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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European archives of oto-rhino-laryngology and head & neck 238 (1983), S. 127-134 
    ISSN: 1434-4726
    Keywords: Zeitauflösung ; Primäres akustisches Rindenprojektionsfeld AI ; Katze ; Binaurales Hören ; Akustisch evozierte Potentiale ; Time resolution ; Primary auditory cortical projection field AI ; Cat ; Binaural hearing ; Evoked response audiometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary The ability of the auditory organ to resolve brief changes in an acoustic signal presented either monaurally or binaurally is not only of great importance in the processing of speech, it is also involved in the localization of sound stimuli and in selective listening. In the latter context, the electric activity of the primary auditory cortical projection field AI of the cat has been studied with the aim of evaluating specific response patterns evoked by brief changes in interaural time difference. The differences in response of the neuron populations sampled by two recording electrodes indicate that, within this area, there are significant differences in temporal resolution ability. Whereas click stimuli elicit distinct potential patterns at the two sites, with a brief change in interaural time difference, a marked response is recorded by only one of the electrodes. This response is characterized by a decrease in amplitude as the interaural time difference is reduced and as the duration of the time-shift stimulus decreases.
    Notes: Zusammenfassung Die Fähigkeit des Hörorgans zur zeitlichen Auflösung kurzzeitiger Signalveränderungen bei monauraler oder binauraler akustischer Stimulation ist nicht nur im Hinblick auf Sprachverarbeitungsprozesse von wesentlicher Bedeutung, sondern betrifft auch die Lokalisation und Selektion im akustischen Umgebungsraum. In diesem Zusammenhang werden elektrophysiologische Untersuchungsergebnisse zur Evozierung spezifischer Reizantwortmuster aus dem primären akustischen Rinderprojektionsfeld AI der Katze bei kurzzeitiger interauraler Laufzeitveränderung vorgestellt. Die verschiedenen Neuronenpopulationen, die durch unterschiedliche Plazierung zweier Ableitelektroden erfaßt werden, deuten auf signifikante Unterschiede im Hinblick auf das Zeitauflösungsvermögen hin. Während für Klickstimulation beide Elektrodenkonfigurationen deutliche Potentialmuster aufweisen, wird für eine kurzzeitige Veränderung der interauralen Laufzeit nur für eine Elektrodenanordnung ein ausgeprägtes Reizantwortmuster evoziert. Dieses ist durch eine abnehmende Erregungsamplitude bei Verkleinerung der interauralen Laufzeitdifferenz und des untersuchten Zeitintervalls gekennzeichnet.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 49 (1983), S. 229-246 
    ISSN: 1432-1106
    Keywords: Cat ; Ventrobasal complex ; Labelled lemniscal axons ; Light and electron microscopy ; Neuron types
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neurons responding to deep or cutaneous stimuli are situated in different parts of the ventrobasal complex. Within the cutaneous region elongated clusters of cells with common place and modality properties project to single columns in the somatic sensory cortex. The present study sought to determine to what extent single lemniscal axons contribute terminals to different regions and to different cell clusters. Lemniscal axons, anterogradely labelled by horseradish peroxidase injected into the medial lemniscus of cats were examined light and electron microscopically. Labelled axons bore one or two, mainly anteroposteriorly oriented, terminal ramifications. These ramifications were relatively small when compared to the length of the complex. Some of the axons bore one or two collaterals that ascended towards the dorsal edge of the complex and formed an additional small ramification there. Electron microscopic analyses of labelled lemniscal axons provided further evidence to that already available that most of their boutons synapse on proximal dendrites of relay neurons and on presynaptic dendrites, presumably belonging to interneurons. A concurrent study of Golgi-impregnated ventrobasal neurons showed three morphological types all with dendritic fields of similar extent. From measurements of the lemniscal terminal ramifications and the counting of counterstained cells it was calculated that 50–120 neurons may receive input from a single terminal ramification. However, because of the restricted extent of the ramifications, the elongated clusters of cells projecting to a single cortical column probably receive input from multiple lemniscal axons and not all members of the cluster receive inputs from the same axons.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 50 (1983), S. 146-148 
    ISSN: 1432-1106
    Keywords: Nonspecific thalamus ; Unit recording ; Visual plasticity ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In alert cat and monkey, a unit type recorded in the region of the thalamic internal medullary lamina seems to provide the extraretinal signal postulated by Singer (1982) to explain the development of mature receptive field properties in cortical visual neurons. These thalamic units are silent (or silenced) during saccades in all directions; they discharge as soon as the eyes assume a new position. The abolition of this discharge by thalamic lesion, or conversely, its elicitation by electrical stimulation could respectively prevent or facilitate plastic changes in visual cortical areas of kittens.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-1106
    Keywords: Cortex ; Thalamus ; Fluorescent method ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The retrograde fluorescent technique was used to label cortical neurons which project to both the caudate nucleus and also to the centromedian-parafascicular (CM-Pf) thalamic nuclear complex. After experimentation with many other pairs of fluorescent tracers, Evans Blue (EB) and Fast Blue (FB) were chosen as the best combination for studying the systems involved. Following injections of EB into the caudate nucleus and FB into the CM-Pf complex, doubly labeled medium-sized pyramidal neurons were present within layer V and VI of specific cortical regions. These cells were found on the inferior bank of the cruciate sulcus, in the anterior limbic area, in the cingulate and anterior sylvian gyri and within the buried cortex of the presylvian sulcus. The doubly labeled cells were relatively few in number compared to the more numerous singly labeled FB (corticothalamic) cells found in layers V and VI, and the very numerous singly labeled EB (corticostriatal) neurons, located in layers II, III, V, and VI.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 52 (1983), S. 235-247 
    ISSN: 1432-1106
    Keywords: Visual cortex ; Receptive field properties ; Orientation selectivity ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The relationship between orientation selectivity and spatial receptive field organization was analyzed. Receptive field maps were made with a dual stimulus technique where an optimally oriented activation slit was presented in the most responsive region to produce activity against which the effect of a test spot in various positions was determined. Both simple and complex cells had receptive fields which were subdivided into adjacent elongated and antagonistic subrogions. When the two stimuli were presented in phase (both ON or OFF simultaneously) the fields had a central enhancement region with a strong suppression flank on one or both sides. Optimal slit orientation was related to the location of the suppression flank relative to the location of the central enhancement region, and the degree of orientation selectivity to the shape of the subregions and the distance between them. Estimated orientation tuning curves calculated from the receptive field maps gave satisfactory first approximations to experimental curves. The relative contribution of enhancement and suppression to orientation selectivity was studied by presenting a test slit in different orientations in phase with an optimally oriented activation slit. The orientation selectivity was produced almost exclusively by the flank suppression indicating that orientation selectivity is produced by inhibitory input. The flank suppression lacked any specific orientation selectivity, and it occurred only when both the central region and the flanks were activated in phase. Orientation selectivity in both simple and complex cells is explained by a receptive field organization where the cells have input from partially overlapping excitatory and inhibitory fields which have their centers slightly displaced from each other.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 166 (1983), S. 291-306 
    ISSN: 1432-0568
    Keywords: Quantitative analysis ; Thalamus ; VB complex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A quantitative analysis was carried out on the thalamic ventrobasal (VB) complex of the cat. The following numerical and metrical parameters of the neuronal elements (cells and fibers) were determined: 1. Volume of nucleus: 27.38 mm3 2. Total number of neurons: 243,000 3. Total number of fibers of medial lemniscus: 26,000 4. Volume of arborization space of one lemniscal fiber: 2.26×106 μm3. Numerical data of relay neurons and lemniscal fibers and their relations as basic factors in the estimation of the degree of divergence and convergence of lemniscal input were calculated and compared. It was found that the probable degree of convergence is four-fold (1–4) and of divergence 27-fold (1–27) with regard to the relationship of fibers and cells in the VB. The quantitative data obtained in the VB and our considerations on convergence and divergence were compared with analogous values obtained for the lateral geniculate body LGB. The differences between the two sensory relay nuclei reflect differences in their modes of impulse transmission.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1432-0568
    Keywords: Placenta ; Uterine microvasculature ; Corrosion casts ; Scanning electron microscopy ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The microvascular architecture of cat uteri from the 22nd to the 62nd day of pregnancy was investigated on corrosion casts by means of scanning electron microscopy. These findings, concerning the endometrial labyrinthine zone, were compared with those on corresponding semithin histological sections. Each area in the zonary girdle of feline placenta is supplied by a centrally located stem-artery. Such a stem-artery displays branching vessels, which partly anastomose with other areas, and originates from the superficial arterial network of the uterus. It straightly crosses the myometrial and labyrinthine layers and branches several times, forming a funnel-shaped system on the fetal side of the labyrinth. Arterioles ramifying from this system enter the septal capillary network of the labyrinthine zone which is composed of single lamellae with progressively complex shapes during pregnancy. This network is oriented in feto-maternal direction. Venules, originating at the end of an area, converge from the lamellae to stem-veins. These veins link the labyrinth and deep endometrial layers with a venous plexus in the myometrium, which, finally, joins the superficial network of uterine veins.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1432-0568
    Keywords: Serotonin fiber ; Hypothalamus ; Immunohistochemistry ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Distribution of serotonin nerve fibers in the hypothalamus of the cat was studied using the peroxidase antiperoxidase (PAP) immunohistochemical method. There was a heavy concentration of serotonin nerve fibers in the nucleus suprachiasmaticus, the nucleus ventromedialis and the nucleus dorsomedialis. The distribution pattern of the serotonergic fibers in the cat was principally similar to that of the rat and monkey. However, species differences were noted in the mamillary complex, the nucleus hypothalamicus anterior, the nucleus paraventricularis and the nucleus supraopticus.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 52 (1983), S. 307-310 
    ISSN: 1432-1106
    Keywords: Strabismus ; Ocular dominance ; Visual cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Cats with a natural convergent squint were discovered within a colony of normal Mill Hill cats. In two of them single unit recording was undertaken in area 17. The ocular dominance distribution showed a clear disruption of binocularity in both hemispheres. This lack of binocular units was comparable to cats with artificial, surgically-induced strabismus and differed significantly from the ocular dominance distribution of a normal control group. The existence of these natural, non-albino squinters strengthens the use of cats as an animal model for strabismic amblyopia.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1432-1106
    Keywords: Cat ; Lateral geniculate nucleus ; Decortication ; Residual neurons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Residual neurons following chronic surgical disconnection from the cortex were studied by light and electron microscopy in the dorsal Lateral Geniculate Nucleus (LGN) of adult cats. One year after operation the volume of the decorticated LGN had shrunken to approximately half that of the control LGN. The number of nerve cells decreased at the same time, to 13–15% of the control, with relatively higher cell loss in A and A1 laminae than in lamina C. The Golgi, Golgi-EM and EM analysis of the residual neurons revealed that they contain two distinct nerve cell types. (1) 55% of all surviving neurons were identified as geniculo-cortical relay cells, while (2) 45% of the persisting nerve cells were interneurons. These data suggest that in the normal LGN of adult cat 7% (or more) of all nerve cells are local interneurons. Finally, those factors which might contribute to the unexpected survival of many relay neurons to the axotomy-caused retrograde degeneration, are considered and discussed.
    Type of Medium: Electronic Resource
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  • 11
    ISSN: 1432-1106
    Keywords: Postural reflexes ; Unexpected postural perturbations ; Electromyographic activity ; Hind limb and forelimb muscles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary EMG responses, vertical and A-P shear forces and kinematics of “automatic postural responses” to unexpected translational perturbations in the headward and tailward directions were studied in cats. Muscles acting on the major joints of the forelimbs and hindlimbs were studied. Movement of the animals in response to perturbation were highly stereotyped and consisted of two phases: (1) motion of the feet during platform movement while the trunk remained relatively stationary followed by (2) active correction of posture by movement of the trunk in the direction of perturbation. Vertical force changes occurred after the perturbation was well underway (latency 65 ms) and were related to the displacement of the center of mass and active correction of trunk position. Shear forces showed both passive (inertial) and active components and suggested that the majority of the torque necessary for po,stural correction was generated by the hindlimb. EMG responses in forelimb and shoulder muscles were most correlated with increase in vertical force, showing a generalized co-contraction in tailward translation (when these limbs were loaded) and little activity when the forelimbs were unloaded. EMG responses in hindlimb showed reciprocal activation of agonists and antagonists during perturbation with strong synergies of thigh and foot flexors in tailward translation and thigh and foot extensors in headward translation. The forelimb EMG patterns were most consistent with the conclusion that the forelimb is used primarily for vertical support during perturbation. It was concluded that hindlimb EMG responses were appropriate for both vertical support and performance of the postural correction. The hindlimb muscle synergies observed during translation are the “mirror image” of those observed in humans by other workers.
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 1432-1106
    Keywords: Visual cortex ; Plasticity ; Catecholamines ; 6-Hydroxydopamine ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Between 4 and 10 weeks of age 10 normally reared kittens were bilaterally implanted with osmotic minipumps. The visual cortex of one hemisphere was infused with 4 mM 6-hydroxydopamine while the other hemisphere received only a vehicle solution. The pumps delivered the solutions at 1 μl/h for one week concurrent with monocular deprivation. Subsequent electrophysiological recording was performed blind and revealed a marked effect of the 6-OHDA treatment: while most cells in the control hemisphere were primarily activated by stimulation of the non-deprived eye, cells in the 6-OHDA-treated hemisphere were significantly more binocular. High pressure liquid chromatography revealed that the loss of normal ocular dominance plasticity in 6-OHDA-infused hemispheres was always accompanied by at least a 50% decrease in cortical norepinephrine levels and a smaller decrease in dopamine levels. Furthermore, there appeared to be a positive correlation of the degree of ocular dominance shift and the relative amount of norepinephrine present. These results are consistent with the hypothesis that catecholamines, especially norepinephrine, are normally required for ocular dominance plasticity during the critical period in kittens.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 52 (1983), S. 87-98 
    ISSN: 1432-1106
    Keywords: Spatial summation ; Simple Cells ; Visual cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Spatial summation was studied quantitatively through width response curves made with an optimally oriented test slit of variable width, and by comparing the response to combined presentation of several parallel slits with the response to each slit alone. Prior to summation analysis, the cell's discharge field (DF) was mapped by presenting a test slit ON and OFF across the receptive field. Activation profiles, showing the extension of subregions where light stimulation increased (enhancement) or decreased the firing rate (suppression), were made by presenting an optimally oriented activation slit in the most responsive DF-position. Against this activity the effects of a parallel test slit were determined in a series of broadside positions. Width response curves were made over the subregions of the DF and the activation profiles. Spatial summation was found in all cells, but the width of the summation region was smaller than the width of the subregions in the respective profiles. The width of the summation region was related to the degree of activation rather than to specific locations within the receptive field. The effect produced by several slits presented together deviated from the algebraic sum of the effects produced by each slit alone. Linear summation was rarely found. Accumulated response curves obtained by integration of DF or activation profiles were compared with width response curves to test linearity of summation. Linear summation throughout the whole receptive field was never found. A satisfactory fit was found only over a narrow region showing that summation was linear within a small part of the summation region. Linearity ended near response maxima or minima in the response profiles. The results indicate that the receptive field of simple cells consists of overlapping excitatory and inhibitory fields, and that the exact location and width of enhancement and suppression zones are determined by an activity-dependent balance between excitatory and inhibitory inputs.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 52 (1983), S. 125-138 
    ISSN: 1432-1106
    Keywords: Vestibulo-ocular reflex ; Secondary vestibular neuron ; Posterior semicircular canal ; Cat ; Rabbit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. The morphology of secondary vertical vestibular neurons was investigated by injection of horseradish peroxidase (HRP) into cells connected to the posterior canal system in rabbits (lateral-eyed animals) and cats (frontal-eyed animals). Vestibular neurons were identified by stimulation with bipolar electrodes implanted into the ampullae of the anterior and posterior (PC) semicircular canals of pigmented rabbits; in the cat, these cells were identified by natural and electrical stimulation. Axons monosynaptically activated by PC stimulation were injected with HRP in the medial longitudinal fasciculus (MLF). These were later reconstructed by light microscopy after the brains had been processed with a DAB-CoCl2 method. 2. In the rabbit the majority of the axons bifurcated after crossing the midline with one branch ascending and the other descending in the MLF. The ascending branches gave rise to collaterals that terminated in both the trochlear nucleus and the inferior rectus subdivision of the oculomotor nucleus. In addition some axons also sent collaterals into the paramedian pontine reticular formation, the periaqueductal grey and the interstitial nucleus of Cajal. The descending branches were followed to the caudal part of the medulla in the MLF and gave rise to collaterals terminating in the vestibular nuclei, the medullary reticular formation, the perihypoglossal nuclei, the abducens nucleus, and the facial nucleus. In another cell type axons crossed the midline without giving off any collaterals and proceeded caudally in the caudal MLF. The synaptic effects of the two types of cells were concluded to be excitatory and inhibitory, respectively. Cell bodies of contralaterally projecting neurons were located in either the medial or ventro-lateral vestibular nuclei. 3. In the cat we observed two neuron classes, with contralaterally projecting axons, whose synaptic effects are presumably excitatory. Their cell somata were located in the medial vestibular nucleus. Termination patterns were similar to both the trochlear and oculomotor nuclei, but neither projected to the abducens nucleus. One class of neurons was almost identical to that found in the rabbit with the main axon bifurcating in the MLF. The second type lacked a descending branch in the MLF. Axon collaterals of the latter type crossed the midline within the oculomotor nucleus after terminating in the inferior rectus subdivision to reach a similar portion of the ipsilateral oculomotor nucleus. Collaterals of these axons also terminated bilaterally in the supraoculomotor region between trochlear and oculomotor nucleus, the interstitial nucleus of Cajal and prerubral loci (including the fields of Forel). In similarity to the rabbit, presumed inhibitory vestibular neurons were found with axons directed caudally in the MLF without brain stem collaterals. 4. Ipsilateral neurons with ascending axons considered to be inhibitory were only studied in the rabbit. Their cell bodies were located in the superior vestibular nucleus, the axon joining the rostral MLF with major termination sites in the superior rectus and in the inferior oblique subdivisions of the oculomotor nucleus. Other terminations were in the paramedian pontine reticular formation and in the medullary reticular formation. 5. These data indicate strong similarities in the morphology of PC linked secondary vestibular neurons in the two species suggesting paramount importance for this wiring pattern in the spatial organization of eye movements. Variations in the termination patern likely reflect different kinematic characteristics of extraocular muscles necessary for the appropriate, but different, type of compensatory eye movements in lateral-versus frontal-eyed animals. We conclude that the termination pattern of secondary vestibular neurons forms a basic part of the neuronal matrix for space-time coordinated eye-movements and other related vestibular functions. This neuronal network provides a morphological basis for a conversion factor for the transformation of vestibular into e.g. extraocular muscle coordinates.
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  • 15
    ISSN: 1432-1106
    Keywords: Posterior lateral suprasylvian area ; Receptive fields ; Synaptic transmission ; Cholinergic antagonists ; Amino acid antagonists ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Extracellular recordings have been made from 118 electrophysiologically identified neurones lying in the posterior lateral suprasylvian area (PLLS and PLMS) of cats anaesthetized with Nembutal. Eighty-one cells were activated synaptically by the electrical stimulation of cortical and subcortical sites known to be the sources of monosynaptic projections to the lateral suprasylvian area; latencies to such activations have been measured. The locations and sizes of the receptive fields of 55 neurones were determined. The direction sensitivity and ocularity of these cells also were examined. The effects of various pharmacological agonists and antagonists have been observed on visual responsiveness and synaptic excitability. The excitatory effects of subcortical (dorsal lateral geniculate nucleus and pulvinar nuclear complex) electrical stimulation on the activity of suprasylvian neurones were reduced substantially by the iontophoretic administration of atropine. Antagonists of the receptors for the excitatory amino acids reduced the effectiveness, on the single cell evoked activity, of stimulation of the ipsilateral 17/18 border region and contralateral homotopic lateral suprasylvian area. Both classes of antagonist reduced the magnitude of neuronal responses to photic stimulation, and these response attenuations were additive when the antagonists were ejected concurrently. All of the pharmacological effects were reversible and reproducible. These data lend support to the proposition that acetylcholine and an excitatory amino acid are mediators of synaptic transmission of cortical visual processes in the lateral suprasylvian area.
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 50 (1983), S. 309-320 
    ISSN: 1432-1106
    Keywords: Red nucleus ; Cerebral cortex ; Intracellular recording ; Topography ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The relations between the cerebral cortex and the red nucleus have been studied in acute, chloralose anaesthetized cats using intracellular recording techniques. Stimulation of the cerebral cortex induces in rubrospinal cells a short latency excitation followed by a long lasting silent period. The evidence is presented that at least a great part of the latter is due to genuine IPSP evoked in these cells. Three populations of rubrospinal neurones have been distinguished according to the cortical origin of their afferents: one group receives projections from the forelimb cortical area. These cells project to the cervical spinal cord and thus should control the forelimb. The second group receives projections from the hindlimb cortical area. These cells project to the lumbar spinal cord and should control the hindlimb. The third group of rubrospinal neurones receives convergent projections from both forelimb and hindlimb cortical areas. If these cells have collateralized axons terminating in both rostral and caudal spinal cord, they could contribute to the coordination of fore- and hindlimb movements. The projections originate in cytoarchitectonic areas 1–5 i.e. in the primary motor and sensory areas and in the rostral portion of the parietal area. No projection has been found from area 6 (premotor) or from area 7 (caudal parietal). The projection upon single rubrospinal cells has been found to originate from large cortical regions with a large overlap between those with excitatory and inhibitory actions. This could indicate the intermingling of cortical cells transmitting both effects.
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  • 17
    ISSN: 1432-1106
    Keywords: Postnatal development ; Geniculocortical projection ; Laminar field potential ; HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Using laminar field potential analysis, we examined responses elicited by both photic and optic nerve stimulations in 30 kittens of 0–65 days of age and in three adult cats. In adult cats, the response in the visual cortex on optic nerve stimulation is a wave complex which consists mainly of surface positive-depth negative (sP-dN) potentials. By contrast, the response in neonates consists of two surface negative — depth positive (sN-dP) waves. In 2 weeks, preceding the sN-dP waves, an sP-dN wave appears. As age increases, the sP-dN wave becomes of higher voltage and the sN-dP waves become of lower voltage. Thus, the configuration of the response resembles that of adult cats in 3–4 weeks. Both photic and optic nerve stimulations elicit responses of the same configuration in the same area. The extent of the responsive area is exactly the same at any age as in adult cats. Using the orthograde HRP method, we examined terminals of the geniculocortical afferent in 23 kittens of 0–43 days of age. The density of labeled terminals in layer I is much higher in kittens before 1 week of age (n = 8) than in kittens after 1 month of age (n = 5), whereas the density of labeled terminals in layer IV is higher in the older kittens than in the younger kittens. These electrophysiological and morphological changes are correlated in reference to the maturation of the neuronal circuit in the visual cortex.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 51 (1983), S. 97-107 
    ISSN: 1432-1106
    Keywords: Cat ; Striate cortex ; Orientation columns ; Multiunit recordings ; Cross-correlation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A series of simultaneous recordings from several striate cortex neurons were made in paralyzed, anesthetized cats. Recordings were obtained with one or two bundles of extra fine wires and originated from one and two cortical orientation columns. Standard PST histograms and, in some cases, response planes were used to analyse the neuronal receptive fields. Functional connectivity between neurons was assessed by cross-correlation of their spike trains. It was found that 61% of neuronal, pairs found within a column shared the same input, either excitatory or inhibitory. Even if neurons in a pair belonged to two different columns separated by 1 mm lateral distance, 40% of pairs still exhibited shared input coordination. This type of coordination could also encompass all combinations of simple and complex fields in the pair. Direct connections between neurons were found almost exclusively within columns: excitatory connections were found in 20% of cases and inhibitory in 8%. Direct connections were often accompanied by the other types of interactions. Only one example of excitatory and one of inhibitory direct connections were found between columns. In both cases preferred orientations were almost identical.
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  • 19
    ISSN: 1432-1106
    Keywords: Cat ; Monocular deprivation ; Short-term reverse occlusion ; Visual cortex ; Lateral geniculate nucleus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The relative efficacy of distributed versus massed reverse occlusion therapy in promoting recovery from the anatomical and physiological effects of monocular deprivation was studied in two experiments performed on kittens raised with one eye occluded from eye-opening until 5 weeks of age. The first experiment explored the effects of different periods (ranging from 0.5 to 4 h) of reverse occlusion imposed daily for 20 days. The second, involving a fixed period of reverse occlusion (20 h), examined recovery with respect to the distribution of that period over a varied number of brief daily sessions. Recovery was assessed in terms of changes in cortical ocular dominance and lateral geniculate cell morphology. Although recovery of both cortical ocular dominance and geniculate cell morphology showed the same overall progression with increasing periods of reverse occlusion, changes were apparent in the lateral geniculate nucleus before changes were evident in cortical ocular dominance. A given period of reverse occlusion was found to be far more effective in promoting recovery when distributed over a number of different exposure sessions than when massed together in just one or two sessions. The data suggest that there is a maximal rate of cortical recovery which is achieved with surprisingly brief daily periods of forced visual exposure of the initially deprived eye.
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 51 (1983), S. 157-171 
    ISSN: 1432-1106
    Keywords: Pretectal complex ; Thalamic lateral dorsal nucleus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The subcortical projections to the lateral dorsal nucleus (LD) of the cat thalamus were studied with retrograde transport techniques. Deposits of horseradish peroxidase (HRP) or fluorescent tracers were placed unilaterally in LD of adult cats, using electrophoretic or pressure injection techniques. Following post-injection survival periods of 1, 2 or 3 days, HRP retrogradely labeled cells were identified in sections reacted with benzidine dihydrochloride; fluorescent labeled cells were identified by fluorescent microscopy. Injections in LD result in retrogradely labeled neurons in all nuclei of the pretectal complex, including the nucleus of the optic tract (NTO), the posterior pretectal nucleus (NPP), the anterior pretectal nucleus (NPA), the pretectal olivary nucleus (NOL), and the medial pretectal nucleus (NPM). Small electrophoretic injections of HRP were used to investigate a possible topographic organization of the pretectal projections. Results from a variety of injection sites indicate only a subtle rostral-caudal gradient. That is, small injection sites in rostral LD result in retrograde labeling of neuron somata in the rostral parts of NTO, NPA and NPP, and throughout NPM. Injections in caudal LD result in labeled cells more caudally situated in NTO, NPA, NPP, and throughout NPM. Injections in the pulvinar (Pul) also result in retrogradely labeled cells in the pretectal complex, particularly NTO, NPP, and NOL. Experiments with injections of distinguishable fluorescent tracers in LD and Pul reveal that many more cells project to Pul than to LD. These experiments also reveal that while neurons that project to LD are intermingled with neurons that project to Pul, the two projections originate from separate sub-populations of cells. These results are discussed in regard to phylogenetic comparison of pretectal projections and subcortical pathways of sensory input to the limbic system.
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  • 21
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    Experimental brain research 51 (1983), S. 405-412 
    ISSN: 1432-1106
    Keywords: Central cervical nucleus ; Cat ; Afferents ; Anterograde degeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Afferent input to the central cervical nucleus (CCN) in the C1–4 segments was studied with degeneration methods after sectioning of dorsal roots (DRs) or lesions in the spinal cord or brain stem. Degeneration in the CCN was heavy after sectioning of the DRs C1–4, moderate after sectioning DRs C5–8, and scanty after sectioning DRs T1–4. One to 2 days after sectioning of the C2 dorsal root the resulting degeneration had a granular appearance. At 4 days after the operation coarser argyrophilic fragments appeared, and this type of degeneration dominated at longer postoperative intervals. Degeneration in the ipsilateral CCN was found after lesions of the ventral and lateral funiculi of the thoracic cord. No degeneration was found after lesions of the dorsal funiculus caudal to T4 or after lesions in the ventral and lateral funiculi of the lumbar cord. Degeneration in the ipsilateral CCN was found after lesions in the brain stem in cases with lesions involving the medial and caudal part of the medulla. These afferents may run in the medial longitudinal fascicle (MLF).
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  • 22
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    Experimental brain research 51 (1983), S. 351-367 
    ISSN: 1432-1106
    Keywords: Cat ; Motor cortex ; Single-unit activity ; Force tracking ; Task relations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary (1) Participation of the motor cortex in initiating muscle contraction in an isometric tracking task was assessed in cats trained to make accurate force adjustments using forelimb muscles, in response to a vibrissal/visual display stimulus. Behavior in the task was characterized by short reaction times. While the task was performed, recordings of single cortical units were made in zones within area 4γ defined by the effects of microstimulation in forelimb muscles and by receptive fields on the forelimb. (2) Two types of receptive fields with different regional distributions were observed. Cells with simple receptive fields (superficial or deep) were seen throughout the area sampled, consisting of the lateral half of the anterior and posterior sigmoid gyri. Cells whose receptive fields had complex features (directional specificity, temporal lability, multiple foci, etc.) were preferentially located in the cortex rostral to the cruciate sulcus. (3) The area of motor cortex rostral to the cruciate sulcus also differed from the area caudal to the cruciate sulcus in the timing of task-related activity. Neurons that were active before response onset (lead cells), and could therefore contribute to response initiation, were preferentially located in the rostral cortex, and, in general, had complex receptive fields. (4) Lead cells were active at a constant latency from the stimulus, rather than being timed to response onset. However, the modulation of their activity was related to both the direction and magnitude of the force response. (5) These results suggest that the pericruciate motor cortex of the cat contains two functional subdivisions: a caudal one concerned with ongoing movement, perhaps under the control of specific sensory inputs from the responding limb, and a rostral one involved in initiating movement. Because behaviorally relevant stimuli can rapidly activate a specialized population of cells in the rostral cortex, this area is able to participate in responses with short reaction times.
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  • 23
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    Experimental brain research 51 (1983), S. 423-432 
    ISSN: 1432-1106
    Keywords: Prefrontal cortex ; Superior colliculus ; Horseradish peroxidase ; Autoradiography ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The cells of origin and terminal distribution of the prefrontal corticotectal projection in the cat has been examined using retrograde cell-labeling with horseradish peroxidase (HRP) and anterograde axon-labeling with HRP or 3H-amino acid autoradiography. All prefrontal neurons labeled from unilateral enzyme deposits in the superior colliculus are pyramidal cells scattered through the thickness of layer V. The ipsilateral prefrontotectal neurons are located most densely in the banks and fundus of the presylvian sulcus and, to a lesser extent, in the anterior and frontal polar part of the gyrus proreus. About 10% as many cells are labeled in the contralateral prefrontal cortex in a similar distribution. Injections of HRP restricted to the superficial layers of the colliculus failed to label cells in the prefrontal cortex. Injections of HRP or 3H-proline-leucine in the region of these prefrontotectal neurons results in axonlabeling mainly, but not exclusively, in the ipsilateral superior colliculus where the labeled fibers are distributed in the layers below the stratum opticum. Labeled axons are especially dense in the intermediate gray layer where, caudally, they are arranged in two horizontally arrayed dorsal and ventral sheets interconnected by periodic columns of dense fiberlabeling interposed between columns of lesser fiberlabeling. Thus, the prefrontotectal projection of the cat here reported is consistent with that described earlier for the rat, but differs markedly from the primate in that prefrontal area 8 in monkeys projects also to the superficial tectal layers.
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  • 24
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    Experimental brain research 49 (1983), S. 28-34 
    ISSN: 1432-1106
    Keywords: Vestibular ; Ocular ; Optokinetic ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ocular movements of naive and adapted cats were recorded by classical electronystagmography techniques during: (1) sinusoidal vestibular stimulation, (2) sinusoidal optokinetic stimulation, (3) sinusoidal additive visual-vestibular stimulation, and (4) sinusoidal conflicting visual-vestibular stimulation. Adaptation of the horizontal vestibulo-ocular reflex (VOR) was produced in adult cats by sustained combined sinusoidal rotation of the cat and its surroundings (fixed-field conditions). This procedure was applied for four hours for four consecutive days. On the fifth day the VOR in darkness, the OKR, the VOR in the light and the visual suppression of the VOR were studied. VOR gain decreased from day to day and some relative frequency-specificity emerged. The gain of the visually inhibited VOR also diminished after training. This change was also frequency-specific. OKN gain, tested by a set of sinusoidal rotations, was found to be virtually unchanged. In the naive cat, VOR modified by the visual stimulus (fixed or moving) could be computed by an algebraic summation of the VOR and OKR eye movement compensations. After training, the gain of the VOR in situations where the VOR was interacting with the OKR remained easily predictable by the algebraic summation of the isolated VOR and OKR compensations.
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  • 25
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    Experimental brain research 49 (1983), S. 84-92 
    ISSN: 1432-1106
    Keywords: Directional specificity ; Receptive field organization ; Opponent processesLateral suprasylvian area ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary For the experiments reported in this study, recordings were obtained from 246 single units in the middle lateral suprasylvian visual area (LS) of 13 cats. 49 of these cells were subjected to detailed quantitative analysis. The receptive field (RF) organization was examined for directionally specific cells by presenting moving single spots on large moving random dot backgrounds. A cell's response to an optimal spot (in terms of size, direction, velocity) moving on a stationary background inside the excitatory RF (ERF) was compared to in-phase (same direction, same velocity) and anti-phase (opposite direction, same velocity) movement of spot and background. In-phase movement resulted in inhibition of the cell's response (3–100%) in 94% of the cells, while anti-phase movement led to reduced inhibition in 52% of the cells or to facilitation (0.5–327%) in 39% of the cells. By changing the direction of background motion with respect to that of the spot, the directional tuning of the in-phase inhibition and anti-phase facilitation effects was determined. We were able to manipulate the size of the background effects by masking out the background for various proportions of the ERF, and maximizing them by restricting background stimulation to the large inhibitory RF (IRF) surrounding the ERF. These results could be best accounted for by a double-opponent-process mechanism with both RF center and RF surround being directionally selective, but with opposite polarity. It is suggested that this type of mechanism could be involved in the processing of object motion.
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  • 26
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    Experimental brain research 49 (1983), S. 457-461 
    ISSN: 1432-1106
    Keywords: Fluorescent retrograde tracing ; Inferior colliculus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary By means of retrograde axonal transport of fluorescent substances, e.g., Propidium Iodide, Fast Blue, and Nuclear Yellow, the present study was made to determine whether or not single neurons in the cat inferior colliculus share ascending and descending projections to the following two pairs of structures, i.e. (1) to the medial geniculate body and cochlear nuclei, and (2) to the superior colliculus and pontine nuclei. Our findings indicate that extremely few neurons, if any, in the inferior colliculus harbor such divergent axon collaterals, although most of the different types of projection neurons are located in the same subdivisions of the colliculus.
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  • 27
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    Keywords: “Fictitious” scratch reflex ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary (1)Pinna stimulation evoked rhythmic oscillations in the spinal cord of the decerebrate curarized cat (“fictitious” scratch reflex). The role of different spinal segments in generation of these oscillations was studied. For this purpose, destruction of the grey matter of one or of several spinal segments was performed. Besides, different numbers of caudal segments were disconnected from the rest of the cord by cooling the lateral surface of the cord. ENGs of muscle nerves and activity of spinal neurons were recorded. (2) Different parts of the lumbosacral spinal cord, i.e. the L3 and L4 segments disconnected from the caudal part of the cord as well as the isolated L5 segment, are capable of generating rhythmic oscillations with a frequency (3–4 Hz) typical of the scratch reflex. (3) Rhythmic activity of the more caudal segments (L6-S1) usually appears only provided the rostral segments (L3–L5) generate rhythmic oscillations. However, when the dorsal surface of the L6-S1 segments is cooled, pinna stimulation evokes rhythmic activity in these segments earlier than in the L3–L5 segments. (4) The hypothesis is advanced that the L3–L5 segments are the “leading” ones, i.e., they determine the rhythm of activity in the whole spinal hindlimb centre.
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  • 28
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    Experimental brain research 96 (1983), S. 65-76 
    ISSN: 1432-1106
    Keywords: Eye movements ; Saccades ; Postsaccadic drifts ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Inspection of eye saccades made by head-fixed, trained cats revealed the existence of many eye shifts at an approximately constant velocity during the deceleratory phase of the saccade or at the end of it. Slow eye movements occurring at the end of a saccade are usually referred to as “postsaccadic drifts”. It is shown that the duration and mean velocity of these “drifts” are related to the amplitude of the movement. The kinematics of these slow eye movements are nevertheless different from those of saccades. Slow movements at the end of the gaze shift have longer durations than those occurring during the intersaccadic interval between a saccade and a reacceleration of the eye. A closer study of the drifts of three trained cats showed that they play an important corrective role in reducing the residual error at the end of a saccade or during an intersaccadic interval. This functional corrective role was demonstrated by relating the amplitude of the slow movement to the amplitude of the residual error when the slow velocity eye shift began. It is therefore proposed to name these eye shifts “slow correcting movements”.
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  • 29
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    Experimental brain research 96 (1983), S. 107-116 
    ISSN: 1432-1106
    Keywords: Gravity ; Eye position ; Extraocular muscles ; Proprioception ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We measured rotation (horizontal, vertical and torsional) and translation (horizontal and vertical) of the paralysed cat's eye in response to 45° steps of orientation presented in a pseudorandom order around the roll and pitch axes (with respect to the horizontal canals). During changes of position of the animal in the roll plane, the eyes rotated towards the lowest part of the orbit (left with left ear down; top when the cat was upside down, etc.) by an average of 0.55°. Changing orientation in the pitch plane evoked vertical rotations of ±1.42° (upwards eye movement during forwards head pitch) and torsional rotations of ±1.3°. All these rotations taken together suggest that the centre of mass is in front of, below and temporal to the centre of rotation. The eyes translated temporally (thus separating by 0.72 mm) during forward pitching and there was a small vertical displacement (0.23 mm) when the animal was upside down. These findings are discussed with respect to a possible role of the extraocular proprioception system.
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  • 30
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    Experimental brain research 96 (1983), S. 141-151 
    ISSN: 1432-1106
    Keywords: Muscles ; Ankle ; Moment arm ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The cat hindlimb muscles have been classified, traditionally, as flexors and extensors, based on their actions in the parasagittal plane and their patterns of recruitment during locomotion and reflex responses. This study provides a detailed examination of the relative magnitudes of the various moment arms of the cat ankle muscles and the interdependent effects of position in the various axes of motion. We used a method based on observing small sliding movements of tendon in response to small angular displacements of the joint. Surprisingly, we found that the ankle joint of the cat permits substantial motion in three axes (eversion/inversion and abduction/ adduction as well as extension/flexion) and many muscles crossing the ankle joint have their largest moment arms about axes other than extension/flexion. These moment arms often depended on the joint position in the axis of the moment arm and, to a lesser degree, on the extension/ flexion angle as well. For some muscles (notably peroneus longus) there was sufficient variability that the predominant action in neutral posture (axis with the largest moment arm) could change from animal to animal, which may be related to heterogeneities of locomotor and reflex recruitment reported in the companion paper.
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  • 31
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    Experimental brain research 96 (1983), S. 125-140 
    ISSN: 1432-1106
    Keywords: Muscles ; Locomotion ; Reflexes ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract During stereotyped behaviors such as locomotion, patterns of muscle recruitment are usually quite consistent from animal to animal, even in the face of many surgical and pharmacological reductions. However, as studies of musculoskeletal structure, neuromuscular architecture, and sensorimotor circuitry become more detailed, it is important to ask whether there is some level of organization at which individual differences begin to dominate. This study concentrated on the small muscles of the foot and ankle, using standardized methods that consistently record stereotypical electromyographic activity from prime mover muscles and that permit wellcalibrated stimulation of cutaneous nerves to elicit reflexes during treadmill locomotion. Some muscles (particularly the main ankle extensors, triceps surae, and plantaris) had stereotyped activity during both unperturbed locomotion and reflex responses. Others had stereotyped activity during locomotion but variable reflex patterns among animals (tibialis anterior, extensor digitorum longus, flexor hallucis longus, and peroneus brevis). Still others had variable locomotor activity but reflexes that were consistent (flexor digitorum longus) or variable for only peroneal nerve stimulation (peroneus longus), only plantar nerve stimulation (peroneus tertius), or the two (flexor digitorum brevis). Among muscles with interanimal variability, there seemed to be no particular correlation between locomotor and reflexive recruitment in a given animal. This functional heterogeneity is discussed in terms of the development of locomotor and reflex programs and in the context of structural heterogeneity of some of these muscles that is described in the companion paper.
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  • 32
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    Experimental brain research 51 (1983), S. 236-246 
    ISSN: 1432-1106
    Keywords: Nucleus of the optic tract ; Monocular deprivation ; Visual responses ; Optokinetic nystagmus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Single cells were recorded extracellularly in the nucleus of the optic tract (NOT) in monocularly deprived cats. Monocular deprivation had no effect on the direction specificity of these neurons, i.e. all cells in the left nucleus preferred movements from right to left and all units in the right nucleus preferred movements from left to right in the visual field. Neurons driven from the deprived eye failed to respond to stimuli moving at velocities above 10°/s whereas neurons driven from the non-deprived eye responded to velocities up to and above 100°/s as do neurons in normal cats. In 8 out of the 10 cats tested all cells in the two nuclei could be influenced only from the contralateral eye irrespective whether this was the deprived or the non-deprived eye. In the other two cats the influence from the non-deprived eye on cells in the ipsilateral NOT was found to be normal. This influence is mediated probably via cortico-fugal projections. In the 8 abnormal cats a clear deprivation effect could be assigned for the first time to the non-deprived eye consisting in a loss of its connections to the ipsilateral NOT. Electrical stimulation of the visual cortex revealed, however, the existence of a connection between the visual cortex and the NOT. A possible explanation for the specific deficit with visual stimulation in the cortico-pretectal synapse ipsilateral to the non-deprived eye is discussed in relation to developmental mechanisms. The conduction velocity of retinal input to the NOT and the output of the NOT to the inferior olive remained uninfluenced by visual deprivation.
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  • 33
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    Experimental brain research 51 (1983), S. 298-303 
    ISSN: 1432-1106
    Keywords: Visual input ; Vestibular nuclei ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Non-cerebellar afferents from visual relays to the vestibular nuclei (VN) of the cat have been re-evaluated with the use of the horseradish peroxidase technique. From our data it can be concluded that: (1) A monosynaptic projection from the nucleus reticularis tegmenti pontis to the VN can be excluded. (2) Monosynaptic projections from the superior colliculus and some of the pretectal nuclei (nucleus of the optic tract, olivary pretectal nucleus) to the nucleus prepositus hypoglossi may constitute polysynaptic visual afferents to the VN, which would account for the residual visual sensitivity of the VN neurons after cerebellar or inferior olivary lesions.
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  • 34
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    Experimental brain research 49 (1983), S. 13-27 
    ISSN: 1432-1106
    Keywords: Cortex around sulcus suprasylvius (PSSC) ; Cat ; Visual association cortex ; Association fibres
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary This paper reports on experiments in which the effect of disconnexion of association fibres from Area 17/18 to the posterior suprasylvian cortex (PSSC) was investigated. In the control experiments, all neurons had large receptive fields in the central 5–10 ° of the visual field without detailled retinotopy. In the medial bank of PSSC, receptive fields were located in the contralateral visual field, while receptive fields of neurons in the lateral bank were located ipsilaterally. Neurons in PSSC could be excited by electrical stimulation of the ipsilateral Area 17/18 boundary, of the medial pulvinar (N. lat. post., pars, lat.) and the lateral geniculate body. About 2/3 of all neurons could be excited from all these regions, although with varying latencies. After acute and chronic subpial undercutting of the representation of the central 5–10 ° of the ipsilateral area 17/18, visual response properties including direction sensitivity, receptive field size and ocularity of PSSC-neurons in the medio-posterior bank did not change significantly. After ablation of the whole contralateral visual cortex (including PSSC and a wide region of the contralateral Clare-Bishop area) the input from the ipsilateral eye was considerably diminished, but other response properties did not change significantly. These essentially negative findings are discussed in relation to different findings of other authors, and it is argued that the subpial undercutting of only the central visual field representation may have prevented damage to the ipsilateral suprasylvian cortex and its afferents, which is difficult to avoid if the whole area 17 is ablated by suction. It is proposed, that association fibres may only “unspecifically” excite neurons in related association areas rather than impose onto them specific response features. These latter are derived, also in association areas, essentially from their thalamic afferents and their intracortical interaction.
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  • 35
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    Experimental brain research 51 (1983), S. 192-198 
    ISSN: 1432-1106
    Keywords: Flocculus ; Nucleus prepositus hypoglossi ; Ultrastructure ; Degeneration ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Small electrolytic lesions were made in the flocculus of two adult cats by means of a stereotactic approach avoiding any damage to the cerebellar nuclei. After a survival time of 3 days the animals were killed and the brains fixed and prepared according to standard procedures for ultrastructural studies. The brains of two unoperated cats were similarly treated and served as normal controls. In the experimental animals a large number of boutons in the rostral part of the nucleus prepositus hypoglossi (Ph) ipsilateral to the floccular lesion showed degenerative changes. These were characterized by hypertrophy, a prominent aggregation of densely packed parallel tubules or concentric arrays of cisternae and a filamentous hyperplasia. Only very rarely were such abnormal boutons seen in the caudal half of the ipsilateral Ph, or on the contralateral side or in the unoperated animals. The degenerating boutons contain clusters of pleomorphic vesicles and they establish symmetrical synaptic contacts with somata, dendritic shafts and dendritic spines. Some of the degenerating boutons appear to be of the en passant type. These findings thus affirm the existence of a direct flocculo-prepositus projection in the cat. It is suggested that this pathway could be responsible for mediating information about eye position and velocity to Ph neurons.
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  • 36
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    Experimental brain research 52 (1983), S. 429-438 
    ISSN: 1432-1106
    Keywords: Posture ; Optokinetic stimulation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The influence of horizontal optokinetic stimulation on posture and postural readjustments, induced by horizontal rotation of a turntable, were studied in the cat. Optokinetic stimulations at constant velocities lead to modifications of posture depending on the velocity of the stimulus. However, habituation as well as interindividual variability of these postural responses make difficult a systematic and quantitative approach to the phenomenon. Optokinetic stimulations at sinusoidal velocities induced reproductible postural responses, whose phase and gain were studied at different velocities and frequencies of stimulation. At low frequencies (from 0.05 Hz to 0.2 Hz) the postural responses tend to lead the position of the Optokinetic stimulus while a lag appears at higher frequencies (up to 1 Hz). In these conditions the gain increases and seems to depend on the performances of the simultaneously elicited oculomotor response. Induced postural readjustments are also modulated by the relative velocity of the visual stimulation with respect to the cat. A given visual input is more effective on an induced postural readjustment than on the posture of a static animal, especially at low frequencies (from 0.05 Hz to 0.3 Hz). These data extend to the cat the strong visual component of the postural control system previously described in other species.
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  • 37
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    Experimental brain research 53 (1983), S. 71-80 
    ISSN: 1432-1106
    Keywords: Thermal sensations ; Spinal cord ; Lesions ; Behaviour ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Cats were trained to discriminate temperature increases or decreases with the paws of one body half in a T-maze. The discriminatory proficiency was found to be inferior compared to cats who may use all four paws. The accomplishments of cats discriminating temperature decreases were superior to those of cats discriminating temperature increases. After transection of one lateral funiculus at the fifth cervical segment all of the cats lost the ability to discriminate temperatures with the contralateral paws. No thermosensory deficiency of the ipsilateral paws was observed. Five out of six cats recovered some ability to discriminate temperature differences with the contralateral paws, but no cat regained its preoperative proficiency within more than one and a half years postoperatively. The findings are taken to indicate the existence of more than one spinal, ascending, thermosensory pathway in the cat.
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  • 38
    ISSN: 1432-1106
    Keywords: Acetylcholine ; Receptor antagonists ; Area 17 ; Mesencephalic reticular formation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Stimulation of the mesencephalic reticular formation facilitates responses in the visual cortex elicited from the optic radiation. Using intraveneous administration of cholinergic antagonists we investigated in adult cats and two kittens whether this effect is mediated by cholinergic mechanisms. When administered alone the muscarinic antagonists atropine and scopolamine and the nicotinic antagonist mecamylamine failed to block reticular facilitation and sometimes even enhanced the effects of reticular stimulation. However, when administered in combination muscarinic and nicotinic antagonists eliminated or significantly reduced the facilitation. This was even true when the two antagonists were administered with a time lag of several hours. These results support the notion that reticular facilitation of cortical responses is mediated by cholinergic mechanisms and suggest that this effect is mediated either by a receptor with a mixed pharmacological property or by two independent pathways acting via nicotinic and muscarinic receptors. This hypothesis is discussed in the context of recent evidence on cholinergic transmission and earlier data on the pharmacology of reticular arousal.
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  • 39
    ISSN: 1432-1106
    Keywords: Excitotoxin lesion ; Basal forebrain ; Area 17 ; Mesencephalic reticular formation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cholinergic afferents to the neocortex controlled by the mesencephalic reticular formation (MRF) are known to transiently facilitate cortical excitability. In an attempt to identify the pathway mediating this effect in the cat visual cortex we combined retrograde tracing techniques with immunocytochemical methods to visualize the acetylcholine-synthesizing enzyme choline acetyltransferase (ChAT). In addition we examined, in acute electrophysiological experiments, whether local neurotoxin injections into nuclei of the basal forebrain interfered with the reticular facilitation of cortical evoked potentials. Cholinergic projections to area 17 originate from different centers in the homolateral substantia innominata/internal capsule, the septal nuclei, and the nuclei of the diagonal band of Broca. No direct cholinergic projection from the MRF to the visual cortex was observed. Retrogradely labelled cells intermingled with ChAT-positive neurons in the brainstem generally revealed immunopositivity for catecholaminergic markers. Local injections of neurotoxins in the substantia innominata blocked reticular facilitation, whereas local lesions of the septal nuclei and the nuclei of the diagonal band had no effect on MRF-induced facilitation. The blockage of the reticular facilitation of cortical evoked responses after unilateral lesions of the substantia innominata was bilateral, suggesting a cooperative interaction between basal forebrain structures of the two hemispheres. The anatomical and physiological data are discussed with respect to possible mechanisms of transient brainstem influences on cortical excitability.
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  • 40
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    Experimental brain research 49 (1983), S. 353-362 
    ISSN: 1432-1106
    Keywords: Climbing fibre projection ; Cerebellar cortex ; Sagittal organization ; Superior colliculus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The climbing fibre pathway from the tectum to posterior cerebellar cortex was investigated in chloralose anaesthetized cats. With low threshold electrical stimulation within the deeper layers of the superior colliculus, climbing fibre responses were recorded in a centrally located, longitudinal area of lobulus VII, oriented perpendicular to the long axis of the folia. This same area showed climbing fibre evoked activity regardless of the side of tectum stimulated. Hence, it was concluded that the tectoolivocerebellar pathway terminates bilaterally in the most medial parts of the cerebellar cortex, the termination zones being denoted the a1 zones. The results were discussed in relationship to recent anatomical knowledge of the tecto-olivary projection and of the olivocerebellar projection to lobulus VII, and indicate that descending paths from the brain stem to the inferior olive might “respect” its intrinsic compartmentalization.
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  • 41
    ISSN: 1432-1106
    Keywords: Motor units ; Classification criteria ; Peroneus longus ; Unit composition ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Recordings were made of isometric contractions of single motor units of the cat's m. peroneus longus (PerL). The units were activated by stimulation of dissected filaments of ventral roots. In accordance with the general principles introduced by Burke et al. (1973), the 80 isolated PerL units were classified into three or four type-categories according to their contractile speed and endurance. Three currently used varieties of a “fatigue index” were calculated and found to give equivalent results. Units with a high, intermediate and low resistance to fatigue were responsible for about 22.5, 25.4 and 52.1% respectively of the total muscle force. Two alternative methods for fast/slow categorization were compared: (i) classifying all units as slow that failed to show a “sag” in partly fused contractions (“sagcriterion”, Burke et al. 1973) and (ii) classifying all units as slow that had a more prolonged twitch contraction time than that of fatigue-sensitive units (‘FF vs. S-criterion’). The relative contribution of slow units to total muscle force was about 2.8 times as great (14 versus 5%) for a classification by the FF vs. S-criterion than for a subdivision according to sagging behaviour. When compared to equivalent data from previously published studies of feline hindlimb muscles, peroneus longus was found to resemble gastrocnemius medialis in relative motor unit composition. The maximum force of individual PerL units was, however, on average ≤ 50% of that reported for corresponding types of gastrocnemius units.
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  • 42
    Electronic Resource
    Electronic Resource
    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 323 (1983), S. 145-148 
    ISSN: 1432-1912
    Keywords: Dopamine vascular receptors ; Gastrointestinal tract ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effect of intravenous infusion of dopamine (10 and 25 μg·kg−1·min−1 consecutively) on visceral blood flow distribution was examined in anesthetized cats using the microsphere technique and electromagnetic flowmetry. Arterial blood pressure did not change in response to dopamine infusion, but blood flow through the superior mesenteric artery, and blood flow in the mucosa-submucosa of the gastric antrum and various gut segments increased significantly. During infusion of the high dose the increase was most marked in the mucosa-submucosa of the antrum (+355%) and distal colon (+371%). By contrast, blood flow decreased in the muscularis-serosa of the gut segments investigated, in the spleen, pancreas, and the hepatic arterial bed. The increase in blood flow through the superior mesenteric artery was blocked by the dopamine antagonist bulbocapnine (10 mg/kg i.v.). The results suggest that the receptors mediating the dopamine-induced vasodilation in the gastrointestinal tract are located in the resistance vessels of the mucosa-submucosa.
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  • 43
    ISSN: 1432-2013
    Keywords: Visceral afferents supplying the colon ; Inferior splanchnic nerves ; Response pattern to distension and contraction of the colon ; Conduction velocities ; Cat ; Visceral nociception
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Afferent fibres, in the inferior splanchnic nerves and lumbar white rami, which supply the colon and its mesentery in the cat, were investigated for their responses to distension and contraction of the colon and to local pressure applied to colon and its mesentery. 1) 63% (177 out of 287) of the axons had resting activity (median 0.3 imp/s). These axons were either unmyelinated (conduction velocity below 2 m/s) or thin myelinated (conduction velocity below 18 m/s). Most axons without resting activity (N=95 out of 106 axons) conducted at less than 1.4 m/s, and most were probably sympathetic efferents. 2) 76 out of 80 afferent units with resting activity (95%) and 8 out of 27 units without (30%) were excited by distension of the colon. The thresholds were largely at intraluminal pressures of around 25 mm Hg or higher. 3) Most afferent units (87%) responded with an increased steady state discharge throughout the distension with or without initial dynamic response. The rest of the afferent units responded only with a transient discharged to distension. 4) Most afferent units reacted in a graded manner to variable intraluminal pressures. 5) In only 43% of the distension-sensitive afferent units could mechanoreceptive sites be located on the wall of the colon or in the mesentery. The majority of the afferent units had one mechanoreceptive site only, some had two. 6) Afferent units reacting to colon distension were also excited by contraction of the colon. 7) The excitability spectrum of visceral afferent fibres in the inferior splanchnic nerves, which are activated by colon distension, suggests that these units are involved in visceral nociception from the colon.
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  • 44
    ISSN: 1432-2013
    Keywords: Muscarinic ; Non-cholinergic synaptic mechanisms ; Sympathetic ganglia ; Vasoconstrictor neurones supplying skeletal muscle and skin ; Chemoreceptor reflexes ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Postganglionic sympathetic neurones supplying skeletal muscle and skin can be activated from the preganglionic site via cholinergic nicotinic, muscarinic and non-cholinergic synaptic mechanisms. The experiments described in this paper were designed in order to show that postganglionic vasoconstrictor neurones supplying skeletal muscle can be activated by the naturally occurring discharge pattern in preganglionicaxons when the nicotinic transmission is blocked. For this purpose, the activity was recorded simultaneously from postganglionic vasoconstrictor axons supplying skeletal muscle and vasoconstrictor axons supplying hairy skin. The preganglionic neurones were driven reflexly by stimulation of the arterial chemoreceptors. 1) During blockade of nicotinic transmission muscle vasoconstrictor neurones were activated via the CNS during stimulation of arterial chemoreceptors. This activation is either generated by muscarinic action of released acetylcholine or by a noncholinergic synaptic mechanism. 2) Postganglionic cutaneous vasoconstrictor neurones were inhibited during stimulation of arterial chemoreceptors. During blockade of cholinergic nicotinic transmission these neurones were not activated reflexly by stimulation of arterial chemoreceptors although they received inputs via cholinergic muscarinic and noncholinergic synaptic mechanisms. 3) The results illustrate that postganglionic vasoconstrictor neurones supplying skeletal muscle can not only be activated via non-nicotinic synaptic mechanisms through synchronous repetitive electrical stimulation of preganglionic axons but also by the discharge pattern produced in preganglionic neurones during stimulation of arterial chemoreceptors.
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  • 45
    ISSN: 1432-2013
    Keywords: Ontogenesis ; Autonomic nervous system ; SA-node ; Rabbit ; Cat ; Guinea pig
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of supramaximal vagus nerve stimulation on heart rate were studied in newborn rabbits, cats and guinea pigs. The analysis of the stimulus-effect curve revealed that the carlier proposed relationship: logI f/I o=H·f (I o is the steady state PP-interval before andI f during stimulation,f is the stimulus frequency, andH the slope of the line) accurately summarizes the relation in rabbits, while with minor deviations it also holds for newborn cats and guinea pigs. Thus, the vagus effect for each nerve and animal is characterized by the slope of the line,H. In rabbits and cats the vagus effect decreased during the first postnatal week to about 1/3 and 1/5 of the initial value at birth. Guinea pigs, however, did not show such a postnatal change of the vagus effect. In comparison with rabbits and cats these animals are born at a relatively late ontogenetic stage. Therefore, we hypothesized that the decrease in vagus effect is related to the stage of development and occurs mainly before birth in this species.
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  • 46
    Electronic Resource
    Electronic Resource
    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 323 (1983), S. 162-167 
    ISSN: 1432-1912
    Keywords: Endogenous histamine ; Release ; Arterial blood pressure ; Hypothalamus ; Cat ; Push-pull cannula
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The posterior hypothalamus of anaesthetized cats was superfused with artificial CSF through a push-pull cannula and the arterial blood pressure was recorded in the femoral artery. The release of endogenous histamine was determined in the hypothalamic superfusate by a radioenzymatic assay. Intravenous injection of sodium nitroprusside elicited a fall of blood pressure which was accompanied by an increase in the rate of release of endogenous histamine in the posterior hypothalamus. Similary, a controlled bleeding lowered the arterial blood pressure and enhanced the release of histamine. The durations of depressor responses to nitroprusside or controlled bleeding coincided with the duration of the changes in the rate of release of histamine. Intravenous injection of chlorisondamine also lowered the arterial blood pressure and augmented the release of histamine. However, the hypotension lasted longer than the increased release of histamine in the hypothalamus. Intravenous injection of noradrenaline elicited a rise in the arterial blood pressure which was associated with an increase in the release of histamine in the posterior hypothalamus. Intravenous injection of tramazoline led to a long-lasting hypertension and to a short-lasting increase in the release of histamine. Transection of the spinal cord at C1/C2 elicited a pressor response which was followed by hypotension. Increase and decrease in the arterial blood pressure were associated with an increased rate of release of endogenous histamine. A second transection of the spinal cord at a higher level did not influence either blood pressure or rate of release of histamine. It is concluded that increases and decreases in the arterial blood pressure enhance the rate of release of endogenous histamine in the posterior hypothalamus of the anaesthetized cat. The alterations in the release of histamine seem to represent an immediate response of the hypothalamus to changes in peripheral blood pressure.
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  • 47
    ISSN: 1432-0878
    Keywords: Substance P ; Radioimmunoassay ; Cerebral arteries ; Choroid plexus ; Dura mater ; Guinea-pig ; Rabbit ; Cat ; Man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Substance P-like immunoreactivity (SPLI) was studied by immunocytochemistry and radioimmunoassay in the cerebral arteries, choroid plexus and dura mater of the guinea-pig, rabbit, cat and man. The highest concentrations were found in cerebral blood vessels: 6.1±2.3 pmol/g (guinea-pig), 9.0±1.1 pmol/g (rabbit), 7.1±0.4 pmol/g (cat), and 2.4±0.9 pmol/g (man). Lower levels were obtained in the choroid plexus and dura mater. The distribution of substance P (SP)-immunoreactive nerve fibres found in various regions of the guinea-pig correlated well with the amount of SPLI measured. Sympathectomy did not alter the concentration of SPLI in the dura mater or in cerebral blood vessels. Electrical field stimulation or 124 mM potassium enhanced the spontaneous efflux of SPLI by 10 and 20%, respectively, from superfused pial arteries in vitro. These data are in support of a functional role of perivascular SP within the cranial circulation.
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  • 48
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    Springer
    European archives of oto-rhino-laryngology and head & neck 238 (1983), S. 17-26 
    ISSN: 1434-4726
    Keywords: Cochlear microphonic ; Phase ; Amplitude ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The cochlear microphonic (CM) was recorded differentially with subcutaneous electrodes at the vertex and a variety of positions on the head and neck of the cat, and the phase and amplitude were compared with simultaneous recordings from vertex and contralateral ear electrodes. Recordings were made in bilaterally hearing animals, both with and without ear canal occlusion, following unilateral labyrinthectomy, and in white-coat cats with hereditary unilateral deafness, and in different age-groups. The cochlear microphonic was in phase with the contralateral recording at all electrode sites except those in the immediate vicinity of the stimulus ear. The amplitude was less at the circumaural positions and greater at cervical locations. The results were consistent in all age-groups and in bilaterally and unilaterally hearing animals. Precise electrode placement in the near-field conditions around the stimulus ear is therefore critical, especially for phase, while far-field conditions would appear to predominate at the remaining electrode sites.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 55-65 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloaddition Reactions of Heterocumulenes, XXVI. Cycloadducts from Aryl Isothiocyanates and 2,2-Disubstituted EnaminesAryl isothiocyanates 1 react with enamines 2 to give two types of 2:1 cycloadducts. Below 50°C, 1a - g and 2 give rise to 6-imino-1,3-thiazine-2-thiones 5, the constitutions of which are proved by an X-ray analysis of 5c. Above 50°C or starting from 4-nitrophenyl isothiocyanate (1h),2,4-dithiouracils 6 are formed. 1:1 cycloadducts of the reactants are detected spectroscopically; on workup, they hydrolyze to give 2-formylthiopropionanilides 9.
    Notes: Arylisothiocyanate 1 und Enamine 2 reagieren zu zwei Typen von 2:1-Cycloaddukten. Unterhalb von 50°C entstehen aus 1a - g und 2 6-Imino-1,3-thiazin-2-thione 5, deren Konstitution durch die Röntgenstrukturanalyse von 5c bewiesen wurde. Oberhalb 50°C oder aus 4-Nitrophenylisothio-cyanat (1h) bilden sich 2,4-Dithiouracile 6. 1:1-Cycloaddukte der Reaktanten lassen sich spektroskopisch nachweisen; bei der Aufarbeitung hydrolysieren sie zu 2-Formylthiopropionaniliden 9.
    Additional Material: 3 Tab.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 544-548 
    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 the Anthraquinonophane [2.0.0](1,4)Benzeno(1,8)anthraquinono(1,4)benzenophaneBoth phenylene rings in the [5.2]paracyclophane subunit of the anthraquinonophane [2.0.0](1,4)benzeno(1,8)anthraquinono(1,4)benzenophane (1) are tilted by 37.6°. They show a boat-like deformation. The carbonyl group pointing towards the interior of the molecule interacts with the paracyclophane system. From this a strong boat-like deformation of the quinone ring of the anthraquinone moiety results.
    Notes: Die beiden Phenylenringe in der [5.2]Paracyclophan-Untereinheit des [2.0.0](1,4)Benzeno(1,8)-anthrachinono(1,4)benzenophans (1) sind um 37.6° gegeneinander geneigt und wannenförmig deformiert. Die Wechselwirkungen der ins Molekülinnere zeigenden Carbonylgruppe mit dem Paracyclophan-System verursachen eine starke wannenförmige Deformation des Chinonringes in der Anthrachinon-Einheit.
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  • 51
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Four- and Five-membered Phosphorus Heterocycles, 55. 1,2,4-Diazaphospholo-[1,2,3]diazaphospholes - Preparation by Phosphaalkene + Nitrilimine Cycloaddition, Decomposition by Nitrile Elimination, and Structural Comparison of Addend and Adduct2,5-Dimethyl-1,2,3-diazaphosphole (1a) reacts with N-Phenylbenzohydrazonoyl chloride (6a) and a base in a sequence of nitrilimine cycloaddition, benzonitrile elimination, and another cycloaddition to give in the second step the 4-anilino derivative 7 of 1a, in the first and third step the 7a-unsubstituted and 7a-anilino-substituted title compound, 3a and 8, respectively. - As shown by the molecular structures, determined by X-ray analysis, there is a 6 π delocalization in 7 which is lost in 8 with remarkably little geometrical change at the phosphorus. - Other nitrilimines add to 1a in the same direction, that is with PC- and CN-bond formation.
    Notes: 2,5-Dimethyl-1,2,3-diazaphosphol (1a) reagiert mit N-Phenylbenzohydrazonoylchlorid (6a) und einer Base in einer Folge von Nitrilimin-Cycloaddition, Benzonitril-Eliminierung und neuerlicher Cycloaddition. In der zweiten Stufe bilden sich dabei das 4-Anilinoderivat 7 von 1a, in der ersten und dritten Stufe entstehen die 7a-unsubstituierte und 7a-anilinosubstituierte Titelverbindung, 3a bzw. 8. - Die röntgenographisch bestimmten Molekülstrukturen zeigen für den Übergang von 7 in 8 die Aufhebung einer 6 π-Delokalisierung bei nur geringen geometrischen Veränderungen am Phosphor. - Auch andere Nitrilimine addieren sich an 1a in gleicher Richtung, also unter PC- und CN-Verknüpfung.
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  • 52
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1415-1421 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermolysis of Ansarane, Ansarene and CubaneThe thermolysis and kinetics of decomposition of cubane 4 and of ring enlarged cubanes, the ansaranes 1 - 3, are described. The relief of strain which will be observed breaking specific bonds has been estimated by the aid of force-field calculations thereby disclosing probable reaction pathways. The gas phase pyrolysis of cubane 4 yields vibrationally excited cyclooctatetraene 5 which fragmentates to benzene and acetylene. The gas kinetics of cyclooctatetraene 5 is reported on as well.
    Notes: Die Thermolyse und Zerfallskinetik ringerweiterter Cubane, der Ansarane 1 - 3, sowie des Cubans 4 selbst, werden beschrieben. Mit Hilfe von Kraftfeldrechnungen wird die Spannungserleichterung beim Bruch bestimmter Bindungen abgeschätzt, und wahrscheinliche Thermolysewege werden aufgezeigt. Das bei der Gasphasenthermolyse von Cuban 4 gebildete schwingungsangeregte Cyclooctatetraen 5 fragmentiert zu Benzol und Acetylen. Über die Gasphasenkinetik von Cyclooctatetraen wird ebenfalls berichtet.
    Additional Material: 1 Ill.
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  • 53
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Existence of a Silaolefin: Synthesis and Crystal Structures of Wittig and Diels-Alder Products in Reactions of Lithiated (Fluorosilyl)diazasilacyclopentenes with Benzaldehyde and MethacroleinLithium salts of 1,2-diaza-3-sila-5-cyclopentenes react with fluorosilanes and aminofluorosilanes to give 4-(fluorosilyl)-substituted compounds 1 - 4. By reaction with tert-butyllithium 1 - 4 themselves form lithium salts 5 - 8, which react with fluorosilanes in a second substitution giving 9 and 10.5 and 7 undergo a Wittig-type reaction with benzaldehyde to form the benzylidene derivative 11. Spirocyclic Diels-Alder adducts (12, 13) are obtained from the reaction of 5 and 6 with 2-methyl-2-propenal. The propenylidene derivative 14 is formed as a by product. With excess 2-methyl-2-propenal, 12 reacts as a dienophile giving the oligocyclic Diels-Alder adducts 15 and 16. The crystal structures of 11 and 15 are reported.
    Notes: Lithiumsalze der 1,2-Diaza-3-sila-5-cyclopentene reagieren mit Fluorsilanen und Aminofluorsilanen zu den 4-(Fluorsilyl)-substituierten Verbindungen 1 - 4. In Reaktion mit tert-Butyllithium bilden 1 - 4 erneut Lithiumsalze (5 - 8), die mit Fluorsilanen unter Zweitsubstitution zu 9 und 10 reagieren. In Wittig-analoger Reaktion reagieren 5 und 7 mit Benzaldehyd zum Benzyliden-Derivat 11. Spirocyclische Diels-Alder-Addukte (12, 13) werden aus 5 und 6 mit 2-Methyl-2-propenal erhalten. Als Nebenprodukt entsteht das Propenyliden-Derivat 14. Mit überschüssigem Dien (2-Methyl-2-propenal) reagiert 12 als Dienophil zu den oligocyclischen Diels-Alder-Addukten 15 und 16. Kristallstrukturen von 11 und 15 werden mitgeteilt.
    Additional Material: 4 Tab.
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  • 54
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 290-298 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Cyclic Silylhydrazines - Crystal Structure of a Five-membered Cross Dimerisation ProductN,N-Bis(fluorosilyl)amines (1 - 3) react with dilithiated hydrazines to give four- and five-membered silylhydrazine rings (4 - 8). The isomerisation of a 3-(tert-butylamino)-1,3-diaza-2,4-disilacyclobutane (8) to a 1,2,4-triaza-3,5-disilacyclopentane (9) has been demonstrated. Lithium salts of silylhydrazines react with fluorosilanes to give substitution products (10 - 15). Dilithiated hydrazine reacts with Me2SiF2 yielding N(SiFMe2)3 (16). The formation of isomeric N-(fluorosilyl)-N,N′-bis(trimethylsilyl)- and N′-(fluorosilyl)-N,N-bis(trimethylsilyl)hydrazines has been accomplished via ring-closure reactions (17 - 19) and confirmed by the crystal structure determination of a five-membered ring cross dimer (19). The ten-membered bicyclic ring system (22) is obtained by the reaction of (14) with dilithiated hydrazine.
    Notes: N,N-Bis(fluorsilyl)amine (1 - 3) reagieren mit dilithiierten Hydrazinen zu vier- und fünfgliedrigen Silylhydrazinringen (4 - 8). Präparativ gelang der Nachweis der Isomerisierung eines 3-(tert-Butylamino)-1,3-diaza-2,4-disilacyclobutans (8) zum 1,2,4-Triaza-3,5-disilacyclopentan (9). Lithiumsalze von Silylhydrazinen reagieren mit Fluorsilanen unter Substitution (10 - 15). Dilithiiertes Hydrazin reagiert mit Me2SiF2 zu N(SiFMe2)3 (16). Die Bildung von isomeren N-(Fluorsilyl)-N,N′-bis(trimethylsilyl)- und N′-Fluorsilyl-N,N-bis(trimethylsilyl)hydrazinen wird durch Ringschlußreaktionen (17 - 19) nachgewiesen und durch die Kristallstrukturuntersuchung eines Kreuz-Dimeren-Fünfrings belegt (19). Der zehngliedrige Bicyclus 22 entsteht in der Reaktion des N,N′-Bis(fluordimethylsilyl)-N,N′-bis(trimethylsilyl)hydrazins(14) mit dilithiiertem Hydrazin.
    Additional Material: 1 Tab.
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  • 55
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 299-322 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Rearrangement of Substituted Bicyclo[2.1.0]pent-2-enes. A Thermal “Walk”-RearrangementThe synthesis and the thermal behaviour of methyl 5-methyl-, 1,5-, and 2,5-dimethylbicyclo-[2.1.0]pent-2-ene-5-carboxylates 3a, b, 4a, b, 5a, b, as well as of 1,5- and 2,5-dimethylbicyclo-[2.1.0]pent-2-ene-5-carbonitriles 6a, 7a, b are reported. The “walk”-rearrangement which is degenerate in the cases of 3a, b could be detected experimentally with the aid of the dimethyl derivatives 4a, b, 5a, b, 6a, and 7a, b. Electrocyclic ring opening to the correspondingly substituted 1,3-cyclopentadienes competes with the “walk”-rearrangements. Already at 0°C the “walk”-rearrangements 4a → 5a, 4b → 5b, and 6a → 7a proceed stereospecifically with inversion at the migrating carbon atom C-5 as postulated by Woodward and Hoffmann (0°C: ΔG* = 21.7, 24.8, and 21.9 kcal/mol). We assume that the surprisingly low activation barriers do not only result from the resonance stabilization of an aromatic transition state but largely from the anomalously high ground-state enthalpy of the bicyclopentene system.
    Notes: Synthese und thermisches Verhalten der 5-Methyl-, 1,5-Dimethyl- und 2,5-Dimethylbicyclo-[2.1.0]pent-2-en-5-carbonsäure-methylester 3a, b, 4a, b, 5a, b und -carbonitrile 6a, 7a, b werden beschrieben. Die in den Systemen 3a, b strukturell entartete „walk“-Umlagerung konnte am Beispiel der Dimethylderivate 4a, b, 5a, b, 6a und 7a, b experimentell nachgewiesen werden. Dazu konkurrierend finden elektrocyclische Ringöffnungen zu den entsprechend substituierten 1,3-Cyclopentadienen statt. Die „walk“-Umlagerungen 4a → 5a, 4b → 5b und 6a → 7a erfolgen bereits bei 0°C stereospezifisch mit der von Woodward und Hoffmann postulierten Inversion am wandernden Kohlenstoff C-5 (0°C: ΔG* = 21.7, 24.8 bzw. 21.9 kcal/mol). Vermutlich resultieren die überraschend niedrigen Aktivierungsbarrieren nicht allein aus der Resonanzstabilisierung eines aromatischen Übergangszustandes, sondern wesentlich aus der anomal hohen Grundzustandsenthalpie des Bicyclopentensystems.
    Additional Material: 7 Tab.
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  • 56
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Substituted Phosphanes, Arsanes, and Stibanes, XXXIII. (Bromomethyl)bis[(trimethylsilyl)methyllarsane: Synthesis and Metalation to Complexes with η1- or η2-Coordinated Arsinomethyl LigandThe pyrolysis of the trialkyldibromoarsorane (Me3SiCH2)3AsBr2 (1) under reduced pressure yields the (bromomethyl)arsane (Me3SiCH2)2AsCH2Br (2) with Me3SiBr elimination via the intermediate formation of the bromodialkylmethylenearsorane Br(Me3SiCH2)2As=CH2. 2 reacts with Na[M(CO)3Cp] (M=Mo, W) to give the transition metal substituted arsanes Cp(CO)3M-CH2As(CH2SiMe3SiMe3)2 (3a,b). These undergo cyclisation with loss of CO and formation of Cp(CO)2M[η2 CH2As(CH2SiMe3)2] (4a,b), the first complexes with an η2-bound arsinomethyl unit, either spontaneously (3a) or upon ultraviolet irradiation or prolonged standing at room temperature (3b). MeI quaternizes the arsane 3b to give the metalated arsonium salt [Cp(CO)3W - CH2As(Me)(CH2SiMe3)2]I (5). The NMR spectra indicate fluxional behaviour for the chiral metallacycles 4a, b. It is caused by a rapid change of the configuration at the metal centre, for which a mechanism, involving a rotation of the dihapto-coordinated ligand about an axis defined by the metal and the centre of the As—C(M) bond, is suggested.
    Notes: Die Pyrolyse des Trialkyldibromarsorans (Me3SiCH2)3AsBr2 (1) bei reduziertem Druck liefert unter Me3SiBr-Eliminierung über die intermediäre Stufe eines Bromdialkylmethylenarsorans Br(Me3SiCH2)2)2As=CH2 das (Brommethyl)arsan (Me3SiCH2)2AsCH2Br (2). Dieses reagiert mit Na[M(CO)3Cp] (M=Mo, W) zu den Übergangsmetall-substituierten Arsanen Cp(CO)3M-CH2As(CH2SiMe3)2 (3a,b), welche sich spontan (3a) bzw. bei UV-Bestrahlung oder längerem Stehenlassen bei Raumtemperatur (3b) unter CO-Verlust in Cp(CO)2M[η2-CH2As(CH2SiMe3)2] (4a,b), die ersten Komplexe mit η2-gebundener Arsinomethyl-Einheit, umwandeln. MeI quartärisiert das Arsan 3b zum metallierten Arsoniumsalz [Cp(CO)3W - CH2As(Me)(CH2SiMe3)2]I (5). Die NMR-Spektren zeigen für die chiralen Metallacyclen 4a, b fluktuierendes Verhalten an. Als Mechanismus für den dafür verantwortlichen schnellen Konfigurationswechsel am Zentralmetall wird die Rotation des dihapto-koordinierten Liganden um eine durch das Metall und den Mittelpunkt der As—C(M)-Bindung verlaufende Achse vorgeschlagen.
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  • 57
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 360-366 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Evidence for 4-Homocubyl Carbenium Ions as Reactive Intermediates4-(Hexafluoroisopropoxy)homocubane (6) is the main product of the thermolysis reaction of N-(4-homocubyl)-N-nitrosoacetamide (9) and of the solvolysis reaction of 4-homocubyl bromide (5) in hexafluoro-2-propanol. This is experimental evidence for 4-homocubyl carbenium ions as intermediates in both reactions. The solvolysis rate of 4-homocubyl bromide at 120°C in the same solvent (k1120°C=1.3 · 10-7s-1) by far exceeds that of 1-norbornyl bromide which does not react at a detectable rate under these conditions. According to force field calculations the strain enthalpy is increasing by as much as 66 kcal · mol-1 in the ionisation of 4-homocubyl bromide. Therefore nonclassical stabilization of the 4-homocubyl carbenium ion is postulated.
    Notes: Bei der Thermolyse von N-(4-Homocubyl)-N-nitrosoacetamid (9) und bei der Solvolyse von 4-Homocubylbromid (5) in Hexafluor-2-propanol entsteht 4-(Hexafluorisopropoxy)homocuban (6) als Hauptprodukt. Dies beweist das Auftrete von 4-Homocubyl-Carbenium-Ionen als Zwischenstufen beider Reaktionen. Die Solvolysegeschwindigkeit von 4-Homocubylbromid bei 120°C in Hexafluor-2-propanol (k1120°C = 1.3 · 10-7 s-1) ist wesentlich höher als die von 1-Norbornylbromid, dessen Solvolyse unter diesen Bedingungen nicht nachweisbar ist. Da die Ionisation von 4-Homocubylbromid nach Kraftfeldrechnungen mit 66 kcal · mol-1 Ansteigen an Spannungsenthalpie verbunden ist, wird für das 4-Homocubyl-Carbenium-Ion eine nichtklassische Stabilisierung angenommen.
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  • 58
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses with Aliphatic Dialdehydes, XXXVII, Synthesis, Structure, and Properties of a [3.3.3.]Decamethinium Cyanine Dye, with Indoline End GroupsThe reaction of the trisaldehyde trisacetal 4 with 1,3,3-trimethyl-2-methyleneindoline (7) and its tetrafluoroborate 8 yields either the δ-substituted heptamethinium cyanine dye 9 or the [3.3.3]decamethinium cyanine dye 10, depending on the reaction conditions. Configuration and conformation of both polymethine dyes have been determined by means of spectroscopic data as well as by X-ray analyses. - The UV/Vis-spectroscopic 〈trimethine shift“ of trinuclear, Y-Conjugated, methinylogous guanidinium ions is compared with the “vinylene shift” of dinuclear, linear-conjugated, vinylogous amidinium ions (Table 1).
    Notes: Durch Umsetzung des Trisaldehyd-trisacetals 4 mit 1,3,3-Trimethyl-2-methylenindolin (7) und dessen Tetrafluoroborat 8 werden je nach Reaktionsbedingungen entweder der δ-substituierte Heptamethinium-Cyaninfarbstoff 9 oder der [3.3.3]Decamethinium-Cyaninfarbstoff 10 erhalten. Konfiguration und Konformation beider Polymethinfarbstoffe werden spektroskopisch sowie durch Röntgenstrukturbestimmungen ermittelt. - Der UV/Vis-spektroskopische „Trimethinsprung“ trinuclearer, Y-konjugierter, methinyloger Guanidinium-Ionen wird mit dem „Vinylensprung“ dinuclearer, linear-konjugierter, vinyloger Amidinium-Ionen verglichen (Tab. 1).
    Additional Material: 3 Ill.
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  • 59
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Sulfur Ylide Complexes, XVIII. The Deoxygenation of anti-Tricarbonyl(1-methyl-3,5-diorganyl-λ6thiabenzene oxide)chromium,-molybdenum, and -tungsten as a Novel Synthetic Route to λ4-Thiabenzene ComplexesFrom the reaction of anti-configurated λ6-thiabenzene oxide complexes 5a-e, 6e, and 7e with sodium bis(2-methoxyethoxy)aluminium hydride λ4-thiabenzene complexes 2a-e, 3e, and 4a are obtained. The hitherto unknown ylidic heterocycles in the novel complexes behave as significantly stronger donor ligands as the related λ6-thiabenzene oxides as is inferred from spectroscopic data.
    Notes: Bei der Reaktion der anti-Konfigurierten λ6-Thiabenzoloxid-Komplexe 5a-e, 6e und 7e mit Natrium-bis(2-methoxyethoxy)aluminiumhydrid werden die λ4-Thiabenzol-Komplexe 2a-e, 3e und 4e erhalten. Nach den Spektren sind die bisher unbekannten ylidischen Heterocyclen in den neuartigen Komplexen deutlich stärkere Donorliganden als die entsprechenden λ6-Thiabenzoloxide.
    Additional Material: 3 Tab.
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  • 60
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 669-680 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Reduction of Benzvalene Ozonide to cis-1,3-Cyclobutanedimethanol with LiAIH4On treatment with LiAlH4 at -30°C the polymeric ozonide of benzvalene (1) gives bicyclo-[1.1.0]butane-endo,endo-2,4-dimethanol (7). At higher temperatures cis-1,3-cyclobutanedimethanol (4) is formed. The stereochemical course of this unusual C—C hydrogenolysis has been elucidated by means of deuterated substrates. For this purpose a complete analysis of the 1H NMR spectra of the labeled cis-1,3-cyclobutanedicarboxylic anhydrides 9a-c had to be carried out. The dialcohol 7 and its bismethyl ether 16 add thiophenol across the central bond to form the cis products 18 and 19, respectively. Acids or Ag+ ions isomerize 7 via cleavage of a lateral bond into the ethers 21.
    Notes: Das polymere Ozonid des Benzvalens (1) wird mit LiAlH4 bei -30°C in Bicyclo[1.1.0]butan-endo,endo-2,4-dimethanol (7) übergeführt, bei höherer Temperatur entsteht cis-1,3-Cyclobutan-dimethanol (4). Mit deuterierten Verbindungen wurde der stereochemische Ablauf dieser ungewöhnlichen C—C-Hydrogenolyse aufgeklärt. Dazu mußte eine vollständige Analyse der 1H-NMR-Spektren der markierten cis-1,3-Cyclobutandicarbonsäureanhydride 9a-c durchgeführt werden. 7 und sein Bismethylether 16 addieren an der zentralen Bindung Thiophenol zu den cis-Produkten 18 bzw. 19. Säure oder Ag+-Ionen überführen 7 unter Öffnung einer seitlichen Bindung in die Ether 21.
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  • 61
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Photoelectron Spectrum of 1,1-Diethoxy-3,3-bis(trifluoromethyl)allene. The Effect of Trifluoromethyl Groups on Cumulative SystemsThe He(I) photoelectron(PE) spectra of 1,1-diethoxy-4,4,4-trifluoro-3-(trifluoromethyl)-1,2-butadiene [1,1-diethoxy-3,3-bis(trifluoromethyl)allene] (1), tetraethoxyallene (3), and tetrakis-(trifluoromethyl)allene (5) have been recorded. A comparison between the PE spectra of 1, 3, and 5 shows that the first band of 1 (8.93 eV) is due to an ionization from the diethoxyethylene fragment and the second band of 1 (11.0 eV) is due to ionization from the bis(trifluoromethyl)-ethylene fragment. The effect of CF3 groups has also been discussed by comparing the PE spectra of bis(trifluoromethyl)ketene (6) and bis(trifluoromethyl)thioketene (7) with the parent compounds. The interpretation is aided by comparing the measured ionization potentials with orbital energies derived from a MINDO/3 or MNDO calculation.
    Notes: Die He(I)-Photoelektronen(PE)-Spektren von 1,1-Diethoxy-4,4,4-trifluor-3-(trifluormethyl)-1,2-butadien [1,1-Diethoxy-3,3-bis(trifluormethyl)allen] (1), Tetraethoxyallen (3) und Tetrakis-(trifluormethyl)allen (5) wurden gemessen. Der Vergleich zwischen den PE-Spektren von 1, 3 und 5 zeigt, daß das 1. Ionisationspotential von 1 (8.93 eV) der Ionisation aus dem Diethoxyethylen-Fragment, das 2. Ionisationspotential von 1 (11.0 eV) der Ionisation aus dem Bis(trifluormethyl)ethylen-Fragment entspricht. Der Effekt der CF3-Gruppen wird zusätzlich anhand eines Vergleichs der PE-Spektren von Bis(trifluormethyl)keten (6) und Bis(trifluormethyl)thioketen (7) mit den unsubstituierten Verbindungen diskutiert. Die Interpretation erfolgt durch Vergleich zwischen den gemessenen Ionisationspotentialen und berechneten Orbitalenergien nach der MINDO/3-oder MNDO-Methode.
    Additional Material: 4 Ill.
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  • 62
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2896-2902 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: cis-Dinitrosylmetal Complexes of Chromium, Molybdenum, and Tungsten with Sulfur-Containing Chelating LigandsOctahedral complexes of the type cis-[M(chelate)2(NO)2] (M = Cr, Mo, W) were prepared by the reactions of the solvent-stabilized dihalogenodinitrosylmetal fragments [MX2-(NO)2]solv (MX2 = CrCl2, MoBr2, WBr2; solv = acetone or acetonitrile) with dithio chelating anions (chelate- = (CH3)2AsS2-, (CH3)2PS2-, (CH3O)2PS2-, (CH3)2N—CS2-). The compounds were characterized by their spectra. Additional chromium complexes, cis-[M(chelat)2(NO)2], were obtained using the chelating ligands Y—CS2- (Y = CH3, CH3S, CH3O), (CH3)2N—COS-, CH3-COS- and (CH3)2N—COSe-.
    Notes: Durch Umsetzung der solvensstabilisierten Dihalogenodinitrosylmetall-Fragmente [MX2-(NO)2]solv (MX2 = CrCl2, MoBr2, WBr2; solv = Aceton oder Acetonitril) mit Dithiochelat-Anionen (chelat- = (CH3)2AsS2-, (CH3)2PS2-, (CH3O)2PS2-, (CH3)2N—CS2-) wurden oktaedrische Komplexe des Typs cis-[M(chelat)2(NO)2] (M = Cr, Mo, W) dargestellt und spektroskopisch charakterisiert. Weitere Chrom-Komplexe cis-[Cr(chelat)2(NO)2] wurden mit den Chelatliganden Y—CS2- (Y = CH3, CH3S, CH3O), (CH3)2N—COS-, CH3-COS- und (CH3)2N—COSe- erhalten.
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  • 63
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2914-2919 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The 7,9-Dimethylbicyclo[4.3.1]deca-2,4,8-trien-7-yl Cation: A Bridged Dihomotropylium IonThe 7,9-dimethylbicyclo[4.3.1]deca-2,4,8-trien-7-yl cation (3) has been generated. Clearly, the two methyl groups disturb but don't suppress the dihomoaromatic delocalization. The question mentioned in the preceding paper1) cannot be answered unequivocally whether two methyl groups in 1,3-position stabilize the allylic cation of the tricyclic ion 1 so strongly that no trihomoaromatic delocalization takes place.
    Notes: Das 7,9-Dimethylbicyclo[4.3.1]deca-2,4,8-trien-7-yl-Kation (3) wird dargestellt. Die beiden Methylgruppen schwächen eindeutig die dihomoaromatische Delokalisierung, unterbinden sie aber nicht. Die in der voranstehenden Arbeit1) gestellte Frage, ob zwei Methylgruppen in 1,3-Anordnung das Allylkation im tricyclischen Ion 1 so stark stabilisieren, daß die trihomoaromatische Delokalisierung unterbunden wird, läßt sich nicht eindeutig beantworten.
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  • 64
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2903-2913 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The 8-Methyl- and 8,10-Dimethyltricyclo[5.3.1.04,ii]undeca-2,5,9-trien-8-yl Cation: A Contribution to the Question of a Bridged Trihomotropylium IonThe methylcyclohexenyl cation 9 is a short lived intermediate. The thermodynamically more stable cyclopentenyl cations 10a and 10b are generated via hydride shift. 10b finally dominates the equilibrium mixture. The dimethylcyclohexenyl cation 16 shows contrary to 9 no hydride shift. The question of a homoaromatic character in 16 has been denied unequivocally due to a comparison of relevant NMR data between 16 and its tetrahydro derivative 17.
    Notes: Das Methylcyclohexenylkation 9 ist eine kurzlebige Zwischenstufe. Es bildet unter Hydriverschiebung die thermodynamisch stabileren Cyclopentenylkationen 10a und 10b, von denen schließlich 10b das Gleichgewichtsgemisch beherrscht. Im Gegensatz zu 9 zeigt das Dimethylcyclohexenylkation 16 keine Hydridverschiebung. Ein NMR-spektroskopischer Vergleich zwischen 16 und seinem Tetrahydroderivat 17 verneint eindeutig die Frage nach einem trihomoaromatischen Charakter von 16.
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  • 65
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2931-2935 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Are Pyramidal Structures Involved in the Decomposition of Aryl-substituted Cyclopentadienyl Cations?Tetra- and pentaaryl-substituted cyclopentadienyl cations undergo dissociation to diaryl-substituted acetylenes and substituted cyclopropenylium ions without any significant skeleton isomerization involving pyramidal or polycyclic carbocation structures.
    Notes: Tetra- und pentaarylsubstituierte Cyclopentadienyl-Kationen zeigen nur eine geringe Tendenz, vor ihrem Zerfall zu Diarylacetylen und substituierten Cyclopropenylium-Ionen Gerüstumlagerungen zu pyramidalen oder polycyclischen Kationen einzugehen.
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  • 66
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2958-2971 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigation of Rearrangement Reactions of Cyclic Allyl and Pentadienyl AnionsBicyclo[3.1.0]hexenyl anion (1) and bicyclo[3.2.0]heptenyl anion (2) rearrange in THF to monocyclic pentadienyl anions, whereas bicyclo[3.3.0]octenyl anion 3 is stable under the reaction conditions. 3 in contrary is formed by the known electrocyclic ring closure of cyclooctadienyl anion 7. Rearrangements of cyclopentenyl anion and pentadienyl anion are not detected. Cyclic allyl anions are alkylated by ethene, formed by cleavage of THF with base or independently added. 6,6-Dimethylcyclohexadienyl anion undergoes slow fragmentation to toluene at room temperature.
    Notes: Bicyclo[3.1.0]hexenyl-Anion (1) und Bicyclo[3.2.0]heptenyl-Anion (2) lagern sich in THF in die monocyclischen Pentadienyl-Anionen um, während für Bicyclo[3.3.0]octenyl-Anion (3) unter den Reaktionsbedingungen keine Ringöffnung beobachtet wird. Statt dessen geht das Cycloocta-dienyl-Anion 7 den bekannten Ringschluß zu 3 ein. Umlagerungsreaktionen für das Cyclopentenyl-Anion und das offenkettige Pentadienyl-Anion treten nicht ein. Cyclische Allylanionen lassen sich mit Ethen, entstanden aus der Spaltung von THF mit Base oder unabhängig zugeführt, alkylieren. Das 6,6-Dimethylcyclohexadienyl-Anion fragmentiert bei Raumtemperatur langsam zu Toluol.
    Additional Material: 4 Ill.
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  • 67
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2920-2930 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Methylenecyclopropanes, VII. Nickel(0)-catalysed Cycloadditions of Methylenecyclopropanes with Alkyl AcrylatesCycloaddition reactions of methylenecyclopropane (1) and of the ring-methylated methylene-cyclopropanes 5, 9 and 12 with alkyl acrylates are performed at nickel(0) catalysts, such as bis(1,5-cyclooctadiene)nickel unter mild conditions (0-50°C). Depending on the degree of methylation of the three-membered ring, 1 and 5 give only alkyl 3-methylenecyclopentane-carboxylates (4 and 6), whereas 9 leads to a mixture of the methylenecyclopentane derivative 10 and the alkyl spiro[2.3]hexanecarboxylate 11, and 12 react to form only the spiro[2.3]hexane derivative 13. With 12 isomerisation to 2,3,3-trimethyl-1,4-pentadiene (15) also takes place. In the case of 9 the ratio of methylenecyclopentane to spiro[2.3]hexanecarboxylate can be influenced by the size of alkyl groups. - In the Ni0-catalysed reactions of 1 with substituted acrylates (methyl crotonate or diethyl maleate) codimerisation to 16 and 17 competes with cyclodimerisation to 2 and 3.
    Notes: An Nickel(0)-Katalysatoren, bevorzugt Bis(1,5-cyclooctadien)nickel, gelingen Cycloadditionen von Methylencyclopropan (1) und dessen am Ring methylierten Derivaten 5, 9 und 12 mit Acrylsäure-alkylestern unter milden Bedingungen (0-50°C). In Abhängigkeit von dem Methylierungsgrad des Dreirings entstehen aus 1 und 5 nur 3-Methylencyclopentancarbonsäure-alkylester (4 bzw. 6), aus 9 Gemische dieser Methylencyclopentan-Derivate (10) mit einem Spiro[2.3]hexancarbonsäure-alkylester (11) oder aus 12 nur das Spiro[2.3]hexanderivat 13. Mit 12 tritt auch Isomerisierung zu 2,3,3-Trimethyl-1,4-pentadien (15) ein, Bei 9 kann das Methylencyclopentan-/Spiro[2.3]-hexancarbonsäureester-Verhältnis durch die Größe des Alkylrestes im Acryl beeinflußt werden. - Dagegen konkurrieren bei den Ni0-katalysierten Reaktionen von 1 mit substituierten Acrylsäureestern (Crotonsäure-methylester, Maleinsäure-diethylester) Cyclodimerisierung zu 2 und 3 mit der Codimerisierung zu 16 und 17.
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  • 68
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Aziridines (Aziranes), 29. N-Acylated or N-Sulfonated Esters of 2-Aminoethylphosphonic Acid by Means of Base Catalyzed Amidoethylation of Diesters of Phosphoric Acid with Activated AziridinesThe sodium salts 2 of diesters of phosphoric acid 1 are amidoethylated at phosphorus with N-acylaziridines 3 or N-sulfonylaziridines 13 under proper reaction conditions at room temperature. In this manner a broad variation of N-acylated or N-sulfonated esters of 2-aminoethylphosphonic acids (5a-u, 15a-i) are obtained, mostly in good yields. 2-Methylated 2-aminoethyl-phosphonic esters are formed selectively in two cases by reaction of 2-methylated activated aziridines.
    Notes: In Form ihrer Natriumsalze 2 lassen sich Phosphorigsäurediester 1 bei Raumtemperatur unter geeigneten Bedingungen mit N-Acylaziridinen 3 oder N-Sulfonylaziridinen 13 am Phosphoratom amidoethylieren. So werden N-acylierte oder N-sulfonierte 2-Aminoethylphosphonsäureester (5a-u, 15a-i) in großer Variationsbreite mit meist guten Ausbeuten erhalten. Ringmethylierte Aziridine führen dabei in zwei Fällen selektiv zu 2-methylierten 2-Aminoethylphosphonsäureestern.
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  • 69
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die Elektronenstruktur von Phosphor-Verbindungen mit Nortricyclan-Struktur. - Modell-Rechnungen und PhotoelektronenspektrenDie unterschiedliche Reaktivität der Phosphor-Verbindungen P4[Si(CH3)2]3 (1) and P7(CH3)3 (2) wird anhand eines einfachen MO-Schemas diskutiert. Das MO-Schema basiert auf semiempirischen Rechnungen (MINDO/3, MNDO) und auf He(1)-photoelektronenspektroskopischen Untersuchungen an 1 und 2. Die Elektronenstruktur ähnlich gebauter Käfigverbindungen mit Nortricyclangerüst wie P73-, P4S3 und P7[Si(CH3)3]3 wird mit 1 und 2 verglichen.
    Notes: The different reactivity of P4[Si(CH3)2]3 (1) and P7(CH3)3 (2) is discussed in terms of a simple MO scheme. This scheme is based on semiempirical calculations (MINDO/3, MNDO) and on He(1) photoelectron spectroscopic investigations on 1 and 2. The electronic structure of similar cage compounds with the nortricyclane skeleton like P73-, P4S3, and P7[Si(CH3)3]3 is compared with 1 and 2.
    Additional Material: 8 Ill.
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  • 70
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2983-2993 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: cis,trans,cis- und trans,trans,trans-l,2,3,4-Tetravinylcyclobutan - Darstellung und einige spektroskopische EigenschaftenDie Titel-Verbindungen 1 und 2 werden mit Hilfe von bekannten Reaktionsfolgen dargestellt. Die He(1) PE-Spektren von 1 und 2 zeigen eine starke Wechselwirkung (β = -1.9 eV) zwischen den Vinylgruppen und dem Vierring. Die räumliche Wechselwirkung zwischen den Vinylgruppen ist nicht meßbar.
    Notes: The title compounds 1 and 2 are prepared using standard procedures. The He(1) PE spectra of 1 and 2 show strong interaction (β = -1.9eV) between vinyl groups and the four-membered ring. The through space interaction between the vinyl groups is found to be minute.
    Additional Material: 5 Ill.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2994-2999 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On a Diazadiboretidine as Four-Electron Donor against Chromium and TungstenThe iminoborane Bu—B = N-tBu (1) is dimerized to the diazadiboretidine 2 by the catalytic action to tert-butyl isonitrile, being trimerized to the borazine 3 without a catalyst. The coordination compounds η4-[BuBN(tBu)]2 · M(CO)4 (4a, b) are formed from (OC)5M(THF) (M = Cr, W) and either 1 and 2. The chromium atom in 4a is coordinated by four CO groups and the two nitrogen atoms of a non-planar molecule 2 at the vertices and by the two boron atoms of 2 above two adjoining faces of a distorted octahedron.
    Additional Material: 1 Ill.
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  • 72
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 3205-3211 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Platinum(II) Complexes of Vinylogous Amino IsocyanidesIsocyanide platinum(II) complexes trans-[(Ph3P)2LPtCl]+Cl- (2) (L = vinylogous aminoisonitrile are formed from cis-(Ph3P)2PtCl2 and L; the cations of 2 have been isolated as PF6- salts (3). At higher temperatures the salts 2 give the neutral complexes cis-(Ph3P)LPtCl2 (4) and PPh3. Treatment of 4 with amines HNR2R3 affords the diaminocarbene complexes cis-[(Ph3P)[(R1R3N)C]PtCl(amine)]+Cl- (isolated as PF6- salts 5) which on heating give the compounds cis-(Ph3P)[R1HN)(R2R3 N)C]PtCl2 (7).
    Notes: Isocyanid-Platin(II)-Komplexe trans-[Ph3P)2LPtCl]+Cl- (2) (L = vinyloges Aminoisonitril entstehen aus cis-Ph3P)2PtCl2 und L; sie werden als stabile PF6--Salze (3) isoliert. Die Verbindungen 2 spalten beim Erhitzen Ph3P ab unter Bildung der neutralen Komplexe cis-(Ph3P)LPtCl2 (4), die sich mit Aminen HNR2R3 zu den Diaminocarben-Komplexen cis-(Ph3P)[R1HN)(R2R3 N)C]PtCl(amine)+Cl2 (7) umsetzen, wobei als Zwischenstufen ionische Verbindungen [(Ph3P)[R1HN)(R2R3N)C]PtCl(amin)] +PF6- (5) gefaßt wurden.
    Additional Material: 4 Tab.
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  • 74
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Alkyl and Aryl Compounds, XXX. Preparation and Crystal Structure of Bis[μ-phenylethynyl-(N,N,N′,N′-tetramethyl-1,3-propanediamine)lithium], (PhC≡CLi·tmpda)2, a Dimeric Compound with Phenylethynyl BridgesThe title compound has been prepared from n-butyllithium, phenylacetylene and N,N,N′,N′-tetramethyl-1,3-propanediamine (tmpda) and its structure determined by X-ray diffraction methods. It represents a first example containing phenylethynyl bridges between alkali metal atoms and is isostructural to the phenyl compounds (PhLi·tmeda)2.
    Notes: Die Titelverbindung wurde aus n-Butyllithium, Phenylacetylen und N,N,N′,N′-Tetramethyl-1,3-propandiamin (tmpda) dargestellt und ihre Struktur röntgenographisch bestimmt. Sie stellt ein erstes Beispiel von Phenylethinyl-Brücken zwischen Alkalimetall-Atomen dar und ist isostrukturell zur Phenylverbindung (PhLi·tmeda)2.
    Additional Material: 1 Ill.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 152-158 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of 2-(Aminomethylene)cyclohexanone Derivatives with DichloroquinonesReaction of dichloro-p-benzoquinones 1 with 2-[(arylamino)methylene]cyclohexanone derivatives 2 yield dibenzofuranone derivatives 4. The structure is proven spectroscopically and by oxidation to 6, which is hydrolysed to 7. The course of the reaction via the intermediate 10 can be proved by its isolation and reaction to 4a.
    Notes: Durch Umsetzung von Dichlor-p-benzochinonen 1 mit 2-[(Arylamino)methylen]cyclohexanon-Derivaten 2 werden die Dibenzofuran-Abkömmlinge 4 erhalten. Ihre Struktur wird spektroskopisch belegt und durch Oxidation zu 6 sowie anschließende Hydrolyse zu 7 chemisch bewiesen. Der Verlauf der Reaktion über das Zwischenprodukt 10 kann durch dessen Isolierung und Umsetzung zu 4a bewiesen werden.
    Additional Material: 7 Tab.
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  • 76
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 136-145 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Radical Anions, I. Synthesis of Acyclic and Cyclic Silylated 1,2-EthenediaminesReactions of radical anions obtained by the reduction of glyoxal diimines RN=CH—CH=NR 3 (3a: R = tert-butyl; 3b: R = 2,6-xylyl) with chlorotrimethylsilane, dichlorodimethylsilane, and dichloromethylsilane afford acyclic N-mono and N,N′-disilylated ene-diamines 6, 8, 9, and cyclic diazasilacyclopentenes 10, 11, 13, respectively. C-Silylation is a minor side-reaction. 13C NMR, IR, and PE data are consistent with a non-planar E-configuration for 8 and Z-configuration for 6. In agreement with MS data and the very low 1. ionisation potentials, the planar heterocycles 10 and 13 on oxidation yield stable, delocalized radical cations, which are characterized ESR-spectroscopically.
    Notes: Durch Reduktion der Glyoxaldiimine RN=CH—CH=NR 3 (3a: R = tert-Butyl; 3b: R = 2,6-Xylyl) erhältliche Radikalanionen reagieren mit Chlortrimethylsilan, Dichlordimethylsilan und Dichlormethylsilan zu offenkettigen N-mono- bzw. N,N′-disilylierten En-diaminen 6, 8, 9 bzw. zu cyclischen Diazasilacyclopentenen 10, 11, 13. C-Silylierung wird nur als Nebenreaktion beobachtet. 13C-NMR-, IR- und PE-Daten belegen eine nicht-planare E-Konfiguration für 8 und Z-Konfiguration für 6. Die planaren Heterocyclen 10 und 13 bilden in Übereinstimmung mit den MS-Daten und der geringen 1. Ionisierungsenergie stabile, delokalisierte Radikalkationen, die ESR-spektroskopisch charakterisiert werden.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 159-175 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkylruthenium(II) Compounds and their β-H-Elimination into (η-2Alkene)hydridoruthenium ComplexesReaction of Cp(PPh3)2RuCl (1) with primary alkylmagnesium halides (alkyl = Et, Pr, n-Bu, i-Bu) leads to the corresponding alkylruthenium complexes 4-7. Above 50°C 4-7 lose a PPh3 molecule and form by Ru-β-H-elimination the (η2-alkene)hydridoruthenium complexes 9-12. With R = isobutyl the intermediately formed, coordinatively unsaturated Cp(PPh3)Ru—R complex can be stabilized by complexation with ethylene (50 bar) as (η2-ethylene)isobutylruthenium complex 15. Mechanistic investigations of the [2-D3]ethyl complex 16 indicate that the Ru-β-H-elimination is reversible. - Rotation of the η2-alkene ligand in 9-12 leads to temperaturedependent 1H NMR spectra. The 31P chemical shifts of 1, 2, 4-7 and 9-12, respectively, are characteristic for the corresponding type of complexes.
    Notes: Durch Umsetzung von Cp(PPh3)2RuCl (1) mit prim. Alkylmagnesiumhalogeniden (Alkyl = Et, Pr, n-Bu, i-Bu) werden die entsprechenden Alkylruthenium-Komplexe 4-7 erhalten. Ab ca. 50°C spalten 4-7 ein PPh3 ab und bilden durch Ru-β-H-Eliminierung die (η2-Alken)hydridoruthenium-Komplexe 9-12. Das intermediär entstehende, koordinativ ungesättigte Cp (PPh3)Ru—R wurde bei R = Isobutyl mit Ethylen (50 bar) als (η2-Ethylen)isobutylruthenium-Komplex 15 abgefangen. Aus mechanistischen Untersuchungen mit dem [2-D3]Ethylkomplex 16 folgt die Reversibilität der Ru-β-H-Eliminierung. - Die Rotation des η2-Alken-Liganden in 9-12 bedingt temperaturabhängige 1H-NMR-Spektren. Die 31P-chemischen Verschiebungen sind bei 1, 2, 4-7 bzw. 9-12 jeweils charakteristisch für den Verbindungstyp.
    Additional Material: 8 Tab.
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  • 78
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 176-185 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkenylruthenium(II) ComplexesThe Cp(PPh3)2Ru—[CH2]nCR=CH2 complexes 2-4 (n = 0.2. R = H; n = 3, R = CH3) are prepared by treatment of the chloride 1 with the appropriate organomagnesium halides. The vinyl complex 2 eliminates a PPh3 ligand above 100°C and reacts with ethylene (20-30 bar) by insertion into the Ru - vinyl bond to give the (η3-1-methylallyl)ruthenium complex 6a. The 3- and 4-alkenyl compounds 3 and 4 isomerize at 80-100°C after dissociation of one PPh3 via an (η2-alkadiene)hydridoruthenium intermediate, e.g. 7, to form the η3-allyl complexes 6, 8, and 9, respectively. The stable (η1,η2-4-alkenyl)ruthenium compounds 10-12 are formed if isomerization by β-H-elimination is prevented by E-configuration of Ru and β-H in a conformatively inflexible cyclopropyl system. The 31P chemical shifts of 2-4 and the (η1-allyl)ruthenium complexes, of 10-12, and of the η3-allyl complexes 6a, 8, 9, 13a are characteristic for the corresponding type of compounds.
    Notes: Die Cp(PPh3)2Ru—[CH2] nCR=CH2-Komplexe 2-4 (n = 0, 2, R = H; n = 3, R = CH3) werden durch Umsetzung des Chlorids 1 mit den entsprechenden Organomagnesiumhalogeniden dargestellt. Die Vinylverbindung 2 spaltet oberhalb 100°C einen PPh3-Liganden ab und reagiert mit Ethylen (20-30 bar) unter Insertion in die Ru - Vinyl-Bindung zum (η3-1-Methylallyl)ruthenium-Komplex 6a. Die 3- und 4-Alkenylverbindungen 3 und 4 isomerisieren bei 80-100°C nach Abspaltung eines PPh3 über (η2-Alkadien)hydridoruthenium-Zwischenstufen, z. B. 7, zu η3-Allyl-Komplexen 6 bzw. 8 und 9. Stabile (η1,η2-4-Alkenyl)ruthenium-Verbindungen 10-12 werden erhalten, wenn die Isomerisierung über β-H-Eliminierung durch E-Konfiguration von Ru und β-H in einem konformativ starren Cyclopropyl-System verhindert ist. Die 31P-chemischen Verschiebungen von 2-4 und den (η1-Allyl)ruthenium-Komplexen, von 10-12 bzw. den η3-Allylverbindungen 6a, 8, 9 und 13a sind jeweils charakteristisch für den Verbindungstyp.
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 186-196 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Heterocyclic Onium Salts with Electron-rich Multiple Bond SystemsThe N-phenylquinolinium salt 4 reacts with ketene diethyl acetal (5) by angular anellation to give 6. On the contrary, with ynamine 2 an open-chain 1:2 adduct (14) with cross-conjugated cyanine structure is obtained which is proved by X-ray analysis. With 1,2,4-triazolium salts and 2 [3+ + 2] cycloaddition-cycloreversion as well as [4+ + 2] cycloaddition are observed. With tetrazolium salt 28 and 2 deprotonation and cycloelimination of N2 occurs. The 5-aryl-substituted tetrazolium salt 32 suffers dealkylation with 2.
    Notes: Das N-Phenylchinoliniumsalz 4 reagiert mit Keten-diethylacetal (5) unter angularer Anellierung zu 6. Mit dem Inamin 2 hingegen gibt 4 ein offenkettiges 1 : 2-Addukt (14) mit kreuzkonjugierter Cyaninstruktur, die durch Röntgenstrukturanalyse bewiesen ist. Bei 1,2,4-Triazoliumsalzen werden mit 2 sowohl [3+ + 2]-Cycloaddition/Cycloreversion als auch [4+ + 2]-Cycloaddition beobachtet. Das Tetrazoliumsalz 28 wird durch 2 deprotoniert und cycloeliminiert N2. Das 5-arylsubstituierte Tetrazoliumsalz 32 wird durch 2 desalkyliert.
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  • 80
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 197-206 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Sulfur Ylide Complexes, XIV. π-Complexes of 1-Alkyl-3,5-diphenyl-λ4-thiabenzenes with Dicarbonylnitrosylchromium1-Alkyl-3,5-diphenyl-λ4-thiabenzene chromium complexes 2a-f are oxidized by NOPF6 in CH2Cl2 at -70°C, yielding the cationic dicarbonylnitrosyl complexes 3a-f. The temperature dependence of the 1H NMR spectra of 3a-f is consistent with a hindered rotation of the ring ligands. The X-ray structure analysis of 3b shows that the molecule in the solid state possesses no local Cs-symmetry.
    Notes: Die 1-Alkyl-3,5-diphenyl-λ4-thiabenzol-Chromkomplexe 2a-f werden durch NOPF6 in CH2Cl2 bei -70°C unter Bildung der kationischen Dicarbonylnitrosyl-Spezies 3a-f oxidiert. Die temperaturabhängigen 1H-NMR-Spektren dieser Komplexe deuten auf gehinderte Rotation der Ringe um das (CO)2(NO)Cr+-Fragment hin. Die Röntgenstrukturanalyse von 3b zeigt, daß das Molekül im Kristall keine lokale Cs-Symmetrie mehr besitzt.
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  • 81
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 215-219 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereologous Crown Ethers: π-Donor Participation in the Complexation of Cations?In the framework of the “stereology concept” the new crown ethers 8, 9, and for comparison 11 have been synthesized and their stability constants with Ag+ ions determined by 1H NMR spectroscopy. The results may be interpreted as evidence for a π-participation of aromatic nuclei of the ligands in the complexation of certain cations.
    Notes: Im Rahmen des „Stereologie-Konzepts“ wurden die neuartigen Kronenether 8, 9 und zum Vergleich 11 synthetisiert und deren Komplexkonstanten gegenüber Ag+-Ionen 1H-NMR-spektroskopisch ermittelt. Die Befunde machen eine π-Donorbeteiligung aromatischer Kerne bei der Komplexierung bestimmter Kationen wahrscheinlich.
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  • 82
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2408-2417 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: AcenazulenedionesReactions of 8-methoxyheptafulvene (1) and quinones 2 give in [8+2]-cycloadditions hydroacenazulenediones 3, which are immediately transformed to acenazulenediones 4 and 5. The yields in the reaction sequence depend on the half-wave-reduction-potentials (E1/2) of 2. Only compounds 2 with E1/2 (in acetonitrile, vs s.c.e.) lower than - 0.5 V lead to cycloadducts in reasonable yields. Properties of the ground and excited states of 4 and 5 are characterized by spectroscopic methods and molecular-orbital-calculations.
    Notes: Die Titelverbindungen 4 und 5 werden über [8+2]-Cycloadditionen aus 8-Methoxyheptafulven (1) und den Chinonen 2 dargestellt. Die Ausbeuten an 4 und 5 hängen von den Halbstufen-Reduktionspotentialen (E1/2) der Chinone 2 ab. Die Cycloadditionen werden nur bei Chinonen mit E1/2 〈 -0.5 V (in CH3CN, vs SCE) beobachtet; stärker oxidierende Chinone führen zur Polymerisation von 1. Die Grundzustandseigenschaften und Eigenschaften der angeregten Zustände von 4 und 5 werden durch spektroskopische Methoden und Berechnungen charakterisiert.
    Additional Material: 2 Ill.
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  • 83
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2437-2446 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Titanium Catalyzed Cyclization of 1,5-HexadienesCp2TiCl (1) and Cp2TiCl2 (2) combined with isopropylmagnesium bromide (molar ratio 1:1 and 1:2, resp.) catalyze the conversion of 1,5-hexadiene into a mixture of the five-membered ring compounds 3 and 4 as well as the linear isomeric hexadienes 5, 6, and 7. THF is most effective in both promoting cyclization as well as suppressing isomerization (3 → 4 and 5 → 6 or 7). The ratio of cyclic to linear products in reactions involving substituted 1,5-hexadienes is found to be dependent upon the position of the substituents. Substitution in the 2- or 2- and 5-position leads to the formation of the open-chain isomers 11 and 12 or 13 and 14, while 3,4-substituted 1,5-hexadienes react to give 〉 99% of the five-membered ring systems 15 and 16 or 17 and 18. A reaction mechanism is discussed which involves Cp2TiH and Cp2(alkenyl)Ti intermediates.
    Notes: Cp2TiCl (1) bzw. Cp2TiCl2 (2) und Isopropylmagnesiumbromid (Molverhältnis 1:1 bzw. 1:2) katalysieren die Umwandlung von 1,5-Hexadien in ein Gemisch der Fünfringverbindungen 3 und 4 sowie der offenkettigen isomeren Hexadiene 5,6 und 7. In THF ist die Cyclisierung am stärksten bevorzugt und die Isomerisierung (3 → 4 oder 5 → 6 bzw. 7) am langsamsten. Bei substituierten 1,5-Hexadienen hängt das Verhältnis cyclischer zu offenkettigen Produkten vom Ort der Substitution ab. Bei Substitution in 2- oder 2- und 5-Stellung entstehen praktisch ausschließlich die offenkettigen Isomeren 11 und 12 bzw. 13 und 14, während in 3,4-Stellung substituierte 1,5-Hexadiene zu 〉 99% die entsprechenden Fünfringverbindungen 15 und 16 bzw. 17 und 18 bilden. Es wird ein Reaktionsmechanismus mit Cp2TiH- und Cp2(Alkenyl)Ti-Zwischenstufen diskutiert.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2474-2485 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Norpinyl-Norbornyl Rearrangements: 2-Methyl- and 2,exo-6-Dimethylbicyclo[3.l.l]heptane DerivativesSolvolyses of 2-methylbicyclo[3.1.1]hept-2-yl-4-nitrobenzoate (9), the nitrous acid deamination of the corresponding amine (4e), and acid-catalyzed rearrangements of various 2-methylbicyclo-[3.1.1]heptane derivatives (4a - c) have been investigated. 2-Methylbicyclo[3.1.1]heptyl (4) and 1-methyl-endo-2-norbornyl (10) products prevailed; minor quantities of 2-methyl-exo-2-norbornyl derivatives (12) were also obtained. The product distributions were independent of the precursor but were strongly affected by the nucleophilicity of the solvent. Our observations are consistent with the 7-bridged norbornyl cation 6 as the predominant intermediate. Further stabilization of 6 by exo-3-methyl substitution is indicated by the results of the acid-catalyzed rearrangement of 2,exo-6-dimethylbicyclo[3.1.1]heptan-2-ol (17).
    Notes: Solvolysen von 2-Methylbicyclo[3.1.1]hept-2-yl-4-nitrobenzoat (9) die Desaminierung des entsprechenden Amins 4e und säurekatalysierte Umlagerungen verschiedener 2-Methylbicyclo-[3.1.1]heptan-Derivate (4a - c) wurden untersucht. 2-Methylbicyclo[3.1.1]heptyl- (4) und 1-Methyl-endo-2-norbornyl-Produkte (10) überwogen, daneben wurden kleinere Mengen an 2-Methyl-exo-2-norbornyl-Derivaten (12) erhalten. Die Produktverteilungen waren vom Ausgangsmaterial unabhängig, wurden aber durch die Nucleophilie des Lösungsmittels stark beeinflußt. Unsere Resultate sprechen für das 7-verbrückte Norbornylkation 6 als vorherrschende Zwischenstufe. Eine weitere Stabilisierung von 6 durch exo-3-Methylsubstitution deuten die Ergebnisse der säurekatalysierten Umlagerung von 2,exo-6-Dimethylbicyclo[3.1.1]heptan-2-ol (17) an.
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2492-2523 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: cis,trans-Oxaaza-bis-σ-homobenzenes - 4H-1,4-OxazocinesThe cis-oxaaza-bis-σ-homobenzene framework has been synthesised via two routes starting from readily accessible materials (11, 25). As expected the N-SO2R derivatives 3a, b are sufficiently stable to be isolated; on heating, they readily and quantitatively undergo [π2 + σ2 + σ2]-cycloreversion to the 4H-1,4-oxazocines 6a, b (3b: t1/2 (60°C) = 33.2 min; ΔG≠ = 104.0 kJ·mol-1). The latter prefer a non-planar, folded conformation. Using a precursor of 3b (27a), the thermally stable trans-oxaaza-bis-σ-homobenzene 9 was obtained in very small yield (2-6%) by two alternative pathways.
    Notes: Mit jeweils gut zugänglichen Ausgangsmaterialien (11, 25) werden zwei Synthesen für das cis-Oxaaza-bis-σ-homobenzol-Gerüst entwickelt. Die erwartungsgemäß isolierbaren N-SO2R-Derivate 3a, b gehen beim Erwärmen rasch und einheitlich die [π2 + σ2 + σ2]-Cycloreversion in die 4H-1,4-Oxazocine 6a, b ein (3b: t1/2 (60°C) = 33.2 min; ΔG≠ = 104.0kJ. mol-1). Letztere bevorzugen eine nicht-planare, gefaltete Konformation. Ausgehend von einem Synthesezwischenprodukt (27a) wird in zwei Varianten und in jeweils sehr geringer Ausbeute (2-6%) auch das thermisch beständige trans-Oxaaza-bis-β-homobenzol 9 hergestellt.
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  • 86
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 970-979 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Reaktivität von 2-Aroylbenzoesäuren, III. 2-(4-Hydroxy-3,5-dimethylbenzoyl)benzoesäureDurch Friedel-Crafts 2-Carboxybenzoylierung von 2,6-Xylenol mit Phthalsäureanhydrid wurde eine neue Verbindung vom p-Acylphenol-Typ erhalten: 2-(4-Hydroxy-3,5-dimethylbenzoyl)benzoesäure (1) (Ausbeute 74%). In einer analogen Reaktion von 2,6-Xylenol mit Tetrabrom- und Tetrachlorphthalsäureanhydrid wurden die Benzoesäure-Derivate 13 bzw. 14 dargestellt. 1 wurde auch mit 93% Ausbeute durch Semi-Stieglitz-Umlagerung von 3,3-Bis(4-hydroxy-3,5-dimethylphenyl)phthalid (9) gewonnen. Verschiedene Reaktionen der Säure 1 führten zu den Derivaten 2-12.
    Notes: Friedel-Crafts 2-carboxbenzoylation of 2,6-xylenol with phthalic anhydride resulted in the formation of a new p-acylphenol type compound: 2-(4-hydroxy-3,5-dimethylbenzoyl)benzoic acid (1) (74% yield). Similar reactions of 2,6-xylenol with tetrabromo- and tetrachlorophthalic anhydride gave the benzoic acid derivatives 13 and 14, respectively. Another practical and efficient (93%) method for preparation of compound 1 was semi-Stieglitz rearrangement of the known 3,3-bis(4-hydroxy-3,5-dimethylphenyl)phthalide (9). Reactions of the acid 1 have been investigated, leading to its derivatives 2-12.
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  • 87
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2564-2573 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: C-Silyl Derivatives of QuinolizinesThe cycloaddition of dimethyl acetylenedicarboxylate (1) to the C-silylated pyridines 2b - f leads to the corresponding partially very labile C-silylated tetramethyl 9aH-quinolizine-1,2,3,4-tetracarboxylates 3b - j, which are rearranged into the isomeric tetramethyl C-silyl-4H-quinolizine-1,2,3,4-tetracarboxylates 4b - g. From 4b - d the silylated dimethyl 3-methoxalyl-4-oxo-4H-quinolizine-1,2-dicarboxylates 6b - d are formed via the quinolizinium perchlorates, from which the perchlorate 5b was isolated.
    Notes: Die Cycloaddition von Acetylendicarbonsäure-dimethylester (1) an die silylierten Pyridine 2b - f führt zu den entsprechenden, z. T. sehr labilen, C-silylierten 9aH-Chinolizin-1,2,3,4-tetracarbonsäure-tetramethylestern 3b - j, die in die isomeren C-Silyl-4H-chinolizin-1,2,3,4- tetracarbonsäure-tetramethylester 4b - g umgelagert werden können. Aus 4b - d entstehen-über die Chinolizinium-perchlorate die silylierten 3-Methoxalyl-4-oxo-4H-chinolizin-1,2-dicarbonsäure-dimethylester 6b - d, wobei das Perchlorat 5b isoliert wurde.
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  • 88
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1107-1117 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangement with Oxygen-Insertion in Azabicyclic Hydroxylamine DerivativesN-Hydroxy-2-azabicyclo[2.2.1]hept-5-ene (1) is rearranged to the oxaazabicyclic compounds 3, 4, and 8 by the reaction with either tosyl or benzoyl chloride. The structure of 3 was proved by X-ray analysis. Experiments with [18O]tosyl chloride as well as products of the intermediate 12 with methanol are consistent with a heterolysis in the intermediate 11 formed by N-tosylation  -  in contrast to the homolytic1) Meisenheimer rearrangement.
    Notes: N-Hydroxy-2-azabicyclo[2.2.1]hept-5-en (1) wird bei der Umsetzung mit Tosyl- und Benzoylchlorid umgelagert zu den Oxaazabicyclen 3, 4 und 8. Die Struktur von 3 wurde durch Röntgenstrukturanalyse bewiesen. Versuche mit [18O]Tosylchlorid sowie die Abfangprodukte mit Methanol sprechen für eine ionische Spaltung in dem durch N-Tosylierung gebildeten Intermediären 11, im Gegensatz zum radikalischen Ablauf der sonst analogen Meisenheimer-Umlagerung.
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  • 89
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1132-1153 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pyrazaboles: Electrophilic Substitutions and Studies of Their Crystal and Molecular StructuresElectrophilically induced substitution reactions at the boron atoms of pyrazaboles, [R2Bpz]2, using 10BBr3 proceed without exchange of the boron atoms. All four substituents R may be exchanged for Br, with the exception of R = C2H5, and variously substituted pyrazaboles are detected by 11B NMR as intermediates. Some of these were isolated. Based on NMR data obtained for the reaction of [(C2H5)2Bpz]2 with BBr3, ionic intermediates are proposed for these exchange reactions. A stepwise interaction also occurs on treatment of the pyrazabole 1a with pyrazole; this is documented by the isolation of the monopyrazol-1-ylpyrazabole 1e.  -  The central B2N4 ring of pyrazaboles adopts a chair, a boat, or a planar conformation in the solid state as shown by X-ray structural studies on five different pyrazaboles. Therefore, packing effects seem to determine the ring conformation.
    Notes: Elektrophil induzierte Substitutionsreaktionen an den Boratomen der Pyrazabole [R2Bpz]2 mit 10BBr3 erfolgen ohne Austausch von Boratomen. Alle vier Substituenten R werden gegen Br substituiert (Ausnahme R = C2H5), wobei 11B-NMR-spektroskopisch verschieden substituierte Pyrazabole als Zwischenprodukte nachgewiesen und in einigen Fällen isoliert wurden. Dabei weisen die NMR-Daten der Umsetzung von [(C2H5)2Bpz]2 mit BBr3 auf eine ionische Zwischenstufe für diese Austauschreaktion hin. Eine schrittweise Substitution erfolgt auch bei der Umsetzung des Pyrazabols 1a mit Pyrazol, wie die Isolierung von Monopyrazol-1-ylpyrazabol 1e zeigt.  -  Nach Röntgenstrukturuntersuchungen an fünf Pyrazabolen liegt der zentrale B2N4-Ring in der Sessel-Boot- oder planaren Konformation vor. Danach scheinen Packungseffekte die jeweilige Konformation im festen Zustand zu bestimmen.
    Additional Material: 7 Ill.
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  • 90
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1118-1131 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Deamination Reactions, 38. The Ring Expansion Route to 2-Norbornyl Cations2-Norbornyl cations have been generated by ring expansion reactions of bicyclo[2.1.1]hex-5-ylmethanediazonium ions (29, 37). The exo isomer 37 yielded exclusively exo-2-norbornanol (30) while the endo isomer 29 produced an exo: endo (30:31) ratio of 6. In both cases 30 was derived from a symmetrical (bridged or rapidly equilibrating) 2-norbornyl cation, as shown by scrambling of a deuterium label. The ring expansion reactions of 1-(bicyclo[2.1.1]hex-5-yl)ethanediazonium ions (50, 58) proceeded stereoselectively, 50 giving rise to exo-3-methyl-2-norbornyl cations (52, 54), and 58 to endo-3-methyl-2-norbornyl cations (60). These observations are explained in terms of conformational preferences of the bicyclo[2.1.1]hexane derivatives. The endo precursor 50 afforded a large fraction of exo-3-methyl-endo-2-norbornanol while the ring expansion of 58 was associated with an exceptional extent of 3,2-hydride shift. 1-(Bicyclo[2.1.1]hex-5-yl)-1-methylethyl cations (68, 72) did not rearrange with formation of 3,3-dimethyl-2-norbornyl cations (69). The unconventional reactions of the 2-norbornyl cations are attributed to distorted conformations which improve overlap of the vacant p orbital with otherwise unfavorably oriented σ bonds. The distorted 2-norbornyl cations intervene in the course of ring expansion but are not thought to represent potential minima.
    Notes: 2-Norbornylkationen wurden durch Ringerweiterung aus Bicyclo[2.1.1]hex-5-ylmethandiazonium-Ionen (29, 37) erzeugt. Das exo-Isomere 37 lieferte ausschließlich exo-2-Norbornanol (30), während das endo-Isomere 29 ein exo/endo-Verhältnis (30/31) von 6 ergab. In beiden Fällen entstand 30 aus einem symmetrischen (verbrückten oder rasch äquilibrierenden) 2-Norbornylkation, wie durch die Verteilung einer Deuterium-Markierung gezeigt wurde. Die Ringerweiterungsreaktionen der 1-(Bicyclo[2.1.1]hex-5-yl)ethandiazonium-Ionen (50, 58) verliefen stereoselektiv; 50 führte zu exo-3-Methyl-2-norbornylkationen (52, 54) 58 zu endo-3-Methyl-2-norbornylkationen (60). Dies wird durch die Vorzugskonformationen der Bicyclo[2.1.1]hexanderivate erklärt. Die endo-Vorstufe 50 ergab einen hohen Anteil an exo-3-Methyl-endo-2-norbornanol, während die Ringerweiterung von 58 mit 3,2-H-Verschiebung in ungewöhnlichem Ausmaß verbunden war. 1-(Bicyclo[2.1.1]hex-5-yl)-1-methylethylkationen (68, 72) zeigten keine Umlagerung zu 3,3-Dimethyl-2-norbornylkationen (69). Die ungewöhnlichen Reaktionen der 2-Norbornylkationen führen wir auf verdrillte Konformationen zurück, welche die Überlappung zwischen dem leeren p-Orbital und sonst ungünstig angeordneten σ-Bindungen verbessern. Die verdrillten 2-Norbornylkationen werden im Zuge der Ringerweiterungsreaktionen durchlaufen, doch dürften ihnen keine Potentialminima zuzuordnen sein.
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  • 91
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1195-1208 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Carboxylic Trifluoromethanesulfonic Anhydrides as Highly Effective Acylation Agents.  -  Perfluoroalkanesulfonic Acid Catalyzed Acylation of ArenesArene- and alkanecarboxylic trifluoromethanesulfonic anhydrides 2 and 5 are highly effective acylation agents, which react without Friedel-Crafts catalysts even with deactivated aromatics to yield aryl ketones 3 and 6, respectively. Acylation of arenes with carbonyl chlorides 4 and catalytic amounts of perfluoroalkanesulfonic acid gives ketones 3 and 6, resp., in good yields. Under similar conditions other strong Brønsted acids show a considerably smaller degree of catalytic effect.
    Notes: Aren- und Alkancarbonsäure-trifluormethansulfonsäure-anhydride 2 bzw. 5 sind starke Acylierungsagentien, die auch mit wenig reaktiven Aromaten, ohne Zusatz von Friedel-Crafts-Katalysatoren, Arylketone 3 bzw. 6 ergeben. Eine mit guten Ausbeuten verlaufende Aromatenacylierung mit Carbonsäurechloriden und katalytischen Mengen Perfluoralkansulfonsäure wird beschrieben. Die katalytische Wirksamkeit anderer starker Brønsted-Säuren unter vergleichbaren Bedingungen ist wesentlich schwächer.
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  • 92
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2711-2713 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Phosphorus, 127. Synthesis of the Hetero Tricyclophosphanes (RP)P4(C2H4)2 (R = Me, Et) und (Me2Si)P4(C2H4)21,2,5,6-Tetraphosphabicyclo[3.3.0]octane (1a) or its dilithium salt (1b) react with geminale element dihalogen compounds such as MePCl2, EtPCl2 or Me2SiCl2 to the hitherto unknown 9-organyl-1,2,5,6,9-pentaphosphatricyclo[3.3.1.02,6]nonanes (2a, 2b) and 9,9-dimethyl-1,2,5,6-tetraphospha-9-silatricyclo[3.3.1.02,6]nonane (3), respectively. This is the first directed synthesis of tricyclophosphane skeletons from a bicyclophosphane.
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  • 94
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereochemistry of the Bicyclo[2.1.0]pentane Ringopening; Thermolysis of Tricyclo[3.2.0.02,4]heptane DerivativesThermolysis of the anti-tricyclic compounds 6, 22 and 34 proceeds preferentially by concerted [σs2+σa2]-reactions and leads to cis,trans-olefines 8, 24 and 37. The rearrangement of the syn-isomers on the other hand seems to be a nonconcerted reaction yielding the diradicals 15, 27 and 36.
    Notes: Die Thermolyse der anti-Tricyclen 6, 22 und 34 erfolgte bevorzugt im Sinne einer konzertierten [σs2+σa2]-Reaktion und führt zu den cis,trans-Olefinen 8, 24 und 37, während für die Umlagerung der syn-Isomeren ein zweistufiger Verlauf über die intermediären Diradikale 15, 27 bzw. 36 wahrscheinlich gemacht wird.
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  • 95
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2765-2774 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Direct Metal Exchange in Phosphinidene-Bridged FeCo2 ClustersThe reactions of the clusters RPFeCo2(CO)9 (1a, R = Me; 1b, R = t-Bu) with [CpNiCO]2 (2) yielded product mixtures which originate from metal exchange reactions as well as from cluster rearrangement and ligand exchange. The crystal structures of the resulting clusters (μ4-MeP)2-Fe2CoNiCp(CO)8 (4) and (μ3-t-BuP)FeCoNiCp(CO)6 (5) were determined.
    Notes: Die Umsetzung der Cluster RPFeCo2(CO)9 (1a, R = Me; 1b, R = t-Bu) mit [CpNiCO]2 (2) führte zu Produktgemischen, die sowohl aus Metallaustauschreaktionen als auch aus Cluster-Umlagerung und Ligandenübertragung resultieren. Von den dabei entstehende Clustern (μ4-MeP)2-Fe2CoNiCp(CO)8 (4) und (μ3-t-BuP)FeCoNiCp(CO)6 (5) wurden Kristallstrukturanalysen durchgeführt.
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  • 96
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2738-2747 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Attempted Halogen Exchange in Methyl Substituted Mono- and DibromocyclobutanesReactions of AgBF4 with 1-bromo-1-methyl- (1a) and with 1,3-dibromo-1,3-dimethylcyclobutanes (2a, 3a) afforded a partial or complete exchange of bromine for fluorine, depending on the reactant ratios. In 1,3-dibromo-1,2-dimethyl- (4a-7a) and in 1,2-dibromo-1,2-dimethylcyclobutanes (8a), however, only one bromine substitutent was exchanged for fluorine. From 8a products having cyclopropane structures (9, 10) and acyclic dihalo compounds (11a, b) were also formed. Reactions of SbCl5 with 1,3-dibromo-1,3-dimethylcyclobutane (2a, 3a) afforded a complete, reactions with 1,3-dibromo-1,2-dimethyl- (7a) and with 1,2-dibromo-1,2-dimethylcyclobutane (8a), however, only a partial exchange of bromine for chlorine. From 8a acyclic products were additionally formed.
    Notes: Umsetzungen von AgBF4 mit 1-Brom-1-methyl-(1a) und mit 1,3-Dibrom-1,3-dimethylcyclobutanen (2a, 3a) führten je nach dem Reaktandenverhältnis zu einem teilweisen oder vollständigen Austausch von Brom gegen Fluor. In 1,3-Dibrom-1,2-dimethyl- (4a-7a) und 1,2-Dibrom-1,2-dimethylcyclobutanen (8a) wurde jeweils nur ein Bromsubstituent gegen Fluor ausgetauscht. Aus 8a entstanden zusätzlich noch Folgeprodukte mit Dreiringstrukturen (9, 10) und acyclische Dihalogenverbindungen (11a, b). Umsetzungen von SbCl5 mit 1,3-Dibrom-1,3-dimethylcyclobutan (2a, 3a) führten zum völligen, mit 1,3-Dibrom-1,2-dimethyl- (7a) und 1,2-Dibrom-1,2-dimethylcyclobutan (8a) dagegen nur zum teilweisen Austausch von Brom gegen Chlor. Aus 8a entstanden daneben auch acyclische Folgeprodukte.
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  • 97
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2748-2764 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chid PFeCoM Clusters: Preparation by Metal Exchange and Investigation of the Optical ActivityThe clusters RPFeCo2(CO)9 (1, R = Me, t-Bu, Ph) react with the organometal dimethylarsenides Cp(CO)3M—AsMe2 (3, M = Mo, W) to form the substitution derivatives RPFeCo2(CO)8-AsMe2-M(CO)3Cp (4, M = Mo; 5, M = W) and the hetero clusters RPFeCoMCp(CO)8 (6, M = Mo; 7, M = W). With R = tert-butyl the tetranuclear clusters t-BuPFeCo2M(AsMe2)Cp(CO)8 (8, M = Mo, W) are isolated as reaction intermediates. From t-BuPCo3(CO)9 (2) and Cp(CO)3Mo-AsMe2 the cluster t-BuPCo2Mo(AsMe2)Cp(CO)6 (9) is formed. The structures of the molybdenum containing clusters 6a and 9 were determined. The compound MePFeCoWCp(CO)8 (7a) is separated into its enantiomers via substitution with the phosphane ligand (-)-menthyl-O—PPh2. The ORD data of these show little resemblance with those of the corresponding sulfurbridged clusters.
    Notes: Die Cluster RPFeCo2(CO)9 (1, R = Me, t-Bu, Ph) setzen sich mit den Organometall-dimethyl-arseniden Cp(CO)3M—AsMe2(3, M = Mo, W) zu den Substitutions-Derivaten RPFeCo2(CO)8-AsMe2 - M(CO)3Cp (4, M = Mo; 4, M = Mo; 5, M = W) und zu den Hetero-Clustern RPFeCoMCp(CO)8 (6, M = Mo; 7, M = W) um. Für R = tert-Butyl können dabei als Zwischenstufen die Vierkerncluster t-BuPFeCo2M(AsMe2)Cp(CO)8(8, M = Mo, W) isoliert werden. Aus t-BuPCo3(CO)9(2) entsteht mit Cp(CO)3Mo-AsMe2 der Cluster t-BuPCo2Mo(AsMe2)Cp(CO)6 (9). Von den molybdänhaltigen Clustern 6a und 9 wurden die Strukturen bestimmt. Die Verbindung MePFeCoWCp(CO)8 (7a) läßt sich mit dem Phosphanliganden (-)-Menthyl-O—PPh2 in die Enantiomeren zerlegen. Deren ORD-Daten zeigen wenig Verwandtschaft mit denen der entsprechenden schwefelverbrückten Cluster.
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  • 98
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2775-2784 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermal Azulene Rearrangements. Synthesis and Thermolysis of [6-13C]AzuleneA specific synthesis of [6-13C]azulene (24) is described. The synthetic sequence outlined in scheme 3 begins with the construction of [4-13C]toluene (17) which is performed in 8 steps starting from [13C]-paraformaldehyde. The suspected scrambling of the label in the dehydrogenation step 16 → 17 can be suppressed by suitable reaction conditions. After extension of the side chain by 3 carbon atoms to give 1-diazo-4-([4-13C]phenyl)-2-butanone (21), the labelled azulene is obtained according to Scott's azulene synthesis (21 → 22 → 23 → 24). The vacuum thermolysis of 24 (1050°C, 10-3-10-2 torr) yields [β-13C]naphthalene (25) as the main produkt (91% of the naphthalene formed) in accordance with the norcaradiene-vinylidene mechanism. The remaining 9% consist of [α-13C]naphthalene. Besides the formation of naphthalene (15% conversion), 24 suffers automerisation to a small extent yielding [5-13C]- and [1-13C]azulene (ca. 3 and 1%, respectively).
    Notes: Es wird eine gezielte Synthese von [6-13]Azulen (24) beschrieben. Die angegebene Synthesesequenz (Schema 3) erfordert zunächst den Aufbau von [4-13C]Toluol (17), der ausgehend von [13C]Paraformaldehyd in 8 Stufen erfolgt. Die auf der Dehydrierungsstufe 16 → 17 zu befürchtende Verteilung der 13C-Markierung im Benzolring kann durch geeignete Reaktionsbedingungen unterdrückt werden. Nach Verlängerung der Seitenkette um 3 Kohlenstoffatome zu 1-Diazo-4-([4-13C]phenyl)-2-butanon (21) wird entsprechend der Scottschen Azulensynthese (21 → 22 → 23 → 24) das markierte Azulen erhalten. Die Vakuumthermolyse von 24 (1050°C, 10-3-10-2 Torr) liefert in Übereinstimmung mit dem Norcaradien-Vinyliden-Mechanismus als Hauptprodukt [β-13C]Naphthalin (25) (91% des gebildeten Naphthalins). Die restlichen 9% entfallen auf [α-13C]Naphthalin. Neben der Naphthalin-Bildung (15% Umsatz) erleidet 24 in geringem Umfang eine Automerisierung zu [5-13C]- und [1-13C]Azulen (ca. 3 bzw. 1%).
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  • 99
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    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 2827-2834 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electron Donor-Acceptor Compounds, XXXI. Electron Donor-Acceptor [3.3]Paracyclophanes with N,N,N′,N′-Tetramethyl-p-phenylenediamine (TMPD) as Donor UnitThe electron donor-acceptor [3.3]paracyclophanes 1 and 2 which contain the combination of N,N,N′,N′-tetramethyl-p-phenylenediamine and p-benzoquinone were synthesized starting from 3 and 4 via 5, 7, 9, 11, 13 and 6, 8, 10, 12, 14, respectively. Charge transfer(CT) absorptions of the pair of isomers 1 and 2 differ considerably as a consequence of the orientation dependence of CT transitions. Based on an X-ray structure analysis, special features of the molecular and crystal structure of 2 are discussed.
    Notes: Die Elektron-Donor-Acceptor-[3.3]Paracyclophane 1 und 2, die die Kombination N,N,N′,N′-Tetramethyl-p-phenylendiamin und p-Benzochinon enthalten, wurden ausgehend von 3 und 4 über 5, 7, 9, 11 und 13 bzw. 6, 8, 10, 12 und 14 synthetisiert. Die Charge-Transfer(CT)-Absorptionen des Isomerenpaars 1 und 2 zeigen als Folge der Orientierungsabhängigkeit des CT-Übergangs beträchtliche Unterschiede. Die Molekülstruktur und Gitterpackung von 2 werden anhand einer Röntgenstrukturanalyse diskutiert.
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 3427-3437 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoextrusion of Nitrogen from 1-Alkenyl-4-alkyl-1,4-dihydro-5H-tetrazol-5-ones and -thiones. Diaziridinones and Carbodiimides with Alkeyl SubstituentsTo test the possibility that tetrazolones and tetrazolthiones photoextrude nitrogen producing intermediates which can be trapped via intramolecular [3 + 2]-cycloaddition to C=C double bonds, several tetrazolones 8 and -thiones 13 with alkenyl substituents were synthesized and subjected to photolysis. On 254 nm photolysis of the tetrazolones 8 in [D3]acetonitrile, [D12]cyclohexane, and [D14]methylcyclohexane as solvents, nitrogen was extruded and diaziridinones 17 were formed in 80-90% yield besides small amounts of by-products (〈 10%). When the photolysis was carried out in [D3]acetonitrile, the latter were identified as urea 18 (photoreduction product) and as the hydrolysis product of 17. The thiones 13 photoextruded nitrogen and sulfur producing carbodiimides. Trapping of an intermediate via [3 + 2]-cycloaddition was not observed.
    Notes: Um zu prüfen, ob aus Tetrazolonen und Tetrazolthionen durch photochemische Stickstoff-Eliminierung Zwischenstufen entstehen, die sich durch intramolekulare [3 + 2]-Cycloaddition an C=C-Doppelbindungen abfangen lassen, wurden einige Tetrazolone 8 und -thione 13 mit Alkenylsubstituenten dargestellt und photolysiert. Mit Licht von λ = 254 nm erhielt man aus den Tetrazolonen 8 in [D3]Acetonitrile, [D12]Cyclohexan und [D14]Methylcyclohexan Stickstoff und 80-90% Diaziridinone 17 neben geringen Mengen Nebenprodukten (〈 10%), die sich in [D3]Acetonitril als Photoreduktionsprodukt, Harnstoff 18, und als Hydrolyseprodukt von 17 erwiesen. Die Thione 13 eliminierten beim Belichten Stickstoff und Schwefel und gaben Carbodiimide. In keinem Fall beobachtete man intramolekulare [3 + 2]-Cycloaddition einer Zwischenstufe.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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