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  • 1970-1974  (3,981)
  • 1965-1969  (4,252)
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  • Inorganic Chemistry  (12,725)
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  • 1
    Electronic Resource
    Electronic Resource
    On different patterns of dendritic bundling in the cerebral cortex of the cat (1974)
    Springer
    Anatomy and embryology 143 (1974), S. 115-126 
    Details
    ISSN: 1432-0568
    Keywords: Cerebral cortex ; Apical dendrites ; Dendritic bundles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In frontal, horizontal and sagittal paraffin sections through the cat's brain regional differences in the pattern of dendritic bundling have been investigated. It is shown that in the gyrus splenialis and suprasplenialis 2–5 apical dendrites of layer IV pyramids approach each other to form vertical bundles which run straight through layer IV. In the posterior sigmoid gyrus, on the other hand, most apical dendrites arising from the pyramidal cells bifurcate immediately above layer V and give rise to obliquely running branches which cross each other before turning upwards and joining other dendrites to take part in the formation of bundles. In this region the dendritic tree of the pyramidal cells seems to be characterized by an unexpectedly high degree of directional specialization.—In functional terms the findings can be summarized by stating that in the visual and sensorimotor regions of the cat's cerebral cortex basic differences exist in the relation between the apical dendrites of layer V pyramids.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00525764
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  • 2
    Electronic Resource
    Electronic Resource
    Crossed reticulo-reticular projections in the medulla, pons and mesencephalon (1974)
    Springer
    Anatomy and embryology 143 (1974), S. 127-134 
    Details
    ISSN: 1432-0568
    Keywords: Reticular formation ; Crossed connections ; Autoradiography ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Injection of radioactive leucine in various regions of the brain stem reticular formation has revealed the presence of ample crossed reticulo-reticular connections in the cat. The terminal area for the crossed fibers are almost mirror images of the injected sites. The findings made is another example that hitherto unknown fiber connections can be demonstrated by axoplasmic protein tracing.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00525765
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  • 3
    Electronic Resource
    Electronic Resource
    Evolution ultrastructurale du labyrinthe de placenta de chatte (1974)
    Springer
    Anatomy and embryology 146 (1974), S. 1-20 
    Details
    ISSN: 1432-0568
    Keywords: Placenta ; Cat ; Differentiation ; Function ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'ultrastructure du labyrinthe de placenta de chatte a été étudiée du 45e au 63e jour de gestation. Cette formation endothéliochoriale est composée: d'un endothélium maternel hypertrophié et de cellules géantes déciduales; d'une couche de «substance inerte interstitielle»; du trophoblaste constitué d'une assise syncytiale continue (syncytiotrophoblaste) et d'une assise cellulaire discontinue (cytotrophoblaste); d'un endothélium foetal accompagné de son environnement mésenchymateux. Les capillaires foetaux envahissent progressivement le syncytiotrophoblaste. L'hypertrophie de l'endothélium maternel diminue en fin de gestation; de ce fait la distance, séparant le sang maternel du sang foetal, peut atteindre en certains points 2 μ. L'endothélium maternel, le syncytiotrophoblaste et l'endothélium foetal présentent des signes ultrastructuraux d'un rôle de transfert. La «substance inerte inerte interstitielle», qui sépare les tissus d'origine maternelle des tissus d'origine foetale, est constante mais d'épaisseur variable; elle est spécifique des structures endothéliochoriales. Les cellules géantes déciduales, dont le nombre diminue en fin de gestation comportent parfois un ou plusieurs «corps glycogéniques». Le syncytiotrophoblaste, siége d'activité de biosynthése de stéroïdes, est riche en ergastoplasme, ce qui autorise à postuler la synthése d'hormones protéiques.
    Notes: Summary The ultrastructure of feline placental labyrinth has been studied from the 45th to the 63rd day of gestation. The endotheliochorial structure is composed of: a thick hypertrophied maternal endothelium with giant decidual cells; an “interstitial inert substance”; a continuous syncytial layer (syncytiotrophoblast) and a discontinuous cellular layer (cytotrophoblast) of trophoblast; and a thin foetal endothelium with its surrounding mesenchyme. Foetal capillaries increasingly invade the syncytiotrophoblast. Maternal endothelial hypertrophy is reduced in the last days of gestation. Thus the interval between maternal and foetal bloods may in some areas become 2 μ, in late pregnancy. Foetal endothelium, syncytiotrophoblast, and maternal endothelium demonstrate ultrastructural features of transfer function. The “interstitial inert substance”, which separates maternal from foetal tissue was always evident though with variable thickness. The giant decidual cells which are reduced in late pregnancy, show one or several “glycogen bodies”. The syncytiotrophoblast, where some steroïd biosynthesis has been demonstrated, has an extensive rough endoplasmic reticulum suggestive of protein hormone synthesis activity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00341379
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  • 4
    Electronic Resource
    Electronic Resource
    Zur histogenese und cytogenese des tapetum lucidum cellulosum der katze (1974)
    Springer
    Anatomy and embryology 146 (1974), S. 141-156 
    Details
    ISSN: 1432-0568
    Keywords: Tapetum lucidum cellulosum ; Cat ; Development ; Light and electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die postnatale Entwicklung des Tapetum lucidum cellulosum der Katze wird mit licht- und elektronenmikroskopischen Methoden untersucht. Bereits am ersten postnatalen Tag sind im Bereich des prospektiven Tapetum zwei Zellarten voneinander zu unterscheiden: 1. mesenchymale Bindegewebszellen und 2. prospektive Tapetumzellen, die durch elektronendichte Tapetumstäbchen gekennzeichnet sind. Die Mesenchymzellen unterteilen als parallel zur Retinaoberfläche ausgebreitete Zellplatten in der Choriodea am hinteren Augenpol den weiten extracellulären Raum in 20–25 etwa 5 μm hohe Schichten. Die Tapetumzellen liegen zwischen den Mesenchymzellplatten und wachsen im Verlaufe der ersten vier postnatalen Wochen innerhalb der Schichten in die Breite, bis sie den extracellulären Raum vollständig ausfüllen und als polygonale Zellen direkt aneinander grenzen. Im weiteren Verlauf der Entwicklung werden die Mesenchymzellplatten rückgebildet, so daß bei der adulten Katze die Tapetumzellschichten direkt übereinander liegen und nur von Netzen elastischer und kollagener Fasern getrennt sind. Die von einer Elementarmembran umgebenen Tapetumstäbchen enthalten einen elektronendichten, in den ersten postnatalen Wochen mit einer Periode von 100 Å quergestreiften Kern. Zunächst nehmen sie an Zahl und Länge zu und füllen am Ende der vierten postnatalen Woche, zu Bündeln von parallel verlaufenden Stäbchen geordnet, das Cytoplasma der Tapetumzellen. Dann nehmen die Tapetumstäbchen an Dicke zu, und ihre Querstreifung wird von einem elektronendichten Material überlagert. Die Entwicklung der Tapetumstäbchen hat eine starke Ähnlichkeit mit der in der Literatur beschriebenen Entwicklung von Melanosomen in Melanocyten. Das Tapetum lucidum cellulosum wird als ein dichter Verband hochdifferenzierter extrakutaner Melanocyten angesehen.
    Notes: Summary The postnatal development of the tapetum lucidum cellulosum of the cat was studied by light and electron microscopy. Already by the first postnatal day two cell types can be distinguished in the prospective tapeta area: 1. mesenchymal cells and 2. prospective tapetal cells, characterized by electron dense, membrane bound, rod-like inclusions. The flattened mesenchymal elements form 20–25 separate layers of cells, which are arranged parallel to the surface of the retina, subdividing the extracellular space of the chorioidea at the posterior pole of the eye into 5 μm high compartments. These compartments contain the tapetal cells which enlarge (in their longitudinal axis) during the first four weeks post partum until they occupy the extracellular space almost completely. At this stage, the tapetal cells are polygonal in shape and closely attached to each other. During the subsequent period of development there is a gradual involution of the mesenchymal cell plates. Thus, in adult cats the individual layers of tapetal cells are only separated from each other by networks of collagen and elastic fibers. The tapetal rods are bound by unit membranes and contain an electron dense core which, during the early postnatal weeks, exhibits a periodic cross-striation (100 Å). The tapetal rods increase in number and length during the first four weeks post partum; by the end of the fourth week, they occupy the whole cytoplasm of the tapetal cells. Parallelly arranged rods are grouped into individual bundles coursing inside the cytoplasm in different directions. Thereafter, the tapetal rods increase in thickness and their cross-striation becomes obscured by an electron dense material. This development of the tapetal rods closely resembles that of melanosomes. Thus the tapetum lucidum cellulosum can be regarded as a compact tissue made up of modified extracutaneous melanocytes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00315591
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  • 5
    Electronic Resource
    Electronic Resource
    Function and interaction of on and off transients in vision II. Neurophysiology (1974)
    Springer
    Experimental brain research 19 (1974), S. 507-521 
    Details
    ISSN: 1432-1106
    Keywords: Cat ; LGN ; Transients ; Antagonistic inhibition ; Sensory storage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neuronal responses to interruptions of light stimuli were studied in 58 X-type and 7 Y-type LGN relay cells with intra- and extracellular recording techniques. The responses to interruption were then compared with responses to either appearing or disappearing light stimuli which had the same luminance and size as the interrupted stimulus. The extent to which responses to interruption differed from those to appearance and disappearance was studied as a function of the interstimulus interval (ISI), the duration of the stimulus before the interruption (t1) and after the interruption (t2). Responses to stimuli appearing after interruptions of up to 500 msec were weaker than those to appearance and disappearance. This difference decreased with increasing ISI. The difference between responses to appearance and interruption increased as t2 decreased, and decreased as t1 decreased. The reverse was true for the difference between responses to disappearance and interruption. Stimulation of the mesencephalic reticular formation consistently reduced the difference between responses to appearance and disappearance compared with those to interruption for all stimulus conditions. These results are discussed in the context of the psychophysical study presented in the preceding paper. It is shown that the neuronal reactions are reflected in detail by the ability of humans to detect appearances and disappearances that occur during interruptions. EPSP sequences recorded from LGN relay cells and relay cell responses conditioned by reticular stimulation suggest that the differentiation of responses to interruption and change partially occurs already in the retina. This differentiation is subsequently enhanced by antagonistic inhibition in the LGN. It is proposed that these inhibitory interactions at peripheral sites of the visual pathway store visual information and serve to reduce the redundancy of responses to short interruptions of the visual input. Centrifugal modulation of LGN inhibition is proposed to control the trade off between temporal integration and temporal resolution.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00236114
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  • 6
    Electronic Resource
    Electronic Resource
    Reflexes in postganglionic fibres within skin and muscle nerves after noxious stimulation of skin (1974)
    Springer
    Experimental brain research 20 (1974), S. 125-134 
    Details
    ISSN: 1432-1106
    Keywords: Somato-sympathetic reflexes ; Cutaneous and muscle postganglionic neurones ; Noxious stimulation of skin ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. Somomato-sympathetic reflexes in postganglionic neurones to skin and muscle induced by noxious stimulation of skin were studied in cats anaesthetized with chloralose. The reflexes were elicited by mechanical damaging stimuli and by temperature stimuli of more than 45°C. 2. In most cutaneous units the spontaneous activity was depressed during noxious stimulation of skin. Some cutaneous units were excited or showed mixed responses. The depression of the spontaneous activity was maximal from the skin area which was innervated by the cutaneous postganglionic neurones and much weaker or not elicitable from other skin areas. 3. Most muscle units were excited during noxious stimulation of skin. This excitation could be elicited from all over the body surface. 4. The effective cutaneous afferent fibres which are involved in these reflexes are the Group III axones which are excitable by mechanical damaging stimuli and the Group IV axones which are excitable by mechanical damaging and/or by thermal noxious stimuli. 5. These investigations reveal that the somato-sympathetic reflexes have opposite organization in cutaneous and muscle postganglionic fibres. The reflex patterns are discussed in relation to a possible central organization of the sympathetic nervous system.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00234007
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  • 7
    Electronic Resource
    Electronic Resource
    Role of visual experience in the development of optokinetic response in kittens (1974)
    Springer
    Experimental brain research 20 (1974), S. 297-302 
    Details
    ISSN: 1432-1106
    Keywords: Cat ; Selective rearing ; Maturation ; OKN ; Perception of motion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. Kittens reared in the dark from birth were exposed one hour a day between the 4th and the 10th week of age, to a visual environment which consisted exclusively of vertical edges moving horizontally at a constant speed, and always in the same direction. Total exposure time varied between 10 and 60 hours. 2. At the 12th week of age, optokinetic nystagmus (OKN) in response to displacements of the visual field, was tested. Displacements in the direction that the kittens had experienced during the exposure period elicited immediately an OKN, the frequency of which was related to the speed of the moving pattern. Displacements in the opposite direction elicited a poorer response, only for slowly moving edges. When the speed of the displacement was increased, OKN failed to adapt and finally disappeared. 3. These results suggest the existence, in this type of visuomotor behavior, of a component built up by early visual experience (adaptative component) overlying another component pre-existing visual experience (pre-programmed component).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00238319
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  • 8
    Electronic Resource
    Electronic Resource
    Attention in the cat: Electrophysiological and behavioural studies (1974)
    Springer
    Experimental brain research 21 (1974), S. 67-82 
    Details
    ISSN: 1432-1106
    Keywords: Sensory transmission ; Lateral geniculate nucleus ; Visual cortex ; Attentive behaviour ; Vigilance ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The behaviour of 6 cats was studied in a vigilance task. Each cat was trained to press a pedal on the floor of a training box. A waiting interval of fixed (FI) or variable (VI) duration then followed, after which a stimulus (S), a spot of light or a tone, was presented for a short period of time. The cat gave a correct response if, during this time, it pressed a panel. The animal was then rewarded with food. When an experiment had been completed using one S the cat was trained to respond to the other. The latency of response following the onset of S was measured for each waiting interval in the VI schedules. It was found that the longer latencies were associated with the shorter waiting intervals; that is, the cats responded more quickly to S as expectancy increased. Between the time the pedal and pand were pressed the optic tract (OT) was shocked not more than once and the response of the LGN and visual cortex recorded. The time at which the shock was delivered varied from 1 trial to the next. The responsiveness of the LGN and visual cortex did not vary during the waiting interval in either of the FI schedules or in the VI schedule in which S was a spot of light. However, in the VI schedule in which S was a tone, the responsiveness of the visual cortex to the thalamocortical input declined as the length of the waiting interval increased. No changes were observed at the LGN or in the presynaptic cortical response. These results contrast with those observed during changes in the level of arousal as assessed by the ECoG. When the ECoG passed from the synchronised to the desynchronised state there was an increase in the amplitude of the postsynaptic LGN response to the OT shock, but no change in the responsiveness of the cortex to the increased thalamocortical input. These changes in transmission in the visual pathways are discussed in relationship to the animal's behaviour and to the inferred state of attention.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00234258
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  • 9
    Electronic Resource
    Electronic Resource
    Electrotonic coupling between motoneurones in the abducens nucleus of the cat (1974)
    Springer
    Experimental brain research 21 (1974), S. 139-154 
    Details
    ISSN: 1432-1106
    Keywords: Electrotonic coupling ; Antidromic responses ; Abducens motoneurone ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The electrical stimulation of the abducens nerve provokes the classical true antidromic invasion of the abducens motoneurone and a depolarization which is often capable of generating full action potentials in the impaled motoneurone. Experiments studying these depolarizations suggest the existence of electrotonic coupling between the abducens motoneurones of the cat. Intracellular activity of the abducens motoneurones was recorded following intracellular stimulation of the impaled neurone and antidromic stimulation of the abducens nerve. Collision between the outgoing action potential and the antidromic volley differentiated the true antidromic spike from the depolarizations which can induce or not action potentials. The latency of the depolarization ranged between 100 and 1200 μsec. Collision demonstrated that the depolarization and the true antidromic action potential have an independent origin. The depolarizations and action potentials which are not conveyed to the motoneurone by its own axon are interpreted to be generated by electrotonic coupling.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00234386
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  • 10
    Electronic Resource
    Electronic Resource
    The lateral reticular nucleus in the cat I. Mossy fibre distribution in cerebellar cortex (1974)
    Springer
    Experimental brain research 21 (1974), S. 473-486 
    Details
    ISSN: 1432-1106
    Keywords: Lateral reticular nucleus ; Reticulocerebellar projection ; Cerebellum ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. The areas of the cerebellar cortex receiving fibres from the mLRN (major portion of the lateral reticular nucleus comprising its parvi- and magnocellular parts) were determined by identifying the low-threshold spots on the cerebellar surface from which 286 mLRN neurones could be antidromically activated. 2. The mLRN fibres terminate bilaterally in the anterior lobe and pyramis, and ipsilaterally in the paramedian lobule. Some fibres terminate also in the rostral part of lobule VI but hardly any in other parts of the cortex. It follows that the mLRN projects almost exclusively to the classical spinal receiving areas. 3. Neurones in the parvi- and magnocellular parts project to similar cortical areas. 4. Two regions in the mLRN were distinguished on the basis of their different projection areas. Region A, a dorsolateral portion of the magnocellular part, projects to the ipsilateral parts intermedia of the anterior lobe and the ipsilateral paramedian lobule. Region B, a ventral portion of the parvi- and magnocellular parts, projects bilaterally to the pars intermedia and vermis of the anterior lobe and sparsely to the pyramis. 5. Neurones throughout the parvi- and magnocellular parts receive monosynaptic excitation from fibres ascending in the ventral part of the ipsilateral lateral funiculus.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237166
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  • 11
    Electronic Resource
    Electronic Resource
    Vertical organization in the visual cortex (area 17) in the cat (1974)
    Springer
    Experimental brain research 21 (1974), S. 315-336 
    Details
    ISSN: 1432-1106
    Keywords: Visual cortex (area 17) ; Cat ; Columnar organization ; Retino-cortical scatter ; Intracortical connections
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. Responses of cortical cells in the cat's area 17 (central and paracentral area), recorded successively during electrode penetrations perpendicular to the surface, were averaged (PSTH). All cells recorded during one penetration were stimulated with the same stimulus, a slowly moving light or dark slit oriented optimally for the first cell recorded. Comparisons between successively recorded cells were completed by simultaneous recordings from two neurones with the same microelectrode tip. Eye movements as an error were excluded by simultaneous recording of a geniculate cell throughout a cortical penetration. 2. The centers of excitatory receptive fields (ERFs) of simultaneously or successively recorded cells during a penetration may be separated by more than 4°. The mean scatter around a column average is 0.81±0.99° in both directions. The scatter is independent of the recording depth. Whereas the optimal orientation of cells recorded during one penetration was generally similar, the optimal direction (forward and backward movement of an optimally oriented stimulus) was variable. 3. The ERF diameters as determined from the PSTH were between 〈0.5° and 7.5°. During each penetration, cells with small (up to 3.0°) and large (〉3.0°) ERFs could be discriminated. The inhibitory fields (determined with the conditioning method of Bishop, Coombs and Henry, 1971) were between 2.0 and 8.5° along both the optimal and the non-optimal orientation axis of a cell. The borders of inhibitory fields of cells collected during one penetration were also scattered though overlapping. 4. Response analysis of simultaneously and successively recorded cells with different stimuli indicated that, in spite of considerable ERF-overlap, cells with small ERFs had separate excitatory inputs and that intracortical excitatory connections between cells recorded during one penetration were improbable. 5. The ERFs of cells with large ERFs covered a field approximately corresponding to the fields of cells with small ERFs. But a convergent input from many small ERF cells to single large ERF cells was excluded because of the incompatible functional properties of both types of cells, which correspond to some extent to simple and complex cells respectively. 6. It is concluded that cells within cortical cylinders are not connected through excitatory contacts with each other and that most cells in area 17 are excited by individual excitatory geniculate or cortical inputs. Inhibitory connections seem to be the most important intracortical connections. 7. In an Appendix it is shown that anatomical and physiological data do not support significant excitatory convergence of specific geniculate afferents on cortical neurones.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235750
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  • 12
    Electronic Resource
    Electronic Resource
    The projection of the superior colliculus onto the reticular formation of the brain stem an experimental anatomical study in the cat (1974)
    Springer
    Experimental brain research 19 (1974), S. 1-19 
    Details
    ISSN: 1432-1106
    Keywords: Reticular formation ; Superior colliculus ; Cat ; Experimental anatomy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Following altogether 18 stereotactically placed lesions of different location and size in the superior colliculus the efferent fibres to the RF and their distribution were traced in silver impregnated, approximately serial sections (Nauta and Fink and Heimer methods), cut in the transverse, horizontal or sagittal plane. The projection to the mesencephalic RF was found to be almost completely ipsilateral, that to the pontomedullary RF largely contralateral. In the mesencephalic RF the fibres end in its dorsal half approximately. In the pons and medulla they supply only the medial 2/3 of the main RF, with two distinct maxima within the total field of termination. One maximum covers the rostral part of the nucleus reticularis gigantocellularis and the adjoining part of the nucleus reticularis pontis caudalis, the other occupies the rostralmost part of the latter and the caudal part of the nucleus reticularis pontis oralis. Of the precerebellar reticular nuclei the contralateral nucleus reticularis tegmenti pontis receives a distinct component of tectal fibres in a small area dorsomedially. Some fibres end in a restricted part of the nucleus reticularis lateralis and in the paramedian reticular nucleus. The tectoreticular projection appears to be organized according to the same principles as other afferents to the RF. In the main RF the areas of termination of the tectoreticular fibres coincide more or less with the areas of termination of corticoreticular, fastigioreticular and vestibuloreticular fibres. These common terminal areas are those which give off the bulk of reticulospinal fibres. Some functional implications of the pattern of organization in the tectoreticular projection are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00233392
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  • 13
    Electronic Resource
    Electronic Resource
    Neuronal activity during eye movements in a visual association area of cat cerebral cortex (1974)
    Springer
    Experimental brain research 19 (1974), S. 467-477 
    Details
    ISSN: 1432-1106
    Keywords: Suprasylvian gyrus ; Cat ; Single neurons ; Eye movements ; Direction sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 270 single neurons from the anterior part of the middle suprasylvian gyrus (AMSS) were recorded in awake and non-paralyzed cats (Chronic preparation). 10% were unresponsive to visual stimulation, the remainder reacted well to moving visual stimuli. Half of the units tested were directionally selective. Horizontal, or downward preferred directions predominated. Most neurons were relative insensitive to changes of shape, orientation, contrast, and velocity of the visual stimulus. Some neurons preferred rapid (100°/sec) jerky movements, others required complex motions of irregular shapes, a few strongly preferred objects moving towards the animal in the midsagittal plane. 40% of neurons yielded phasic On-Off reaction to flashing stationary spots. Habituation to repeated stimulation was a common feature and occured in 50% of AMSS neurons. In 19% of neurons tested the discharge rate was not affected by saccadic eye movements, when the animal faced a patterned background. Among the remainder two types of saccade associated responses could be distinguished. Type I discharged prior to or simultaneously with the onset of saccades. This early response was usually associated with saccades of particular directions. Saccades in total darkness yielded weaker and less consistent responses. Type II discharged subsequent to the onset of the saccades after a latency of 40 msec (type IIa), 40–80 msec (type IIb) and 80 msec (type IIc). Responses of type IIa are probably consequences of the retinal effects of eye movements. The saccade associated responses of type Ia, IIb and IIc are tentatively interpreted as results of an eye movement-synchroneous subcortical input, which facilitates transmission in AMSS neurons. Presaccadic facilitation, which generates type Ia responses, may be functionally related to shifts of attention prior to eye movements. It is suggested that postsaccadic facilitation, which underlies the reactions of type IIb and IIc, may be a correlate of visual attention during the fixation period.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00236111
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  • 14
    Electronic Resource
    Electronic Resource
    The organization of projections from the cerebellar nuclei to the contralateral motor cortex in the cat (1974)
    Springer
    Experimental brain research 19 (1974), S. 36-60 
    Details
    ISSN: 1432-1106
    Keywords: Cerebellar nuclei ; Motor cortex ; Evoked potentials ; Topographical organization ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. A topographical study of cerebello-cortical relations was conducted in cats anesthetized with chloralose. The potentials evoked by punctate stimulation of the cerebellar nuclei were recorded at various sites in the contralateral motor cortex. A map of the cortical responses obtained by stimulating each of the cerebellar nuclei was established. For this purpose, the stimulation thresholds as well as the response amplitudes, polarity and latency were noted. 2. Local stimulation of each cerebellar nucleus evoked responses in particular regions of the contralateral motor cortex. When a stimulus was applied to the interpositus nucleus, short latency responses were recorded in the lateral part of the area 4. Dentate nucleus stimulation induced short latency responses in the medial part of area 4 and in area 6. Furthermore, late responses were also recorded laterally in area 4. 3. The interpositus nucleus was found to project to the portion of motor cortical area controlling the distal forelimb with only a fast conducting pathway. The fastigial nucleus seems to be connected with proximal and axial motor areas. The projection system of the dentate nucleus appears to have a temporal organization: a fast conducting pathway was found to project to the axial and proximal motor area while a slower one seems to transmit impulses to the motor area of the forelimb extremity. 4. The functional aspects suggested by the temporal organization of the cerebellocortical inputs and the distribution of each nucleus projections on the motor cortical areas are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00233394
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  • 15
    Electronic Resource
    Electronic Resource
    Lack of fixed order of recruitment in cat motoneuron pools (1974)
    Springer
    Experimental brain research 20 (1974), S. 101-114 
    Details
    ISSN: 1432-1106
    Keywords: Size principle ; Motoneurons ; Cat ; Recruitment ; Neurophysiology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Henneman et al. have shown that a wide variety of stimuli activate motoneurons in the order of their sizes, though some reversals occur. It is not clear which motoneurons should be included in the “pool” from which recruitment by size takes place. The “pool” may consist of 1. all the motoneurons to a given muscle 2. all the motoneurons in a given ventral root or 3. all the motoneurons activated by a given stimulus. We have examined recruitment in the pool of fibers to a given muscle. A variety of mechanical stimuli to cat's legs were used to elicit bursts of activity in gastrocnemius motor units. In 30% of pairs of units, one unit had a consistently lower threshold, i.e. it always began and ended a burst. In the other 70%, either unit could start or end a burst. For 48% of motor unit pairs recorded in either the medial or lateral gastrocnemius, each unit of the pair had runs of firing of at least 10 spikes while the other was totally inactive. By the same criterion, 23% of pairs of temporalis units showed differential activity. During spontaneous breathing there was no consistent recruitment order in 24% of pairs of units in throat respiratory muscles. These data indicate that reversals of recruitment order are relatively common for motoneurons innervating the same muscle. We discuss the possibility that size principle may hold for motoneurons in a single ventral rootlet whose somas are anatomical neighbors (even though they innervate different muscles), but not for motoneurons that are anatomically distant in the cord (even though they innervate the same muscle).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00234005
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  • 16
    Electronic Resource
    Electronic Resource
    Effect of differential blocking of motor axons on antidromic activation of Renshaw cells in the cat (1974)
    Springer
    Experimental brain research 20 (1974), S. 135-143 
    Details
    ISSN: 1432-1106
    Keywords: Cat ; Renshaw cell ; Antidromic activation ; Differential blocking
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Attempts were made to study differences in the relative effectiveness of different size ranges of motor axons to Renshaw cells by differential blocking of larger fibers of the gastrocnemius nerve in cats anesthetized with Nembutal. 1. Differential blocking of larger fibers in the nerve was successfully obtained by applying trapezoid wave current to the nerve. 2. It was shown that more than half (58.1%) of the Renshaw cells receive homogeneous inputs from a motor axon collaterals, 25.8% of the cell receive collateral inputs from a certain group of fibers, and 12.5% of the Renshaw cells were activated by “γ range” fibers.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00234008
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  • 17
    Electronic Resource
    Electronic Resource
    Reflexes in postganglionic fibres within skin and muscle nerves after mechanical non-noxious stimulation of skin (1974)
    Springer
    Experimental brain research 20 (1974), S. 115-123 
    Details
    ISSN: 1432-1106
    Keywords: Somato-sympathetic reflexes ; Postganglionic fibres to skin and muscle ; Natural stimulation of skin ; Hair-follicle receptors ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. Somato-sympathetic reflexes in postganglionic neurones to hairy skin and to muscle produced by mechanical non-noxious stimulation of skin were studied in cats anesthetized with chloralose. Most of the postganglionic fibres investigated were spontaneously active and had presumably vasoconstrictor function. 2. In 60% of the cutaneous postganglionic neurones stimulation of hairs induced predominantly excitation. This excitation was mostly followed by a slight depression of the spontaneous activity. In 30% of the neurones the spontaneous activity was depressed or predominantly depressed by these stimuli. 3. In most muscle postganglionic neurones the spontaneous activity was depressed by stimulation of hairs. 4. In both types of neurones the reflexes were produced by activity in hair follicle receptors with Group II afferents. Hair follicle receptors with Group III afferents most probably also contributed to this effect. Except for a slight depression of the spontaneous activity in some cutaneous postganglionic neurones by slowly adapting receptors, mechanical stimulation of other types of receptors with Group II afferents had no effect on the postganglionic neurones. 5. Reflexes in postganglionic neurones could be elicited by stimulation of hairy skin all over the body surfaces.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00234006
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  • 18
    Electronic Resource
    Electronic Resource
    Projections thalamiques des noyaux vestibulaires: Etude histologique chez le chat (1974)
    Springer
    Experimental brain research 20 (1974), S. 273-283 
    Details
    ISSN: 1432-1106
    Keywords: Vestibular nuclei ; Thalamic projections ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Electrolytic lesions were placed into the left vestibular nuclei of 22 adult cats. Silver impregnation for degenerated terminal fibres of serial sections revealed the existence of a relay of the corticopetal vestibular pathway in the contralateral thalamus. Its main afferent fibres originate in the superior and medial vestibular nuclei. By crosschecking the results it was possible to demarcate a focus of vestibular projections in the ventro-caudal part of the thalamus, situated between the centre median, the ventro-basal group and the caudal segment of the ventro-lateral nucleus. The direct ascending afferents of this focus are relatively few in number. The functional significance of this vestibular relay with regard to the proprioceptive influx passing through this region of the thalamus is open to discussion.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00238317
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  • 19
    Electronic Resource
    Electronic Resource
    Bilateral semicircular canal inputs to neurons in cat vestibular nuclei (1974)
    Springer
    Experimental brain research 20 (1974), S. 285-296 
    Details
    ISSN: 1432-1106
    Keywords: Ampullary nerve ; Cat ; EPSP ; IPSP ; Vestibular neuron
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The six ampullary nerves in both labyrinths were separately stimulated by electric pulses in anesthetized cats. Resulting responses in neurons in the vestibular nuclei were recorded intracellularly. Almost all the vestibular neurons showed an EPSP in response to stimulation of the ipsilateral ampullary nerve. These neurons were subclassified as A-, L-, and P-neuron receiving specific projections from the anterior, lateral and posterior canal, respectively. Three fourths of the vestibular neurons recorded from received an IPSP in response to stimulation of the contralateral ampullary nerve. Plane-specific contralateral inhibition was found in most of vestibular neurons; i.e. A-, L-, and P-neuron received IPSP from the contralateral posterior, lateral, and anterior ampullary nerve, respectively. Approximately two thirds of vestibular neurons exhibiting the plane-specific inhibition were recorded in the medial vestibular nucleus. A collision test of impulses in primary afferent fibers were performed during recording of ipsilateral EPSPs produced by strong stimulation of more than one ampullary nerve. No positive evidence was provided for the existence of neural convergence on single vestibular neurons from different ampullary nerves on the same side. It is suggested that the plane-specific contralateral inhibition increase the sensitivity of vestibular neurons during head rotation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00238318
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  • 20
    Electronic Resource
    Electronic Resource
    Responses of cat vestibular neurons to sinusoidal roll tilt (1974)
    Springer
    Experimental brain research 20 (1974), S. 347-362 
    Details
    ISSN: 1432-1106
    Keywords: Vestibular nuclei ; Tilt response ; Sinusoid ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Extracellular recordings were made in the lateral and inferior vestibular nuclei of decerebrate, unanesthetized cats. The firing patterns of single units were studied using small amplitude sinusoidal roll tilts of from 0.01 Hz to 1.0 Hz. Three-fourths of the tilt-sensitive units showed greater modulation of their firing rates as the frequency of the sinusoidal tilt was increased. The responses of cells in both nuclei were similar. These responses were virtually unchanged in cats with chronically plugged semicircular canals, indicating a probable otolith origin for the dynamics of the tilt response.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237380
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  • 21
    Electronic Resource
    Electronic Resource
    Somatosensory cortical involvement in responses to noxious stimulation in the cat (1974)
    Springer
    Experimental brain research 20 (1974), S. 363-374 
    Details
    ISSN: 1432-1106
    Keywords: Pain ; Somatosensation ; Cerebral cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The experiment examines the role of the cerebral cortex in regulating responses to noxious stimulation by studying the effects of cortical ablations in cats on escape from electric shock applied to the foot pads. The latency of escape as a function of shock intensity was measured before and after bilateral ablations of various portions of the cat's somatosensory cerebral cortex. Ablations of the second somatosensory cerebral cortex significantly increased the escape response threshold. If the sulci bordering this region were included in the ablation, the threshold increase was greater and longer-lasting. Ablations of the primary somatosensory cortex increased latencies at most intensities of electric shock, but did not change the response thresholds. Ablations of both primary and second somatosensory cortex increased response thresholds and response latencies. None of these ablations altered the responses, however, if the cat had been overtrained for six to seven months prior to surgery. The results suggest that the second somatosensory region and the sulci bordering the second somatosensory region in the cat cerebral cortex are involved in responses to noxious stimulation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237381
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  • 22
    Electronic Resource
    Electronic Resource
    An intracellular study of neuronal organization in the visual cortex (1974)
    Springer
    Experimental brain research 21 (1974), S. 45-66 
    Details
    ISSN: 1432-1106
    Keywords: Visual cortex ; Efferent cells ; Non-efferent cells ; Synaptic connection ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neuronal connections in the visual cortex of cat (areas 17 and 18) were studied with intracellular recording and electrical stimulation techniques under Nembutal anaesthesia. Four types of axonal projection were seen; 1. association efferent cells projecting to adjacent cerebral cortex on the ipsilateral side, 2. commissural efferent cells to visual cortex on the contralateral side, 3. corticofugal efferent cells to the ipsilateral lateral geniculate body and superior colliculus, and 4. non-efferent cells whose projection is confined within the visual cortex. Both association and commissural efferent cells were located in layer III, corticofugal efferent cells in layer V and non-efferent cells in layers II–VI. Upon these cells two types of synaptic actions were exerted by the specific visual afferents that originate from the lateral geniculate body; 1. type I, monosynaptic excitation plus disynaptic inhibition and 2. type II, disynaptic excitation plus trisynaptic inhibition. Type I effects were found in layers III–V, and type II in layers II and VI. In the border region between areas 17 and 18 monosynaptic excitation and disynaptic inhibition were produced also by the commissural efferents originating from the contralateral visual cortex. On the basis of these results, a possible neuronal circuitry in the visual cortex is postulated.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00234257
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  • 23
    Electronic Resource
    Electronic Resource
    The lateral reticular nucleus in the cat III. Organization of component activated from ipsilateral forelimb tract (1974)
    Springer
    Experimental brain research 21 (1974), S. 501-513 
    Details
    ISSN: 1432-1106
    Keywords: Lateral reticular nucleus ; Spinoreticular tract ; Cerebellum ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. The activation of neurones in the mLRN (major portion of lateral reticular nucleus comprising its parvi- and magnocellular parts) by two spinal tracts ascending through the ventral part of the lateral funiculus has been studied by recording from 277 neurones of which 187 could be antidromically activated by stimulation of the cerebellar surface. Forty-eight % of the neurones were activated by the bVFRT and described in a previous paper (Clendenin et al., 1975b) and 12% were activated by a previously unknown tract denoted the ipsilateral forelimb (iF) tract and described in the present paper. 2. The iF-tract is activated by stimulation of nerves in the ipsilateral forelimb only. The response consists of a train of impulses with a high initial frequency and an almost constant latency. Cutaneous afferents and high threshold muscle afferents contribute to the excitation which is mediated by interneurones. 3. The responses to stimulation of peripheral receptors were weak and difficult to classify. 4. The iF-tract activates neurones in the dorsolateral portion of the magnocellular part of the mLRN which projects to the ipsilateral pars intermedia of the anterior lobe and the ipsilateral paramedian lobule. 5. The possible information carried by the iF-tract is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237168
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  • 24
    Electronic Resource
    Electronic Resource
    On the origin of the corticotectal projections in the cat (1974)
    Springer
    Experimental brain research 21 (1974), S. 433-439 
    Details
    ISSN: 1432-1106
    Keywords: Superior colliculus ; Visual cortex ; Layer V-pyramids ; Clare Bishop area ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Stereotaxic injection of horseradish peroxidase into the superior colliculus produced retrograde labelling of layer V pyramides in the Clare Bishop area and the lateral bank of the suprasylvian sulcus, in area 17,18 and 19. Single labelled cells were also found scattered in the splenial, the suprasplenial, the lateral and the suprasylvian gyri. In the cruciate sulcus no labelled cells were observed. Autoradiographically, the lateral bank of the suprasylvian sulcus was also shown to give rise to fibres to the superior colliculus.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237905
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  • 25
    Electronic Resource
    Electronic Resource
    The lateral reticular nucleus in the cat II. Organization of component activated from bilateral ventral flexor reflex tract (bVFRT) (1974)
    Springer
    Experimental brain research 21 (1974), S. 487-500 
    Details
    ISSN: 1432-1106
    Keywords: Lateral reticular nucleus ; Bilateral ventral flexor reflex tract (bVFRT) ; Spino-reticulo-cerebellar path ; Cerebellum ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. Neurones in the lateral reticular nucleus (LRN) activated by the bilateral ventral flexor reflex tract (bVFRT-LRN neurones) were identified by their responses to stimulation of fibres descending in the contralateral ventral quadrant of the spinal cord which activate the bVFRT neurones monosynaptically. 2. Eighty-eight of the 134 bVFRT-LRN neurones encountered could be antidromically activated at a low stimulus strength from small areas of the cerebellar surface assumed to represent cortical termination points. 3. The bVFRT-LRN neurones occurred throughout the parvi- and magnocellular parts of the LRN and terminated bilaterally in the anterior lobe and sparsely in the ipsilateral paramedian lobule and in the pyramis. 4. The responses evoked in the bVFRT-LRN neurones on stimulation of the contralateral ventral quadrant at C5 and L1 made it possible to estimate the approximate spinal level from which the bVFRT fibres originated. On this basis the bVFRT-LRN neurones were divided into cervical, thoracic, and lumbar groups receiving bVFRT afferents from mainly one spinal level and a convergence group receiving bVFRT afferents from several levels. 5. The different bVFRT-LRN groups received excitation from different combinations of nerves in the four limbs. 6. The cervical, thoracic and lumbar groups of the bVFRT-LRN neurones occurred in successively more ventrolateral portions of the LRN. 7. The cervical, thoracic and lumbar groups of the bVFRT-LRN neurones terminated in successively more rostral areas of the anterior lobe. 8. The organization of the bVFRT-LRN path is compared with that of the ventral and rostral spinocerebellar tracts. The possible function of the bVFRT-LRN path is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237167
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  • 26
    Electronic Resource
    Electronic Resource
    Effets de la stimulation des fibres et des mécanorécepteurs splanchniques sur l'activité unitaire du cortex somesthésique (1974)
    Springer
    Pflügers Archiv 348 (1974), S. 127-137 
    Details
    ISSN: 1432-2013
    Keywords: Splanchnic Afferents ; G.I. and Peritoneal Receptors ; Cortical Projections ; Microelectrode Technique ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The experiments were performed on cats anesthetized with chloralose or Nembutal. The unitary activity of cortical neurons was recorded in the SI and SII areas by means of extracellular glass microelectrodes. The neurons showed frequently a spontaneous discharge (irregular or regular tonic discharge bursts of spikes). The electrical stimulation of contralateral splanchnic nerves produced different effects on a great number of the neurons: 1. early short activation, 2. late activation, 3. early and late complex activation, 4. partial or total inhibition of the spontaneous activity. These effects were obtained in the different cortical layers. Similar results have been observed by mechanical stimulation of the splanchnic receptors located in the gastro-intestinal tract and in the peritoneum. However in this case, the duration and the amplitude of inhibition and activation were generally weaker.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00586475
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  • 27
    Electronic Resource
    Electronic Resource
    Junctions in the central nervous system of the cat (1974)
    Springer
    Cell & tissue research 148 (1974), S. 577-586 
    Details
    ISSN: 1432-0878
    Keywords: Node of Ranvier ; Axonal-glial junctions ; Cat ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The paranodal zone of myelinated nerve fibers from the CNS of cats has been studied by means of the lanthanum technique and after freeze-etching. Special interest was given to the axonal-glial zones of contact in this region. Examination of the membranes of the paranodal pockets and the axolemma revealed that the membrane thickenings which occur between the adjacent membranes actually consist of bands. The bands show a specific pattern of diagonal running subunits 10 nm apart. These substructures of the axonal side of the membrane contacts protrude outwards, i.e. towards the glial membrane, where they fit into depressions on the glial membrane surface. This arrangement in form of a “zip-fastener” makes the whole structure very flexible. The subdivision of the bands was identified with both techniques. The different membrane aspects obtained by the freeze-etching technique are discussed in respect to the splitting theory, and a hypothetical model of this membrane specialization is presented.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00221941
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  • 28
    Electronic Resource
    Electronic Resource
    Electron microscopic investigation of synaptic organization of the trochlear nucleus in cat (1974)
    Springer
    Cell & tissue research 150 (1974), S. 409-423 
    Details
    ISSN: 1432-0878
    Keywords: Synaptic organization ; Trochlear nucleus ; Cat ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Two distinct types of neuron in the cat trochlear nucleus (one large, one small) are described, the α- and γ-motoneurons, respectively. Four types of terminals are observed which establish axo-dendritic synapses. Two of them (Types I and II) perform axo-somatic synapses as well. Terminals en passant (Types I and II) are predominant. The Type I terminal is long and slender with a characteristic distribution of the axoplasmic organelles and the unique feature of a relative narrowing of the synaptic cleft as compared to the width of the neighboring extracellular space. Its vesicle population is pleomorphic and a conspicuous glial barrier surrounds the synaptic zones. The Type II terminal differs slightly from Type I, revealing a wider synaptic cleft and lacking a characteristic distribution of the axoplasmic organelles. The type III terminal is rarely observed performing axo-somatic synapses, but is a common finding in the neuropil. Post-junctional dense bodies are often present in its axodendritic synapses. The Type IV nerve terminal performs axo-dendritic synapses and is characterized by a rich content of large granulated vesicles. Axo-axonal synapses are observed only very rarely. The synaptic organization of the feline trochlear nucleus is compared with the synaptic morphology of the oculomotor nuclei of inframammalian species (Waxman and Pappas, 1971). In addition to certain similarities (e.g., richness of synapses en passant), significant differences are encountered: the present study provides no morphological evidence for electrotonic transmission in the trochlear nucleus of cat.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00220147
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  • 29
    Electronic Resource
    Electronic Resource
    Some observations on the ultrastructure of the central amygdaloid nucleus in the cat (1974)
    Springer
    Cell & tissue research 151 (1974), S. 489-498 
    Details
    ISSN: 1432-0878
    Keywords: Limbic system ; Cat ; Amygdaloid body ; Light and electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The present study was undertaken to re-examine the central nucleus of the cat in Nissl stained sections, to describe its fine structural characteristics, and to compare the lateral subdivision of this nucleus with the putamen. In Nissl preparations, it was observed that the lateral subdivision of the central nucleus contains a fairly homogeneous population of small cells while the putamen contains both small and large cells. It is the presence of a few large cells at the lateral periphery of the lateral part of the central nucleus that makes the boundary between the two nuclei indistinct. Examination of the fine structure of the medial and lateral subdivisions of the central nucleus revealed the presence of many boutons containing flattened vesicles and fewer with spheroid vesicles. In contrast, most of the boutons in the putamen have spheroid vesicles. It is concluded that the lateral subdivision of the central nucleus may be distinguished from the putamen, except at its most lateral border, by its homogeneous population of small cells and its many boutons containing flattened vesicles.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00222994
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  • 30
    Electronic Resource
    Electronic Resource
    Junctions in the central nervous system of the cat (1974)
    Springer
    Cell & tissue research 149 (1974), S. 121-135 
    Details
    ISSN: 1432-0878
    Keywords: Astrocytic membranes ; Cat ; Orthogonal particle-complexes ; Freeze-etching
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Fixed and unfixed astrocytic membranes from the CNS of the cat were studied by means of the freeze-etching technique. A variable number of gap junctions was detected in astrocytic membranes. They are characterized by the well known hexagonal composition of their subunits. Besides this type of highly ordered membrane-bound particles, a second one was found. It is composed of four single particles (diameter 5 nm) which form an orthogonal subunit with a side length of about 10 nm. These membrane-associated orthogonal particle complexes (MOPC) could be observed in different stages of aggregation and expansion. They reveal an accumulation in membranes of the marginal glia layers and in the perivascular astrocytic end-feet. Unfixed, glycerol treated membranes, however, do not show these structures. After glycerol treatment of the unfixed membranes by immersion, the MOPC disintegrate to single particles which form clusters of various extension. The clustering phenomenon is dependent on the length of the time of exposure to glycerol. Shortening of the glycerol treatment by intravasal perfusion of the cryoprotectant agent causes an decrease of the clusters. Fragments and transient forms of the MOPC become visible. By variation of different physico-chemical parameters of the washing solution a similar effect on the MOPC was not achieved. The discussion deals with probable functional aspects of the MOPC. They are considered to act as membrane-bound functional multienzyme complexes which a) might play a role in mediating transmembrane passage of metabolites, or b) are essential for CSF control mechanisms, or c) have a functional relation to the nexus.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00209055
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  • 31
    Electronic Resource
    Electronic Resource
    Nerve endings in the arteria centralis retinae (1974)
    Springer
    Cell & tissue research 150 (1974), S. 143-145 
    Details
    ISSN: 1432-0878
    Keywords: Arteria centralis retinae ; Cat ; Innervation ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Terminal axons emerging from the inner plexiform layer of the cat retina reach the wall of the arteria centralis retinae, as revealed by electron microscopy. Numerous unusually large dense core vesicles (about 1000 Å in diameter), of different electron densities, occur in the varicosities of these axons. These observations may be compatible with the idea of an innervation of the central artery of the retina which is non-autonomic, possibly intrinsic in nature.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00220387
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  • 32
    Electronic Resource
    Electronic Resource
    Junctions in the central nervous system of the cat (1974)
    Springer
    Cell & tissue research 148 (1974), S. 565-576 
    Details
    ISSN: 1432-0878
    Keywords: Central myelin ; Junctions ; Cat ; Freeze-etching ; Lanthanum impregnation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In male and female cats central myelin was studied using the freeze-etching technique, and after impregnation with lanthanum as a tracer. The freeze-fractured and etched faces of the myelin reveal membrane formations which in many respects resemble tight junctions. The formations consist of parallel rows of particles on one half of the membranes matched by corresponding furrows on the other membrane half. These structures occur across the width of the myelin sheath and are most common in that part of the myelin underlying the external cytoplasmic loop. They are interpreted as correlates of the radial component of the i-line which occurs in cross-sections of central myelin after potassium permanganate staining. In the paranodal zone the lanthanum-impregnated myelin displays punctate fusions between the outer leaflets of the oligodendrocytic membranes. These findings strongly suggest that tight junctions are a common feature in the central myelin. The arrangement of the membrane fusion in relation to the elements of the lamellar complex and their functional significance is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00221940
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  • 33
    Electronic Resource
    Electronic Resource
    Hypothalamic projections to the amygdala in the cat (1974)
    Springer
    Cell & tissue research 151 (1974), S. 499-508 
    Details
    ISSN: 1432-0878
    Keywords: Limbic system ; Cat ; Amygdaloid body ; Hypothalamus ; Stereotaxic lesions ; Light and electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In order to determine the origin of the hypothalamo-amygdaloid connections in the cat, small lesions were placed at various rostro-caudal levels of the hypothalamus. The animals were sacrificed after a period of 4, 8 or 11 days and the brains stained with the Nauta (1957), Fink and Heimer (1967) or Wiitanen (1969) method for the demonstration of degenerating axons and their terminals. It was observed that the anterior hypothalamic nucleus sends a small projection to the medial subdivision of the central nucleus and to the basal and lateral nuclei of the amygdala. The lateral preoptic area sends a larger projection to the anterior amygdaloid area, both subdivisions of the central and basal nuclei, and to the lateral and medial nuclei. No degeneration was observed in the amygdala following lesions in the medial preoptic area, the ventromedial nucleus or the lateral hypothalamic area caudal to the anterior hypothalamic area. In a series of animals with lateral preoptic lesions, the site of termination of degenerating boutons on neurons of the amygdaloid nuclei was determined and the course of the degenerative process followed over a period ranging from 2 to 15 days. Many of the boutons, especially in the earlier stages of degeneration, appeared to be of the B3 type, containing flattened vesicles and forming symmetrical synaptic contacts with dendrites or somata. With longer post-operative survival times, however, they became increasingly electron dense and shrunken, so that the bouton type could not be determined.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00222995
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  • 34
    Electronic Resource
    Electronic Resource
    Photoelektronenspektren und Moleküleigenschaften, XXVI. Die Delokalisation von Schwefel-Elektronenpaaren in Alkylsulfiden und -disulfiden (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 68-77 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoelectron Spectra and Molecular Properties, XXVI. The Delocalisation of Sulfur Electron Pairs in Sulfides and DisulfidesThe photoelectron (PE) spectra of sulfides R—S—R (R=H, CH3, C2H5, n- und i-C3H7, n- and tert-C4H9) and disulfides R—S—S—R (R=H, CH3, C2H5, n- and i-C3H7, tert-C4H9, —[CH2]4—) are comparatively discussed. For sulfides the first ionization energy, which decreases as expected with increasing degree of alkylation, can also be obtained from the charge transfer excitation energies of their σ-complexes with tetracyanoethylene (TCNE). Disulfides show a splitting of the first PE-band in a clear dependence on the dihedral angle of the sulfur electron pairs. All observations can be rationalised within MO models as interactions of the sulfur electron pairs with the σ-skeleton and/or with each other.
    Notes: Die Photoelektronen(PE)-Spektren von Sulfiden R—S—R (R=H, CH3, C2H5, n- und i-C3H7, n- und tert-C4H9) und Disulfiden R—S—S—R (R=H, CH3, C2H5, n- und i-C3H7, tert-C4H9, —[CH2]4—) werden vergleichend diskutiert. Bei den Sulfiden R—S—R kann die mit steigendem Alkylierungsgrad erwartungsgemäß abnehmende erste Ionisierungsenergie auch aus den Charge-transfer-Anregungsenergien ihrer σ-Komplexe mit Tetracyanäthylen (TCNE) abgelesen werden. Bei Disulfiden R—S—S—S—R wird eine Aufspaltung der ersten PE-Bande in deutlicher Abhängigkeit vom Diederwinkel zwischen den Schwefel-Elektronen-paaren beobachtet. Die Befunde lassen sich mit MO-Modellen als Wechselwirkungen der Schwefel-Elektronenpaare mit dem σ-Gerüst und/oder untereinander verstehen.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070109
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  • 35
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    Electronic Resource
    Ylid-Komplexe von Nickel-alkylen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 93-101 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nickelalkyl Ylid ComplexesFrom reactions of [(CH3)3P]3 Ni(CH3)2 and [(CH3)3P]2Ni(CH3)Cl with the ylid (CH3)3PCH2, molecular (1) an ionic complexes (2) are obtained, containing three covalent Ni—C-σ-bonds of square planar nickel atoms. These bonds are strongly stabilized by the proximity of the ylid onium center. Excess ylid converts 2 into a binuclear complex 3, where the metal atoms are bridged by dimethylphosphonium-bismethylid units, with formation of [(CH3)4P]Cl as a byproduct. An isoelectronic dimethylphosphinate complex, 4, containing a similar eight-membered ring structure, has also been prepared.
    Notes: Durch die Reaktion von Dimethyltris(trimethylphosphin)nickel und Methylbis(trimethyl-phosphin)nickel-chlorid mit Trimethylmethylenphosphoran werden molekulare (1) bzw. ionische (2) Ylid-Komplexe erhalten, in denen das quadratisch-planar konfigurierte Nickel-atom jeweils drei kovalente Ni—C-σ-Bindungen ausbildet. Diese Bindungen werden durch das Onium-Zentrum der Ylide erheblich stabilisiert. 2 liefert mit überschüssigem Ylid unter Abspaltung von [(CH3)4P]Cl einen zweikernigen Komplex 3, dessen Metallatome durch Dimethylphosphonium-bis-methylid-Brücken verbunden sind. Hierzu existiert ein isoelektronischer Dimethylphosphinat-Komplex 4, der ebenfalls Achtringstruktur besitzt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070111
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  • 36
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    Electronic Resource
    Reaktionen carbonyl-stabilisierter Sulfonium-ylide des 1,3-Dithiolans mit Acylierungsmitteln und aktivierten Acetylenen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 123-127 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of carbonyl-stabilized Sulfonium-ylides of 1,3-Dithiolane with Acylating Reagents and Activated AcetylenesIn aqueous sodium hydroxide monophenacyl-1,3-dithiolanium bromides 3 form carbonylstabilized 1,3-dithiolanium-1-phenacylides 4. These yield with acylation reagents and activated acetylenes new resonance-stabilized sulfonium-ylides 6, 8, 10.
    Notes: Monophenacyl-1,3-dithiolanium-bromide 3 bilden in wäßriger Natronaluge carbonyl-stabilisierte 1,3-Dithiolanium-1-phenacylide 4. Diese reagieren mit Acylierungsmitteln und aktivierten Acetylenen zu neuen mesomeriestabilisierten Sulfonium-yliden 6, 8, 10.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070115
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  • 37
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    Über Aminosäuren und Peptide, IX. Über Pyruvoylaminosäuren (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 145-151 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Amino Acids and Peptides, IX. On Pyruvoyl Amino AcidsAmino acid derivatives were tranformed to Pyruvoyl amino acid derivatives by use of pyruvoyl chlorid, p-nitrophenyl pyruvate, hydroxymaleic anhydride and the DCC-procedure. The application range of the different acylations is discussed. A convenient method for the preparation of pyruvoyl chloride is given.
    Notes: Aminosäurederivate werden mit Brenztraubensäurechlorid, Brenztraubensäure-p-nitrophenylester, Hydroxymaleinsäureanhydrid und mit Hilfe des DCC-Verfahrens zu Pyruvoylaminosäurederivaten umgesetzt. Die Anwendungsbreite der verschiedenen Acylierungen wird verglichen. Ein Weg zur praktischen Herstellung von Brenztraubensäurechlorid wird ausgearbeitet.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070118
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  • 38
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    Kristall- und Molekülstruktur von Hexakis(phenylthio)äthan (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 253-262 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of Hexakis(phenylthio)ethaneThe structure of hexakis(phenylthio)ethane has been determined by single crystal X-ray diffraction. The phase determination was carried out by means of the Symbolic Addition Method. The structure has been refined with 1780 observed reflections to an R-value of 10.9%. The pseudo bodycentered unit cell contains two molecules, which are situated at the center at 0, 0, 0 and 1/2, 1/2, 1/2, respectively. The bodycentering is almost perfect for the six sulfur atoms, but does not involve the central ethane bonding, which implies that the sulfur atoms, that are connected by the centering, are bonded to different carbon atoms. The six sulfur atoms are staggered around the ethane C—C bond. The S—C—S angles of 113° are larger than the ideal tetrahedrane angles by the same amount by which the S—C—C angles of 105° are smaller. The ethane C—C distances are 1.59 and 1.56 Å respectively.
    Notes: Die Struktur des Hexakis(phenylthio)äthans wurde mit Röntgenmethoden bestimmt. Die Phasenbestimmung wurde mit der symbolischen Additionsmethode durchgeführt. Die Struktur wurde unter Benutzung von 1780 beobachteten Reflexen bis auf einen R-Wert von 10.9% verfeinert. Die pseudoinnenzentrierte Elementarzelle enthält zwei Moleküle, die um die Symmetriezentren in 0, 0, 0 bzw. 1/2, 1/2, 1/2 gelagert sind. Die Innenzentrierung ist nahezu genau für die sechs Schwefelatome, aber gilt nicht für die zentrale Äthanbindung, was zur Folge hat, daß die durch Zentrierung verbundenen Schwefelatome an verschiedene Kohlenstoffatome gebunden sind. Die sechs Schwefelatome sind gestaffelt um die Äthan-C—C-Bindung angeordnet. Die S—C—S-Winkel sind mit 113° etwas größer, die S—C—C-Winkel mit 105° um denselben Betrag kleiner als der Tetraederwinkel. Die Äthan-C—C-Abstände betragen 1.59 bzw. 1.56 Å.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070131
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  • 39
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    Benzothiazol-N-oxide, II. Über eine neue Synthese substituierter 2-Benzothiazolone (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 305-316 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Benzothiazole N-Oxides, II. New Synthesis of Substituted 2-BenzothiazolonesIn the presence of phosphoryl chloride, 2-carbamoylbenzothiazole N-oxides undergo a new intramolecular redox reaction to give 2-benzothiazolones. In two cases investigated, also 2-ethoxycarbonylbenzothiazole N-oxides undergo this rearrangement. The spectroscopic data are discussed.
    Notes: 2-Carbamoylbenzothiazol-N-oxide gehen in Gegenwart von Phosphoroxychlorid eine neuartige intramolekulare Redoxreaktion unter Bildung von 2-Benzothiazolonen ein. In zwei untersuchten Fällen unterliegen unterliegen auch 2-Äthoxycarbonylbenzothiazol-N-oxide dieser Umlagerung. Spektroskopische Daten werden diskutiert.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070136
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  • 40
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    Aromatische Sulfenylchloride, IX. Herstellung, Oxidation und spektroskopische Untersuchung von 1-substituierten (5-Tetrazolyl)aryldisulfiden (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 299-304 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aromatic Sulfenyl Chlorides, IX. Preparation, Oxidation, and Spectroscopic Investigation of 1-Substituted 5-Tetrazolyl Aryl Disulfides1-Substituted 5-tetrazolyl mesityl disulfides were synthesized which on oxidation with hydrogen peroxide gave disulfide S2, S2-dioxides (thiolsulfonates). The structure of these as well as that of the 1-substituted 5-tetrazolyl p-tolyl disulfide S2, S2-dioxides synthesized earlier was elucidated by means of their i. r. and n. m. r. spectra. The supposed structures have been established by synthesis.
    Notes: Es wurden 1-substituierte (5-Tetrazolyl)mesityldisulfide hergestellt, welche zu Disulfid-S2, S2-dioxiden (Thiosulfonate) oxidiert wurden. Deren Struktur und die der früher hergestellten 1-substituierten (5-Tetrazolyl)p-tolyldisulfid-S2, S2-dioxide wurde anhand ihrer IR- und NMR-Spektren wahrscheinlich gemacht. Die angenommenen Strukturen wurden durch Synthese bewiesen.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070135
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  • 41
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    Lithio-1,3,5-trithiane Erzeugung, Umsetzung mit Elektrophilen und Verwendung als nucleophile Acylierungsmittel (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 367-379 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Lithio-1,3,5-trithianes Generation in Solution, Reactions with Electrophiles, and Use in Nucleophilic Acylation1,3,5-Trithiane and 2-mono- as well as 2,4,6-trisubstituted trithianes are shown to be metallated by n-butyllithium in THF. Reaction of the lithio derivatives thus obtained with electrophiles leads to more highly substituted trithianes which in some cases can be isolated in a pure form. The n.m.r. spectra of the products at room temperature are described. Mercury(II)-assisted solvolysis of alkyltrithianes „liberates“ the most highly substituted carbon with formation of carbonyl compounds or their O-acetals. This completes a sequence of reactions which suggests use of lithiotrithianes as reagents for nucleophilic acylation. Advantages and disadvantages of this procedure compared to the dithiane method are discussed.
    Notes: 1,3,5-Trithian selbst sowie 2-mono- und 2,4,6- trisubstituierte Trithiane lassen sich mit n-Butyllithium in Tetrahydrofuran metallieren. Umsetzung der Lithiumderivate mit Elektrophilen führt zu höher substituierten Trithianen, die teilweise in reiner Form isoliert werden können. Die NMR-Spektren der erhaltenen Produkte bei Raumtemperatur werden beschrieben. Quecksilber(II)-assistierte Solvolyse von alkylierten Trithianen führt zu Carbonyl-verbindungen oder deren O-Acetalen unter „Herauslösung“ des höchstsubstituierten C-Atoms, was die Verwendung von Lithiotrithianen als nucleophile Acylierungsmittel ermöglicht. Vor- und Nachteile gegenüber der Dithian-Methode werden diskutiert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070202
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    Electronic Resource
    Über die Abhängigkeit der Bindungslängen in einigen N,O-Dibenzoylhydroxylaminen von der Verdrillung der Carboxyl- und Hydroxamsäuregruppen gegen die Benzolkerne Die Kristallstrukturen von N,O-Dibenzoyl-(C14H11NO3), N,O-Bis(2- chlorbenzoyl)-(C14H9Cl2NO3), N-Benzoyl-O-p-toluoyl- (C15H13NO3) und N-Benzoyl-O-o-toluoylhydroxylamin (C15H13NO3) (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 398-413 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Dependence of the Bond-length in some N,O-Dibenzoylhydroxylamines on the Torsion of the Carboxylic and Hydroxamic Groups against the Benzene Nuclei. The Crystal Structures of N,O-Dibenzoyl-(C14H11NO3), N,O-Bis(2-chlorobenzoyl)-(C14H9Cl2NO3), N-BenzoylO-p-toluoyl- (C15H13NO3), and N-Benzoyl-O-o-toluoylhydroxylamines (C15H13NO3)The crystal structures of four N,O- dibenzoylhydroxylamines - 1: N,O-dibenzoylhydroxylamine (C14H11NO3), 2: N,O- bis(2-chlorobenzoyl)hydroxylamine (C14H9Cl2NO3), 3: N-Benzoyl-O-p toluoylhydroxylamine (C15H13NO3), 4: N-benzoyl-O-o- toluoylhydroxylamine (C15H13NO3) - have been determined by X-ray techniques, using direct methods for phase determination. The torsion angles ϕ of the C—C- bonds between the phenyl groups and the hydroxamic acid groups or the carboxylic groups, respectively, have been calculated. The values of the intramolecular distances of these bonds, plotted versus cos2 ϕ, can be approximated by a straight line. Extrapolating to ϕ = 90°, the pure sp2-sp2-C—C-single-bond is found to be 1.513 Å.
    Notes: Die Kristallstrukturen von vier N,O- Dibenzoylhydroxylaminen - 1: N,O-Dibenzoylhydroxylamin (C14H11NO3), 2: N,O -Bis(2-chlorbenzoyl)hyroxylamin (C14H9Cl2NO3), 3: N-Benzoyl-O-p-toluoylhydroxylamin (C15H13NO3), 4: N- Benzoyl-O-o-toluoylhydroxylamin (C15H13NO3) - wurden röntgenographisch unter Anwendung direkter Methoden zur Lösung des Phasenproblems bestimmt. Die C—C- Bindungslängen zwischen den Phenylgruppen einerseits und den Hydroxamsäure- bzw. Carboxylatgruppen andererseits lassen sich als Funktion der Verdrillungswinkel ϕ dieser Bindung durch eine Gerade darstellen, wenn man die Bindungslängen gegen cos2 ϕ aufträgt. Der reine sp2-sp2-C—C- Einfachbindungsabstand (ϕ = 90°) ist danach 1.513 Å.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070205
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  • 43
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    Eine neue Synthese für Tetracyclo[3.3.0.02,8.04,6]octan-3-one durch intramolekulare [2π + 2 σ]-Thermocycloaddition (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 680-685 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Synthesis of Tetracyclo[3.3.0.02.8.04.6]octan-3-ones by Intramolecular Thermal [2π + 2σ]-CycloadditionThe synthesis of the tetracyclooctanone 19 by thermolysis of the tricyclic acetal 15 and subsequent removal of the acetal group is described. Thus, a third synthetic access to this system is now available. The reaction involves the cycloaddition of a thermally ring-opened cyclopropane to a double bond.
    Notes: Die Synthese des Tetracyclooctanons 19 durch Thermolyse des tricyclischen Acetals 15 und anschließende Entacetalisierung wird beschrieben. Damit bietet sich ein dritter synthetischer Zugang zu diesem System an. Die Reaktion beinhaltet die Cycloaddition eines thermisch ringgeöffneten Cyclopropans an eine Doppelbindung.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070240
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  • 44
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    Notiz zur Alkylierung des Dithizons (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 717-720 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070247
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  • 45
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    Notiz zur thermischen Valenzisomerisierung des Norpinens (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 731-734 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070251
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  • 46
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    Pteridine, LX. Synthese und Oxidationsverhalten von 7,8-Dihydroxanthopterinen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 785-795 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pteridines, LX. Synthesis and Autoxidation of 7, 8-DihydroxanthopterinsThe synthesis of 7,8-dihydroxanthopterin (18) and of various N- and C-methyl derivatives (19-27, 30) is described. Their pKa values and u.v. spectra have been determined and the behaviour during autoxidation has been investigated. The monoanions are subject to autoxidation which is catalysed strongly by ammonia and primary amines. A mechanism for the autoxidation is discussed in which the existence of various intermediates is based on the oxidative behaviour of differently blocked N- und C-methyl derivatives.
    Notes: Die Synthese des 7,8-Dihydroxanthopterins (18) und verschiedener N- und C-Methyl-Derivate (19-27, 30) wird beschrieben. Ihre pKa-Werte und UV-Spektren werden bestimmt und ihr Autoxidationsverhalten untersucht. Die Monoanionen unterliegen der Autoxidation, welche durch Ammoniak und primäre Amine stark katalysiert wird. Ein Mechanismus wird diskutiert und verschiedene Zwischenprodukte anhand von blockierten N- und C-Methyl-Derivaten wahrscheinlich gemacht.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070305
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  • 47
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    Die Kristall- und Molekülstruktur des 6,6-Bis(dimethylamino)fulvens (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 832-837 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of 6,6-Bis(dimethylamino)fulvene6,6-Bis(dimethylamino)fulvene crystallizes in the space group Pn21a, the lattice constants being ao = 13.344 Å, bo = 7.844 Å and co = 9.438 Å. The structure has been solved by superposition and by direct methods in the space group Pnma. The structure was refined by block-diagonal-least-squares to R = 0.037.
    Notes: Das 6,6-Bis(dimethylamino)fulven kristallisiert in der Raumgruppe Pn21a mit den Gitter-konstanten ao = 13.344 Å, bo = 7.844 Å und co = 9.438 Å. Die Struktur wurde durch Superposition und anschließende Resymmetrisierung der Patterson-Funktion und mit direkten Methoden in der zentrosymmetrischen Obergruppe Pnma gelöst.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070309
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  • 48
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    Brom-Lithium-Austausch an Vinyl- und Aryl-bromiden mit tert-Butyllithium Zur Ringerweiterung über Dibromcarbenaddukte (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 847-853 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bromine/Lithium Exchange in Vinyl and Aryl Bromides with tert-Butyl Lithium. On the Ring Enlargement via Dibromocarbene AdductsTwofold molar excess of tert-butyl lithium replaces vinylic and arylic bromine by lithium. The tert-butyl bromide formed is dehydrohalogenated rapidly to isobutene by tert-butyl lithium even at very low temperatures. Transformation of 1-bromo-1-cyclooctene and - cyclononene via the lithium derivatives to vinyl thioethers 1d, e, and i in high yields opens up a simple alternative route from olefin dibromocarbene adducts to ring enlarged ketones. The bromobenzenes 2a and 3a reveal that the Br/Li-exchange described here is not accompanied by arine formation; it is feasible even in the presence of sensitive benzylic CH2-groups as present in 3.
    Notes: Vinylisch und an Aromaten gebundenes Brom läßt sich quantitativ mit zweifachem molarem Überschuß an tert-Butyllithium gegen Lithium austauschen. Das entstehende tert-Butylbromid wird selbst bei tiefen Temperaturen von tert-Butyllithium rasch zu Isobuten dehydrohalogeniert. Die Überführung von 1-Brom-1-cycloocten und -1-cycloneone in Vinylthioäther 1d, e und i über die Lithiumderivate ist in hoher Ausbeute möglich und eröffnet einen einfachen Weg von Dibromcarbenaddukten an Olefine zu ringerweiterten Ketonen. Am Beispiel der Brombenzole 2a und 3a wird gezeigt, daß der hier beschriebene Br/Li-Austausch nicht von Arin-Bildung begleitet und auch in Gegenwart der empfindlichen benzylischen CH2-Gruppe von 3 durchführbar ist.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070311
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  • 49
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    Über N-Vinylimidazolcarbonsäureester (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 892-897 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N-VinylimidazolecarboxylatesN-Vinylation of imidazolecarboxylates with vinyl acetate leads to the formation of the N-vinylimidazoles 3a, 3b, 6, 8a, 8b und 9a. The structures are determined by mass and n.m.r. spectra. 3a, 6, 8a are polymerizable.
    Notes: Durch N-Vinylierung von Imidazolcarbonsäureestern mit Vinylacetat werden die N-Vinylimidazole 3a, 3b, 6, 8a, 8b und 9a, erhalten. Die Strukturen werden mit Hilfe von NMR-und Massen-Spektren gesichert. 3a, 6, 8a und 8bsing polymerisationsfähig.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19741070316
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    Heterocyclisierungen, XIII. Neue polycyclische Pyrimidine mit Brückenkop-Stickstoff (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 929-936 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclizations, XIII. New Polycyclic Pyrimidines with Bridge-Head NitrogenThe base-catalized condensation of 2,3,3-trimethyl-3H-benz[f]indole (9) with dielectrophilic iso(thio)cyanates to polycyclic pyrimidines with bridge-head nitrogen (11, 15, 16) in most cases involves preliminary formation of 1: 2 adducts followed by elimination of diacylamides. Contrary to this the less nucleophilic 2,3,3-trimethyl-3H-pyrrolo [2,3-b]pyridine (20) affords the analogue pyrimidines by intermediacy of 1:1 adducts and elimination of water or ethanol solely.
    Notes: Die basenkatalysierte Kondensation von 2,3,3-Trimethyl-3H-benz[f] indol (9) mit dielektrophilen Iso(thio)cyanaten zu polycyclischen Pyrimidinen mit Brückenkopf-Stickstoff (11, 15, 16) verläft meist über die Bildung von 1:2-Addukten als Zwischenstufe und Eliminierung von Diacylamiden. Dagegen liefert das weniger nucleophile 2,3,3-Trimethyl-3 H-pyrrolo[2.3-b]-pyridin (20) analoge Systeme (22, 23) ausschließlich über 1: 1-Addukte und Eliminierung von Wasser bzw. Äthanol.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070321
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    Alkaloide aus Rhamnaceen, XVIII. Amphiin-F, -G und -H, weitere Peptidalkaloide aus Ziziphus amphibia A. Cheval (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 686-697 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkaloids from Rhamnaceae, XVIII. Amphibine-F, -G and -H, further Peptide Alkaloids from Ziziphus amphibia A. Cheval.From the complex mixture of crude alkaloids from Ziziphus amphibia A. Cheval., in addition to the already described Amphibines-A, -B, -C, -D and -E, three further peptide alkaloids Amphibine-F, -G and -H have been isolated and their structures elucidated (1-3). Amphibine-F and -G (1, 2) belong to the class of cyclic peptide alkaloides having a fourteen-membered ring system made up from trans-3-hydroxyproline, p-hydroxystyrylamine and an α-aminoacid. Amphibine-H (3) has a thirteen-membered ring system formed from 5-hydroxy-2-methoxystyrylamine and the aminoacids trans-3-hydroxyproline and phenylalanine.
    Notes: Aus dem komplexen Rohbasengemisch von Ziziphus amphibia A. Cheval. wurden neben den bereits beschriebenen Amphibinen-A, -B, -C, -D und -E drei weitere Peptidalkaloide Amphibin-F, -G und -H isoliert und in der Struktur geklärt (1-3). Die Amphibine-F und -G (1, 2) zählen zu den Cyclopeptidalkaloiden mit 14 gliedrigem Ringsystem aus trans-3-Hydroxyprolin, p-Hydroxystyrylamin und einer α-Aminosäure. Das Amphibin-H (3) weist ein 13 gliedriges Ringsystem auf, das aus den Aminosäuren trans-3-Hydroxyprolin und Phenylatanin sowie aus 5-Hydroxy-2-methoxystyrylamin gebildet wird5).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070241
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  • 52
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    Über die Darstellung neuer Chlorformamidine (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 698-705 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Preparation of New ChloroformamidinesAction of phosphine/carbon tetrachloride or dichlorotriphenylphosphorane on N,N,N′-trisubstituted ureas leads to the formation of even such chloroformamidines which are not or only difficultly obtainable by the conventional methods. The spectroscopic and analytic data of the new compounds are given.
    Notes: Durch Einwirkung von Phosphin/Tetrachlorkohlenstoff oder von Dichlortriphenylphos-phoran auf N,N,N′-trisubstituierte Harnstoffe können auch solche Chlorformamidine dargestellt werden, die nach den bisherigen Methoden nicht oder nur schwer zugänglich sind. Die spektroskopischen und analytischen Daten der neuen Verbindungen sind angegeben.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070242
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  • 53
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    Notiz über eine verbesserte Methode zur spezifischen Freisetzung oder Acylierung primärer Hydroxylgruppen ausgehend von pertrimethylsilylierten Polyolen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 721-724 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070248
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  • 54
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    Notiz zur transanularen n/π-Wechselwirkung in 2,5-Dihydrofuran (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 725-726 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070249
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  • 55
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    Heterosubstituierte Fulvene, VIII. Indeno[2,1-c]-1,2-dithiole, eine Gruppe neuer Pseudoazulene (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 739-744 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Fulvenes, VIII. Indeno[2,1-c]-1,2-dithioles, a Group of New PseudoazulenesAcylation of 2-pyrrolidinoindene (4) with carboxylic acid chlorides and subsequent hydrolysis leads to the 1-acyl-2-indanones 6, which have been condensed with diacetyl disulfide in aequous perchloric acid/acetic acid to afford the 8H-indeno[2,1-c]-1,2-dithiolium-perchlorates 7. These are deprotonated with N-ethyldiisopropylamine to yield the indeno[2,1-c]-1,2-dithioles 10, a group of new pseudoazulenes.
    Notes: Acylierung von 2-Pyrrolidinoinden (4) mit Carbonsäurechloriden und nachfolgende Verseifung liefert die 1-Acyl-2-indanone 6, die mit Diacetyldisulfid in wäßriger Perchlorsäure, Eisessig zu den 8H-Indeno[2,1-c]-1,2-dithiolium-perchloraten 7 kondensieren. Letztere lassen sich durch N-Äthyldiisopropylamin zu den Indeno[2,1-c]-1,2-dithiolen 10, einer Gruppe neuer Pseudoazulene, deprotonieren.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070301
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  • 56
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    Stereochemie und reaktives Verhalten tetrahalogenierter 2,3-Diazabicyclo[3.2.0]hept-2-ene und Bicyclo[2.1.0]pentane (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 759-770 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereochemistry and Reactivity of Tetrahalogenated 2,3-Diazabicyclo[3.2.0]hept-2-enes and Bicyclo [2.1.0] pentanesThe addition of diazoalkanes to tetrahalogenated cyclobutenes 1-3 leads to 6,6,7,7-tetrahalo-2,3-diazabicyclo[3.2.0]hept-2-enes 4-8, the structure and stereochemistry of which are determined by means of n. m. r. spectroscopy. Thermal decomposition of 4, 5, and 8 in boiling toluene affords the tetrahalobicyclo[2.1.0]pentanes 9, 10, and 12 in good yields. Under the same conditions 7 decomposes in a stereospecific manner to form 11 and small amounts of 13. Sodium methoxide converts 9-11 into the cyclobutenes 14 and 15. Under the influence of sulfuric acid 10 forms the cyclobutenedione 16 or a mixture of cyclopentenones 18, 19 depending on the reaction conditions.
    Notes: Addition von Diazoalkanen an die tetrahalogenierten Cyclobutene 1-3, führt zu 6,6,7,7-Tetrahalogeno-2,3-diazabicyclo[3.2.0]hept-2-enen 4-8, deren Konstitution und Stereochemie auf NMR-spektroskopischem Weg ermittelt wurde. Durch thermische Zersetzung der Bicyclen 4,5 und 8 in siedendem Toluol erhält man in guten Ausbeuten Tetrahalogenobicyclo-[2.1.0]pentane 9,10 und 12. Unter gleichen Bedingungen entstehen aus 7 in stereospezifischer Reaktion 11 sowie geringe Mengen des Cyclobutens 13. Mittels Natriummethylat werden die Bicyclen 9-11 zu den Cyclobutenen 14, 15 abgebaut; unter dem Einfluß von konz. Schwefelsäure entsteht aus 10 je nach Reaktionsbedingungen das Cyclobutendion 16 bzw. ein Gemisch der Cyclopentenone 18 und 19.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070303
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  • 57
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    Ein Eintopfverfahren zur Überführung von Aldehyden in Nitrile (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1221-1227 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conversion of Aldehydes into Nitriles without Isolation of IntermediatesAldehydes are converted into nitriles without isolation of the intermediates by treating their oximes with carbodiimides in the presence of copper(II)ions and triethylamine. The entire process requires 3 hours at room temperature; it is unsuccessful if the oxime does not form or is consumed by competition reactions.
    Notes: Aldehyde können ohne Isolierung von Zwischenprodukten in Nitrile übergeführt werden, indem ihre Oxime in Gegenwart von Kupfer(II)-Ionen und Triäthylamin mit Hilfe von Carbodiimiden dehydratisiert werden. Der gesamte Prozeß erfordert bei Raumtemperatur durchweg 3 Stunden. Das Verfahren versagt, wenn die Oximbildung gestört ist oder das Oxim Konkurrenzreaktionen eingeht.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070418
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  • 58
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    Synthese und Reaktivität von Silicium-Übergangsmetallkomplexen, V. Die modifizierte Alkalisalz-Eliminierungsmethode  -  ein genereller Weg zu Komplexen mit Silicium-Übergangsmetall-Struktureinheiten (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 979-995 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Reactivity of Silicon Transition Metal Complexes, V. The Modified Alkali Salt Elimination Method  -  a General Procedure for the Synthesis of Silicon Transition Metal CompoundsThe heterogeneous reaction of the sodium carbonylmetallates Na[Fe(CO)2π-C5H5], Na[M(CO)3π-C5H5] (M=Mo, W), and Na[Mn(CO)5] with various halo- and organohalosilanes leads to the formation of the corresponding silyl complexes. The new compounds are characterized by spectroscopy and the chemical properties are described. The results of a decomposition study of the trimethylsilyl-VIB transition metal complexes are discussed in connection with former synthetic experiments. Exchange reactions of these species with heterosiloxanes can be used for a qualitative estimation of relative metal-metalloid bond reactivity.
    Notes: Die Umsetzung der komplexen Metallate Na[Fe(CO)2π-C5H5], Na[M(CO)3π-C5H5] (M=Mo, W) und Na[Mn(CO)5] mit verschiedenen Halogen- und Organohalogensilanen führt in heterogener Reaktion zu den Silylkomplexen dieser Metalle. Die neuen Verbindungen werden spektroskopisch charakterisiert und ihre chemischen Eigenschaften beschrieben. Die Ergebnisse einer Zerfallsstudie der Trimethylsilyl-VIB-Übergangsmetallkomplexe werden im Zusammenhang mit früheren Syntheseversuchen diskutiert. Der Verlauf von Austauschreaktionen der gleichen Verbindungen mit Heterosiloxanen (Ge, Sn) ermöglicht eine qualitative Abschätzung der Reaktivität der Metall- Metalloideinheit.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070326
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    Untersuchungen an 4-Pyronen, 51 Aminoalkylierung von Chromonen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1057-1065 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on 4-Pyrones, 51. Aminoalkylation of ChromonesThe aminoalkylation of 2-methylchromones (1b, e and 2b, c) leads to the formation of benzopyrano[3.2-c]pyridinium chlorides (9a-d and 11a-e).
    Notes: Die Aminoalkylierung von 2-Methylchromonen (1b, e sowie 2b, c) führt zu Benzopyrano-[3.2-c]pyridinium-chloriden (9a-d sowie 11a-e).
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070334
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  • 60
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    Berichtigung (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1069-1069 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070336
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    Massenspektrometrische Untersuchung von Amiden, VII Intramolekulare Wechselwirkungen bifunktioneller Gruppen bei der elektronenstoßinduzierten Fragmentierung von Piperididen und Piperideiden (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1081-1091 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mass Spectrometric Investigation of Amides, VII. Intramolecular Interactions of Bifunctional Groups in the electron Impact Induced Fragmentation of Piperidides and PiperideidesThe activation energy ∊ for the electron impact induced splitting of the N-carbonyl bond in bifunctional amides is estimated. A clear correlation is shown of ∊ with the ring size of the transition state and the nucleofuge or nucleophilic properties of the nitrogen groups. Furtheron by means of [D]-labelled model compounds selective hydrogen migrations have been established.
    Notes: Die Aktivierungsenergie ∊ für die elektronenstoßinduzierte Spaltung der N-Carbonylbindung bifunktioneller Amide wird bestimmt. Es ergibt sich ein klarer Zusammenhang von ∊ mit der Ringgröße des Übergangszustandes und den nucleofugen bzw. nucleophilen Eigenschaften der Stickstoffgruppen. Ferner werden mit Hilfe [D]-markierter Modellverbindungen selektive Wasserstoffübertragungen nachgewiesen.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19741070403
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  • 62
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    Über die Natur des Benzonorbornen-2-yl-Kations, II. Solvolyse von Isopropyliden-substituierten Benzonorbornen-2-yl-Estern (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1126-1135 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Nature of Benzonorbornen-2-yl Cations, II. Solvolysis of Isopropylidene-substituted benzonorbornen-2yl EstersThe 2-epimeric at C-7 and C-3 substituted benzonorbornenols 4a, 6a, 7a and 8a are synthesized. The rate of solvolysis of the tosylates 4b and 6b is measured in acetic acid, that of the 3,5-dinitrobenzoates 7b and 8b in 90% dioxane. The solvolysis products are determined in 80% acetone puffered with 2,6-lutidine. The epimeric 7-isopropylidene derivatives 4b and 6b solvolyse by a different mechanism; the exo derivative 4b reacts exclusively with assistance of the benzene ring, the endo compound by participation of the homoallylic double bond. The epimeric 3-isopropylidene derivatives 7b and 8b solvolyse to a common intermediate allylic ion 10. The kexo/kendo ratio is reduced to 9 due to the presence of this neighbouring group, which is a measure of the steric factor in the secondary benzonorbornen-2-yl system.
    Notes: Die epimeren Benzonorborneole 4a und 6a sowie 7a und 8a werden synthetisiert. Die Solvolysegeschwindigkeit der Tosylate 4b und 6b wird in Eisessig, die der 3,5-Dinitrobenzoate 7b und 8b in 90 proz. Dioxan gemessen. Die Reaktionsprodukte werden in 80 proz., mit 2,6-Lutidin gepuffertem Aceton bestimmt. Die epimeren 7-Isopropyliden-Verbindungen 4b und 6b solvolysieren nach einem unterschiedlichen Mechanismus; die exo-Verbindung 4b reagiert ausschließlich mit Beteiligung des Aromaten, die endo-Verbindung 6b mit der der Isopropyliden-Doppelbindung. Die epimeren 3-Isopropyliden-Verbindungen 7b und 8b solvolysieren zu einem gemeinsamen Allyl-Ion 10 als produktbestimmende Zwischenstufe. Das Verhältnis kexo/kendo wird durch diese Nachbargruppe auf 9 herabgesetzt, welches ein Maß für den sterischen Anteil des sekundären Benzonorbornen-2-yl-Systems ist.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070407
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    Übergangsmetall-Carben-Komplexe, LXXII. Spaltung der Doppelbindung von 1-Vinyl-2-pyrrolidon und β-substituierten 1-Vinylpyrrolidonen bei der Umsetzung mit Pentacarbonyl(methoxyphenylcarben)chrom(0) (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1156-1161 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXXII. Cleavage of the Double Bond of 1-vinyl-2-pyrrolidone and β-Substituted 1-Vinylpyrrolidones by Reaction with Pentacarbonyl(methoxyphenylcarbene)chromium(0)Pentacarbonyl(methoxyphenylcarbene)chromium(0) reacts with 1-vinyl-2-pyrrolidone to form α-methoxystyrene by transfer of a methylene group to the carbene moiety. The origin of the transfered methylene group is proved by using methylsubstituted 1-vinylpyrrolidones. The reaction products are identified by their i.r., 1H n.m.r., and mass spectra. As reaction mechanism a cyclic transition state is proposed, which explains the breaking and following formation of a double bond analogously to the heterolytic fragmentation according to Grob.
    Notes: Bei der Umsetzung von Pentacarbonyl(methoxyphenylcarben)chrom(0) mit 1-Vinyl-2-pyrrolidon entsteht durch Übertragung einer Methylengruppe auf den Carben-Rest α-Meth-oxystyrol. Durch Einsetzen methylsubstituierter 1-Vinylpyrrolidone wird die Herkunft der übertragenen Methylengruppe bewiesen. Die Produkte werden anhand ihrer IR-, 1H-NMR- und Massenspektren identifiziert. Als Reaktionsmechanismus wird ein cyclischer Übergangszustand vorgeschlagen, der - in Analogie zur heterolytischen Fragmentierung nach Grob - die Spaltung und Neuknüpfung einer Doppelbindung erklärt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070411
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    Photochemische Reaktionen, XXIII. Über Photocyclisierungen von 9-Benzylidenxanthenen und 9-Benzylidenthioxanthenen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1207-1212 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemical Reactions, XXIII. The Photocyclisation of 9-Benzylidenexanthenes and 9-BenzylidenethioxanthenesDehydrocyclisations of the 9-benzylidenexanthenes in u.v. or sunlight (6a-6d→7a-7d) were realized. 6 may be considered as derived from stilbene, and 7 as derived from phenanthrene. Therefore the photoprocess 6→7 is analogue to the photoprocess cis-stilbene → phenanthrene.
    Notes: Dehydrocyclisierungen der Benzylidenxanthene im UV-oder Sonnenlicht (6a-6b→7a-7d) wurden durchgeführt. Da 6 als substituierte cis-Stilbene und 7 als substituierte Phenanthrene aufgefaßt werden können, liegen Analogiereaktionen zu dem Photoprozeß cis-Stilben → Phenanthren vor.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070416
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    Darstellung und dynamisches Verhalten von Mono- cyclopentadienylarsinen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1228-1234 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Dynamic Behaviour of Mono-cyclopentadienylarsinesMono-cyclopentadienylarsines (3a-e) are synthesized by the reaction of cyclopentadienyl-trimethylsilane (1) or cyclopentadienyllithium (5) with the halogenoarsines 2a-e. They are very sensitive against air and moisture and thermally unstable. The cp-ligands are σ-bonded; the molecules have a fluxional structure. The rapidity of the degenerate metallotropic rearrangements is influenced by the other ligands on the arsenic atom.
    Notes: Mono-cyclopentadienylarsine (3a-e) werden durch Umsetzung von Cyclopentadienyl-trimethylsilan (1) oder Cyclopentadienyllithium (5) mit den Halogenarsinen 2a-e dargestellt. Sie sind äußerst luft- und feuchtigkeitsempfindlich und thermisch instabil. Es liegen σ-gebundene Cp-Liganden und Moleküle mit fluktuierender Struktur vor. Die Geschwindigkeit der entarteten metallotropen Umlagerungen wird durch die anderen Liganden am Arsenatom beeinflußt.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19741070419
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    Enhydrazine, 9. 1-Alkyl-3-hydroxypyrazole aus Hydrazonen oder Hydrazinen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1318-1328 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enehydrazines, 9. 1-Alkyl-3-hydroxypyrazoles from Hydrazones or HydrazinesReaction of dimethyl acetylendicarboxylate with hydrazinen oder Alkyl hydrazonen gives the methyl 1-alkyl-3-hydroxy-5-pyrazolecarboxylats 9 and 13a-e, subsequent saponification and decarboxylation gives the 1-alkyl-3-hydroxypyrazoles 11 and 15a-e. The cyclization of 13f to lactone 19a is a structure proff. Starting from benzaldehyde hydrazones, 2-pyrazoline-4,5-dicarboxylic esters are the main products.
    Notes: Durch Umsetzung von Acetylendicarbonsäure- dimethylester mit Hydrazinen oder Alkyl-hydrazonen erhält man die 1-Alkyl-3-hydroxy-5-pyrazolcarbonsäure-methylester 9 und 13a-e, durch Verseifung und Decarboxylierung hieraus die 1-Alkyl-3-hydroxypyrazole 11 und 15a-e. Die Cyclisierung von 13f zum Lacton 19a ist strukturbeweisend. Bei Verwendung von Benzaldehyd-hydrazonen entstehen hauptsächlich 2-Pyrazolin-4,5- dicarbonsäureester.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070428
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    Elektrophile Addition von Dischwefeldichlorid an Alkine, 3. Umsetzung asymmetrisch substituierter Alkine mit Dischwefeldichlorid (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1334-1343 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrophilic Addition of Disulfur Dichloride to Alkynes, 3. Reaction of Asymmetric of Asymmetric Substituted Alkynes with Disulfur DichlorideDisulfur dichloride adds to the triple bond of asymmetric substituted alkynes to afford vinyl sulfides, which are constitution isomers. Substituents R with a negative I-effect yield „Markownikof“ products whereas a positive I-effect leads to the formation of „anti-Markownikoff“ products. The addition is always trans. The obtained sulfides are oxidized with H2O2 in glacial acetic acid to yield the corresponding sulfones.
    Notes: Die bei der elektrophilen Addition von Dischwefeldichlorid an asymmetrische Alkine gebildeten Vinylsulfide sind Konstitutions -Isomere. Substituenten R mit negativem Induktionseffekt führen zu „Markownikoff“-Produkten, während ein positiver I-Effekt „anti-Markownikoff“-Orientierungen liefert. In allen Fällen erfolgt eine trans-Addition. Die erhaltenen Sulfide werden nach der Oxidation mit Wasserstoffperoxid/Eisessig als Sulfone isoliert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070430
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  • 68
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    Oxidative Additionsreaktionen von Nitroalkanen an Tetrakis(triphenylphosphin)platin(0) (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1371-1379 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Oxidative Addition Reactions of Nitroalkanes to Tetrakis(triphenylphoshine)platinum(0)The oxidative addition of nitromethane to Pt(PPh3)4 in polar protic solution provides a convenient and safe method for the preparation of trans-(Ph3P) 2Pt(CNO)2 Pt(CNO2)(3). From Pt(PPh3)4 and nitromethane or 2-nitropropane cis-(Ph3P) 2Pt(NO2)2 (2) is obtained. The reactions of Pd(PPh3)4 or Rh(PPh3)2CO)Cl with CH3NO2 or some of its derivatives afford isocyanato compounds. Formaidoxime hydrochloride reacts with Pt(PPh3)4 to give trans-(Ph3P)2Pt-(CN)Cl (4).
    Notes: Die oxidative Addition von Nitromethan an Pt(PPH3)4 in polarem, protischem Medium liefert gefahrlos und in guter Ausbeute trans-(Ph 3P)2Pt(CNO)2 (3). Aus Pt(PPh3)4 und Nitromethan bzw. 2-Nitropropan wird cis-(Ph3P)2Pt(NO2)2 (2) erhalten. Die Umsetzungen von Pd(PPh 3)4 oder Rh(PPh3)2(CO)Cl mit Nitromethan oder Methylnitrolsäure führen zu Isocyanatoverbindungen. Formaldoxim-hydrochlorid reagiert mit Pt(PPh 3)4 zu trans-(Ph3P)2Pt(CN)Cl (4).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070434
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    Botrydial, ein Sesquiterpen-Antibiotikum aus der Nährlösung des Pilzes Botrytis cinerea (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1720-1730 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Botrydial, a Sesquiterpene Antibiotic from the Culture Solution of the Fungus Botrytis cinereaThe antibiotic botrydial (3) and its dihydro derivative (1) were isolated from the culture solution of the fungus Botrytis cinerea. Their structural formulas were elucidated by means of a series of chemical transformations together with the application of spectroscopic methods, especially a detailed analysis of the n.m.r. spectra. The basic skeleton of botrydial is a bicyclic, non-isoprenoid sesquiterpene system.
    Notes: Aus der Nährlösung des Pilzes Botrytis cinerea wurden das antibiotisch wirksame Botrydial (3) und sein Dihydroderivat (1) isoliert. Durch eine Folge chemischer Umwandlungen, verbunden mit der Anwendung spektroskopischer Methoden, insbesondere einer detaillierten Analyse der NMR-Spektren, wurden ihre Konstitutionsformeln abgeleitet. Botrydial liegt ein bicyclisch nicht-isoprenoides Sesquiterpenskelett zugrunde.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19741070530
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    Natürlich vorkommende Terpen-Derivate, XXXIV. Notiz über die Synthese des Furanoeremophilans (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1767-1768 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070535
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    Natürlich vorkommende Terpen-Derivate, XXXVI. Synthese von 8-Hydroxybrickellol und Dehydronerol-isovalerat (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1773-1776 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occuring Terpene Derivatives, XXXVI. Synthesis of 8-Hydroxybrickellol and Dehydronerol isovalerateThe sesquiterpene 7 named 8-hydroxybrickellol as well as the isovalerate of dehydronerol (14) have been synthesized.
    Notes: Das 8-Hydroxybrickellol benannte Sesquiterpen 7 sowie der Isovaleriansäureester des Dehydronerols (14) werden synthetisch dargestellt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070602
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    Die Reaktionen von Phosphor-yliden mit überschüssigem Alkohol und mit Alkanthiol (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1420-1427 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reactions of Phosphorus Ylids with Excess Alkohol and AlkanethiolThe alkoxytetraalkylphosphoranes of the formula R4POR′, obtained from equimolar amounts of ylid and alkohol, which contain pentacoordinate phosphorus atoms, are converted into ionic products (1 - 7) by addition of excess alkohol. In these compounds phosphonium cations R4P⊕ are accompanied by hydrogen-bonded hydrogenalkoholate anions of the types [R′O…H…OR′]⊖, [H2(OR′)3]⊖, and [H3(OR′)4]⊖. This structure is proposed on the basis of n.m.r., i.r., and Raman-spectroscopic data. With ylids and alkanethiols only salt-like products R4P⊕RS⊖ are formed.
    Notes: Die aus äquimolaren Mengen von Yliden und Alkoholen zugänglichen, kovalent gebauten Alkoxytetraalkylphosphorane R4POR′ mit pentakoordinierten Phosphoratomen werden durch Addition von überschüssigem Alkohol in die Produkte 1 - 7 verwandelt, in welchen Phosphonium-Kationen R4P⊕ den wasserstoffbrückenverknüpften Hydrogenalkoholat-Anionen vom Typ [R′O…H…OR′]⊖, [H2(OR′)3]⊖ und [H3(OR′)4]⊖ gegenüberstehen. Der Strukturvorschlag stützt sich auf NMR-, IR- und Raman-spektroskopische Untersuchungen. Aus Yliden und Alkanthiolen entstehen nur die salzartigen Phosphonium-alkanthiolate R4 P⊕RS⊖.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070503
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    Umlagerungen 3-substituierter Norbornandiazonium-Ionen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1472-1482 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangements of 3-Substituted Norbornanediazonium Ions3-Oxonorbornane-2-endo-diazonium ions (1), generated by acid-catalyzed decomposition of 3-diazonorcamphor (5) in alcoholic solutions, produce derivatives of endo-bicyclo[2.2.1]heptane 3 and bicyclo [3.1.1]heptane derivatives 4, varying with the nucleophilicity of the solvent. This suggests the 7-bridged ion 2 as intermediate, which plays also an important part in the deamination of 3,3-dimethoxynorcamphor tosylhydrazone (16) in alkaline solutions as shown by the formation of 3 and 4. In the alkaline deamination of 3,3- dimethoxy-5-norbornen-2-on tosylhydrazone (32) in methanol the homoallylic ion 34 is dominating.
    Notes: 3-Oxonorbornan-2-endo-diazonium-Ionen (1), erzeugt durch sauer katalysierte Zersetzung von 3-Diazonorcampher (5) in alkoholischen Lösungen, ergaben endo-Bicyclo[2.2.1]heptan-3 und Bicyclo[3.1.1]heptan-Derivate 4, deren Menge von der Nucleophilie des eingesetzten Lösungsmittels abhängig ist. Dies läßt das 7-verbrückte Ion 2 als Zwischenstufe vermuten, welches auch bei der Desaminierung des 3,3-Dimethoxynorcampher-tosylhydrazons (16) in alkalischen Lösungen eine entscheidende Rolle spielt, wie die Bildung der Produkte 3 und 4 beweist. Bei der alkalischen Desaminierung des 3,3-Dimethoxy-5-norbornen-2-on-tosylhydrazons (32) in Methanol ist jedoch die Homoallylumlagerung zum Kation 34 produkt-bestimmend.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070507
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    Derivate des Guanidins mit N—S- und N—P-Bindungen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1536-1544 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Derivatives of Guanidines Containing Phosphorus and SulfurN-Chloroguanidines 1 react with tervalent phosphorous compounds or with sulfides to yield N-guanylphosphine imidium (3) or sulfimidium salts (9). Dehydrohalogenation gives the respective N-guanyl phosphine imides and sulfimides. The structure and reactions of these compounds are discussed.
    Notes: Die Umsetzung von N-Chlorguanidinen 1 mit tervalenten Phosphorverbindungen sowie Sulfiden führt zu N-Guanylphosphinimidium- (3) bzw. -sulfimidium-Salzen (9). Durch Dehydrohalogenierung werden die entsprechenden Phosphinimide und Sulfimide erhalten. Die Eigenschaften dieser Verbindungen - insbesondere die Struktur-und Bindungsverhältnisse-sowie ihre Reaktionen werden untersucht.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070514
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    Konformationsanalyse, III. exo-Anomerer Effekt und Circulardichroismus von Glycopyranosylaziden (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1568-1578 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conformational Analysis, III. exo-Anomeric Effect and Circular Dichroism of Glycopyranosyl AzidesTetra-O-acetyl-aldopentopyranoses and penta-O-acetyl-aldohexopyranoses react readily with trimethylsilyl azide in the presence of BF3 or SnCl4 to afford the corresponding glycosyl azides 1a - 11 (table 1). Only the anomeric glycosyl azide having the azido group „trans“ to the 2-acetoxy group is obtained in each case. The polarization of the Cl—Nx and Nx—Nz bonds in glycosyl azides is such that in both cases the dipole is directed toward Nx. It can be deduced that glycosyl azides, like methyl glycopyranosides, should exhibit an exo-anomeric effect which strongly favors the conformers 9 and 12. The application of the azide-octant rule predicts a negative Cotton effect for the α-D-glycosyl azide 12 and a positive effect for the β-D-glycosyl azide 9. Circular dichroism measurements are in good agreement with these predictions, indicating the operation of an exo-anomeric effect in the glycosyl azides.
    Notes: Tetra-O-acetyl-pentopyranosen und Penta-O-acetyl-hexopyranosen setzen sich mit Trimethylsilylazid bei Gegenwart von BF3 oder SnCl4 leicht zu den entsprechenden Glycosylaziden 1a bis 11 um (Tab. 1). Es entsteht stets nur das anomere Glycosylazid, in dem die Azidogruppe und 2-OAc „trans“ zueinander angeordnet sind. In Glycosylaziden sind die Bindungen Cl—Nx und Nx—Nz in der Weise polarisiert, daß der Dipol in beiden Fällen zum Nx weist. Hieraus wird abgeleitet, daß bei Glycosylaziden wie bei Methylglycosiden ein exo-anomerer Effekt wirksam sein sollte, der die Konformeren 9 und 12 stark bevorzugt. Die Anwendung der Azid-Oktantenregel sagt für das α-D-Glycosylazid 12 einen negativen, für das β-D-Glycosylazid 9 einen positiven Cotton-Effekt voraus. Messungen des Circular-dichroismus stimmen mit diesen Voraussagen gut überein, was für einen exo-anomeren Effekt bei Glycosylaziden spricht.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070517
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    Thermisch induzierte Reaktionen von Imidazolderivaten, IV. Die Kinetik der thermischen Umlagerung von 2,4,4-Thriaryl-5-mathylthio-4H-imidazolen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1645-1648 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermally Induced Reactions of Imidazole Derivatives, IV. Kinetics of the Thermal Rearrangement of 2,4,4-Triaryl-5-methylthio-4H-imidazolesThe thermal rearrangements of the title compounds 1a - d into the 2,4,5-triarylimidazoles 2 in different solvents and at different temperatures are first order reactions. No linear relation exists between the effect of the p-substituents of the migrating aryl groups on the reaction rates and their Hammett-Brown σ+ values. The solvent has practically no effect on the rearrangement rate of 1c. The activation parameters of the rearrangement 1c → 2c are given.
    Notes: Die thermische Umlagerung der Titelsubstanzen 1a - d in die 2,4,5-Triarylimidazole 2 in verschiedenen Lösungsmitteln und bei verschiedenen Temperaturen folgt einem Geschwindigkeitsgesetz 1. Ordnung. Der Einfluß des p-Substituenten der wandernden Arylgruppe ändert sich nicht linear mit den Hammett-Brownschen σ+-Werten. Das Lösungsmittel hat praktisch keinen Einfluß auf die Umlagerungsgeschwindigkeit von 1c. Die Aktivierungsparameter der Umlagerung 1c → 2c werden angegeben.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070522
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    Vinyl-Kationen, 15. Darstellung und Solvolyse der stereoisomeren 1-Brommethylen-2-methylcyclopropane (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1676-1683 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vinyl Cations, 15. Preparation and Solvolysis of the Stereoisomeric 1-Bromomethylene-2-methylcyclopropanesThe stereoisomeric 1-bromomethylene-2-methylcyclopropanes (6Z and 6E) are synthesized and their solvolysis rates and products in ethanol/Water mixtures are determined. 6Z and 6E solvolyse at approximately the same rates. Both isomers yield only the rearranged products 12, 14, 16 and 18, which are formed from both isomers in the same ratio. The products as well as the kinetic data are explained by assuming the formation of the stabilized cyclopropylidenemethyl cation 7.
    Notes: Die stereoisomeren 1-Brommethylen-2-methylcyclopropane (6Z und 6E) wurden dargestellt und die Solvolysegeschwindigkeiten sowie die Produkte in Äthanol/Wasser-Gemischen bestimmt. 6Z und 6E solvolysieren dabei etwa mit gleicher Geschwindigkeit. Aus beiden Isomeren entstehen ausschließlich die umgelagerten Produkte 12, 14, 16 und 18 im gleichen Mengenverhältnis. Produktanalyse und Kinetik werden mit der Bildung des stabilisierten Cyclopropylidenmethylkations 7 erklärt.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19741070526
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    Dispiro[2.0.2.4] deca-7,9-dien und Vergleichsverbindungen: Darstellung, UV-, NMR- und Photoelektronen-spektroskopische Untersuchungen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1684-1701 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dispiro[2.0.2.4]deca-7,9-diene and Related Model Compounds: Synthesis, U.V, N.M.R, and Photoelectron-Spectroscopic InvestigationsDispiro[2.0.2.4]deca-7,9-diene (4) and spiro[2.5]octa-4,6-diene (5 can be obtained from the corresponding monoolefins 6 and 10, respectively, by bromine addition and subsequent dehydrobromination. The u. v. spectra of 5 and 4 with λmax = 269 nm (log ε = 3.4) and 284 nm (3.7), respectively, show bathochromic shifts of their longest wavelength bands as compared to 1,3-cyclohexadiene. An analysis of the 1H n. m. r. chemical shifts and H, H-coupling constants for the olefinic protons in 4 indicates that there is no cyclic electron delocalization in this ring system. The six-membered ring in 4 is only slightly flatter than the one in 1,3- cyclohexadiene. The photoelectron spectroscopic data of 4, 5, spiro[2.5]octane (13), spiro[2.5]oct-4-ene (15), dispiro[2.0.2.4]decane (14), and dispiro[2.0.2.4]dec-7-ene (16) demonstrate the effect of the interaction between π-orbitals and cyclopropyl Walsh-orbitals; an assignment for the first bands in the p. e. spectra of these compounds is proposed.
    Notes: Dispiro[2.0.2.4] deca-7,9-dien (4) und Spiro[2.5]octa-4,6-dien (5) lassen sich aus den entsprechenden Monoolefinen 6 bzw. 10 durch Bromierung und anschließende Dehydrobromierung gewinnen. Die UV-Absorptionen von 5 und 4 mit λmax = 269 nm (log ε = 3.4) bzw. 284 nm (3.7) sind bathochrom verschoben gegenüber denjenigen des 1,3-Cyclohexadiens. Aus einer Analyse der Chemischen Verschiebungen und H,H-Kopplungskonstanten der olefinischen Protonen im 1H-NMR-Spektrum von 4 ist zu schließen, daß 4 kein cyclisch delokalisiertes Elektronensystem enthält. Der Sechsring in 4 ist nur wenig stärker eingeebnet als derjenige im 1,3-Cyclohexadien. Anhand der Photoelektronen-Spektren von 4, 5 sowie Spiro[2.5]octan (13), Spiro[2.5]oct-4-en (15), Dispiro[2.0.2.4]decan (14) und Dispiro[2.0.2.4]dec-7-en (16) wird der Effekt der Wechselwirkung zwischen π-Orbitalen und Cyclopropyl-Walsh-Orbitalen aufgezeigt; für die jeweils ersten Banden in den PE-Spektren dieser Verbindungen wird eine Zuordnung vorgeschlagen.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070527
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    Asymmetrische Hydrierungen mit 1,4-Bis(dimethylamino)- (2S,3S)-und -(2R,3R)-butan-2,3 -diol(DBD)/Lithiumaluminiumhydrid (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1748-1763 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Asymmetric Hydrogenation with 1,4-Bis(dimethylamino)-(2S,3S)- and -(2R,3R)-butane-2,3-dio(DBD)/Lithium Aluminium HydrideThe diaminodiol 6 (DBD) mentioned inthe in the title is readily available in two steps from commercial diethyl tartrate. It reacts with lithium aluminium hydride (LAH) or deuteride to give chirally modified 1:1-complexes which reduce aldehydes, ketones, and ozonides to optically active carbinols in optical yields of up to 75%. Since both enantiomers of DBD are to accessible, both dextro- and levo-rotatory products may be prepared at will. DBD is easily separated from products and recovered without loss of activity. The (-)- DBD-LAH-complex reduces both dialkyl and aryl alkyl ketones to give samples enantiomerically enriched with carbinols of (S)- configuration, while the (+)-DBD-complex acts the other way around. This result is independent of the mode of preparation of the complex, of the ratio of reducing reagent over substrate, of addition of alcohols or water, of reaction temperature, or solvent. The effects of some of these influences upon the optical yields are large. Optimum conditions are given; the efficiency of the DBD-LAH-complex is compared with similar chirally modified LAH derivatives already known. A mechanism explaining the stereochemical results is proposed.
    Notes: Das aus Weinsäureester in zwei Stufen leicht zugängliche, im Titel genannte Diaminodiol 6 (DBD) setzt sich mit Lithiumaluminiumhydrid (LAH) und -deuterid zu chiral modifizierten 1: 1-Komplexen um. Diese reduzieren Aldehyde, Ketone und Ozonide zu opt. aktiven Carbinolen in optischen Ausbeuten bis zu 75%. Da beide Enantiomeren von DBD zugänglich sind, lassen sich gezielt (+)- oder (-)-drehende Produkte darstellen. DBD ist von den Produkten bequem abtrennbar und ohne opt. Verluste zurückgewinnbar. Mit (-)-DBD-LAH- Komplex entstehen Dialkyl- und Alkyl-aryl- carbinole mit (S)-, aus dem enantiomeren Komplex mit (R)-Konfiguration des Überschußenantiomeren. Dies ist völlig unabhängig von Darstellungsmodus des Komplexes, molarem Verhältnis von Reduktionsmittel und Substrat, Zusätzen von Alkoholen oder Wasser, Reaktionstemperatur oder -lösungsmittel. Die Einflüsse dieser Faktoren auf die opt. Ausbeuten, für die optimale Bedingungen angegeben werden, sind indessen zum Teil groß. Vergleiche mit bekannten Komplexen aus LAH und anderen chiralen Liganden werden gezogen. Es wird ein Vorschlag zur Erklärung der stereochemischen Befunde gemacht.
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    Natürlich vorkommende Terpen-Derivate, XXXVII. Synthese des Sesquiterpens aus Elvira biflora DC (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1777-1779 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occurring Terpene Derivatives, XXXVII. Synthesis of the Sesquiterpene from Elvira biflora DCThe aromatic sesquiterpene 11 isolated from Elvira biflora DC has been synthesized starting with the p-cresol 2-butenyl ether (1).
    Notes: Das aus Elvira biflora DC isolierte aromatische Sesquiterpen 11 wird ausgehend vom p-Cresol-2-butenyläther (1) synthetisiert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070603
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  • 81
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    Reaktionsverhalten von Nitril-yliden verschiedener Provenienz (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1823-1834 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactivity of Nitrile Ylides of Different OriginThermolysis and photolysis of 2,3-dihydro- 1,4,2λ5-oxazaphospholes 2, photolysis of 1- azetines 3 as well as 1,3-elimination of hydrogen chloride from imidoyl chlorides 4 proceeds via the nitrile ylide intermediate 1. This is deduced from the same product ratio of the isomeric cycloadducts 5:6 on trapping with acrylic acid esters.
    Notes: Die Thermolyse und Photolyse von 2,3-Dihydro-1,4,2λ5-oxazaphospholen 2, die Photolyse von 1-azetine 3 wie auch die 1,3-Eliminierung von Chlorwasserstoff aus Imidoylchloriden 4 verläuft über die Nitril-ylid-Zwischenstufe 1. Dies wird aus dem jeweils gleichen Produkt-verhältnis der isomeren Cycloaddukte 5:6 bei der Abfangreaktion mit Acrylsäureestern abgeleitet.
    Additional Material: 9 Tab.
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  • 82
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    1,8-Di-tert-butyl-[9-13C]-9-fluorenyl, Bis (2-tert-butylphenyl) [α-13C]methyl und ihre Dimeren (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1903-1914 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,8-Di-tert-butyl-[9-13C]-9-fluorenyl, Bis(2-tert-butylphenyl)[α-13C]methyl and their DimersThe preparation of the title compounds is reported. The 1H n. m. r. spectra of the dimers of 1 and [9-13C]-1, respectively, yield the cyclohexadiene structure 12 for the dimer. The 1H n. m. r. spectrum of [α-13C]-2 dimer confirms structure 1411). The e. s. r. results of 1 and 2 are discussed.
    Notes: Die Darstellung der Titelverbindungen wird beschrieben. Die 1H-NMR-Spektren der Dimeren von 1 bzw. [9-13C]- 1 ergeben die Cyclohexadien-Struktur 12 für das Dimere. das 1H-NMR-Spektrum des [α-13C]- 2-Dimeren bestätigt die Struktur 14 11). Die ESR-Ergebnisse (a(H) und a(13C)) von 1 und 2 werden diskutiert.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19741070614
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  • 83
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    Photochemie kleiner Ringe, 30. Photochemie β, γ-ungesättigter Aldehyde. - Mechanismus der Photofragmentierung phenylsubstituierter Cyclopentencarbaldehyde (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1835-1855 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemistry of Small Rings, 30. Photochemistry of β,γ-Unsaturated Aldehydes.  -  Mechanism of the Photofragmentation of Phenyl-substituted CyclopentenecarbaldehydesA new synthesis of β,γ-unsaturated cyclopentenecarbaldehydes 1 by thermolysis of bicyclo-[3.1.0]hexenols 13 is described. Photolysis of the aldehydes 1 in benzene solution affords the cis-configurated cyclopentenes 2 in good yields. Cyclopentaphenanthrenes 16 are isolated as byproducts. 2 undergoes an electrocyclic reaction to form 17, which is then dehydrogenated to 16. The quantum yields of the photofragmentation and -cyclization are Φ2 = 0.23 and Φ16 = 0.07, respectively. From the emission spectra of 1a the energy of the singlet and triplet state is calculated to ES1 = 84.1 and ET1 = 62.2 kcal/mole. The kinetics of photoreactions 1 → 2 → 16 are studied using ED- and EDQ-diagrams. Sensitization studies demonstrate that the photoreaction 1 → 2 can also occur via a triplet state, but with reduced effectivity. Since quenching with piperylene is ineffective the reaction 1 → 2 very probably involves predominantly an n-π-singlet state. The mechanism proposed for the stereospecific, intramolecular reaction 1 → 2 involves the formation of a formyl allyl radical as a main intermediate.
    Notes: Eine neue Synthese von β,γ-ungesättigten Cyclopentencarbaldehyden 1 durch Thermolyse von Bicyclo [3.1.0]hexenolen 13 wird beschrieben. Die Photolyse der Aldehyde 1 in Benzol ergibt in guten ausbeuten die cis-konfigurierten Cyclopentene 2 und als Nebenprodukte die Cyclopentaphenanthrene 16.2 geht durch elektrocyclischen Ringschluß in 17 über, das unter Dehydrierung in 16 umgewandelt wird. Die Quantenausbeuten der photofragmentierung bzw. -cyclisierung betragen Φ2 = 0.23 bzw. Φ16 = 0.07. aus den Emissionsspektren von 1a wird die Energie von singulett- und Triplett-Zustand zu ES1 = 84.1 bzw. ET1 = 62.2 kcal/mol errechnet. Die Kinetik der Photoreaktionen 1 → 2 → 16 wird mit Hilfe von Ed- und EDQ-Diagrammen näher studiert. Wie Sensibilisierungsstudien zeigen, kann die Photoreaktion 1 → 2, wenn auch mit geringerer Effektivität, über einen Triplett-Zustand verlaufen. Sie läßt sich mit Piperylen nicht löschen, weshalb die Reaktion 1 → 2 weitgehend über einen angeregten n-π-S1-Zustand formuliert wird. Für den Mechanismus der stereospezifischen, intramolekularen (D-Markierung) Reaktion 1 → 2 wird ein Formyl-Allyl-Radikalpaar als Wesentliche Zwischenstufe vorgeschlagen.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19741070609
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    Photoelektronenspektren und Moleküleigenschaften, XXXIV. Cyanamid (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1882-1890 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoelectron Spectra and Molecular Properties, XXXIV. CyanamideThe PE spectrum of cyanamide is easily assigned by comparison with that of the isoelectronic acetonitrile. The orbital sequence obtained is supported by vibrational fine structures, by the PE spectrum of dimethylcyanamide, and by CNDO calculations. Furthermore, the calculated charge densities render possible an appreciation of properties of cyanamide and its alkyl derivatives.
    Notes: Das PE-Spektrum von Cyanamid läßt sich durch Vergleich mit dem des isoelektronischen Acetonitrils zwanglos zuordnen. Die so abgeleitete Orbitalreihenfolge wird durch Schwingungsfeinstrukturen, das PE-Spektrum von Dimethylcyanamid sowie durch CNDO-Rechnungen gestützt. Die berechneten Ladungsdichten erlauben darüber hinaus. Eigenschaften von Cyanamid und seinen Alkylderivaten zu verstehen.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19741070612
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  • 85
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    Kondensierte Ringsysteme VI. Synthese des [4.2.2]Propella-7,9-diens, eines 1,4-überbrückten Dewar-Benzols (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1915-1924 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensed Ring Systems, VI. Synthesis of [4.2.2]Propella-7,9-diene, a Dewar Benzene Bridged in 1,4-PositionThe reaction of 8,11-dithia [4.3.3] propellane (1, n = 4) with N-chlorosuccinimide and monoperphthalic acid yields a mixture of four isomeric dichlorinated disulfones (2, n = 4). The major isomer 7 is formed in 40% yield. Upon treatment of 2 (n = 4) with potassium tert-butoxide at low temperatures [4.2.2] propella-7,9-diene2) (3, n = 4) is obtained. The constitution of 3 (n = 4) is deduced by 1H and 13C n. m. r as well as mass spectrometry.
    Notes: Die Umsetzung des 8,11-Dithia [4.3.3] propellans (1, n = 4) mit N-Chlorsuccinimid und Monoperphthalsäure führt zu einem Gemisch von vier isomeren dichlorierten Disulfonen (2, n = 4), von denen das Hauptprodukt 7 in 40proz. Ausbeute entsteht. 2 (n = 4) läßt sich mit Kalium-tert-butylat bei tiefen Temperaturen in das [4.2.2]Propella-7,9-dien2)(3, n = 4) überführen, dessen Konstitution durch die 1H-, 13C-NMR- und Massenspektren bewiesen wird.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19741070615
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  • 86
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    Photoisomerisierung in Bicyclo[3.2.2]nona-6,8-dien-Derivaten (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1988-1997 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoisomerisation Reactions in Bicyclo[3.2.2]nona-6,8-diene DerivativesFrom the photochemical behavior of suitably substituted derivatives (dicarboxylic ester 3a, dicarboxylic acid 3b, bis(trifluoromethyl)-derivative 3c) it is concluded, that in the bicyclo-[3.2.2]nona-6,8-diene skeleton 1 (n = 3) the [2π + 2π]-Cycloaddition to 2 (n = 3) neither by direct nor by sensitized excitation takes place. Instead 1,3-alkyl shift (3a → 6a) and di-π-methane-rearrangement 3a → 7a, 3c → 8c) are observed. Arguments for this behavior differing from the lower homologues 1 (n = 0, 1, 2) are discussed.
    Notes: Aus dem photochemischen Verhalten geeignet substituierter Derivate (Diester 3a, Dicarbonsäure 3b, Bis-trifluormethyl-Derivat 3c) wird geschlossen, daß im Bicyclo[3.2.2]nona-6,8-dien-Gerüst 1 (n = 3) die [2π + 2π]-Cycloaddition zu 2 (n = 3) weder bei direkter noch bei sensibilisierter Lichtanregung stattfindet. Als Ersatzreaktionen werden 1,3-Alkylverschiebung (3a → 6a) und Di-π-Methanumlagerung (3a → 7a, 3c → 8c) beobachtet. Gründe für dieses von den niedrigeren Homologen 1 (n = 0, 1, 2) abweichende Verhalten werden diskutiert.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19741070621
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    PFT-13C-NMR- und Massenspektren von HeterocyclenNMR-Spektroskopische Studien, 3: 1. und 2. Mitteilung: H. Dürr und W. Bujnoch, Liebigs Ann. Chem. 1973, 1691; H. Dürr und H. Kober, Chem. Ber. 106, 1565 (1973).. - 1,2-Diazaspio[4.4]nonatetraene, Azaindolizine und 3aH-Indazole (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2037-2049 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: PFT-13C-N.M.R. and Mass Spectra of Heterocycles.  -  1,2-Diazaspiro[4.4]nonatetraenesl Azaindolizines, and 3aH-Indazoles13C n.m.r. spectra obtained by the pulse Fourier transform method of 1,2-diazaspiro[4.4]-nonatetraenes 1, azaindolizines 2, and 3aH-indazoles 3 are described. A combination of highest and lowest field resonances allows an unambigous distinction between 1 and 2. A similiar approach is suggested for 3. Estimated increments from model compounds agree well with the c.m.r. spectra. „Strickspektren“ demonstrate the effect of the substituents on the chemical shift of 1 - 3. The mass spectra of 1 - 3 are discussed briefly.
    Notes: Die mit der Puls-Fourier-Transform-Methode erhaltenen 13C-NMR-Spektren von 1,2- Diazaspiro[4.4]nonatetraenene 1, Azaindolizinen 2 und 3aH-Indazolen 3 werden beschrieben. aus einer Kombination von Höchst-und Tiefstfeld-Resonanzfrequenzen konnten die Strukturen 1 und 2 eindeutig unterschieden werden. Eine entsprechende Analyse wurde für 3 vorgenommen. Inkrementabschätzungen führten zu meist guter Übereinstimmung mit den gemessenen Spektren. Aus den Strichspektren kann der durch die verschiedenen Substituenten hervorgerufene Einfluß auf die chemischen Verschiebung von 1 - 3 werden kurz diskutiert.
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    URL: http://dx.doi.org/10.1002/cber.19741070626
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    Notiz über die Biogenese von Polyinamiden (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2120-2122 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070633
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  • 89
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    Substituenteneffekte pericyclischer Reaktionen: Das Cycloheptatrien-Norcaradien-Problem, untersucht an C-7-monosubstituierten VerbindungenVorhergehende Mitteil. in dieser Reihe: l.c.17)). (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2095-2114 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Substituenteffects in Pericyclic Reactions: The Cycloheptatriene-Norcaradiene-Problem, investigated in C-7-Monosubstituted CompoundsCharacteristic features of the cycloheptatriene-norcaradiene potential curves can be simulated by using methyl cations, which are stabilized by heterofunctional groups and bound to C-7: 1. The potential curve corresponding to low energy cycloheptatriene is realized for the 7-bis(alkylamino)methyl cation 9a 2. Cycloheptatriene and norcaradiene are energetically comparable in the case of the 7-alkoxy(amino)methyl cations. At room temperature 9b - e and 10b - e form a fast dynamic equilibrating system. 3. Norcaradiene 10f comprises the lower minimum of the potential curve for the 7-(1,3-dioxolan-2-ylium) cation. In 10f the substituent is in the exo-position. Using variable temperature 1H-n.m.r., thermodynamic parameters are determined for the equilibria 9b - e ⇋ 10b - e. The influence of C-7-substituents on the cycloheptatriene-norcaradiene equilibrium is discussed and visualized using the MO-model.
    Notes: Methylkationen, stabilisiert durch nachbarständige Alkoxy-oder Alkylaminogruppen und gebunden an C-7, ermöglichen es, drei charakteristische Lagen des Cycloheptatrien-Norcaradien-Gleichgewichtes zu simulieren: 1Mit energieniedrigem Cycloheptatrien-Niveau im 7-Bis(alkylamino)methyl-Kation 9a.2Mit nahezu energiegleichen Cycloheptatrien- und Norcaradien-Grundzuständen in den 7-Alkoxy(amino)methyl-Kationen 9b-e ⇋ 10b - e. 3. Mit energieniedrigem Norcaradien-Grundzustand in der 7-(1,3-Dioxolan-2-ylium)-Verbindung 10f. In 10f ist der Substituent exo-ständig. Thermodynamische Daten der schnellen und reversiblen Gleichgewichte 9b - e ⇋ 10b - e werden bestimmt. Die C-7-Substituentenbeeinflussung des Cycloheptatrien-Norcaradien-Gleichgewichtes wird diskutiert und durch das MO-Modell beschrieben.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19741070631
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    Ein neues Verfahren zur Darstellung von Organylfluorphosphoranen RnPF5-n (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2169-2175 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Easy Way for the Preparation of Organylfluorophosphoranes RnPF5-nOrganylfluorophosphoranes can easily be synthesized by reaction of phosphines or chlorophosphines with CCl4 and HF-donors, especially phenylcarbamoyl fluoride.
    Notes: Eine einfache Synthese der Organylfluorphosphorane beruht auf der Umsetzung von Phosphinen und Chlorphosphinen mit CCl4 und HF-Donatoren, vorzugsweise Phenylcarbamoyl-fluorid.
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    URL: http://dx.doi.org/10.1002/cber.19741070705
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  • 91
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    Zur Reaktion von Cyclopropenonen mit Enaminen, 2. Methylphenyl- und Phenylcyclopropenon und Enamine (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2215-2237 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Cyclopropenones with enamines, 2. Methylphenyl- and Phenylcyclopropenone and EnaminesThe reaction of methyphenylcyclopropenone (2) with enamines 4a-d and phenycyclopropenone (3) with enamines 4a, c, h at 20°C leads to 2-azoniabicyclo[3.1.0]hex-3-en-3-olates 6, which are isomerized thermally to 2,4-pentadienamides 8. These are also formed directly from 2, 3 and enamines 4 at 80 °C and are accompained in some cases (enamines 4g, h) by β-enaminoketones (5a - c). The constitution and configuration of these „1:1-adducts“ is derived from spectral and chemical evidence. The reaction of 3 with enamines 4 yields as main products „2:1-adducts“ for which the structure of spiro-lactones 20, 21 is assumed on the basis of spectroscopic and chemical data. Some aspects of the mode of formation of these products are discussed.
    Notes: Die Reaktion von Methylphenylcyclopropenon (2) mit den Enaminen 4a - d und Phenyl-cyclopropenon (3) mit den Enaminen 4a, c, h bei 20 C führt zu 2-Azoniabicyclo[3.1.0]hex-3-en-3-olaten 6, die thermisch zu 2,4 -Pentadienamiden 8 isomerisieren. Diese werden bei 80 °C auch direkt aus 2,3 und Enaminen 4 gebildet und sind in einigen Fällen (Enamine 4g, h) von β-Enaminoketonen (5a-c) begleitet. Konstitution und Konfiguration dieser „1:1-Addukte“ wird aus spektroskopischen Kriterien und chemischen Reaktionen abgeleitet. Bei der Umsetzung von 3 mit Enaminen 4 entstehen als Hauptprodukte „2:1-Addukte“ für die aufgrund spektroskopischer und chemischer Befunde die Struktur von Spirolactonen 20, 21 anzunehmen ist. Einige Aspekte zum Bildungsmechanismus dieser Produkte werden diskutiert.
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    Zur Reaktion von Cyclopropenonen mit Enaminen, 1. Diphenylcyclopropenon und Enamine (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2186-2214 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Cyclopropenones with Enamines, 1 Diphenylcyclopropenone and EnaminesDiphenylcyclopropenone (1) reacts with the enamines 9 at 0-20°C to yield the 2-azoniabicyclo[3.1.0]hex-3-en-3-olates 10, whereas at 80°C the main products of the reaction are the 2,4-pentadienamides 25; compounds 10 are isomerized to the amides 25 at 20°C. The structure of the betaines 10 is deduced from their spectral data, their C-protonation (leading to 17), their O-alkylation (leading to 19), and their ring opening reactions with nucleophiles such as water, alcohols, and amines (leading to 20, 23, 24). The structure of the amides 25 is proven by means of spectral data and independent synthesis of the tetrahydro derivatives 26. The reaction of 1 with some enamines 9 produces as by-products the β-enamino ketones 30 and α-amino cyclopentenones 31, which are isomeric with 25. Their structure is confirmed by means of spectra and chemical degradation reactions. Some aspects of the mechanism of the reaction of diphenylcyclopropenone with enamines are discussed on the basis of the constitution of the products 10, 25, 30, and 31.
    Notes: Die Reaktion von Diphenyclyclopropenon (1) mit den Enaminen 9 führt bei 0-20°C zu den 2- Azoniabicyclo[3.1.0]hex-3-en-3-olaten 10, bei 80°C zu den 2,4-Pentadienamiden 25 als Hauptprodukten die Verbindungen 10 werden bei 80°C zu den Amiden 25 isomerisiert. Die Struktur der Betaine 10 wird aus ihren spektroskopischen Daten, ihrer C-Protonierung (zu 17), ihrer O-Alkylierung (zu 19) und ihrer Ringöffnung mit nucleophilen Agentien wie Wasser, Alkoholen und Aminen (zu 20, 23, 24) bewiesen. Der Konstitutionsbeweis der Amide 25 wird über ihre Spektren und über die unabhängige Synthese von Tetrahydroderivaten 26 geführt. Als Nebenprodukte der Reaktion von 1 mit einigen Enaminen 9 werden zu 25 isomere β-Enaminoketone 30 und α-Aminocyclopentenone 31 isoliert. Deren Konstitution wird durch Spektren und Abbaureaktionen gesichert. Aufgrund der ermittelten Konstitutionen 10, 25, 30, 31 werden einige Aspekte des Mechanismus der Reaktion von Diphenylcyclopropenon mit Enaminen erörtert.
    Additional Material: 8 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070707
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  • 93
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    Die Synthese von Purinnucleosid-6-sulfonaten (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2284-2294 
    Details
    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 Purinenucleoside-6-sulfonates6(1H)-Purinethone-9-(β-D-ribofuranosid) (1), the corresponding 5′-monophosphate 7, and the 5′-triphosphate 8 as well as 2-amino-6(1H)- purinethione-9-(β-D-ribofuranoside) (2) and 2-amino-6(1H)-purinethione-9-(β-D-2′-deoxyribofuranoside) (3) have been converted to the sulfonates 4,9,10,5, and 6 by reaction with sulfite ions in the presence of oxygen. The sulfonates 4 and 5 reacted in aqueous ammonia with good yields to give adenosine and 2,6-diaminopurine-9-(β-D-ribofuranoside), respectively. 4 and 9 react with aziridine to form 6-(1-aziridinyl)purine-9-(β-D-ribofuranoside) (15) and the corresponding 5′-monophosphate 16. 5 and 6 fluoresce with high quantum yields on excitation in the near u. v. It was shown by means of fluorescence spectroscopy, absorption spectroscopy, and comparison with authentic material that irradiation of 1, 2 and 3 by light of the wavelength 235 nm in the presence of oxygen affords the purinenucleoside-6-sulfonates 4, 5 and 6.
    Notes: 6(1H)-Purinthion-9-(β-D-ribofuranosid) (1), das entsprechende 5′-Monophosphat (7) und 5′-Triphosphat (8) sowie 2-Amino-6(1H)-purinthion-9-(β-D-ribofuranosid) (2) und 2-Amino-6(1H)-purinthion-9-(β-D2′-desoxyribofuranosid) (3) wurden durch Reaktion mit Sulfitionen in Gegenwart von Sauerstoff quantitativ in die entsprechenden Sulfonsäurederivate 4,9,10,5,6 übergeführt. Die Sulfonate 4 und 5 ließen sich bei Raumtemperatur mit wäßrigem Ammoniak in guten Ausbeuten zu Adenosin bzw. 2,6-Diaminopurin-9-(β-D-ribofuranosid) umsetzen. 4 und 9 reagierten mit Aziridin zu 6-(1-Aziridinyl)purin-9-(β-Dribofuranosid) (15) bzw. dem 5′-Monophosphat 16. 5 und 6 fluoreszieren mit hoher Quantenausbeute im langwelligen ultravioletten Licht. Mit Hilfe der Fluoreszenzspektroskopie, Absorptions-spektroskopie und durch Vergleich mit authentischem Material konnte die Bildung der Purinnucleosid-6-sulfonate 4, 5 und 6 auch bei der Bestrahlung von 1, 2 und 3 mit Licht der Wellenlänge 325 nm in Gegenwart von Sauerstoff nachgewiesen werden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070713
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  • 94
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    2-Propyl-cis-perhydrochinolin-5α-ol (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2326-2328 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2-Propyl-cis-perhydroquinolin-5α-olReaction of 1,3-cyclohexanedione with 1-chloro-3-hexanone (2), followed by reductive amination yields 2-propyl-1,2,3,4,5,6,7,8-octahydro-5-quinolinon (4). On hydrogenation with Pt in acetic acid 2-propyl-cis-perhydroquinolin-5α-ol (5) is obtained.
    Notes: Ausgehend von 1,3-Cyclohexandion wurde durch Umsetzung mit 1-Chlor-3-hexanon (2) und nachfolgende reduktive Aminierung das 2-Propyl-1,2,3,4,5,6,7,8-octahydro-5-chinolinon (4) erhalten. Hieraus entsteht bei der Hydrierung mit Pt in Eisessig 2-Propyl-cis-perhydrochinolin-5α-ol (5).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070717
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  • 95
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    Studien über elektronegativ substituierte Thiocarbonylverbindungen, 2. Trithiocarbonat-S,S-dioxide (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2345-2361 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies of Electron-Depleted Thiocarbonyl Compounds, 2. Trithiocarbonate S,S-DioxidesEleven trithiocarbonate S,S-dioxides 1 were prepared by treatment of chlorodithioformates with sulfinic acid salts and their properties investigated. In the reaction of methyl chlorodithioformate with sodium methanesulfinate, methyl (methylsulfonyl)(methylthio)methyl trithiocarbonate (4a) is formed instead of the expected 1. Compounds 4 can also be obtained by reduction of 1 with sulfinates, thiophenols, or tetrabutylammonium borohydride. Sodium diethyl methylmalonate is thioacylated by S′-phenyl S-p-tolyl trithiocarbonate S,S-dioxide (1i) to yield diethyl methyl(phenylthiothiocarbonyl)malonate(13), while the less bulky phenyllithium attacks 1i in a nucleophilic manner at the thiono sulfur to yield S′,S″-diphenyl S-p-tolyl trithioorthoformate S,S-dioxide (15). Inverse addition of Grignard solutions to 1 produces the 1-sulfonyl -1,2,2-trithioethylenes 19.
    Notes: Durch Umsetzung von Chlordithioformiaten mit Sulfinsäuresalzen wurden elf Trithiocarbonat-S.S-dioxide 1 dargestellt und auf ihre Eigenschaften untersucht. Bei der Umsetzung von Methyl-chlordithioformiat mit Natrium-methansulfinat bildet sich statt des erwarteten 1 Methyl-[(methylsulfonyl)(methylthio)methyl]-trithiocarbonat (4a). Die Verbindungen 4 erhält man auch bei der Reduktion von 1 mit Sulfinaten, Thiophenolen oder Tetrabutylammoniumboranat. Natrium-methylmalonsäure-diäthylester wird von S′-Phenyl-S-p-tolyl-trithiocarbonat-S,S-dioxid (1i) zu Methy(phenylthiothiocarbonyl)malonsäure-diäthylester (13) thioacyliert, während das weniger sperrige Phenyllithium 1i nucleophil am Thionschwefel unter Bildung von S′.S″-Diphenyl-S-p-tolyl-trithioorthoformiat-S,S-dioxid (15) angreift. Inverse Addition von Grignard -Verbindungen an 1 führt zu den 1-Sulfonyl-1,2,2-trithioäthylenen 19.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070720
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  • 96
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    Heterocyclische Dicarbonsäureester, III. Zur Reaktion von 4,5-Dihydro -2,3-furandicarbonsäure-dimethylestern mit 1,2-Diaminen.  -  Synthese von 3-(5-Alkyl -2-oxotetrahydro-3-furanyliden)-2-chinoxalinonen, -2-pyrazinonen und -1,4-diazepin-2-onen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2397-2404 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic Dicarboxylic Acid Esters, III. Reaction of Dimethyl 4,5-Dihydro-2,3-furandicarboxylates with 1,2-Diamines.  -  Synthesis of 3-(5-Alkyl-2-2oxotetrahydro-3-furanylidene)-2-quinoxalinones, -2-pyrazinones, and -1,4-diazepine-2-onesTreatment of the dihydrofurandicarboxylic acid esters 4a-c with 1.2-diamines does not result in normal ester aminolysis but in ring cleavage followed by lactonization. According to the diamine used the quinoxalinones 14, 15a-c, the pyrazinones 11-c, and the diazepinones 16a, c are obtained. The independent synthesis of the compounds 11a, 14a, 15a by condensation of the different diamines with α-ethoxalyl-γ-butyrolactone as well as the tabulated i. r. and n. m. r. data confirm the proposed structures.
    Notes: Dihydrofurandicarbonsäureester vom Typ 4a-c reagieren mit 1,2-Diaminen nicht im Sinne einer normalen zweifachen Ester-Aminolyse, sondern unter Ringöffnung und anschließender Lactonisierung. Entsprechend dem eingesetzten Diamin erhält man die Chinoxalinone 14.15a-c, die Pyrazinone 11a-c sowie die Diazepinone 16a, c. Die unabhängigen Synthesen der jeweiligen Grundkörper 11a, 14a, 15a durch Kondensation der verschiedenen Diamine mit α-Äthoxalyl-γ-butyrolacton, wie auch die aufgeführten IR- und NMR-Daten bestätigen die angenommenen Strukturen.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070723
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  • 97
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    Ungewöhnlicher Verlauf einer Acetalhydrolyse bei einer Homotropiliden-Synthese (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 3053-3069 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Unusual Course of an Acetal Hydrolysis during a Synthesis of HomotropilideneAcetals 3a-c are synthesized by Diels-Alder reaction of cyclopropene and 1-methyleyclopropene with tetrachlorocyclopentadienone acetals. Dechlorination of the adducts leads to the acetals 4a-c; their reaction with diazomethane yields 8a-c. Hydrolysing the acetals 8a, b the ketone 9 (35%) and a rearranged product 10 (65%) are formed. The hydrolysis of the acetal 8c gives only the rearranged products 11a-c. The constitution and the stereochemistry of all new products is confirmed by 1H and 13C n.m.r. spectroscopy, in the case of alcohol 11a by using Eu(fod)3 as a shift reagent. The mechanism of the hydrolysis is explained by the nature of the intermediate carbenium-oxonium ion and its steric shielding by the exo-cyclopropane ring.
    Notes: Durch Diels-Alder-Reaktion von Cyclopropen bzw. 1-Methylcyclopropen mit Tetrachlor-cyclopentadienon-acetalen werden die Acetale 3a-c erhalten. Die Dechlorierung der Addukte liefert die Acetale 4a-c, deren Homologisierung mit Diazomethan zu den tetracyclischen Acetalen 8a-c führt. Durch Hydrolyse der Acetale 8a, b entsteht zu 35% das Keton 9 und zu 65% ein Umlagerungsprodukt der Struktur 10. Je nach den angewandten Bedingungen lassen sich bei der Hydrolyse des Acetals 8c nur Umlagerungsprodukte 11a-c isolieren. Die Konstitution und Stereochemie der neuen Verbindungen wird durch 1H- und 13C-NMR-Spektroskopie, z. T. unter Anwendung von Lanthanoiden-Shift-Reagenzien, gesichert. Der Hydrolysenmechanismus wird über das intermediäre Carbenium-Oxonium-Ion und dessen sterische Abschirmung durch den exo-Dreiring erklärt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070928
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  • 98
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    Beiträge zur Chemie des Bors, LXVII. Silaborazine aus Cyclosilazanen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 3113-3120 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, LXVII. Silaborazines from CyclosilazanesPhenyldichloroborane reacts with [(CH3)2SiNH]3 (5) to yield the disilaboranine 8, the monosilaborazine 7, and/or B,B′, B″-triphenylborazine (9), depending on the ratio of the reactants. Reaction with octamethylcyclotetrasilazane, [(CH3)2SiNH]4 (12), in a 1:1 molar ratio leads to NH4Cl, 8, and a polymer. Product analysis shows that only part of 8is formed by direct SiN-cleavage, the other part results from a substitution leading to NH4Cl.
    Notes: Phenylbordichlorid reagiert je nach Molverhältnis mit [(CH3)2SiNH]3 (5) zum Disilaborazin 8, Monosilaborazin 7und/oder B,B′, B″-Triphenylborazin (9). Bei der Umsetzung mit Octamethylcyclotetrasilazan, [(CH3)2SINH] 4 (12), im Molverhältnis 1:1 entstehen NH4Cl, 8 und Polymere. Aus der Stoffbilanz folgt, daß nur ein Teil von 8über direkte Silazanspaltung entstehen Kann; der andere ist die Folge einer zu NH4Cl führenden Substitutionsreaktion.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070932
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  • 99
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    Anwendungen der 13C-Resonanz-Spektroskopie, XVI. Notiz über das 13C-NMR-Spektrum von Benzoloxid-Oxepin (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 3149-3151 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070937
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  • 100
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    Zum Mechanismus der Desulfurierung von 1,3-Benzodithiol-2-thion mit Triäthylphosphit (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 3155-3163 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Mechanism of Desulfuration of 1,3-Benzodithiole-2-thione with Triethyl PhosphiteThe reaction of title compound 1 with triethyl phosphite in the presence of capture-reagents is investigated. With alcohols the reaction yields 12 and 13, with piperidine 17, with carbonyl compounds 20-23, and with enamines 24. The results are explained by a thiophilic attack of triethyl phosphite on 1 with generation of the 1,3-dipole 14 and subsequent reactions.
    Notes: Die Reaktion der Titelverbindung 1 mit Triäthylphosphit in Gegenwart von Abfangreagentien wird untersucht. Mit Alkoholen werden 12 und 13, mit Piperidin 17, mit Carbonylverbindungen 20-23 und mit Enaminen 24 erhalten. Die Ergebnisse werden mit einem thiophilen Angriff des Phosphits auf 1 unter Bildung des 1,3-Dipols 14 und dessen Folgereaktionen erklärt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741071001
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