-ketimine 17a und b mit Orthoestern zugänglich.
    Additional Material: 5 Tab.
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  • 94
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2794-2801 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Alkylidenetriphenylphosphoranes, XXVIII. New Syntheses of α-Branched β-Ketocarboxylic AcidsThe reaction between acyl chlorides 1 and (1-alkoxycarbonylalkylidene)triphenylphosphoranes 2 in a molar ratio of 1:1 gives rise to the formation of phosphonium chlorides 3. The electrolysis of these phosphonium salts leads to the formation of triphenylphosphine and α-branched β-ketocarboxylic acid esters 6. The reaction between 1 and 2 in a molar ratio of 1:2 produces allenic carboxylic acid esters 8, which react with piperidine (9) to form enamines 10. Acidic hydrolysis of the latter compounds also yields the β-ketoesters 6.
    Notes: Säurechloride 1 und [1-Alkoxycarbonyl-alkyliden]-triphenylphosphorane 2 reagieren im Molverhältnis 1:1 zu Phosphoniumsalzen 3, deren Elektrolyse neben Triphenylphosphin α-verzweigte β-Keto-carbonsäureester 6 ergibt. Setzt man die aus 1 und 2 im Molverhältnis 1:2 entstehenden 8 mit Piperidin (9) um, so erhält man Enamine 10, bei deren saurer Hydrolyse ebenfalls die Verbindungen 6 entstehen.
    Additional Material: 2 Tab.
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  • 95
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 2885-2893 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the knowledge of the Organo Phosphorus Compounds, XII. The Reaction of Thiophosphoryl Derivatives with Grignard Reagents and the Analysis of the Mixtures by n. m. r. Double-Resonance MethodsThe reaction of t-C4H9MgCl with (CH3)nP(S)X3-n (n = 0, 1, 2; X = Cl, Br) and of CH3MgX′ (X′ = Br, J) with (t - C4H9)nP(S)X3 - n ( 1, 2; X = Cl, Br) is investigated. The complex mixtures obtained are favourably analysed double-resonance methods as f. i. in the case of the formation of CH3(t-C4H9)P(S)J.
    Notes: Die Einwirkung von tert.-Butylmagnesiumchlorid auf (CH3)nP(S)X3-n (n = 0, 1, 2; X = Cl, Br) und die Reaktion von CH3MgX′ (X′ = Br, J) mit (t-C4H9)nP(S)X3-n (n = 1, 2; X = Cl, Br) werden untersucht. Komplexe Reaktionsgemische lassen sich vorteilhaft mittels NMR-Doppelresonanztechniken analysieren, wie u. a. am Beispiel der Bildung von (CH3(t-C4H9)-P(S)J gezeigt wird.
    Additional Material: 4 Ill.
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  • 96
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3580-3590 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organometallic Lewis Bases, II. Organometallic Sulfur Complexes of Molybdenum, Manganese, Rhenium, and IronThe reaction between bis(trimethyltin) sulfide (1) and the pentacarbonyl halides of manganese and rhenium yields the dimers [(CO)4M—S—Sn(CH3)3]2 (M = Mn, Re). These compounds upon heating lose carbon monoxide to form the oligomers [(CO)3M—S—Sn(CH3)3]n. In the case of M = Mn two isomers are isolated (6a, 7) for which n is probably 3 and 4. The trimethyltin group in the above compounds can be replaced by the groups Mn(CO)5, Re(CO)5, and Fe(CO)2C5H5. The resulting complexes are the first organometallic compounds of the manganese group containing elemental sulfur as a ligand. An unusual reaction between 1 and C5H5Mo(CO)3Cl results in the formation of new sulfur complexes of molybdenum (3, 4).
    Notes: Die Umsetzung von Bis(trimethylzinn)-sulfid (1) mit den Pentacarbonylhalogeniden des Mangans und Rheniums ergibt die Dimeren [(CO)4M—S—Sn(CH3)3]2 (M = Mn, Re). Diese verlieren beim Erhitzen CO unter Bildung der Oligomeren [(CO)3M—S—Sn(CH3)3]n. Dabei werden für M = Mn zwei Isomere isoliert (6a, 7), für die n wahrscheinlich 3 und 4 ist. Die Trimethylzinngruppe in diesen Verbindungen läßt sich durch die Gruppen Mn(CO)5, Re(CO)5 und Fe(CO)2C5H5 ersetzen, wobei erstmals Komplexe der Manganreihe mit elementarem Schwefel als Ligand gebildet werden. Mit C5H5Mo(CO)3Cl liefert 1 in ungewöhnlicher Reaktion neue Schwefelkomplexe des Molybdäns (3, 4).
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  • 97
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3605-3614 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Cotarnone with Ammonia. Formation and Transformations of Cotarnimine, a Stable Atraldimine BaseDue to a competition of the vinyl and formyl group cotarnone (2) reacts with ammonia at temperatures below 20° to give a stable araldimine base 8, whereas at 80° norcotarnine (4) is formed by cyclisation. As supported by preparative and spectroscopic evidence, 4, is not formed by internal cyclisation of the imine 8, but presumably by addition of ammonia to the vinyl group of 2 and subsequent condensation.
    Notes: Bedingt durch eine Konkurrenz der Vinyl- und Formylgruppe entsteht bei der Reaktion des Cotarnons (2) mit Ammoniak unter 20° eine stabile kristalline Araldimin-Base 8, bie 80° dagegen durch Cyclisierung Norcotarnin (4). Aufgrund präparativer und spektroskopischer Untersuchungen wird angenommen, daß 4 nicht durch eine innermolekulare Cyclisierung des Imins 8, sondern durch Ammoniakaddition an die Vinylgruppe von 2 und nachfolgende Kondensation entsteht.
    Additional Material: 3 Ill.
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  • 98
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3619-3622 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occuring Coumarine Derivatives, VI. On the Constituents of Capnophyllum SpeciesWhereas the roots of C. peregrinum contain only small amounts of acetylenic compounds, from the aerial parts several coumarine derivatives are isolated. The structures are elucidated by spectroscopic methods.
    Notes: Während die Wurzeln von C. peregrinum (L.) Lange nur Spuren von Acetylenverbindungen enthalten, findet man in den oberirdischen Teilen mehrere Cumarin-Derivate. Die Strukturen wurden durch spektroskopische Methoden aufgeklärt.
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  • 99
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3661-3666 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Some Cleavage Reactions of the Silicon-Nitrogen Bond in N.N-Dimethyl-N′,N′-bis (trimethylsilyl) hydrazineThe combination of (CH3)2NN[Si(CH3)3]2 (1) with COF2 produces [(CH3)2NNCO]2 (2). The reaction of 1 with POF3 in acetonitrile leads to (CH3)2NN(POF2)Si(CH3)3 (3). Treatment of 1 with P2O3F4 yields a compound which reacts further with acids to give (CH3)2NN(H)POF2 (4). Compound 4 is also isolated as a secondary product in the preparation of 3. The combination of 1 with POCl3 yields (CH3)2NN(POCl2)2 (5). An analogue of compound3, (CH3)2NN(PSF2)Si(CH3)3 (6), is produced by the reaction of PSF3 with 1.
    Notes: Bei der Umsetzung von (CH3)2NN[Si(CH3)3]2 (1) mit COF2 entsteht [(CH3)2 NNCO]2 (2). Die Reaktion von 1 mit POF3 in Acetonitril führt zu (CH3)2NN(POF2)Si(CH3)3 (3). Mit P2O3F4 setzt sich 1 zu einer Verbindung um, die mit Säuren weiter zu (CH3)2NN(H)POF2 (4) reagiert. Die Verbindung 4 ist auch als Nebenprodukt bei der Darstellung von 3 zu isolieren. Bei der Umsetzung von 1 mit POCl3 ist (CH3)2NN(POCl2)2 (5) zu gewinnen. Analog zu 3 ist aus PSF3 mit 1 (CH3)2NN(PSF2)Si(CH3)3 (6) erhältlich.
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  • 100
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3684-3695 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complexes between Metals and Aromatic Compounds, CXIV. Preparation and Reactions of Dicyclopentadienyldivanadiumpentacarbonyl, (C5H5)2V2(CO)5Na2[C5H5V(CO)3], obtained by shaking C5H5V(CO)4 with Na amalgam in tetrahydrofuran, yields with 2 n HCl green binuclear diamagnetic (C5H5)2V2(CO)5 instead of a hydride. Its structure is discussed on the basis of i. r., 1H n. m. r. and mass spectra. It reacts with n-donors D to form either C5H5V(CO)3D and C5H5V(CO)2D2 or (C5H5)2V2(CO)4D complexes. NO yields C5H5V(NO)2CO.
    Notes: Na2[C5H5V(CO)3], durch Schütteln von C5H5V(CO)4 mit Na-Amalgam in Tetrahydrofuran erhalten, ergibt mit 2n HCl statt eines Hydrids grünes, zweikerniges, diamagnetisches (C5H5)2V2(CO)5. Dessen Struktur wird anhand von IR-,1H-NMR- und Massenspektren diskutiert. Mit n-Donoren D können daraus entweder C5H5V(CO)3D-und C5H5V(CO)2D2- oder aber (C5H5)2V2(CO)4D-Komplexe entstehen. No ergibt C5H5V(NO)2CO.
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