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  • 1
    ISSN: 1432-0568
    Keywords: Placenta ; Fetal microvasculature ; Corrosion casts ; Scanning electron microscopy ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The fetal microvascular architecture of the feline near-term placenta was investigated using scanning electron micrographs of partially fractured corrosion casts from plastic-filled vessels. The findings were compared with those on corresponding semithin histological sections. The branches of both umbilical arteries and veins roughly follow a course parallel to the zonary girdle on the allantochorionic side of the feline placenta in an acute-angled pattern of ramifications. They join the double-layered capilary networks in the chorionic lamellae of the labyrinth, which generally exhibit a chorio-uterine orientation and are partially twirled. On the allantochorionic side of the labyrinth, these fetal capillary networks are “suspended” on the maternal stem-artery-system of the placenta; on the uterine side, they have peduncular or tuft-like endings of capillary loops and are flattened by the uterine septa, which at this level converge into the maternal veins. The chorionic capillary lamellae have a variable breadth and length and therefore need shorter or longer arterioles and venules from the allantochorionic side to become irrigated at any level of the labyrinth. As a result, the feline placenta is characterized by a generally one-way crosscurrent type of materno-fetal blood flow.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 170 (1984), S. 29-43 
    ISSN: 1432-0568
    Keywords: Anatomy ; Anterograde tracing ; Dorsal column nuclei ; Midbrain ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The termination of the fibers from the dorsal column nuclei (DCN) to the midbrain has been investigated in the cat with the degeneration method, the anterograde horseradish peroxidase (HRP) method and autoradiography after 3H-leucine injections. The results show that the DCN project to several midbrain regions. The external nucleus of the inferior colliculus (IX) receives the heaviest projection from both the gracile and cuneate nuclei. The DCN fibers form three joint terminal zones in IX. Each terminal zone contains clusters with dense aggregations of DCN fibers. Fairly dense terminal networks are found in the posterior pretectal nucleus (PP) and the compact part of the anterior pretectal nucleus (PAc) as well. More scattered DCN fibers are present in the cuneiform nucleus (CF), the lateral part of the periaqueductal gray (PAG1), the red nucleus (NR), the nucleus of the brachium of the inferior colliculus (B), the mesencephalic reticular formation (MRF) and the intermediate and deep layers of the superior colliculus (SI, SP). The projections to all regions are mainly contralateral. Most of the few ipsilateral fibers terminate in IX. A somatotopic organization was seen in IX and NR. The gracile fibers terminate preferentially in the caudal and lateral part of IX and the cuneate ones preferentially in its rostral and medial part. In the red nucleus the gracile fibers terminate ventral to the cuneate ones. In the pretectal region there was a predominance for gracile fibers. There also appeared to be quantitative differences in the projections from various levels of the gracile nucleus, with more midbrain projecting fibers originating in the rostral than in the middle and caudal parts of the nucleus.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 170 (1984), S. 177-186 
    ISSN: 1432-0568
    Keywords: Cecum ; Cat ; Macroscopic anatomy ; Light, scanning and transmission electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In a series of comparative anatomical studies on the ceca of various mammals the cat was chosen as representative of a “typical” carnivore. In the domestic cat, the cecum is conspicuously small and macroscopically relatively undifferentiated in comparison to most herbivores. Microscopically (light, scanning and transmission electron microscopy), however, it is characterized by an abundance of goblet cells and enterocytes rich in organelles, suggestive of functional activity. In addition to the morphological description, which also includes arterial supply and mesenteries of the cecum, the discussion is focussed on 1) the possible functional significance of the numerous goblet cells 2) a general categorization of the different types of ileal-caeco-colical junctions and 3) speculations concerning the justification for considering the carnivore cecum as being rudimentary.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 170 (1984), S. 265-277 
    ISSN: 1432-0568
    Keywords: Midbrain ; Spinal cord ; Cat ; Degeneration-HRP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The projections to the midbrain from the spinal cord have been investigated in the cat with the degeneration technique and by using horseradish peroxidase (HRP) as an anterograde tracer. Two types of spinal cord lesions were performed: 1) Cordotomies at cervical or thoracic levels transecting the ventral and lateral funiculi. 2) Transections of the ventral, ventrolateral, dorsolateral or dorsal funiculus, respectively, at cervical levels. In the anterograde tracing experiments HRP was injected into the spinal cord at cervical, lumbar or sacral levels. The results show large projections to the lateral and ventrolateral parts of the periaqueductal gray (PAG1), the posterior pretectal nucleus (PP) and the nucleus of Darkschewitsch (D). More moderate projections go to the medial division of the periaqueductal gray (PAGm), the cuneiform nucleus (CF), the mesencephalic reticular formation (MRF), lateral part of the deep layer of the superio colliculus (SP) and magnocellular medial geniculate nucleus (GMmc), while scattered spinal fibers are present in the dorsal part of the periaqueductal gray (PAGd), the external inferior collicular nucleus (IX), the intermediate layer of the superior colliculus (SI), the lateral part of the red nucleus (NR) and in the Edinger-Westphal portion of the oculomotor nucleus (3). In addition a few fibers are present in the interstitial nucleus of Cajal (CA) and anterior pretectal nucleus (PAc). The results indicate that at midcervical levels most of the spinomesencephalic fibers ascend in the ventral funiculus, with only a moderate fraction ascending in the ventral half of the lateral funiculus. Almost no fibers ascend in the dorso-lateral funiculus and none appear to pass in the dorsal funiculus. No distinct somatotopic pattern was found in the spinomesencephalic projections, but more fibers from cervicobrachial segments terminate in the rostral than in the caudal parts of the terminal fields in PAG, CF, SP and IX, while the lumbar fibers were more numberous in the caudal parts. PP seems to receive spinal fibers mainly from the caudal half of the cord.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 54 (1984), S. 95-106 
    ISSN: 1432-1106
    Keywords: Cerebellothalamic projections ; Pallidothalamic projections ; Ventral nuclei of thalamus ; Autoradiography ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Injections of 3H-leucine were made in the entopeduncular nucleus or dentate nucleus of the cerebellum in eight cats. The terminal projection zones of both pathways in the thalamus were studied using the sagittal plane and their relationships to one another as well as to cytoarchitectural boundaries of thalamic nuclei were compared. The data indicate that the territories controlled by the two projection systems are almost entirely segregated. The segregation is mainly along the antero-posterior axis as the main pallidal projection zone occupies the medio-ventral VA while the main dentate projection zone lies posterior to it in the VL. Furthermore, the dorsolateral part of the VA not occupied by pallidal projections receives dentate projections. In the VM, both afferent systems terminate in the lateral part of the nucleus with pallidal territory located anteriorly and dentate territory located posteriorly, again without overlap. As the delineations of nuclear subdivisions in the ventral thalamus of the cat have been a subject of some controversy, it is suggested that the boundaries of the VA, VL and VM in the cat thalamus be defined on the basis of basal ganglia and cerebellar projection zones.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 54 (1984), S. 107-120 
    ISSN: 1432-1106
    Keywords: Corticospinal collaterals ; Sensorimotor cortex ; Corticobulbar pathways ; Fluorescent tracers ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The fluorescent retrograde double-labeling technique has been used to determine whether corticospinal neurons in the cat sensorimotor cortex distribute collaterals to the lower brain stem reticular formation. In this study the fluorescent tracers Nuclear Yellow and Diamidino Yellow 2HCl were used in combination with Fast Blue. One tracer was injected unilaterally in the spinal cord and the other was injected ipsilaterally in the bulbar medial reticular formation. The distribution of the retrogradely labeled neurons was studied in the contralateral hemisphere. In the sensorimotor cortex a large population of neurons was found which were labeled from the spinal cord and were double-labeled from the brain stem. These branching neurons were concentrated in the rostromedial part of area 4 and the adjoining lateral part of area 6. In this region the percentages of corticospinal neurons which were double-labeled from the brain stem ranged from 5% laterally to 30% medially. In two cats it was demonstrated by means of the anterograde transport of HRP that the corticobulbar fibers from this region which must include the corticospinal collaterals are distributed to the reticular formation of the lower brain stem. In view of the fact that the double-labeled neurons are concentrated in the anterior part of the motor cortex, those branching neurons are in all likelihood involved in the control of neck, back and shoulder movements. This control is probably exerted by way of two routes i.e. by way of the direct corticospinal connections to spinal interneurons, and by way of the indirect cortico-reticulospinal connections established by the cortical fibers to the bulbar reticular formation. The present findings suggest that this dual control may be exerted by one and the same cell.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 53 (1984), S. 259-276 
    ISSN: 1432-1106
    Keywords: Motor cortex ; Thalamocortical ; Corticocortical ; HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary (1) Ipsilateral cortico-cortical and thalamo-cortical projections to the cat motor cortex were determined from the locations of retrogradely labeled neurons following single small intracortical injections of HRP in area 4γ. These projections were also examined by studying the distribution of anterogradely transported axonal label following multiple injections of HRP or of tritiated amino acids in areas 1–2 of SI and in area 2pri (SII). (2) The number of retrogradely labeled cells in areas 1–2 and in area 2pri differed markedly between HRP injection sites located in the precruciate (anterior sigmoid gyrus) and postcruciate (posterior sigmoid gyrus) subregions of area 4γ. These associational projections from primary and secondary somatosensory cortices were dense to postcruciate subrogions but weak to the precruciate subregions. (3) The associational projections from areas 1–2 and from area 2pri to the postcruciate subregion of area 4γ were topographically organized, but no clear topographic organization could be demonstrated for the precruciate projection. (4) Anterograde terminal labeling following injection of either HRP or tritiated amino acids into areas 1–2 and area 2pri confirmed the preferential projection of somatosensory cortex to the postcruciate subregion of motor cortex. The projection from somatosensory areas 1–2 was uniform over its terminal field, but that from area 2pri was more patchy and complex. (5) HRP injections in area 4γ gave rise to lamellae of labeled neurons in the ventrolateral nucleus of thalamus (VL). A topographic relationship was found between the site of injection and the location of the lamella of labeled neurons. (6) The percentage of retrogradely labeled neurons in the shell zone surrounding the border of the ventrolateral nucleus and the ventrobasal complex (VB) was greater following postcruciate than precruciate injections, whereas fewer retrogradely labeled neurons were found in central lateral nucleus (CL) after postcruciate injections than after precruciate injections. (7) These observations support the hypothesis that differential cortical and thalamic projections to different subregions of area 4γ may give rise to the different physiological properties of neurons observed in these subregions (Vicario et al. 1983; Martin et al. 1981).
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 54 (1984), S. 283-288 
    ISSN: 1432-1106
    Keywords: Skin potential response ; Cat ; Pyramidal tract ; Reticulospinal tracts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Pyramidal command of Skin Potential Response (SPR) was investigated in 20 cats paralyzed by gallamine and under a halothane anaesthetic. For each animal, a transection of the medulla sparing only the pyramidal tract was carried out. The pyramidal tract and Mesencephalic Reticular Formation (MRF) were stimulated before and after the transection. Results taken before transection show that the SPR can be elicited from stimulation of the pyramidal tract and the MRF. After transection, stereotaxic stimulations of the pyramidal tract still evoked the SPR even after aspiration of the medullary tissue posterior to the section and overlying the pyramids. Control reticular stimulations with higher stimulus intensities failed to evoke the SPR. These results show that stimulation of the pyramidal tract can elicit the SPR independently of reticulospinal neurons. It is hypothesized that a group of corticospinal fibers could transmit volleys having autonomic activity on preganglionic autonomic neurons of the intermediate zone of the grey matter.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 54 (1984), S. 377-381 
    ISSN: 1432-1106
    Keywords: Pupillo-constrictor areas ; Afferents ; HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Afferents of the cortical pupillo-constrictor areas (PCAs) of the cat were studied using the horseradish peroxidase method. PCAs receive heavy cortical inputs from areas 7, 19, 21, the lateral suprasylvian area, the splenial visual area, and subcortically from the claustrum, the intralaminar nuclei, the pulvinar-lateral posterior nuclear complex.
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  • 10
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    Springer
    Experimental brain research 55 (1984), S. 134-144 
    ISSN: 1432-1106
    Keywords: Cat ; Tracking ; Isometric ; Updating ; Delayed feedback
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. In cats trained to track a moving display by making rapid, isometric force adjustments, responses are characterized by extremely short reaction times (60–70 ms) and a stereotyped temporal configuration. The animal uses early derivatives of display movement to scale force responses to target stimuli of different sizes according to a learned relationship between initial display motion and required force (Ghez and Vicario 1978a, 1978b). In the present study we altered that relationship by using double stimulation and delayed feedback to assess the animals' ability to update their responses. 2. In experiments where a second target stimulus followed the first after a controlled interval (15–120 ms) on random trials, the animal modified its response in the appropriate direction with little or no increase in reaction time. When the second stimulus called for a return to baseline, the animal aborted the ongoing response. When the second stimulus called for a doubling of force, the animal increased its phasic force output; however, this increase was not sufficient to reach the new target level and late responses were emitted. 3. The control response which followed each experimental double stimulation trial showed consistent differences from other controls in the amplitude of both peak force and peak dF/dt. Control responses following trials calling for a return were reduced in size; those following stimuli requiring response doubling were increased. We concluded that the experimental trials not only elicited modification of ongoing responses but also caused the animal to alter its internalized gain function relating initial display derivatives to required force. 4. In experiments where feedback was delayed after giving a first target stimulus such that the compensatory display failed to reflect the animal's initial response, the animal emitted a new updated response 70–80 ms after the first. The display trajectory which caused the cat to update its response on delayed feedback trial was identical to that of control trials with long reaction times. In this case, however, the information eliciting response updating had to be derived as a difference between the actual display trajectory and that expected by the animal, based on its experience with the tracking task. This suggests that the animal develops an internal model of display properties which is used to determine when a new response is required.
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  • 11
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    Electronic Resource
    Springer
    Experimental brain research 55 (1984), S. 152-157 
    ISSN: 1432-1106
    Keywords: Deafferentation ; Cross reinnervation ; Contractile properties ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Cross-reinnervations were effected between the extensor digitorum longus and soleus muscles in the cat hind limb. At the same time dorsal root section or ganglionectomy was performed over segments L6-S1. Completeness of the deafferentation was subsequently confirmed either by dissection or by dorsal root recording. The isometric and forcevelocity properties of the muscles were measured. In animals with a unilateral cross plus deafferentation the conversion of the contractile properties of the normally slow-twitch soleus to those resembling a fast-twitch muscle was typical of that seen with an intact afferent supply. In cats with a bilateral cross-reinnervation and unilateral deafferentation there was no significant difference in the degree of transformation between the two sides. It is concluded that at least for the conversion of a slow-twitch to a fast-twitch muscle afferent feedback does not play a major role.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 53 (1984), S. 462-466 
    ISSN: 1432-1106
    Keywords: Visual cortex ; Contralateral connections ; Thalamus ; Cat ; Sub-cortical commissures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Contralateral corticofugal projections from visual cortical areas to thalamic nuclei were demonstrated in the cat using anterograde transport of tritiated proline. Thalamic nuclei receiving projections from contralateral visual cortex include both subdivisions of the lateral-posterior nucleus, the posterior nucleus of Rioch, and the posterior nuclear complex.
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  • 13
    Electronic Resource
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    Springer
    Experimental brain research 56 (1984), S. 458-467 
    ISSN: 1432-1106
    Keywords: Cat ; Postnatal development ; Phrenic motoneurones ; Intercostal motoneurones ; Horseradish peroxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The localization and morphology of spinal respiratory motoneurones (phrenic and intercostal) were studied in the cat by retrograde labelling using Horseradish Peroxidase (HRP), at different stages of postnatal development. At birth, the distribution of the phrenic and intercostal motoneurones in the cervical and thoracic ventral horn, respectively, is similar to that observed in adult animals. At birth, the phrenic and intercartilaginous motoneurone somata have respectively 60% and 40% of their adult volume, appearing much more developed than the motoneurones involved in the motor control of limbs. During postnatal development, the phrenic and intercartilaginous motoneurones undergo a characteristic sagittal elongation without evident modification along their transverse axes. From birth, the ratio of the somatic volume to that of its corresponding motor column markedly decreases inside of the phrenic column compared to the data obtained in the limb's muscle motor columns by other authors. Similar determinations in intercostal motor columns give intermediate values between those obtained from the phrenic column and from the motor system. These results indicate that the motoneurones innervating the respiratory muscles have some specific features of development.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 54 (1984), S. 253-258 
    ISSN: 1432-1106
    Keywords: Lateral geniculate nucleus ; Pretectal nuclei ; Superior colliculus ; Parabigeminal nucleus ; Reticular formation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The ascending connections from the brainstem to the dorsal division of the lateral geniculate nucleus were examined using retrograde transport of horseradish peroxidase. Labelled cells were identified in a variety of structures, including the nucleus of the optic tract (NOT), the posterior pretectal nucleus (NPP), the superior colliculus (SC), the parabigeminal nucleus (PBN), the midbrain reticular formation (MRF), locus coeruleus and nucleus sub-coeruleus, the substantia nigra (SN), and parts of the raphe complex. The projections from NOT, NPP, MRF, LC and PBN were all bilateral in origin. The most intense labelling was observed in the nucleus of the optic tract and the superior colliculus. Colliculo-geniculate cells were located primarily in the superficial gray lamina II1 and II2 of Kaneseki and Sprague (1974), but sparse labelling was also observed in lamina II3 and in statum opticum (lamina III). Consistent with the report of Harrell et al. (1982), these cells represent a morphologically diverse population, which includes stellate cells, granule cells, and both vertical and horizontal fusiform cells. A similarly diverse population of cell types contributes to the geniculate projection arising from NOT. These results confirm and extend earlier descriptions of the brainstem projections to the cat LGNd, and serve to emphasize the diversity of brainstem influences over the geniculate.
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  • 15
    ISSN: 1432-1106
    Keywords: Central cervical nucleus ; Spinocerebellar tract ; Neck muscle afferents ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Extracellular and intracellular recordings were made from spinocerebellar tract neurones of the central cervical nucleus (CCN) in C1–C3 segments of the anaesthetized cat. These neurones were identified by antidromic activation from the cerebellar peduncle. Stimulation of the ipsilateral dorsal root elicited extracellular spikes or EPSPs with a monosynaptic latency in almost all CCN neurones in the same segment (segmental input). Late excitatory effects were also observed in about one third of CCN neurones. The monosynaptic EPSP was occasionally followed by an IPSP. The excitatory input from the dorsal root to CCN neurones was extended over several segments for some CCN neurons (extrasegmental input). Monosynaptic excitation was evoked in CCN neurones after stimulation of dorsal neck muscle nerves as well; i.e. splenius (SPL), biventer cervicis and complexus (BCC), rectus capitus dorsalis, and obliquus capitus caudalis. Thresholds for this excitation were near the threshold of the nerve, suggesting that it originated from group I fibres. The component of excitation added after strong stimulation of neck muscle nerves would be attributed to group II fibres. When a CCN neurone received excitatory input from the nerve of one muscle, it was generally not affected by stimulation of other nerves in the same segment. Such muscle specificity of segmental input was the principal pattern of connexion of neck muscle afferents with CCN neurones. In some cases, however, excitatory convergence from SPL and BCC nerves onto single CCN neurones or excitation from the SPL nerve and inhibition from the BCC nerve were also observed. Nearly half of the CCN neurones received input from one muscle nerve of the same segment and not from the afferent of the same muscle of different segments, indicating a segment specificity of input. In the remaining CCN neurones, weaker excitatory effects were induced from afferents of different segments as well. In such extrasegmental effects, inputs to CCN neurones from caudal segments predominated in frequency over those from rostral segments. The origin of extrasegmental input was generally confined to the same muscle. Low threshold muscle afferents from the SPL and BCC were intraaxonally stained with HRP. The collaterals of the stained fibre distributed branchlets and terminals to the CCN, laminae VII, VIII, and motor nuclei. Two fibres responding to local muscle prodding or stretch showed a similar morphology. The findings indicated that muscle spindle afferents from primary endings projected to the CCN.
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  • 16
    ISSN: 1432-1106
    Keywords: Central cervical nucleus ; Spinocerebellar tract ; Cerebellum ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Spinocerebellar tract (SCT) neurones in and around the central cervical nucleus (CCN) were physiologically identified by antidromic activation of these cells on stimulation of the cerebellum. Among the Spinocerebellar tract cells thus identified, those ascending the contralateral spinal funiculi were found in the CCN and ventralwards, whereas those ascending the ipsilateral funiculi existed mostly dorsal to the CCN partly overlapping with crossed cells in the nucleus. Mapping sites from which CCN cells were antidromically activated showed that axons of the CCN-SCT cross at the same segment, ascend the ventral funiculus initially, the lateral funiculus at rostral C1 and the lateral border of the medulla to reach the cerebellar peduncle, enter the cerebellum mainly via the restiform body but possibly also via the superior peduncle. Systematic mapping of stimulation within the cerebellum indicated that the CCNSCT projects to the medial part of the anterior lobe and the posterior lobe bilaterally. Projection to lobules I–II was found in almost all CCN-SCT cells examined. Three fourths of CCN-SCT cells projected to the posterior lobe, as revealed by less extensive mapping. Mapping of axonal regions of the same single CCN-SCT cells showed that they project multifocally in the cerebellum, where projection to lobules I–II was common and that to other areas varied with individual cells. Conduction velocites decreased within the cerebellum probably as the result of repeated branching. Mossy fibre responses evoked on stimulation of the C2 dorsal root in cats with the transected dorsal funiculi were shown to be mediated mostly via the CCN-SCT. Mapping the field potential showed that the response was by far the largest in lobules I–II. This suggested that the terminals provided by the CCN-SCT are the densest in these lobules.
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  • 17
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    Experimental brain research 55 (1984), S. 325-332 
    ISSN: 1432-1106
    Keywords: Endogenous peroxidase ; Light and electron microscopy ; Spinal cord ; Dorsal column nuclei ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Endogenous peroxidase-like activity was investigated with a combined light and electron microscopical technique in 15 cats. The lateral cervical nucleus, the dorsal column nuclei, and segments C6 and L5 of the spinal cord were incubated with diaminobenzidine-tetrahydrochloride (DAB) or tetramethylbenzidine (TMB). After histochemical reaction with DAB a considerable amount of activity was found in nerve cells, astrocytes and pericytes. The neuronal labelling was mainly located in mitochondria of axon terminals and in dendrites whereas the astrocytic and pericytic activity was found in cytoplasmic dense bodies. The quantity of stained structures differed considerably between the animals. In TMB reacted tissue endogenous peroxidase-like activity was only sparsely seen. It was found mainly in frozen sections, in which the neuropil and perivascular structures sometimes contained granules and irregular filaments. The significance of the findings is discussed in relation to observations in tracer studies using horseradish peroxidase.
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  • 18
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    Springer
    Experimental brain research 55 (1984), S. 49-59 
    ISSN: 1432-1106
    Keywords: Accessory optic system ; Vestibulo ocular reflex ; Optokinetic nystagmus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Horizontal vestibulo-ocular reflex (VOR) and optokinetic nystagmus (OKN) were studied before and after lesions within the accessory optic system (AOS) in the cat. Post-lesion retinal input to the AOS was evaluated using the autoradiographic technique. Unilateral lesion of the lateral terminal nucleus of the AOS (LTN) and the resulting retinal deafferentation of the medial terminal nucleus of the AOS (MTN) induced a spontaneous nystagmus in the dark whose slow phase was directed ipsilaterally to the lesion. VOR gain was reduced for both directions with a maximal decrease for stimulation directed ipsilaterally to the lesion. OKN gain obtained for both directions of binocular stimulation was decreased, mainly when the stimulus was directed contralaterally to the lesion. After two postoperative weeks, spontaneous nystagmus disappeared and the VOR symmetry recovered simultaneously. A symmetrical OKN was only observed after one month. In spite of the known visual selectivity for vertical direction in LTN-MTN cells, the results of this study support a functional involvement of these nuclei in horizontal VOR and OKN.
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  • 19
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    Experimental brain research 56 (1984), S. 162-166 
    ISSN: 1432-1106
    Keywords: Vestibular nerve afferents ; Semicircular canal biophysics ; Semicircular canal time constants ; Vestibular neurophysiology ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The response properties of cat horizontal canal afferents (N = 81) were characterized by three parameters: their long time constants (τ), low frequency gain constants (G1), and middle frequency gain constants (Gm). An average value of each of these parameters was calculated for each of eight animals and comparisons were made across animals. There were significant differences between individual animals in their average values of τ and Gm. There was also a significant negative correlation between τ's and Gm's. An animal with a larger average τ tended to have a smaller average Gm. We also used anatomic data on membranous canal duct diameter from the literature to independently estimate the potential effect of interanimal anatomic variability on the predicted range of τ and Gm values in a population. We then compared the data from our 81 afferents with the predictions from the anatomic data.
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  • 20
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    Experimental brain research 55 (1984), S. 197-204 
    ISSN: 1432-1106
    Keywords: Phrenic and laryngeal motoneurones ; Inspiratory on-switch ; Stimulation ; Mesencephalic structures ; Patterned response ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In anaesthetized cats (chloralose-urethan) the effects of brief tetanic electrical stimulation (50 to 100 ms) of the mesencephalic central gray matter and reticular formation on the inspiratory on-switch were studied during the expiratory (E) phase on the gross and unitary activities of phrenic, laryngeal inspiratory and laryngeal expiratory nerves. On the inspiratory laryngeal and phrenic nerves, stimulation elicited a short latency gross response concomitant with the train: the inspiratory Primary Response (Prim.R.) which is followed by an inspiratory Patterned Response (Patt.R.) of longer duration which corresponded to the inspiratory on-switch. The Patt.R. generally appeared from the Prim.R. within a latent period (Silent Phase: Sil.P.) as long as 100 ms. On the expiratory laryngeal nerve, stimulation elicited a brief activation (expiratory Prim.R.) concomitant with the beginning of the inspiratory laryngeal Prim.R. and which rapidly stopped as the latter continued during the stimulus train. The inspiratory Prim.R. corresponded to a simultaneous activation of both early and late (so defined during their spontaneous discharge) inspiratory motoneurones. The laryngeal motoneurones were more strongly activated than the phrenic ones. During the inspiratory Patt.R. all the phrenic motoneurones presented a recruitment delay earlier, compared with the spontaneous one, whereas the recruitment drastically changed from an inspiratory laryngeal motoneurone to another. Thus, the two pools of motoneurones presented different properties of activation. During the inspiratory Sil.P. no concomitant expiratory laryngeal activation was observed when most of the inspiratory motoneurones were inactive. As some inspiratory laryngeal motoneurones did not stop firing, the existence of some central respiratory neurones exhibiting a similar persistent activity and subserving the inspiratory on-switch mechanisms may be hypothesized.
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  • 21
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    Experimental brain research 54 (1984), S. 203-211 
    ISSN: 1432-1106
    Keywords: Ascending auditory pathway ; Inferior colliculus ; Medial geniculate body ; Cat ; Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ascending projections from the nucleus of the brachium of the inferior colliculus (NBIC) in the cat were studied by the autoradiographic tracing method. Many fibers from the NBIC ascend ipsilaterally in the lateral tegmentum along the medial border of the brachium of the inferior colliculus. At midbrain levels, fibers from the NBIC end in the superior colliculus, the pretectum, the central gray and the peripeduncular tegmental region bilaterally with ipsilateral predominance. NBIC fibers to the superior colliculus are distributed densely to laminae VI an III throughout the whole rostrocaudal extent of the colliculus. In the pretectum, NBIC fibers terminate in the anterior and medial nuclei and the nucleus of the posterior commissure. NBIC fibers to the dorsal thalamus are distributed largely ipsilaterally. Many NBIC fibers end in the dorsal and medial divisions of the medial geniculate body, but few in the ventral division. The NBIC also sends fibers to the suprageniculate, limitans and lateralis posterior nuclei and the lateral portion of the posterior nuclear complex; these regions of termination of NBIC fibers constitute, as a whole, a single NBIC recipient sector. Additionally, the NBIC sends fibers to the centralis lateralis, medialis dorsalis, paraventricular and subparafascicular nuclei of the thalamus.
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  • 22
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    Experimental brain research 54 (1984), S. 395-405 
    ISSN: 1432-1106
    Keywords: Neonatal ; Bilabyrinthectomy ; Recovery ; Locomotion ; Vision ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Four cats labyrinthectomized shortly after birth (DELAB) exhibited the classical vestibular syndrome and recovery, while their motor development was otherwise unimpaired. As adults, they were tested for visual vestibular substitution in a locomotor task with either orientation requirements (tilted platforms) or balance requirements (narrow platforms). Visual motion cues or static visual cues were controlled using normal or stroboscopic lighting, or darkness. Measurements of the average speed of locomotion showed that: Although all cats increase their speed when more visual cues become available, a marked deficit occurs in darkness only in the DELAB cats. With either vestibular cues alone or static visual cues alone, cats are able to reach the same level of performance in the tilted platform test, which suggests a total visual-vestibular interchangeability in orientation. DELAB cats perform very poorly in the narrow rail test. When continuous vision is allowed in the narrow rail test the DELABs' performance rises but does not match that of the control group. A specific deficit in balance for the DELAB group is thus reduced by normal continuous vision as compared to stroboscopic vision, suggesting a significant, though imperfect, substitution of motion visual cues for the missing dynamic vestibular cues. Dynamic visual cues play only a minor role in most situations, when locomotory speed is high. This results support the view that both the vestibular and the visual system can subserve two distinct functions: dynamic information may stabilize the stance in narrow unstable situations, during slow locomotion. and static orientation cues may mainly control the direction for displacement. Possible interactions between head positioning and body orientation in the DELAB cats are discussed.
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  • 23
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    Experimental brain research 55 (1984), S. 470-482 
    ISSN: 1432-1106
    Keywords: Congenital microstrabismus ; Cat ; Visual cortex ; Binocularity ; Visual axis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Twenty-nine pigmented offspring of an innately esotropic female cat exhibited varying deficits in the number of binocular cells recorded in area 17 of the visual cortex as compared to 12 normal cats. Misalignment of the two eyes in these cats was found in the awake as well as in the paralysed state. Pupillography combined with measurements of visual disparity yielded abnormal esotropia of up to 8.4° under paralysis, which corresponds to an abnormal convergence of the freely moving eyes of up to 14° (average 7.4°). In the majority of animals cortical binocularity was found reduced by the two eyes controlling independent sets of separate units (U-shaped ocular dominance distribution) whereas in 7 cats the reduction was due to a partial loss of one eye's influence. The proportion of monocular units correlated with the degree of crossover of the visual axes (r = 0.73). Anatomical investigation of the retinofugal projections revealed normal appearance in three previously recorded cats in which more than 50% of cortical units had been monocularly driven. The small angles of esotropia and the “normal” appearance of eye position judged by the pupillary positions in the orbit of these cats, might suggest that we found an animal model for microstrabismus.
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  • 24
    ISSN: 1432-1106
    Keywords: Optic nerve section ; Cat ; Pattern ERG ; Retinal morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Previous experiments have shown that the ERG response to alternating gratings vanishes gradually within 4 months after transection of the optic nerve, changes begin after 2–3 weeks. The response to gratings of low spatial frequencies deteriorates earlier than the response to gratings of high spatial frequencies (Maffei and Fiorentini 1981). Quantitative analysis of ganglion cell sizes in retinal wholemounts shows that ganglion cell shrinkage and ganglion cell loss begin at three weeks in the periphery of the retina, particularly in the temporal retina. The same morphological alteration subsequently becomes apparent also in the area centralis and the nasal retina, respectively. The main and early cell loss occurs among medium sized ganglion cells, supposedly the beta-cells. Among the alpha-cells only shrinkage is observed up to two months postoperatively. Light- and electron microscopic examination of cross sections through the retina show that pathological changes are restricted to the innermost layers.
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  • 25
    ISSN: 1432-1106
    Keywords: Glutamatergic synapses ; Vestibular nerve lesion ; Vestibular nuclei ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Evidence that glutamate acts as a neuro-transmitter in vestibular nerve fibers was sought (1) by electron microscope radioautographic identification of the uptake sites of [3H]-glutamic acid after incubation of slices of cat vestibular nuclei, and (2) by measuring changes in sodium-dependent high affinity glutamate uptake in nerve endings containing homogenates from normal and deafferented vestibular nuclei 8 to 11 days after unilateral vestibular nerve lesion. Electron microscopic radioautography revealed that glutamate had been taken up by numerous nerve endings projecting over the whole vestibular nuclear complex. The biochemical approach indicated that after section of the vestibular nerve, a significant decrease in high affinity glutamate uptake occurred in the vestibular nuclei, which lost their exclusively ipsilateral projection. This decrease varied from one area of the deafferented vestibular nuclei to another, reaching −58% in the lateral area of the central part corresponding to the ventral lateral vestibular nucleus and the rostral part of the descending vestibular nucleus. It is concluded that glutamate (or aspartate) is used by the vestibular nerve fibers as a neurotransmitter in the vestibular nuclei.
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  • 26
    ISSN: 1432-1106
    Keywords: Spinal cord ; Scratch reflex ; Ventral spino-cerebellar tract ; Spino-reticulo-cerebellar pathway ; Cerebellum ; Cooling the nervous tissue ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary (1) The “fictitious” scratch reflex was evoked in decerebrate curarized cats by pinna stimulation. Activity of neurons of the ventral spinocerebellar tract (VSCT) from the L4 and L5 segments of the spinal cord as well as of neurons of the spinoreticulo-cerebellar pathway (SRCP) from the lateral reticular nucleus of the medulla oblongata was recorded. Cooling and destruction of different parts of the lumbo-sacral enlargement of the spinal cord were performed. (2) Cooling of the L5 or L6 segment abolished the rhythmic activity in the greater part of the spinal hindlimb centre but did not affect the generation of rhythmic oscillations in the remaining (rostral) segments of the lumbo-sacral enlargement. Under these conditions, neither the rhythmic activity of VSCT neurons located rostral to the thermode nor that of SRCP neurons changed. (3) A normal rhythmic activity of SRCP neurons also persisted after destruction of grey matter in the L3 and L4 segments. It can be concluded that activity of these neurons is independent of whichever part of the enlargement generates rhythmic oscillations. (4) From these observations a hypothesis is advanced that the main content of signals conveyed by the VSCT and SRCP to the cerebellum is the information regarding activity of the generator of rhythmic oscillations that is located in the L3-L5 spinal segments.
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  • 27
    ISSN: 1432-1106
    Keywords: Corticocortical connections ; Motor cortex ; Areas 4, 5a, 5b, 7 ; Posterior parietal lobe ; Retrograde transport of HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neurons in the parietal region of the cerebral cortex, projecting to the ipsilateral distal forelimb area of the motor cortex (area 4γ) were identified in the cat brain using the horseradish peroxidase (HRP) retrograde tracing method. After making microinjections of HRP into the distal forelimb area of the motor cortex, clusters of HRP-labeled cell bodies were observed in different regions of the ipsilateral parietal cortex. In particular these clusters of labeled cells were found in areas 5a, 5b and 7. The area 5a cluster is formed from closely packed irregularly-shaped cells, the area 5b cluster is made up of dispersed medium-sized pyramidal cells, while area 7 contains a cluster of widely dispersed small pyramidal cells. Typically, labeled cell bodies were found in lamina III of cortex. Labeled cell bodies were neither observed in the contralateral cortex nor in the visual cortex (areas 17, 18 and 19). Since parietal cortex receives projections from primary somatosensory and visual cortex, the projections from parietal to motor cortex may well form the neural substrate for the processing of convergent sensory information used in voluntary movements.
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  • 28
    ISSN: 1432-1106
    Keywords: Cat ; Rat ; Spinal tract neurons ; Retrograde HRP transport ; Procedure and evaluation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Modifications have been made in Mesulam's method for labelling neurons by retrograde transport of horseradish peroxidase, with tetramethylbenzidine as chromogen, with the object of increasing the extent of labelling of dendrites and axons. A procedure was devised specifically for studying spinomedullary and medullospinal tract systems, involving implanting easily-made HRP-agar pellets into areas of controlled damage in particular spinal fascicles, and sealing the site of implant with cyanoacrylate glue. Lesions of other fascicles were often made to limit transport to the implanted fascicle. Fourth-order dendrites were regularly labelled over long (30 cm or more) transport distances: axons were also labelled over this whole distance, often allowing exact study of the initial course of particular axons. Controls in both cat and rat showed that the uptake of HRP under these circumstances occurred almost wholly from the region of axonal damage at the site of implant which can be characterized histologically.
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  • 29
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    Archives of toxicology 55 (1984), S. 178-181 
    ISSN: 1432-0738
    Keywords: Cat ; Phospholipids ; Acrylamide ; Neuropathy ; Lipids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Treatment of cats with acrylamide, either 7.5 or 15 mg/kg IM, once a day for 10 days, resulted in increases of 31 and 47% in the phospholipid content of sciatic nerve, respectively, from a control level of 41.1±2.7 mg/kg wet weight. Determination of the distribution of individual phospholipids indicated no significant differences between control cats and those receiving a cumulative dose of 150 mg/kg acrylamide. In a separate experiment, cats were treated with the 150 mg/kg dose of acrylamide and the sciatic nerve was divided into proximal and distal portions at the level of the triceps surae nerve. Significant increases in phospholipid content were observed in both the proximal and distal portions of peripheral nerve of the acrylamide-intoxicated cats. This effect was present even when the phospholipid content was expressed in terms of total protein, dry weight or total lipid. Total weight of nerve segments, however, was significantly decreased in the neuropathic animals. The data are consistent with a focal degeneration of axons with relative sparing of phospholipids.
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  • 30
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    Pflügers Archiv 401 (1984), S. 304-314 
    ISSN: 1432-2013
    Keywords: Visual cortex ; Contrast/response function ; Orientation and direction sensitivity ; Ocularity ; Binocular responses ; Feature specific responses ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The responses of neurons in area 17 were tested as a function of various stimulus parameters. The thresholds of individual cortical neurons were at contrasts between 0.01 and 0.1 (increment of 0.5×10−1 cd/m−2 on a background of 3 cd/m−2), the dynamic ranges were 1.0–2.0 log units of increment, and all cells showed a response decrease at increments above a certain maximum (supersaturation response). The averaged contrast/response curve for all neurons was S-shaped in the logarithmic plot, had a dynamic range of 2.5 log units, reached its maximum at a contrast of 0.75 and supersaturated above this level. The contrast/ sensitivity curves changed their slope under different stimulus conditions. They became flatter when the non-dominant eye was stimuated as compared to dominant eye stimulation or when the stimulation was done at a non-optimal orientation or direction, and they became steeper when both eyes were stimulated. But the maximum was reached at the same contrast and supersaturation was seen above maximum contrast no matter whether a cell was stronlgy (e.g. binocular stimulation at optimal orientation) or weakly excited (non-dominant or non-optimal orientation stimulation). After normalization, the averaged population contrast/response curves were virtually identical at all stimulus conditions. It was concluded, that range as well as maximum and supersaturation of cortical contrast/response curves are determined before the input reaches the cortex, and that the cortical cells summate, essentially, linearly. The findings furthermore demonstrate that the supersaturation of the cortical input must be due to subtractive inhibition, and that the same is true for the orientation sensitive inhibition in the cortex itself. Both, the peripheral contrast and the cortical orientation dependant inhibition cannot be explained by multiplicative inhibition. The fact, that the responses of neurons depend on many variables relativates their significance for feature representation.
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  • 31
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    Cell & tissue research 235 (1984), S. 675-682 
    ISSN: 1432-0878
    Keywords: Endocrine pancreas ; Angioarchitecture ; Cat ; Scanning and transmission electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary By the use of scanningand transmission electron microscopy, the possible sources of errors in interpretation of the microcirculation of the pancreas can be reduced in comparison to the classical India-ink injection method. Sphincter-like structures in the capillary wall of the cat pancreas are established by pericytes. These sphincters encircle the junctional zones between the endocrine and exocrine capillaries. They are assumed to be regulatory structures of blood flow and to regulate indirectly hormone secretion according to demand.
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  • 32
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    Cell & tissue research 237 (1984), S. 181-183 
    ISSN: 1432-0878
    Keywords: Reissner's fiber ; Scanning electron microscopy ; Spinal cord ; Cat ; Rabbit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The caudal portion of Reissner's fiber was examined by scanning electron microscopy (SEM) in the spinal cord of the cat and rabbit. In some preparations of both species the fiber displayed in the sinus terminalis of the central canal either stump-like terminations or structural modifications such as knot-like swellings and convolutions. In the same area homogeneous material could also be found, which obviously originated from the disintegrating fiber.
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  • 33
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    Cell & tissue research 238 (1984), S. 151-158 
    ISSN: 1432-0878
    Keywords: Skeletofusimotor innervation ; Muscle spindles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Endings of four β skeletofusimotor axons in a spindle of the cat tenuissimus muscle were examined in semithin (1-μm thick) and ultrathin transverse serial sections. Two (dynamic) β axons terminated on the nuclear bag1 intrafusal muscle fiber and on extrafusal fibers of the dark type. Two (static) β axons terminated on the nuclear chain intrafusal fibers and extrafusal fibers of the intermediate type. The degree of indentation of axon terminals into the muscle surface, thickness of the sole plate and extent of folding of subjunctional membranes differed among intrafusal and extrafusal terminations of the same axon. Endings of β axons on the bag1 and chain fibers were also morphologically dissimilar. Motor axons may not determine ending morphology. Rather the form and structure of a β bag1 or chain ending may be determined by the type of intrafusal fiber on which the ending lies and the ending's distance from the primary sensory axon.
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  • 34
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    Helvetica Chimica Acta 67 (1984), S. 47-53 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The He(Iα) photoelectron (PE) spectra of tris(perfluorocyclobuta)benzene 4(F)3,3,4,4,7,7,8,8,11,11,12,12-Dodecafluorotetracyclo[8.2.0.02,5.06,9]dodeca-1,5,9-triene, tris(perfluorocyclopenta)benzene 5(F)1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Octadecafluoro-2,3,4,5,6,7,8,9-octahydro-1H-trindene., tetrakis(perfluorocyclobuta)cyclooctatetraene 6(F)3,3,4,4,7,7,8,8,11,1l,l2,l2,l5,15,16,16-Hexadecafluoropentacyclo[12.2.0.02,5.06,9.010,13]hexadeca-1,5,9,13-tetraene., and of tetrakis(perfluorocyclopenta)cyclooctatetraene 7(F)1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-Tetracosafluoro-1,2,3,4,5,6,7,8,9,10,11,12-dodeca-hydrotetracyclopenta[a,c,e,g]cyclooctene. are reported. A tentative assignment of the PE spectra is derived by empirical correlation with those of relevant reference compounds. The results suggest that 6(F) retains the D4h-conformation in the gas phase, i.e. A conformation with a planar cyclooctatetraene ring, as observed in the crystal. All four compounds exhibit a sharp increase of their first ionization energies, relative to the corresponding parent hydrocarbons, due to the perfluoro effect.
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  • 35
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene (1) has been used to prepare complexes of the type [PtL(1)] (L = C2H4, CH2=CH—CO2Me, PhC≡CPh, MeC≡CMe, MeO2CC≡CCO2Me, (i-Pr)O2CC≡CCO2(i-Pr), Ph3P and CO). It is shown that these complexes are less labile than the corresponding species [PtL(Ph3P)2]. The preparation of complexes trans-[PtX(R)(1)] by oxidative addition of RX (RX = PhCH2Br and Mel) to [Pt(C2H4)(1)] is described. The isolation of [PtO2(CH3)2CO(1)] is also reported.
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  • 36
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical anions of the compounds N1N, N3N and N5N, in which two naphthalen π-systems are separated by 1, 3 and 5 spirobonded cyclobutane rings, respectively, and tha tof the reference compound N1, containing one naphthalene π-system and one cyclobutane ring, have been studied by ESR and ENDOR spectroscopy under a variety of experimental conditions. The intramolecular electrons spin transfer between the two π-moieties in N3N.⊖ and N5N.⊖ is slow on the hyperfine time-scale, irrespective of the applied conditions. It is also slow in N1N.⊖, except for media of high solvating power. In such media, with a slight reduction of N1N to its radical anion, a paramagnetic species is observed, the hyperfine data for which are consistent with N1N to its radical anion, a paramagnetic species is observed, the hyperfine data of which are consistent with N1N.⊖, undergoing a fast intramolecular electron spin tansfer. The ESR and ENDOR spectra of this species are superimposed on those characteristic of a slow transfer. It is suggested that the fast and slow transfer involve the syn- and anti-conformations, respectively, since the distance, r, between the two naphthalene π-systems of N1N.⊖ is considerably shorter in the former than in the latter (r = 740 vs. 880 Pm for the distance between the centres of the π-systems). Glassy solutions of exhaustively reduced N1N display signals of the dianion triplet state, whereas no such signals are found for N3N and N5N. The zero-field splitting parameter, D, is 4.7 mT, corresponding to r ≈ 480 pm.
    Additional Material: 5 Ill.
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  • 37
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Loss of CH3., CH4, C2H4, C3H5., C3H6 and C3H7 from the molecular ions of a number of 13C-labeled analogs of 4,4-dimethyl-1-pentene was studied both in normal (source) 70-eV electron impact (EI) spectra dn in metastable spectra. For loss of CH3. in the source, 96% of the methyl comes frm positions of 5, 5′ and 5″, while the remainder comes from position 1. In the metastable spectra, loss of C-1 (16%) and C-3 (9%) is increasing in importance. The loss of ethylene is a particular case: either C-1 or C-3 are lost with any other C-atom from positions 2,5,5′, and 5″ (8 × 10%) in the metastable spectra, the probability for simultaneous loss of C-1 and C-3 being 6%. If C-1 seems to these two positions become completely equivalent in the metastable time range. The T-values (kinetic energy release) for the different positions show small, but statisticaly different values and a small isotope effect. Loss of C3H5 (allylic cleavage) is 100% C-1, C-2 and C-3, i.e., no evidence for skeletal rearrangement is seen. This is also true for loss of C3C6 (McLafferty rearrangement) within the source, but in metastable decay the other positions gain in importance. The neutral fragment C3H7. appears to be the the result of consecutive loss of CH3. and C3H4, rather than a one-step loss of propyl radical or the inverse reactions sequence. No metastable reaction can be seen for this reaction. Decomposition of labeled C6H11+ and C5H10+ secondary ions occurs in an essentially random fashion.
    Additional Material: 6 Tab.
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  • 38
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    Helvetica Chimica Acta 67 (1984), S. 450-454 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Up to now the synthesis of para-substituted phenyl-terpyridine ligands was difficult with respect to the purification of the reaction products. We have found that these compounds can easily be isolated as hydrobromides from acetic acid. Starting from the hydrobromides the purification turned out to be easy. Synthesis of para-substituted Cl-, Br-, H3C-, H2BrC-, HO- 2,6-Bis(2-pyridyl)-4-phenylphyridine is reported.
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  • 39
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    Helvetica Chimica Acta 67 (1984), S. 441-449 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexation of Silver(I) by Cyclic TetraminesThe nature of Ag(I)-complexes with 1,4,8,11-tetraazacyclotetradecane (1), 1,5,9,13-tetraazacyclohexadecane (2) 1,5,10,14-tetraazacyclooctadencane (3) and 1,6,11,16-tetraazacycloeicosane (4) is studied. The effect of ring size on disproportionation of the Ag() cation in the presence of ligand is reported. The stability of Ag(I)-complexes with 3 and 4 in aqueous solution is determined by means of potentiometric titration.
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  • 40
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    Helvetica Chimica Acta 67 (1984), S. 625-627 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 41
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 42
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    Helvetica Chimica Acta 67 (1984), S. 625-639 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical Ions of Bridged [14] Annulenes. Investigations on the Influence of Frontier Orbitals on Reactivity and BondingThe radical anions and the radical cations derived from trans-15, 16-dimethyl-1, 4:8,11-ethandiyliden[14]annulene (6), trans-15-methyl-1,4:8,11-ethandiyliden[14]annulene (7) and cis-15, 16-propano-1,4:8,11-ethandiyliden[14]annulene (8) are described. The hyperfine data of the radical anions 6, 7 and 8 resemble those of the structurally related radical anions of trans-10b, 10c-dimethyldihydropyrene (4) and trans-10b, 10c-dihydropyrene (5). This finding leads to the conclusion, that the change in the relative arragement of the saturated bridge within the fourteen-membered π-perimeter by passing from 4 (5) to 6 (7, 8) does not in fluence the energetic sequence of the lowest unoccupied molecular orbitals. The behavior of 6 and 7 towards oxidation parallels the photochemical reactivity of 4. The hyperfine coupling constants of the radical cations derived from 6 and 7 indicate that the removal of an electron is accompanied by an isomerization of the molecular framework. The investigation of the electron transfer process gby cyclic voltammetry supports these findings. The radical cations prefer the cyclophane-like structures 6a and 7a, in which the central σ-bond (C(15)-C(16) bond) is broken.
    Additional Material: 7 Ill.
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  • 43
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    Helvetica Chimica Acta 67 (1984), S. 664-668 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical behaviour of the title compound 1a is compared to that of the non-fluorinated parent ketone 2-methylcyclohexanone (1b). Substitution of the CH3- group on C(2) by a trifluoromethyl group strongly enhances 2H- and RH- reduction product formation in cyclohexane or 2-propanol and oxetane formation in the presence of 2-methylpropene as olefinic component. Under all these conditions 1b exclusively undergoes a-cleavage, a process observed for 1a only in non-reducing solvents as benzene or tert-butyl alcohol.
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  • 44
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of β-keto-acetals, derived from non-enolisable β-diketones, with sulfonic acids in boiling benzene resuots in a smooth retro-Claisen-type fragmentation. The acetal-C-atom is thereby transformed into a carboxylic ester via a dialkoxycarbenium ion, which is dealkylated by the sulfonate counter-ion. Application of this reaction to the diastereomeric monoacetals 3 and 4, derived from cis-9-methyl-decalin-1,8-dione (1), followed by transesterification with CH3OH, yields optically pure 4-(2′-methyl-3′-oxocyclohexyl)butyrate 9 ((+)-9 from 3, (-)-9 from 4) and the monosulfonate of Meso-2,3-butanediol (-)-13 (Scheme 2). Unexpectedly, this cleavage proceeds as well with monoacetal 26, obtained by acetalization of trans-9-methyl-decalin-1,8-dione (27) with 2,2-dimethyl-1,3-propanediol (Scheme 7). Some attempts, aiming at an isomerization of the cis- and trans-decalin derivatives 3 and 24, or 25 and 26, via the postulated carboxonium intermediate, were not successful.
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  • 45
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    Helvetica Chimica Acta 67 (1984), S. 856-865 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkylation of bicyclo[3.3.0]octane-2,8-dione (1), which is prepared by a modification of the procedure described in the literature, gives the methyl- and propynyl-derivatives 6 and 7 (Scheme 1). In addition to the method described previously (Scheme 2), 9-methyl-cis-decalin-1,8-dione 9 is obtainable stereoselectively either by cyclization of keto-acid 16, or by aldol cyclization of keto-aldehyde 26 and oxydation of the resulting alcohols 24 and 25 (Scheme 4). The β-keto-alcohols 24 and 25 undergo a base-catalyzed isomerization; the trans-decalin isomers 27 and 28 are not detected in this equilibrium mixture (Schemes 4 and 5)l. Monoreduction of cis-dione 9 gives the endo-alcohol 25, while 27 is the favored product of the reductin of trans-dione 10 (Scheme 4). Optically pure (+)-25 can be prepared from (9S,10R)-monoacetal 29 (Scheme 5).
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  • 46
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new tripeptide (dimer), bis[(L-cysteine-S-acetyl)-L-hemicystinyl(S2 → S2)-D-valine] (6) was synthesized by coupling N-(tert-butoxycarbonyl)-S-carboxymethyl-L-cysteine benzyl ester (1) with S-trityl-L-cysteinyl-D-valine benzyl ester and subsequent removal of the protecting groups. After reduction of the disulfide, the free tripeptide Cys (CH2CO-Cys-D-Val) (Ib) was used as a substrate of isopenicillin-N synthetase in a cell-free conversion to 6-[2-((D-2-amino-2-carboxyethyl)thio)acetamido]penicillanic acid (IIa).
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  • 47
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    Helvetica Chimica Acta 67 (1984), S. 902-905 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the title compounds is described.
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  • 48
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    Helvetica Chimica Acta 67 (1984), S. 927-927 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 49
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Resolution of racemic cis-3-(2-aminophenylthio)-2-hydroxy-3-(4-methoxyphenyl) propionic acid (2) via the cinchonidine salt 3, and brucine salt 4, isolation of the calcium salts (+)- and (-)-5, as well as their cyclization to enantiomeric 1,5-benzothiazepines (+)- and (-)-1, are described. X-Ray single-crystal analysis reveals (2S, 3S) absolute configuration of (+)-1 on the basis of tentative comparison of CD data with those for the 1,4-benzodiazepine derivative (+)-8 of known absolute configuration.
    Additional Material: 4 Ill.
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  • 50
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    Helvetica Chimica Acta 67 (1984) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 51
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    Helvetica Chimica Acta 67 (1984), S. 927-933 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis ad Structure of Zinc Complexes of 2-Amino-1-azetinesThe 2-dimethylamino-3,3-dimethyl-1-azetines 7a and 7b have been synthesized in analogy to the procedure reported by Ghosez et al. [1] (Scheme). The crystal structure of 1-benzhydryl-azetidindimethyliminium chloride 5a, a precursor of azetine 7a, has been established by X-ray diffraction analysis. Treatment of azetines 7a and 7b with ZnBr2 in CH2Cl2/MeCN yielded tetrahedral bis (azetine)dibromozinc complexes 8a and 8b, respectively (Scheme 2). The molecular structure of 8a has been determined by X-ray diffraction analysis too.
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  • 52
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    Helvetica Chimica Acta 67 (1984), S. 947-952 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioselective synthesis of (+)- and (-)-cis-2-methyl-4-propyl-1,3-oxathine 8 and 9 form (E)-2-hezen-1-ol (1) as common starting material is described. The two enantiomeric forms exhibit different organoleptic properties.
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  • 53
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    Helvetica Chimica Acta 67 (1984), S. 959-963 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyanothyl-subsituted cylohexyl cyclohexanoates, bi(cyclohexanes) and phenyl cyclohexanes were synthisized. Their mesmorphic behaviour is compared to that of the corresponding cyano derivatives. (Cyanoethyl)cyclohexyl cyclohenxanoates show mesmorphic properties in contrast to the corresponding cyano derivative. Separation of the cyano substituent from the rigid core of an anisotropic aliphatic compound by methylene groups enhances the thermodynamic stability of the mesophase. In aromatic compound, the cyanoethyl group leads to lower clearing points. These phenomena are attributed to teh influence of steric effects on the packing density and to the dependence of the clearing point on molecular association.
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  • 54
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    Helvetica Chimica Acta 67 (1984), S. 1000-1002 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nα-L-Iysine with a 2-carboxy-4, 6-dinitrophenyl (Dncp) haptenic group on the ε-amino function is a potent anaphylactogen in the guinea pig. We prepared Nε -Dncp- Nα-benzoly-L-Iysinamide and Nε-Dncp-Nα-benzoyl-L-lysyl-1-aminopropane where the carboxyl group of Iysine is blocked. Both compounds were non-elections of anaphylaxis.
    Additional Material: 1 Tab.
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  • 55
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    Helvetica Chimica Acta 67 (1984), S. 21-28 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C45- and C50-Carotenoids. Synthesis of Optically Active Acyclic C15-End GroupsThe optically active C15-end groups (S)-12, (S)-13 and (R)-14 were prepared from the C12-synthon (S)-11 in good chemical and optical yield. These C15-end groups are suitable compounds for the synthesis of optically active C45- and C50-carotenoids.
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  • 56
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the crystal structure of the title compound at 98 K the dimethylamino group has pyramidal geometry. The nitrogenlone pair is not directed towards the triple bond; instead, one N—CH3 bond lies almost in the plane of the disubstituted ring, directed away from the triple bond, while the other N—CH3 bond and the lone pair are directed to opposite sides of the plane, nearer to the acetylene. There is a remarkably short intramolecular contact (2.39 Å) between a methyl H- and an acetylenic C-atom. The Taft σI parameter of the arylethynyl substituent appears to be similar to that of a carboxylic ester, judging from the bond-angle deformation at the ipso-C-atom.
    Additional Material: 5 Ill.
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  • 57
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Heart Glycosides of the Arrow Poison of Lophopetalum toxicum LOHERFrom the cytotoxic and positive inotropic acting bark extract of the Philippinan Lophopetalum toxicum eight heart glycosides have been isolated and their structures have been elucidated mainly by field-desorption-MS- and 1- and 13C-NMR spectroscopy. Besides the known k-Strophanthidin (1), Antiarigenin (6) and β-Antiarin (Antiarigenin-3-β-O-α-L-rhamnoside, 10) the following mono- and diglycosides could be identified: strophanthidin-3-β-O-α-6-desoxy-D-allopyranoside (strophalloside, 2), strophanthidin-3-β-O-β-6-desoxy-D-glucopyranoside (= Strophanthidin chinovoside, 3), strophanthidin-3-β-O[-4Oβ-D-allopyranosyl-β-6-desoxy-D-allopyranoside] (4), strophanthidin-3-β-O-[3-O-β-D-glucopyranosyl-β-6-desoxy-D-talopyranoside] (5), antiarigenin-3-β-O-[3-O-β-D-gulopyranosyl-β-6-desoxy-D-talopyranoside] (7), antiarigenin-3-β-O-[4O-β-D-allopyranosyl-β-6-desoxy-D-allopyranoside] (8), and antiarigenin-3-β-O-β-6-desoxy-D-allopyranoside (antiallosid) (9). The structure of strophanthidinchinovoside (3) could be confirmed by synthesis.
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  • 58
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A recent controversy on the interpretation of the ESR spectrum of ionized oxirane is clarified on the basis of the electronic absorption spectra of ionized tetramethyloxirane and 9,10-octalineoxide. The results favour a ring-opened structure for oxirane molecular cation, resulting from C—C bond cleavage and being iso-π-electronic to allyl radical.
    Additional Material: 3 Ill.
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  • 59
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Acylation of Acetylenes with β,γ-Unsaturated Acid Chlorides, A New Synthesis of 5-Substituted 2-CyclopentenonesThe acylation of acetylenes with α,α-disubstituted, β,γ-unsaturated acid chlorides under Friedel-Crafts-type conditions leads to 5-substituted 2-cyclopentenones. Phenols are formed with β,γ-unsaturated acid chlorides bearing at least one α-H-atom. These transformations are explained by the intramolecular cyclization of the initially formed vinyl cation, which, in the cases of α,α-disubstituted acid chlorides, is followed by ring contraction. The reaction leading to 2-cyclopentenones is applied to the synthesis of some spiro[4.4]nona- and spiro[4.5]deca-2,6-dienones.
    Additional Material: 1 Tab.
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  • 60
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    Helvetica Chimica Acta 67 (1984), S. 113-119 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Arylazonaphthalenes with all the potential cyclopalladation sites (one peri- and three ortho-positions) substituted by methyl or ethyl groups react with stoicheiometric or catalytic amounts of sodium tetrachloropalladate(II) to the corresponding 2-arylbenzo[g]indazoles. Possible mechanisms for the catalytic cyclization reaction are proposed.
    Additional Material: 1 Tab.
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  • 61
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1n, π*-Excitation of the γ,δ-epoxy-enone (E)-3 leads exclusively to the conformers (Z)-3A + B. On 1π, π*-excitation of (E)-3, in addition to (Z)-3A + B, products 6-9 arising from a carbene intermediate e are formed. However, products of an isomerization via C(γ), O-bond cleavage of the oxirane were not formed on either mode of excitation. On thermolysis, at 80° the conformer (Z)-3A is transformed into (Z)-3B, which on photolysis returns to (Z)-3A and (E)-3. At 160°, however, (Z)-3B rearranges to the isomers 6, 10 and 11.
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  • 62
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    Helvetica Chimica Acta 67 (1984), S. 866-869 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selective oxidation of benzylic methylene groups through UV irradiation in acetone/water/FeCl3 mixtures is reported. This method applied to a series of model compounds, provides an easy access to the corresponding 1-oxo derivative. Thus, tetralin gives a 100% yield of 1-tetralone, indane leads to 60% of 1-indanone, and diphenylmethane is oxidized to benzophenone with 80% yield. However, under the same conditions, alkyl-substituted aromatic hydrocarbons such as toluene, ethyl- and propylbenzene lead to low yields of aldehydes or ketones. Isochromane furnishes a mixture of two substances which can be interconverted, namely the expected l-isochromanone (9%) and the corresponding hydroxy acid (23%). We failed to apply the method to nitrogen heterocycles containing benzylic groups such as 1,2,3,4- and 5,6,7,8-tetrahydroquinoline as they do not react due to the formation of complexes which precipitate from the solutions.
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  • 63
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pure pencillin N α-sulfoxide (1) and penicillin N β-sulfoxide (2) were obtained by HPLC and tested as substrates for deacetoxycephalosporin C synthetase (DXCS). Neither one of the sulfoxides was utilized under conditions of conversion of penicillin N (8) to deacetoxycephalosporin C (9). The cephalosporin C α and β-sulfoxides (3 and 4, resp.) were also prepared. Relative stabilities of the sulfoxides 3 and 4 are discussed by interpretation of the 13C-NMR spectra.
    Additional Material: 9 Ill.
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  • 64
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Business C,D,E,F,G,H,J,K,L und M, Ten New Tetranortriterpenes from Entandrophragma Bussei HarmsTen new tetranortriterpenes, busseins C, D, E, F, G., H, J, K, L and M have been isolated from the petroleum ether extract of the timber of Entandrophragma bussei Harms. utilizing separation by high-pressure liquid chromatography (HPLC). The structural assignments are based mainly on spectral evidence. For the 1H-NMR spectroscopy extensive use of nuclear Overhauser effects (NOE) was made.
    Additional Material: 2 Ill.
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  • 65
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    Helvetica Chimica Acta 67 (1984), S. 928-930 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 66
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alcohols and phenols are efficiently nitrated with thionyl chloride nitrate or thionyl nitrate, even in the presence of an aromatic moiety. While thionyl chloride nitrate is suitable for nitration of primary OH-groups in carbohydrates, thionyl nitrate is reactive enough to react with secondary OH-groups as well. These reagents permit the highly selective nitration of the 5′-,2′5′- and 3′, 5′-OH-groups of ribonucleosides to produce either mono-or diprotected nitro derivatives in high yields. Carbon acids and the enol form of some ketones are efficiently nitrated with trifluoromethanesulfonyl nitrate/potassium tert-butoxide. Lutidine N-oxide (2,6-(CH3)2C5H3N O) was found to have a marked effect on nitration reactions. Similarly, thionyl chloride nitrite and thionyl nitrite exhibit an excellent capacity for nitrosation of the aforementioned substrates.
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  • 67
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    Helvetica Chimica Acta 67 (1984), S. 934-938 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical cations and the radical of 1,2-bis(phenalen-1-ylidene)ethane (1), 1,2-bis(phenalen-1-ylidene)ethene (2) and pentaleno[1,2,3-cd: 4,5,6-c′ d′]diphenalene (3) have been characterized by ESR and ENDOR spectroscopy. The ease of formation of these radical ions and their π-spin distributions are interpreted in terms of a simple model correlates the frontier orbitals of 1, 2 and 3 with the nonbonding MO's of two phenalenyl π-systems.
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  • 68
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    Helvetica Chimica Acta 67 (1984), S. 939-946 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 1-(2-propynyl)pyridinium salts 3 described. Compounds 3 react with a second pyridine molecule, in the presence of the corresponding hydrochloride, to form products of type 4, Certain bases cause the 1-(2-propynyl)pyridinium salts 3 to rearrange into 1-propadienylpyridinium salts. 5. Diethylamine converts compounds 3 into 1-acetonylpyridinium salts 8. Moreover, treatment of 3 or 5 with sodium methoxide gives enol ether sof type 9, which can be hydrolyzed to teh ketones 8. Addition of bromine to some of teh unsaturated compounds is also reported.
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  • 69
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    Helvetica Chimica Acta 67 (1984), S. 953-958 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: IR-spectroscopic investigations of light-induced rearrangement reactions of nitrosooxymethane (CH3ONO3), nitrosooxyethane (CH3CH2ONO) and N,N-dimethylnitrosamine ((CH3)2NNO) in low-temperature rare-gas matrices have established that these molecules are transformed in two photolysis steps to the previously unknown C-nitroso compounds nitrosomethanol (CH2(OH)(NO)), 1-nitrosoethanol (CH3CH(OH)(NO)), and methyl(nitrosomethyl)amine CH2(NO)(NH)(CH3). Evidence for a similar rearrangement reaction has been advanced for N-Nitrosopyrrolidine which is converted to C-nitrosopyrrolidine . The matrix-isolation technique in combination with wavelength-selective irradiation allowed to trap and characterize an intermediate of rearrangement which revealed to be nitroxyl (HNO) complex (CH2…HNO, CH3CHO…HNO, CH3N = CH2…HNO, and ). Since these findings have a close resemblance with rearrangement reactions of more complex nitrosooxy compounds, nitrosamines, or nitrosohydrazines used in organic synthesis, it is suggested that also in these reactions nitroxyl is present as an intermediate species.
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  • 70
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    Helvetica Chimica Acta 67 (1984), S. 964-967 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Epoxycarotenoids: Isolation of 1,2-Epoxy-1,2-dihydrolycopene from TomatoesThe optically active, 1,2-epoxy-1,2-dihydrolycopene was isolated from tomatoes. Its constitution was established by comparison with the racemic synthetic compound.
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  • 71
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Epoxycarotenoids: Synthesis, 1H-NMR and CD Studies of (S)-1,2-Epoxy-1,2-dihydrolycopene and (S)-1′,2′-Epoxy-1′, 2′ -dihydro-γ-caroteneThe synthesis of (S)-1,2-epoxy-1,2-dihydrolycopene ((S)-1) and (S)-1′, 2′ -epoxy- 1′, 2′ -dihydro-γ-carotene ((S)-2) are described. The CD spectra of the (all-E)-isomers and of the isomers (7Z, S)-1 and (7′Z, S)-2 are discussed. The comparison of the CD spectra of the synthetic (S)-1 and the compound isolated from the tomatoes proves the (S)-configuration of the natural product.
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  • 72
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    Helvetica Chimica Acta 67 (1984), S. 1003-1011 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plectranthons A, B, C, and D. Diterpenoid Phenanthrene-1,4-diones from Leaf-glands a Plectranthus sp. (Labiatae)The following structures of four new 1,4-phenanthraquionones, isolated in minute amounts from the coloured leaf-glands of a Plectranthus sp. obtained from the borders of Lake Kiwu2, Rwanda, are proposed: plectranthon A (1; 3-hydroxy-5, 7,8-trimethyl-2-(2-propenyl)phenanthrene-1, 4-dione), plectranthon B (2; 2-(2ξ-acetoxypropyl)-3-hydroxy-5,7,8-trimethylphenanthrene-1,4-dione), plextranthon C (3; 3-hydroxy- 7,8-diemethyl-2-(2-propenyl)phenanthrene-1,4-dione), and plectranthon D (4; 3-hydroxy-7,8,10-trimethyl-2-(2-propenyl)phenanthrene-1,4-dione). 2-(2ξ-Hydroxypropyl)-3,6-dihydroxy-5,7,8-trimethylphenanthrene-1,4-dione (11), a compound very similar to 1-4, was prepared by a Wagner-Meerwein, rearrangement of coleon E (5). Biogenetically, the plectranthons are derived from abietanoic precursors. The compounds 1, 2 and 4 are the first natural C20-phenanthrenes of diterpenoid origin.
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  • 73
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidative hydroboration of exo- (1) and end-Fe(CO)3 (2) complexes of 5,6-dimethylidenebicyclo[2.2.2]oct-2-ene are highly stereoselective and give endo -alcohol 3 and exo -alcohol 4 as major products, respectively, Collins oxidations of 3 and 4 furnish the corresponding exo -Fe(CO)3 -complexed 5,6-dimethylidene-2-bicyclo-[2.2.2]octanone 7 and 8. NaBH4 reduction of exo-complexes 7 gives a mixture of 3 and isomeric exo-alcohol 18, whereas reduction of endo-complexes 8 gives the endo-alcohol, endo-complexes 19, as the sole product. The base-catalyzed H/D exchange of 7 and 8 afford the dideuterated exo-complex 35 and the monodeuterated endo-complex 32, respectively. Oxidative hydroborations of the exo-(9) and endo-Fe(CO)3 (10) complexes of 5,6-dimethylidenebicyclo[2.2.1]hept-2-ene give the corresponding exo-alcohols 39 and 40. Oxidation of 39 and 40 gives the exo- and endo-complexes 41 and 42, respectively, of 5,6-dimethylidene-2-bicyclo[2.2.]heptanone. Only Hexo —C(3) can be exchanged in 42, wheres both H-atoms at C(3) in 41 are exchangeable. The endo-Fe(CO)3 group in 8 and 42 blocks the base-catalyzed H/D exchange of Hendo —C(3), thus providing a test for the configuration of Fe(CO)3 group in these systems. These studies have led to a revision of the iron configurations proposed by Hansen et al, [2] for 1, 2, 9 and 10.
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  • 74
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    Helvetica Chimica Acta 67 (1984), S. 361-364 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 75
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvolysis rate constants in MeOH and t-BuOh are compared for β-methyl and β-phenyl derivatives of two cycloakyl systems. It appears that the β-phenyl derivatives solvolyse at te same rate as the β-methyl ones. The lack of deceleration is attributed to phenyl assistance. It is established by configurational analysis of the reaction products, that those products which necessarily originate from a cationic species are the most abundant ones. It is suggested that these reactions could proceed through ion-pair intermediates, which are nucleophilically solvated by phelyl or by the solvent. A parallel between phenyl assistance and ‘SN2 (intermediate)’ mechanism, suggested by Bentely & Schleyer, is drawn.
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  • 76
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    Helvetica Chimica Acta 67 (1984), S. 361-372 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependence of the water self-diffusion coefficients (D), as well as those of low- and high-field (stationary and time-dependent) specific conductivities (K), have been determined in the percolation regime of ternary mixtures of water, AOT, and oil. For the first time a pronounced similarity in the behavior of D and κ was detected giving instructive hints about the large variations in the specific conductivities of these systems. Results from kinetic and stationary experiments are consistent with a network-structure model of micro phases in the percolation regime in which the micro phases retain their discrete character.
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  • 77
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Facile synthesis of derivatives of 2,4-diphenyl-3-azabicyclo[3.3.1]nonane and 7,9-diphenyl-8-azabicyclo[4.3.1]decaneThe facile synthesis of hydantoins, cyanhydrins and aminonitriles derived from 2,4-diphenyl-3-azabicyclo[3.3.1]nonanone and 7,9-diphenyl-8-azabicyclo[4.3.1]decanone is described. Configurations at C(9) or C(10) of the new compounds wth pharmaceutical and synthetical utility is deduced from their spectral properties.
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  • 78
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    Helvetica Chimica Acta 67 (1984), S. 1328-1347 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the D-arabino- and D-ribo-ortholactones 13a-f and 15b-f and their treatment with Zn leading to the unsaturated esters 14a-d and 16a-d are described. Possible fragmentation mechanisms are discussed. The results were only compatible wit a concerted, nonsynchronous process, where both the axial lone pair of the ring oxygen atom and the lone pair formed during rupture of the C(5), O-bond participate in the elimination of the axial and of the equatorial C(1)-alkoxy groups, respectively.
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  • 79
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    Helvetica Chimica Acta 67 (1984), S. 1368-1373 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This communication reports ESR-spectroscopic investigations of the radical anion of 1,8-dimethyl[14]annulene (1) which possesses a flexible molecular framework allowing configurational and conformational mobility. The ESR and ENDOR spectra indicate that at higher temperatures (T 〉 160 K), \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{- \atop \dot{}} $\end{document} exists as a mixture of several distinct isomers. One of them, the sole product at T 〈 160 K, is found to be energetically preferred. The configuration and the conformation of this species can be determined by interpretation of the hyperfine data in terms of a singly occupied MO of the 14-membered π-perimeter.
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  • 80
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    Helvetica Chimica Acta 67 (1984), S. 1386-1396 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-(tert-Butyl)-3,7-dehydrotropone (7-(tert-butyl)bicyclo[3.2.0]hepta-1(7),2,4-trien-6-one; 1) was found to dimerize reversibly to 2A by [2 + 4]-cycloaddition/cycloreversion reaction. The equilibrium lies on the side of the highly strained dimer 2A in the solid state, and on the side of the monomer 1 in solution. The [2 + 4]-reaction is fully perisite-, regio- and stereoselective. Above room temperature, 1 irreversibly formed a decarbonylated dimer 6, probably via the intermediate 9A or 9B, which resulted either from a dimerisation of 1 by [4 + 6]-cycloaddition or from a sigmatropic rearrangement of the originally formed dimer 2A or 2B. Similary, the 6-bromo derivative 14 afforded the corresponding decarbonylated dimer 15. Should the formation of 6 and 15 be due to a primary cycloaddition then that reaction is fully peri-, site- and regioselective. Mild LiAlH4-reduction of 6 and subsequent acetylation yielded the acetate 11, the structure of which was established by an X-ray analysis. More vigorous LiAlH4-treatment also reduced the terminal fulvenoid double bond of 6 and acetylation of the crude product led to the acetated 12 and 13.
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  • 81
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    Helvetica Chimica Acta 67 (1984), S. 1427-1428 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 82
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    Helvetica Chimica Acta 67 (1984), S. 1427-1438 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electromotive Behaviour of Liquid-membrane Electrode Assemblies Based on Enantiomer-selective Chiral IonophoresA comprehensive theoretical treatment is given for the potentiometric behavior of enantiomer-selective membrane electrodes based on chiral ionophores and plasticizers. The membrane model allows for free and complexed enantiomeric or racemic ions (e.g. ephedronium and l-phenylethylammonium ions) as well as for achiral interfering ions. Experiments are derived for the determination of the stoichiometry and the relative stability of enantiomeric ion/enantiomeric ligand complexes, and for the analytical measurement of the enantiomeric excess of ions in solution.
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  • 83
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water exchange of square-planar Pd(H2O)24+ has been studied as a function of temperature (240 to 345 K) and pressure (0.1 to 260 MPa, at 324 K) by measuring the 17/O-FT-NMR line-widths of the resonance from coordinated water at 27.11 and 48.78 MHz. The following exchange parameters were obtained: k298ex = (560 ± 40) s-1, ΔH* = (49.5 ± 1.9) kJ mol-1, ΔS* = - (26 ± 6) J K-1 mol-1 and ΔV* = - (2.2 ± 0.2) cm3 mol-1. The values refere to an aqueous perchlorate medium with an ionic strength between 2.0 and 2.6 m and a perchloric-acid concentration between 0.8 and 1.7 m, and are interpreted in terms of an associative (a) activation for the exchange. The exchange rate for Pd(H2O)24+ is 1.4 × 106 times faster than for Pt(H2O)24+ at 298 K. A comparison with reactions between other nucleophiles and Pd(H2O)24+ is also made.
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  • 84
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of Organometallic Compounds, XX. Selectivity of 1,4-Addition of Benzyltitanium Compounds with BenzylildenacetoneTetrabenzyltitanium and dialkoxydibenzyltitanium compounds give essentially 1,4- addition with trans-4-phenyl-3-buten-2-one.
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  • 85
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aminative Reductive Coupling of Aromatic Aldehydes to N,N,N′,N′-Tetraalkyl-1,2-diarylethylenediamines, Induced by Tris(dialkylamino)methylvanadium (IV)In a novel type of reaction, certain aromatic aldehydes (benzaldehyde, p-methoxybenzaldehyde, 1-naphthaldehyde, furan-2-carbaldehyde) and secondary amines are coupled to give N,N,N′,N′-tetraalkyl-1,2-diarylethylenediamines 1-6. The reagents are tris(dialkylamino)methylvanadium(IV) compounds (cf. Eqn. 2). These are generated in situ either from isolable chlorotris(dialkylamino) vanadium(IV) (Eqn. 3), or preferably, from an Et2O/pentane solution of VCl4 which is treated sequentially with 3 equiv. of lithium dialkylamide, 1 equiv. of MeLi, and 0.8 equiv. of an aromatic aldehyde, to give the products 1-6 in a one-pot preparation (Scheme 2). The yields range from 14 to 54%. The diastereoisomeric mixtures (meso- and (±)-forms) obtained are separated by chromatography (Al2O3, petroleum ether/Et2O/Et3N), and the pure stereoisomers fully characterized. A mechanism of the reductive coupling induced by CH3V (NR2)3 is proposed (Scheme 1).
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  • 86
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    Helvetica Chimica Acta 67 (1984), S. 1506-1514 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several oxidative, reductive and C,C-cleavage reactions were performed starting from the three bicyclo[4.2.1]nona-3,7-diene-2-one derivatives 1, 5 and 18. The oxidations were selective and led to the diols 2,8 and 9, and the epoxides 6,9, and 20. The reductions were selective only in the case of 20 21; otherwise they led to mixtures of the alcohols 10 and 11, and of the dienes 14 and 15. The periodate ring cleavages afforded the functionalized cycloheptane derivatives 3, 12, 13 and 16. Configurational assignments were made on the basis of detailed 1H-NMR and X-ray analysis of 20.
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  • 87
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    Helvetica Chimica Acta 67 (1984), S. 1531-1534 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Red-Coloured Abietanoids from Leaf-Glands of Plectranthus strigosus BENTH.Chromatographic examination of the red-coloured diterpenoids from the South-African title plant yielded the following compounds: parviflorone A(1), parviflorone B (2), parviflorone C(3), parviflorone E (4) parviflorone D (5), parviflorone F (6), parviflorone G (7), and parviflorone H (8). Compounds 7 and 8 represent new variants of these quinone methides.
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  • 88
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polar Diterpenoids from Leaf-Glands of Plectranthus argentatus S. T. BLAKEFrom the red leaf-glands of the Australian Plectranthus argentatus the following novel diterpenoids were isolated: coleon-U-quinone (1), 8α,9α-epoxycoleon-U-quinone (3), 6β-formyloxy-7α-hydroxyroyleanone (7), and 5,6-dihydrocoleon U (10), besides the already known compounds 6β, 7α-dihydroxyroyleanone (4), 7α-acetoxy-6β-hydroxyroyleanone (5), and 7α-formyloxy-6β-hydroxyroyleanone (6). Epoxydation of 1 by perborate led in 32% yield to the epoxyquinone 3.
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  • 89
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    Helvetica Chimica Acta 67 (1984), S. 1568-1571 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Partially protected 4- or 5-hydroxy-sugar oximes were transformed into 5- or 6-membered 1-C-nitroglycosyl chlorides, respectively, by reaction with NaOCl under phase-transfer conditions. With the exception of the oxidation of the gluco-derivative 1 giving the anomers 6 and 7, the reactions were completely diastereoselective.
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  • 90
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    Helvetica Chimica Acta 67 (1984), S. 1572-1579 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and the liquid-crystal temperatures of sixty 4-cyano-2-fluorophenyl and 4-cyano-3-fluorophylen 4-substituted benzoates are described. The nematic-isotropic liquid transition temperatures of the most of these novel esters are only marginally lower than those of the corresponding esters containing an H-atom in place of the F-substituent. In several instances, the clearing points of the F-substiuted-phenyl esters are higher than those of the non-substituted-phenyl esters. The nematic ranges of several of the new esters are markedly broader than those of the analogous non-F-substituted-phenyl esters.
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  • 91
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    Helvetica Chimica Acta 67 (1984), S. 1588-1592 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H-NMR and vapor-pressure osmometry results are presented, which indicate the occurrence of a rapid equilibrium involving the head-to-head dimerization of β44-helices in chloroform solutions of HCO-L-Ile-(D-AIle-L-Ile)4-OMe. This equilibrium typifies the one that, in Urry's view, would be responsible for the formation and breaking down of the ion-conducting channels formed by gramicidin A in lipid bilayers.
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  • 92
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and liquid-crystal transition temperatures of forty ester derivatives of 2-fluoro-4-hydroxybenzonitrile and 3-fluoro-4-hydroxybenzonitrile are reported. The esters contain the trans-1,4-disubstituted cyclohexane or the 1,4-disubstituted bicyclo[2.2.2]octane rings (some contain an additional phenyl ring). Many of the novel F-substituted esters exhibit substantially higher nematic-isotropic transition temperatures than the corresponding unsubstituted esters. The order of clearing points of these laterally substiuted esters differing only in the presence of a benzene ring and the above-mentioned rings id established.
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  • 93
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    Helvetica Chimica Acta 67 (1984), S. 1598-1602 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of New Morphine Partial Structure 15,16-SecomorphinanThe synthesis of a new morphine partial structure, 15,16-secomorphinan, is described. One of the series, (±)-15, 16-secocyclorphan (5), has the analgesic potency of morphine and exhibits good binding to the opiate receptor.
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  • 94
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diastereoselective Synthesis of Novel Mannich (Bases1) through Titanium ReagentsTrichlorotitanium dialkylamino-alkoxides (2; titanates of N, O-hemiacetals) are generated either from the corresponding lithium alkoxides and titanium tetrachloride (Scheme 1) or by addition of trichloro-dialkuylamino-titanium to aldehydes. The electrophilic (dialkylamino) alkylating reagents 2 are used to convert lithium enolates to β-dialkylamino-ketones and -esters 5 (Mannich bases), see Scheme 2 and Table. One diastereoisomer of the products 5g-5p thus obtained with cyclohexenolate is formed preferentially (66-84%). The configuration of the products of this first diastereoselective version of the Mannich reaction could not yet be determined. A typical procedure for carrying out the reaction is given.
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  • 95
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    Helvetica Chimica Acta 67 (1984), S. 1612-1615 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new, practical method for the optical resolution of bicyclic ketones if illusttrated by the preparation of (+)-(1R,4R)-7-oxabicyclo[2.2.1]bept-5-en-2-one ((+)-1) and (+)-(1R, 2S,4R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yul acetate ((+)-4). It involves the diastereoselective formation of a brucine complex with the corresponding cyanhydrine mixture.
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  • 96
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of three-coordinate bis(dialkylphosphinomethyl)benzo[c]phenanthrene Ag(I) complexes, alkyl= t-Bu, (1b), and cyclohexyl, (1c), anion = BF4, CIO4, CIO4, NO3, Cl, Br, I, have been prepared and thier 31P-NMR characteristics recorded. The solid state structures of [Ag(1b)Br], [Ag(1b)Cl] and [Ag(1b)CIO4] have been determined by X-ray diffraction. The Ag atom in these complexes shows distorted trigonal geometry. Selected bond lengths and angles are as follows: Ag-P = 2.463(4) Å and 2.433(5) Å, P-Ag-P=141.6(2)° in the bromo complex, Ag-P = 2.457(2) Å and 2.427(2) Å, P-Ag-P = 142.6(1)° ion the chloro complex, and Ag-P = 2.394(2) and 2.393 (2) Å, P-AG-P = 161.5(1)° in the perchlorato complex.
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  • 97
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    Helvetica Chimica Acta 67 (1984), S. 1625-1629 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new syntheses of verrucarinic acid (2S, 3R-dihydroxy-3-methylpentanoic acid) and its derivatives, suitably protected for the further conversion to macrocyclic trichothecenes, are described. The first one makes use of a diastereoselective alkylation of a (-)-(S)-malic acid ester and the regioselective reductin of one carboxyl function toa methyl group. The second approach involves a stereoselective addition of an allylsilane to a chiral glyoxylate.
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  • 98
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Control of the Catalytic Synthesis of Pyridine from Alkynes and Nitriles by the (η6-Borinato)-Nigands at Cobaltη6-Borinato groups as ligands at cobalt have unique effects on the chemo- and negioselectivity of the catalytic co-cyclization of alkynes and nitriles. The turnover number of the conversion of acrylonitrile and acetylene to give 2-vinylpyridine is considerably enhanced. Cyano compounds wih polar substitutents such as amino or thio groups can also be reacted. The homogeneous reaction of HCN with acetylene giving pyridine has been achieved for the first time.
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  • 99
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The endocyclic double bond C(2), C(3) in 5,6-dimethylidene-7-oxabicyclo[2.2.1]-hept-2-ene (1) can he coordinated selectively on its exo-face before complexation of the exocyclic s-cis-butadiene moiety. Irradiation of Ru3(CO)12 or Os3(CO)12 in the presence of 1 gave tetracarbonyl [(1R,2R, 3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo[2.2.1]-hept-2-ene)]ruthenium (6) or -osmium (8). Similarly, irradiation of Cr(CO)6 or W(CO)6 in the presence of 1 gave pentacarbonyl[(1R, 2R, 3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene)]chromium (10) or -tungsten (11). Irradiation of complexes 6 and 11 in the presence of 1 led to further CO substitution giving bed-tricarbonyl-ae-bis[(1R,2R,3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene)]ruthenium (7) and trans-tetracarbonyl[(1R,2R,3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo-[2.2.1]hept-2-ene)]tungsten (12), respectively. The diosmacyclobutane derivative cis-m̈-[(1R,3R,3S,4S)-(5,6-dimethylidene-7-oxabicyclo[2.2.1]hepta-2,3-diyl)]bis(tetracarbonyl-osmium) (Os-Os) (9) wa also obtained. The Diels-Alder reactivity of the exocyclic s-cis-butadiene moiety in complexs 7 and 8 was found to be significantly higher than that of the free triene 1.
    Type of Medium: Electronic Resource
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  • 100
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The products generated by heating 5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene (1) with Fe2(CO)9, Ru3(CO)12, Os3(CO)12, Cr(CO)3(MeCN)3, (or W(CO)5(MeCN) or by treatment with Fe-atoms have been characterized by spectroscopic methods. Apart from the expected η2- and η4-complexes of the triene 1, condensation products are formed which arise from the formal [4 + 2]-cyclodimerization of 1 involving the endocyclic double bond of one molecule and the diene moiety of a second. The [4 + 2]-cyclodimerization is catalyzed by Os3(CO)12 in MeOH and gives 1,4-epoxy-7-methoxy-2,3-dimethylidene-1,2,3,4,4a,9,9a,10-octahydroanthracene (15)). Fe-Atoms induce a stereoselective [2 + 2]-cyclodimerization pf 1 which involves its endocyclic double bond and produces the dimer 8.
    Type of Medium: Electronic Resource
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