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  • Electronic Resource  (6,688)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of anesthesia 2 (1988), S. 113-114 
    ISSN: 1438-8359
    Keywords: Sevoflurane ; Minimum alveolar concentration ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Eight adult cats of either sex were studied. The minimal alveolar concentration (MAC) for sevoflurane in the cats was found to be 2.58 ± 0.30% (mean ± SD). The ratios of MAC values between sevoflurane and halothane, enflurane and isoflurane in cats were very similar to those ratios found in humans and dogs. This observation suggests that the results of this study are correct and allows us to estimate unknown MAC values for sevoflurane in other species using known MAC values for other anesthetic agents. (Doi M, Yunoki H, Ikeda K: The minimum alveolar concentration of sevoflurane in cats. J Anesth 2: 113–114, 1988)
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Neurosurgical review 11 (1988), S. 87-94 
    ISSN: 1437-2320
    Keywords: Cat ; CSF ; CT scans ; experimental hydrocephalus ; syringomyelia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two methods were used to induce a model of experimental hydrocephalus and hydrosyringomyelia in the cat: a) injection of kaolin into the cisterna magna and b) closure of the lateral apertures of the fourth ventricle with cotton swabs. The pathological changes in the brain ventricles and the central canal of the spinal cord were monitored and documented at regular intervals by computed tomography (CT). The CT method is particularly advantageous for studies of this kind because the animals can be examined frequently without risking disturbances in cerebro-spinal fluid dynamics or tissue damage that would result from introduction of contrast media into the ventricular system. Our results and others reported earlier suggest that the dilated central canal acts as a kind of spontaneous CSF deviation route from the ventricles to the subarachnoid space. In spite of the tendency of the animals to recover in a clinical sense, the internal CSF space continued to expand; in cats the disease is progressive, a fact that is readily evident in follow-up CTs. This characteristic indicates that the spontaneous “shunt system” from the fourth ventricle through the dilated central canal to the spinal CSF spaces does not function well enough. Possible explanations for hydrocephalus compensation and the development of hydrosyringomyelia in experimental animals are discussed.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 337 (1988), S. 53-57 
    ISSN: 1432-1912
    Keywords: Endogenous histamine release ; Mamillary body ; Medial amygdaloid nucleus ; Ultradian rhythm ; Suprachiasmatic nucleus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The mamillary body and the medial amygdaloid nucleus of cats anaesthetized with sodium pentobarbital were bilaterally and simultaneously superfused through push-pull cannulae with CSF and the release of endogenous histamine was determined in the superfusates. Collection of the superfusates in 10 min time periods revealed that histamine was rhythmically released in the two areas with frequencies of one cycle/90 min (mamillary body) or one cycle/135 min (medial amygdaloid nucleus). Collection of the superfusates in time periods of 2 min revealed the existence of an additional ultradian rhythm with a frequency of approximately one cycle/19 min in both areas. Bilateral lesions of the suprachiasmatic nucleus did not seem to influence the pattern of histamine release in the mamillary body and the medial amygdaloid nucleus, but the rate of histamine release was decreased in the mamillary body. It is concluded that the ultradian rhythms of histamine release in the mamillary body and the medial amygdaloid nucleus are not dependent on the integrity of the suprachiasmatic nucleus. The rate of histamine release in the mamillary body seems to be under the influence of excitatory neurons which originate from the suprachiasmatic nucleus.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 177 (1988), S. 277-283 
    ISSN: 1432-0568
    Keywords: Lateral reticular nucleus ; Oculomotor region ; Retrograde transport of WGA-HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary By means of retrograde transport of the wheat germ agglutinin-horseradish peroxidase complex, afferent fibres to the lateral reticular nucleus from the oculomotor and accessory oculomotor nuclei were demonstrated in the cat. Small iontophoretic ejections were made into the main part of the lateral reticular nucleus from a ventral approach. Significant numbers of retrogradely labelled neurons were found bilaterally in all parts of the oculomotor nucleus. The majority was of small size and distributed along the dorsal and lateral boundaries of the nucleus. Some labelled neurons were located just outside these boundaries, in the periaqueductal gray and the adjacent mesencephalic reticular formation. Retrogradely labelled neurons were also found in the accessory oculomotor nuclei: The interstitial nucleus of Cajal featured a substantial number of labelled neurons. Some labelled neurons were consistently found also in the nucleus of the posterior commissure, but no labelled neurons were found in the nucleus of Darkschewitch. The labelled neurons in the interstitial nucleus of Cajal were of different sizes and located bilaterally, mainly in its rostral part. Caudal as well as rostral parts of the main lateral reticular nucleus appear to receive the descending afferents from the oculomotor region, but higher numbers of labelled neurons were found subsequent to ejections in the rostral part. The findings are discussed and some comments are made concerning the lateral reticular nucleus as a possible relay nucleus for oculomotor input to the cerebellum.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 177 (1988), S. 285-295 
    ISSN: 1432-0568
    Keywords: Accessory optic system ; Rabbit ; Cat ; Dog Monkey
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The three-dimensional fiber pathways of the accessory optic system in the rabbit, cat, dog and monkey were studied in whole-mounted preparations of the diencephalon and the midbrain, without sectioning, by anterograde labeling of retinal axons with horseradish peroxidase (HRP). HRP histochemical studies on alternate serial coronal sections were also performed. The rabbit accessory optic system exhibited two fasciculi (the inferior fasciculus, and the superior fasciculus consisting of the anterior fibers and the posterior fibers) and three terminal nuclei (the medial terminal nucleus, and the anterior and posterior porcions of the lateral terminal nucleus), but lacked the dorsal terminal nucleus. In the cat and dog, only the posterior fibers of the superior fasciculus were detected. The inferior fasciculus and the anterior fibers of the superior fasciculus were absent. The medial terminal nucleus and the posterior portion of the lateral terminal nucleus were commonly observed in the cat and dog. The cat accessory optic system possessed the dorsal terminal nucleus, and the dog accessory optic system possessed the anterior portion of the lateral terminal nucleus. The monkey (Macaca fuscata) accessory optic system consisted of the posterior fibers of the superior fasciculus, but blacked the inferior fasciculus and the anterior fibers of the superior fasciculus. Most of the posterior fibers terminated in the well-developed posterior portion of the lateral terminal nucleus located on the upper surface of the cerebral peduncle. A small number of posterior fibers projected to the poorly-developed medial terminal nucleus. Based on these findings, species differences in the mammalian accessory optic system were discussed.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 178 (1988), S. 67-75 
    ISSN: 1432-0568
    Keywords: Retrograde transport of WGA-HRP ; Oculomotor nucleus ; Cerebellar nuclei ; Cerebellar cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The cytoarchitecture of the feline oculomotor nucleus was examined in sections stained with thionin and neutral red. Five different subdivisions (caudal central, paramedian, ventral, dorsomedial and dorsolateral divisions) can be identified on each side of the midline. This observation is discussed, and our findings are compared to previous studies of the cytoarchitecture or central muscular representation of the oculomotor nucleus in which different subgroups have been distinguished. Implants or injections of the wheat germ agglutinin-horseradish peroxidase complex have revealed that all five subdivisions project to different parts of the cerebellar cortex and nuclei. Retrogradely labelled cells were found in the oculomotor nucleus in 18 cases following deposition of tracer in the fastigial and interposed nuclei and certain regions of the anterior, posterior and flocculonodular lobes. The projection is bilateral and appears to have its main termination in flocculus. It originates from small neurons, especially from those located along the dorsal border of the oculomotor nucleus.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1432-0568
    Keywords: Motoneurons ; Infrahyoid muscles ; Spinal cord ; HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The distribution of cell bodies and the peripheral course of axons of infrahyoid motoneurons were examined in the cat by the retrograde horseradish peroxidase method after application of the enzyme to the peripheral nerve branches supplying the infrahyoid muscles. Infrahyoid motoneurons were observed to constitute a slender cell column, which extended from a level of the caudal part of the hypoglossal nucleus usually to the most caudal level of the C1 cord segment, or occasionally to the lower levels of the C2 cord segment. The cell column was located immediately lateral to that of motoneurons of the spinal accessory nerve. In the cell column, thyrohyoid motoneurons were distributed in the medulla oblongata; sternohyoid motoneurons were located somewhat more cranially than sternothyroid motoneurons in the medulla oblongata and cervical cord. However, the level of craniocaudal distribution of thyrohyoid, sternohyoid or sternothyroid motoneurons highly overlapped. The experiments involving severance of the hypoglossal and/or cervical nerves indicated that axons of thyrohyoid and sternohyoid motoneurons passed via the roots of both hypoglossal and C1 nerves, that axons of sternohyoid motoneurons passed via the C1 nerve roots, and that axons of infrahyoid motoneurons innervating the conjugated part of the sternohyoid and sternothyroid muscles passed usually via the C1 nerve roots, or occasionally via the roots of both C1 and C2 nerves.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 178 (1988), S. 59-65 
    ISSN: 1432-0568
    Keywords: Retrograde transport of WGA-HRP ; Edinger-Westphal nucleus ; Cerebellar nuclei ; Cerebellar cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The cerebellar projection from the Edinger-Westphal nucleus was studied in the cat by means of retrograde transport of the wheat germ agglutinin-horseradish peroxidase complex. The present findings give evidence that the flocculus is the main terminal area. However, small tracer implants and injections into various parts of the cerebellar nuclei and cortex revealed projections also to the fastigial and interposed nuclei and to most parts of the anterior and posterior lobe cortices. The projecting neurons are small and located bilaterally throughout the Edinger-Westphal nucleus. No topical differences between the projections to different parts of the cerebellum were found.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 72 (1988), S. 543-561 
    ISSN: 1432-1106
    Keywords: Spinocerebellar neurons ; Cerebellar peduncles ; Axonal course ; Horseradish peroxidase ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Among the newly discovered spinocerebellar cell groups, those at lumbar and more caudal levels of the cat's spinal cord were studied with regard to which of the two cerebellar peduncles, the restiform body or the superior cerebellar peduncle, is used by their axons. Bilateral injections with horseradish peroxidase were made into either of the anterior lobe or the posterior cerebellar termination area for spinocerebellar fibers, following unilateral transections of either the superior cerebellar peduncle or the restiform body, combined with low contralateral transections of the lateral and ventral funiculi. Following transection of the superior cerebellar peduncle, labeled neurons were found ipsilateral to the transection in the column of Clarke and in laminae IV–VI at L 3–L 7. Contralaterally, labeled neurons were found in the ventromedial nucleus and lamina VIII of the ventral horn in the sacro-coccygeal segments and in the medial part of lamina VII at L 6 and more caudal levels. All these neurons were regarded as sending their axons through the restiform body. Following transection of the restiform body, labeled neurons were found in the following areas contralateral to the transection: the dorsolateral nucleus of the L 3–L 6 segments, the lateral part of lamina VII at L 3–L 5/6, the medial part of lamina VII in L 6 and more caudal segments, and the ventrolateral nucleus of L 4–L 5. Ipsilaterally, labeled neurons were found in lamina VIII at L 4–L 6. All these neurons were regarded as sending their axons through the superior cerebellar peduncle. In addition to new information about the peduncular routes of spinocerebellar neurons, the study has given confirming evidence as to the crossing conditions for different spinocerebellar cell groups. The findings should be useful in future studies on the organization of the spinocerebellar systems.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 72 (1988), S. 562-576 
    ISSN: 1432-1106
    Keywords: Spinocerebellar neurons ; Cerebellar cortex ; Fluorescent tracers ; Double labeling ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The collateral projections of spinocerebellar neurons located in the L 2 to Ca 1 spinal segments in the cat were investigated by retrograde fluorescent double labeling technique. Rhodamine labeled latex microspheres (Rm) and Fast Blue (FB) were used for injections into the cerebellum in 8 cats. Two additional cats, with injections of Fluoro-Gold (FG) combined with Rm were excluded because lipofuchsin autofluorescence obscured the labeling. After injections with one tracer unilaterally in the paramedian lobule and another tracer bilaterally in the anterior lobe, double labeled neurons were found on the side of the paramedian lobule injection in the column of Clarke at L 2–L 4, laminae IV–VI at L 2–L 5 and the dorsolateral nucleus at L 2–L 6. After bilateral injections of one tracer in lobule VIII B and another in the anterior lobe, double labeled neurons were found bilaterally in the column of Clarke at L 2–L 4, laminae IV–VI at L 2–L 5, the medial part of lamina VII at L 6–L 7 and in certain cell groups at sacro-coccygeal levels. Neurons in the lateral part of lamina VII at L 3–L 5 and the ventrolateral nucleus of L 4–L 5 were labeled exclusively from injections in the anterior lobe. The findings indicate that spinocerebellar neurons at lumbar and more caudal levels of the cat spinal cord have different projection patterns in the cerebellum. A certain number of neurons which project to the anterior lobe have divergent axon collaterals supplying also the posterior vermis and/or the paramedian lobule. Other neurons project to the anterior or to the posterior lobe only.
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  • 11
    ISSN: 1432-1106
    Keywords: Anterior semicircular canal ; Vestibular nuclei ; Vestibulo-collic ; Neck motoneuron ; Unitary EPSP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Unit activites of secondary vestibular neurons that selectively responded to stimulation of the anterior semicircular canal nerve (ACN) were recorded extracellularly in the anesthetized cat. Axonal pathways and projections in the spinal cord of the ACN-activated neurons were examined by recording their antidromic responses to stimulation of the lateral and medial vestibulospinal tracts (LVST and MVST), and the bilateral neck extensor motoneuron pools in the C1segment (C1dorsal rami [DR] motoneuron pools). In order to determine whether the neurons had ascending axon collaterals to the extraocular motoneurons, the contralateral (c-) inferior oblique (IO) motoneuron pool was also stimulated. Twenty-seven neurons sent their axons to the ipsilateral (i-) C1DR motoneuron pool via the LVST without any projection to the extraocular motoneuron pool. All the cells except one were located in the ventral part of the lateral vestibular nucleus. This pathway produced monosynaptic EPSPs with short time-to-peak and short half-width in C1DR motoneurons (16/16 motoneurons). Eight neurons sent axons to the i-C1DR motoneuron pool via the MVST without any to the extraocular motoneuron pool. Cell somata were located in the descending nucleus or in the ventral part of the lateral nucleus. These neurons did not produce postsynaptic potentials (PSPs) in any C1DR motoneurons. All thirty-five neurons sending axons to the c-C1DR motoneuron pool have ascending axon collaterals to the c-IO motoneuron pool.
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 1432-1106
    Keywords: Area 18 ; Receptive field ; Velocity ; Spatial frequency ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The spatial frequency tuning curves of neurones of area 18 depend upon the velocity of the visual stimulus. The higher the velocity the lower the spatial frequencies to which the cell is tuned. Since in area 17 the size of the cell receptive field is inversely related with the optimal spatial frequency to which the cell responds, we have investigated whether the shift of the optimal spatial frequency with the velocity corresponds to a “change” in the receptive field size. We recorded extracellularly from neurones in area 18; for each cell we selected two gratings, one of high spatial frequency drifting at low velocity and another of low spatial frequency drifting at high velocity to which the cell gave comparable responses. The results show that the masking of the cells receptive field which abolishes the response to the high frequency low velocity grating does not prevent the cell from responding to the low frequency high velocity grating. We conclude that the size of the receptive field of neurones in area 18 depends upon the characteristics (spatial frequency and velocity) of the visual stimulus.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 71 (1988), S. 33-46 
    ISSN: 1432-1106
    Keywords: Columns ; Visual cortex ; Orientation ; Ocular dominance ; Maps ; Cat ; Development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In the visual cortex of four adult cats ocular dominance and orientation columns were visualized with (3H)proline and (14C)deoxyglucose autoradiography. The two columnar systems were reconstructed from serial horizontal sections or from flat-mount preparations and graphically superimposed. They share a number of characteristic features: In both systems the columns have a tendency to form regularly spaced parallel bands whose main trajectory is perpendicular to the border between areas 17 and 18. These bands frequently bifurcate or terminate in blind endings. The resulting irregularities are much more pronounced in the ocular dominance than in the orientation system. The periodicity of the columnar patterns was assessed along trajectories perpendicular to the main orientation of the bands and differed in the two columnar systems. The spacing of the ocular dominance stripes was significantly narrower than the spacing of orientation bands. The mean periodicity of a particular columnar system was virtually identical in the two hemispheres of the same animal but it differed substantially in different animals. However, the spacing of orientation columns covaried with that of the ocular dominance columns, the ratios of the mean spacings of the two columnar systems being similar in the four cats. The superposition of the two columnar systems revealed no obvious topographic relation between any of the organizational details such as the location of bifurcations, blind endings and intersections. We suggest the following conclusions: 1. The developmental processes generating the two columnar systems seem to obey the same algorithms but they act independently of each other. 2. The space constants of the two systems are rigorously specified and appear to depend on a common variable. 3. The main orientation of the bands in both columnar systems is related to a) the representation of the vertical meridian, b) the anisotropy of the cortical magnification factor, and c) the tangential spread of intracortical connections.
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  • 14
    ISSN: 1432-1106
    Keywords: Postural reflexes ; Unexpected postural perturbations ; Electromyographic activity ; Muscle synergies ; Motor control ; Hindlimb muscles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effect of the direction of unexpected horizontal perturbations of stance on the organization of automatic postural responses was studied in cats. We recorded EMG activity in eight proximal and distal muscles of the hindlimb along with vertical forces imposed by the limbs in awake behaving cats while they stood on an hydraulic platform. Postural responses to motion of the platform in 16 different horizontal directions were recorded. Vertical force changes were consistent with passive shifts of the center of mass and active correction of stance by the animals. When the perturbation was in the sagittal plane, vertical force changes began about 65 ms following initial platform movement. When the perturbation contained a component in the lateral direction, latency for vertical force changes was about 25 ms and an inflection in the vertical force trace was observed at 65 ms. No EMG responses were observed with latencies that were short enough to account for the early force component and it was concluded that this force change was due to passive shifts of the center of mass. The amplitude of the EMG responses of each muscle recorded varied systematically as perturbation direction changed. The directions for which an individual muscle showed measurable EMG activity were termed the muscle's “angular range of activation.” No angular range of activation was oriented strictly in the A-P or lateral directions. Most muscles displayed angular ranges of activation that encompassed a range of less than 180°. Onset latencies of EMG responses also varied systematically with perturbation direction. The amplitude and latency relationships between muscles, which made up the organization of postural responses, also varied systematically as perturbation direction was changed. This result suggests that direction of perturbation determines organizational makeup of postural responses, and for displacements in the horizontal plane, is considered a continuous variable by the nervous system.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 73 (1988), S. 329-342 
    ISSN: 1432-1106
    Keywords: Dorsal roots ; Locomotion ; Sprouting ; Cat ; Plasticity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Previous studies showed that after complete hindlimb deafferentation in cats, the ipsilateral descending pathways mediated recovery of overground, goal-directed locomotion and accurate placement of the deafferented limb. In the present study deafferentations sparing one dorsal root (L6) were performed to see if the descending systems would still be responsible for the recovery. The partially deafferented hindlimb is initially impaired in postural reflexes and accurate placement during locomotion but considerable recovery occurs. A similar pattern of severe impairment and subsequent recovery is observed in cats in which the only lesion is L1 hemisection. When a hemisection is added 6 months later to chronic spared-root deafferentation the recovery (from the latter lesion) is temporarily reversed but the animals recover again in a fashion similar to that after hemisection alone. Since there is no recovery of overground locomotion when hemisection is added to complete deafferentation but there is when deafferentation is incomplete, the descending pathways apparently are not responsible for maintaining the recovery when one dorsal root is spared as they are when all are cut. The results suggest that a competitive or hierarchical control over residual systems may regulate recovery of motor function.
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  • 16
    ISSN: 1432-1106
    Keywords: Axonal branching ; Vestibulo-ocular ; Vestibulo-collic ; Neck motoneurons ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Unit activities of 148 secondary vestibular neurons related to the posterior semicircular canal were recorded extracellularly in anesthetized cats. Axonal projections of these neurons were examined by their antidromic responses to stimulation of the excitatory target motoneurons of the contralateral (c-) inferior rectus muscle (IR) and bilateral (bi-) motoneuron pools of longus capitis muscles, neck flexors, in the C1 segment (C1LC). The neurons were classified into 4 groups according to their axonal projections. The first group of neurons, termed vestibulo-oculo-collic (VOC) neurons, sent axon collaterals both to the c-IR motoneuron pool and to the c-C1LC motoneuron pool. The majority of them (72%) were located in the descending nucleus. The second group of neurons were termed vestibuloocular (VO) neurons and sent their axons to the c-IR motoneuron pool but not to the cervical cord. Most of them (86%) were located in the medial nucleus. The third group of neurons, termed vestibulo-collic (contralateral) (VCc) neurons, sent axons to the cC 1LC motoneuron pool via the contralateral ventral funiculus but not to the oculomotor nuclei. They were mostly (75%) found in the descending nucleus. The last group of neurons were vestibulo-collic (ipsilateral) (VCi) neurons, which gave off axons to the ipsilateral (i-) C1LC motoneuron pool via the ipsilateral ventral funiculus but not to the oculomotor nuclei. One of them also sent an axon collateral to the c-C1LC motoneuron pool. The majority of them (74%) were located in the ventral part of the lateral nucleus. It was also observed in some of the VOC and VCi neurons that they produced unitary EPSPs in the c-C1LC and i-C1LC motoneurons, respectively. Their synaptic sites were estimated to be on the cell somata and/or proximal dendrites of the motoneurons.
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 72 (1988), S. 191-194 
    ISSN: 1432-1106
    Keywords: Visual cortex ; Ablation ; Orientation discrimination ; Contrast ; Redundancy ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Intact animals can make fine orientation discriminations over a wide range of contrasts. After ablation of area 17 deficits in orientation discrimination are observed only at low contrast. The relevance of this finding for the design of sensitive ablation experiments is discussed.
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  • 18
    ISSN: 1432-1106
    Keywords: Preoptic area ; Amygdala ; Medial forebrain bundle ; Medial basal hypothalamus ; LH ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neuronal responses were recorded extracellularly in the preoptic region of 11 male castrate cats following stimulation in the ‘medial’ group of amygdalar nuclei (medial, basomedial, basolateral). The latency of responses varied with the site of stimulation and could be explained if connections to the preoptic region were made through both the stria terminalis and the ventral amygdalofugal pathway. Projection of 13% of orthodromically excited preoptic units to the medial basal hypothalamus was established by collision tests following stimulation in these regions. The amygdalar excitation was probably exerted through the amygdalofugal pathway. In 5/6 cats the amygdalar stimulation was successfully used to raise plasma LH levels. In one cat no preoptic units projecting to the medial basal hypothalamus were found and in the cat which failed to increase plasma LH in response to amygdala stimulation, 5 such units were found. We conclude the pathway from the amygdala through the preoptic region to the hypothalamus may not be the way in which amygdalar stimulation affects LH release in the cat. Projection of 10% of orthodromically excited preoptic units in the medial forebrain bundle was established by collision tests in 3 cats. These identified units were driven from amygdalar sites thought to project to the preoptic region by ventral amygalofugal pathways.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 71 (1988), S. 231-240 
    ISSN: 1432-1106
    Keywords: Cat ; Retinal electrophysiology ; Electroretinogram ; Neurotransmitters ; Dopamine ; Serotonin ; Aminophosphonobutyric acid (APB)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Anatomical structures of the cat retina were related to functional changes induced by the application of dopaminergic and serotonergic substances. We report on the contribution of dopaminergic and serotonin accumulating retinal neurones to retinal activity as reflected by the electroretinogram. The effect of dopaminergic neurones was investigated by the application of the neurotoxin 6-hydroxydopamine (6-OHDA) which is known to destroy dopaminergic neurones, and injections of either serotonin (5-HT) or the analogue 5,6-dihydroxytryptamine (5,6-DHT) were used to monitor the effects of indoleamines. In control experiments aminophosphonobutyric acid (APB), an agonist of glutamate transmission, was injected. Conventional immunohistochemical methods identified dopaminergic and serotonin accumulating neurones, and the electrophysiological data obtained from the same animals were related to the anatomical structures influenced by the respective substances. Destruction of dopaminergic amacrine cells by 6-OHDA increased the ERG b-wave amplitude. Accumulation of indoleamines by certain amacrine cells also caused an increase of the ERG b-wave. However, intravitreal injection of APB completely blocked the bwave. The data show that ERG mass responses can be used to monitor transmitter-specific effects on retinal circuitry.
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  • 20
    ISSN: 1432-1106
    Keywords: Opiate ; Receptor ; Vision ; Cat ; Mu ; Kappa ; Delta
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The distributions of μ, δ, and χ opiate receptors within visual regions in the cat cortex, thalamus and midbrain were determined by in vitro autoradiography. The overall distribution of receptors was examined using [3H]-etorphine, a ligand that nonselectively labels all types of opiate receptors. [3H]-[D-Ala2, N-Me-Phe4, Gly(ol)5]-enkephalin (DAGO) was used to selectively label μ receptors, [3H]-[D-Pen2,5]-enkephalin (DPDPE) for δ receptors, and [3H]-bremazocine for χ receptors. Each of the areas examined showed clear opiate receptor binding with [3H]-etorphine and a differential distribution of μ, δ, and χ receptors. Compared to other cortical regions, opiate binding in layers 3 and 4 of areas 17 and 18 was sparse. In the adjacent areas a more uniform distribution across layers was observed. The density of χ opiate receptors was greater in cortex than in subcortical structures, whereas the reverse was the case for μ receptors. Nevertheless, all three types of opiate receptors were found in the ventral and dorsal subdivisions of the lateral geniculate (LGN), the pulvinar complex, and the suprageniculate nucleus. In the midbrain, the superficial layers of the superior colliculus were heavily labelled with the μ, receptor ligand, and modestly with the χ ligand. Compared with other midbrain and diencephalic areas, δ binding was low in the superior colliculus. These results suggest that the diverse effects of opiates on visual perception are mediated by the unique distributions of opiate receptor types throughout the visual areas in the brain.
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  • 21
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    Experimental brain research 69 (1988), S. 497-508 
    ISSN: 1432-1106
    Keywords: Binocular interaction ; Perigeniculate nucleus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We have recorded from single cells in the perigeniculate nucleus (PGN) of the cat to determine their response properties. Quantitative tests have been conducted with sinusoidal gratings. Using optimal stimulus parameters, determined monocularly, we explored binocular interaction by varying the relative phase between dichoptically presented gratings. Monocularly, cells exhibit varying degrees of response specificities with respect to stimulus orientation and spatial frequency. Binocularly, we have identified six types of response. The most prominent, type 1, found for half the cells, is phase-specific binocular interaction at the fundamental frequency component of the drifting grating. For these cells, mean response rate is independent of interocular phase. The remaining types of binocular responses involve varying degrees of interaction at different harmonic components. For a quarter of the sample, no binocular interaction was observed. To investigate the role of cortical input to PGN, visual cortex was removed from some cats. Subsequent study of PGN cells indicated that response properties were generally similar to those found in intact animals. We conclude that PGN response properties are determined primarily by subcortical inputs.
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  • 22
    ISSN: 1432-1106
    Keywords: Cat ; Nucleus medialis dorsalis ; Ventral tegmental area ; Nucleus accumbens ; Pericruciate cortex ; Attentional mechanisms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In anaesthetized cats, single units were recorded from the ventrolateral part of n. medialis dorsalis (MD) of the thalamus. Cells were tested for their ortho- or antidromic short latency responses to single electrical shocks applied to the pericruciate cortex (PCx) and to either the mesencephalic ventral tegmental area (VTA) or the nucleus accumbens (ACC). Some reciprocal direct connections were thus shown to exist between MD and PCx, i.e. a cortical area posterior to the main classical MD “prefrontal” projection zone. Reciprocal direct connections were also identified physiologically between MD and VTA and between MD and ACC. Coupled stimulations showed that some MD cells could serve as a relay for a pathway from VTA to cortex, others for a reciprocal pathway from PCx to VTA, and still others, for a pathway from PCx to ACC. These findings are compared to previous — mostly anatomical — data obtained in other species, mainly rat. Their functional meaning is also discussed, in the light of previous results on the roles of MD, VTA and ACC in the control of immobility during focused attentive behaviour in cat.
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  • 23
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    Experimental brain research 73 (1988), S. 553-568 
    ISSN: 1432-1106
    Keywords: Cat ; Visual cortex ; Acetylcholine ; Nicotinic receptors ; Iontophoresis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Radioligand binding assays, receptor autoradiography and iontophoresis have been used to look for evidence of a nicotinic component to the actions of acetylcholine in cat visual cortex. [3H]Nicotine bound to a uniform population of high affinity binding sites in cat primary visual cortex. This binding was inhibited by nicotine agonists and antagonists but not muscarinic antagonists. The concentration of nicotinic binding sites was about 10% of that of muscarinic binding sites measured with [3H]N-methylscopolamine. The muscarinic sites were resolved into M1 and M2 subtypes. Quantitative receptor autoradiography showed that there were muscarinic sites in all layers, although they were least abundant in layer IV of area 17. In contrast, the nicotinic sites were most concentrated in layer IV in area 17. The concentration of this labelling was reduced at the 17/18 border and also at the 18/19 border. Layer I of the cingulate and suprasylvian gyri were also labelled. Electrolytic lesions of the lateral geniculate nucleus (LGN) led to a loss of nicotinic binding sites in layer IV of area 17, indicating that these sites are most likely located on the LGN terminals. Iontophoresis of mecamylamine, a nicotinic antagonist, decreased evoked responses in visual cortex, providing evidence that the [3H]nicotine binding sites are functional receptors and suggesting that the release of acetylcholine onto these receptors on the LGN terminals facilitates the input of visual information into visual cortex.
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  • 24
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    Experimental brain research 69 (1988), S. 509-521 
    ISSN: 1432-1106
    Keywords: Vestibulo-ocular reflex ; Cat ; Norepinephrine ; Neuronal adaptation ; 6-hydroxydopamine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The vestibulo-ocular reflex (VOR) operates to stabilize the eyes in space during movements of the head. The system has been described as having a gain of approximately -1 since stimulation of the semi-circular canals brought about by head movements will have the effect of causing the eyes to rotate an equal amount in the opposite direction. Change in the gain of the VOR has been put forth as a model to study plasticity in the central nervous system. Since numerous studies have implicated norepinephrine (NE) in neuroplasticity and modifiability of neural circuits, we attempted to determine the effect of NE depletion (via 6-hydroxydopamine (6-OHDA) intra-cisternal injection) on the modifiability of the VOR. We have found that cats increase the gain of their VOR over a four hour period when rotated in the horizontal plane in a manner equal but opposite to the rotation of a surrounding opto-kinetic drum. The entire group of animals manifests a statistically significant decrement in their ability to increase VOR gain when central stores of norepinephrine are depleted via intra-cisternal injection of 6-OHDA. Individual animals manifest a wide variety of gain changes (0.98 to 1.62). We have found that there were two groups of cats — high and low gain modifiers. The greatest reduction in VOR gain increase after NE depletion was observed in the high gain modifiers. No difference was observed in the low gain modifiers. These same animals tested for VOR modification after amphetamine injection, produced similar results. Alertness during the VOR modification task, as estimated by saccadic eye movement counts, was unchanged after NE depletion. NE levels, measured by HPLC-EC, after depletion were reduced to the greatest extent in the cerebellum. There was also a substantial reduction of NE in the visual cortex with less of a reduction in the brain stem.
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  • 25
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    Experimental brain research 71 (1988), S. 21-32 
    ISSN: 1432-1106
    Keywords: Voiced vocalization ; Hypothalamic stimulation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Voiced vocalizations evoked by hypothalamic stimulation were studied in a series of six awake adult cats. Electrical stimulation was found to evoke vocalizations at numerous sites within the hypothalamus, ranging from A+8 to A+16. Regions showing the largest number of responsive sites were the preoptic region, the ventromedial area, the perifornical region, the lateral and the dorso-medial hypothalamus. The form of the evoked calls was generally similar to the spontaneous calls of the same animal. Call latency, duration, and intensity were not significantly affected by changes in stimulus intensity or duration but all three of these call parameters were significantly affected by changes in stimulus frequency. In general, call latency was longest at sites in the rostral hypothalamus and shortest at sites in the caudal hypothalamus. This study is the first to investigate systematically voiced call producing areas in the hypothalamus of awake cats and to document similarities between these calls and spontaneously produced voiced calls.
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  • 26
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    Experimental brain research 72 (1988), S. 264-278 
    ISSN: 1432-1106
    Keywords: Convergent strabismus ; Cat ; Area 18 ; Temporal properties ; Contrast sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Single-cell recording experiments were carried out to determine whether rearing kittens with surgically induced convergent strabismus (esotropia) alters the development of receptive field (RF) properties of neurons in area 18. In agreement with previous work on kittens with divergent strabismus (exotropia), there was a marked loss of binocularly driven cells in area 18 of esotropic cats. In contrast to the striate cortex of strabismic cats, the spatial properties of area 18 neurons, including receptive-field size and spatial frequency tuning, did not differ from those in normal controls. On the other hand, we found that contrast thresholds, measured at an optimal spatial frequency, were significantly elevated, and that the contrast gain in many cells was reduced in strabismic cats. These deficits were observed in both eyes, though the cells dominated by the deviating eye had a lower response amplitude at all contrasts. Furthermore, temporal frequency tuning curves were abnormal in strabismic cats in that the optimal frequencies and temporal resolutions were shifted to lower values. These effects were also bilateral. Velocity tuning, measured with a high-contrast bar stimulus, revealed that area 18 neurons in strabismic cats were unable to respond to very high velocities compared to normals. This reduced response was more severe when measured with the deviating eye in spite of the bilateral nature of the deficit. Finally, latencies to electrical stimulation of the optic chiasm or the optic radiation were significantly longer in strabismic cats. The magnitude of these effects was virtually the same for both eyes. From these observations, we conclude that the temporal properties of area 18 neurons, particularly the cells abilities to follow fast temporal modulations, are affected by raising kittens with surgically induced convergent strabismus.
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  • 27
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    Experimental brain research 72 (1988), S. 503-509 
    ISSN: 1432-1106
    Keywords: Strabismic amblyopia ; Cat ; Lateral geniculate nucleus ; Acuity ; X-cell ; VEP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The acuities of X-cells from the dorsal lateral geniculate nucleus (LGN) were measured in five cats raised with a convergent strabismus, surgically induced by tenotomy. The acuities of cells driven by the strabismic eye were not significantly different from the acuities of cells driven by the non-deviating eye over the range of eccentricities in the visual field studied (from the area centralis to over 20°). The data were also similar to X-cell acuities in the LGN of 3 normal cats. Lowered acuities of LGN X-cells driven by the deviating eye of an esotropic cat in which the strabismus was created by myectomy confirm a previous finding of a retinal locus of amblyopia associated with that preparation. In contrast, the results here implicate the visual cortex as the initial site of the deficit in spatial processing in amblyopia arising from tenotomy strabismus.
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  • 28
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    Experimental brain research 71 (1988), S. 147-152 
    ISSN: 1432-1106
    Keywords: Eye movements ; Vestibulo-ocular reflex ; Otoliths ; Off-vertical-axis rotation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The response to off-vertical-axis rotation (OVAR) was measured in cats under circumstances in which the signals from the horizontal semicircular canals and otoliths were opposed. Opposition was achieved by sudden acceleration or deceleration during constant velocity OVAR. The degree of opposition was expressed as a canal/otolith ratio where a ratio of unity indicated agreement. For a canal/otolith ratio of 1, the OVAR gain (eye velocity/ stimulus velocity) was 0.73 (±0.13). The steady-state OVAR response was, however, reduced if the canals and otoliths were opposed. The reduction depended on the degree of opposition with a fall-off of 0.15 gain/(unit of canal/otolith ratio). These findings are discussed with respect to the central velocity store and the mechanism underlying the generation of the OVAR response.
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  • 29
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    Experimental brain research 71 (1988), S. 262-272 
    ISSN: 1432-1106
    Keywords: Swallowing ; Synaptic potential ; Hypoglossal motoneuron ; Extrinsic tongue muscle ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The postsynaptic potentials produced in cat genioglossus and styloglossus motoneurons (GG- and SG-Mns) during swallowing were studied. During swallowing elicited by placing water on the dorsum of the tongue, the GG-muscle discharged for 80–210 ms (mean±S. D. 123±31 ms, N=59) and was abruptly suppressed, and the SG-muscle began discharging in synchrony with the GG-muscle and discharged for 200–360 ms (mean+ S. D. 247±36 ms, N=59). The GG and the SG-Mns were identified if unitary muscle activity followed the induced spike of the motoneuron one-for-one. During swallowing, excitatory postsynaptic potentials (EPSPs) were evoked in the SG-Mns regardless of the respiratory drive on the SG-Mns, and inhibitory postsynaptic potential (IPSP) or EPSP-IPSP was evoked on the GG-Mns regardless of the respiratory drive on the GG-Mns. By increasing the intracellular concentration of chloride ions, the IPSP elicited in the GG-Mn during swallowing was turned into a depolarizing potential. In immobilized cats, a depolarizing potential and a depolarizing-hyperpolarizing potential sequence was evoked successively on a tongue retractor motoneuron and a tongue protruder motoneuron by repetitive electrical stimulation of the superior laryngeal nerve.
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  • 30
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    Experimental brain research 73 (1988), S. 78-90 
    ISSN: 1432-1106
    Keywords: Otoliths ; Nystagmus ; Labyrinth ; Eye movements ; Velocity storage mechanism ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1) In the alert cat, nystagmus induced by off-vertical axis rotation (OVAR) was recorded following steps in head velocity or ramps of velocity at constant acceleration below canal threshold. Dependence of nystagmus characteristics on tilt angle of rotation axis and head velocity was studied. Similar results were obtained with both types of stimulation. 2) Mean and modulation amplitude of horizontal eye velocity increased with tilt angle in the range 0–30 degrees. 3) Both variables increased also with head velocity, but with different trends, probably because they are set by different mechanisms. When head rotational velocity was increased above 80°/s, mean eye velocity progressively decreased to zero. 4) In spite of variations from one animal to another, some regularity was observed in the phase of eye velocity modulation. In several cases, a reduction in phase lead of eye velocity with respect to conventional origin of phases (nose-down position) was observed when head velocity increased. 5) Time constant of post-OVAR nystagmus decreased with the tilt angle of the rotation axis from gravity, but not with the orientation of the head with respect to rotation axis. 6) The results could be accounted for by a general equation describing the vestibulo-ocular reflex, provided that estimates of kinematic variables of head movement (head rotational and translational velocities), and visual target distance could be computed by the Central Nervous System.
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  • 31
    ISSN: 1432-2013
    Keywords: Peripheral chemoreceptors ; Central chemoreceptors ; Control of respiration ; Dopamine ; Haloperidol ; Domperidone ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We investigated the effects of the dopamine antagonists haloperidol and domperidone on the ventilatory response following square-wave changes in end-tidal CO2 during normoxia in chloralose-urethane anaesthetized cats. In 7 cats these responses were measured before (control, 28 runs) and after the administration of 1 mg/kg haloperidol i.v. (26 runs) and in 8 other cats before (39 runs) and after 0.5 mg/kg domperidone i.v. (34 runs). Each response was separated into a slow central and a fast peripheral part by fitting two exponential functions to the measured ventilation. These functions have as parameters a CO2 sensitivity, a time constant, a time delay and an apnoeic threshold B (extrapolated PETCO2 of the steady-state response curve at zero ventilation). Haloperidol significantly diminished the peripheral (Sp) and the central (Sc) ventilatory sensitivity to CO2 and the B-value (P〈0.001). The ratio Sp/Sc, the time constants and the time delays were not significantly changed. Domperidone only diminished the B-value significantly (P〈0.001). Since domperidone does not readily cross the blood-brain barrier, its effect was a CO2 independent increase of the ventilation mediated by the peripheral chemoreceptors. Haloperidol exhibited, besides the peripheral stimulatory effect a depressant central effect due to an action on the central integrative structure, resulting in a proportional decrease of Sp and Sc.
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  • 32
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    Psychopharmacology 95 (1988), S. 268-270 
    ISSN: 1432-2072
    Keywords: Aminotetralin ; Apomorphine ; Cat ; Emesis ; Limb flicks
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Apomorphine-induced limb flicks in cats have been ascribed to a central dopamino-mimetic action of the drug. In these experiments we investigated the role of receptors located outside the blood-brain barrier (BBB) in the induction of limb flicking. Domperidone, a dopamine-receptor blocker which does not readily pass through the BBB, antagonised the induction of limb-flicks induced by apomorphine. This suggests that limb flicking behaviour may involve interactions with receptors located before the BBB. In contrast, 6-amino-5,6,7,8-tetrahydro-1,2-naphtalenediol HBr (6-ATN), a dopamine-agonist which does not penetrate the BBB, did not induce limb flicks, indicating that receptor stimulation outside the BBB alone is not sufficient to induce limb flicks. We suggest that limb flicks in cats is a behaviour which can be elicited by combined activation of centrally located dopamine receptors and dopamine receptors in the area postrema.
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  • 33
    ISSN: 1432-0878
    Keywords: Neurokinin A ; Substance P ; Dental pulp ; Immunohistochemistry ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The distribution and origin of neurokinin A (NKA)-like immunoreactivity were investigated in feline dental pulp by an indirect immunofluorescence method. NKA-containing nerve fibres with varicosities, which entered the dental pulp via apical foramen, were distributed throughout this tissue. Many NKA-containing nerve fibres were localized around blood vessels, but some were observed apart therefrom. At the odontoblastic layer, thin NKA-containing nerve fibres were observed running straight toward the pulp-predentinal border between odontoblasts. After inferior alveolar nerve section, all NKA-containing nerve fibres disappeared in the dental pulp, while the removal of the superior cervial ganglion resulted in no change in the distribution of these fibres. The correlation of NKA-like immunoreactivity and substance P (SP)-like immunoreactivity was also investigated by double-immunofluorescence technique. The distribution of NKA-containing nerve fibres was very similar to that of SP-containing nerve fibres; it appeared that all NKA-containing nerve fibres contained SP.
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  • 34
    ISSN: 1432-0878
    Keywords: Calcitonin gene-related peptide (CGRP) ; Vasoactive intestinal polypeptide (VIP) ; Merkel cells ; Free nerve endings ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Calcitonin gene-related peptide (CGRP)-and vasoactive intestinal polypeptide (VIP)-immunoreactivity were observed to coexist in Merkel cells of cats. No differences in peptide content were found between Merkel cells located in epithelia of the hard palate, in hairy and glabrous skin of the upper lip, and in vibrissae follicles. CGRP-and VIP-immunoreactive nerve fibres were also found near CGRP/VIP-immunoreactive Merkel cells. In the vibrissae follicles some CGRP-and VIP-immunoreactive nerve terminals end abutting on the glassy membrane. Other CGRP immunoreactive nerve fibres penetrate the epithelium of the skin and end within it. Electron microscopy of vibrissae follicles revealed that Merkel cell neuntes are not immunostained and that immunostained nerve fibres form unmyelinated bundles before ending freely. Thus, CGRP-and VIP immunoreactive nerve fibres in cat skin do not end as Merkel cell neuntes but as different kinds of free nerve endings.
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  • 35
    ISSN: 1432-0878
    Keywords: Corticotropin-releasing factor (CRF) ; Medulla oblongata ; Inferior olive ; Immunohistochemistry ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Corticotropin releasing factor (CRF)-immunoreactive (IR) perikarya, visualized by the indirect immunoperoxidase method in colchicine-pretreated cats, were localized in many discrete regions of the medulla oblongata. They were found mainly in the dorsal aspect and midline of the medulla oblongata, and more rostrally in the ventrolateral portion. Our results also demonstrated CRF-IR neurons in the rostrocaudal extent of the inferior olive, probably projecting to the cerebellar cortex via thick axons visualized along the lateral edge of the medulla. CRF-IR olivary cells were also found in the pontine cat from which the forebrain was removed, but neither in hypophysectomized nor adrenalectomized cats.
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  • 36
    ISSN: 1432-0878
    Keywords: Calcitonin gene-related peptide ; Regulatory peptides ; Paravertebral ganglia ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Paraffin sections of cervical and upper thoracic paravertebral ganglia of the cat were investigated by immunohistochemistry using antisera directed against calcitonin gene-related peptide (CGRP). The relationships of CGRP-immunoreactive structures to those exhibiting immunoreactivity to antisera against other regulatory peptides and dopamine-β-hydroxylase (DBH), respectively, were studied in consecutive sections. Singly scattered CGRP-immunoreactive neuronal perikarya were observed in the superior and middle cervical ganglia as well as in the stellate ganglion. These neurons also displayed immunoreactivity to vasoactive intestinal polypeptide (VIP), and some additionally exhibited faint substance-P immunoreactivity. DBH- and neuropeptide Y-immunoreactive ganglion cells were not identical with CGRP-immunoreactive neuronal cell bodies. According to the immunoreactive properties of varicosities, which abut on CGRP/VIP-immunoreactive perikarya, three types of CGRP/VIP-immunoreactive ganglion cells could be distinguished: (1) CGRP/VIP-immunoreactive neurons being surrounded by somatostatin-immunoreactive nerve fibers, (2) neurons being approached by both DBH- and met-enkephalin-immunoreactive varicosities, and (3) neurons receiving both DBH- and neurotensin-immunoreactive fibers. The stellate and upper thoracic ganglia harbored clusters of intensely VIP-immunoreactive somata, which lacked CGRP-immunoreactivity. Fine somatostatin-immunoreactive and coarse CGRP-immunoreactive fibers were distributed within these clusters, whereas patches of neurotensin-immunoreactive fibers were complementarily arranged. At all segmental levels investigated, a few postganglionic neurons were approached by both CGRP-immunoreactive and substance P-immunoreactive varicosities, but lacked a VIP-immunoreactive innervation. Therefore, CGRP/substance P-immunoreactive fiber baskets appeared rather to be of extraganglionic origin than to emerge from intraganglionic CGRP/VIP/SP neurons. CGRP-immunoreactive cell bodies or fibers were absent in clusters of small paraganglionic cells, but some of the solitary paraganglionic cells displayed CGRP-immunoreactivity. Our findings establish the presence of CGRP-immunoreactivity in a population of sympathetic neurons in the cat. A highly differentiated, segment-dependent organizational pattern of neuropeptides in cervico-thoracic paravertebral ganglia was demonstrated.
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  • 37
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    Cell & tissue research 253 (1988), S. 83-93 
    ISSN: 1432-0878
    Keywords: Pacinian corpuscle ; Axonal spines ; Inner core lamella ; Inner core cleft ; Elastica ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultrastructure of cat mesenteric Pacinian corpuscles in cross and longitudinal sections has been examined. The terminal ends of lamellar cells of the inner core have been identified in longitudinal sections through the proximal portion of the inner core. These terminal bulbous expansions contain characteristic concentric membranes of rough endoplasmic reticulum and in some cases masses of oval membranous inclusions. The central axon as seen in cross section is oval in profile, having X-(short) and Y-(long) axes, and each axonal face is characterized by specializations of the axolemma. At the X-axis, the inner lamellae of the inner core tightly abut a smooth axolemma, with no intervening connective tissue matrix, in a manner reminiscent of a neuroepithelium. The axolemma of the Y-axis has numerous axonal spines (microspikes) that project into the cleft in the inner core. The extent of the axolemma having axonal spines can only be appreciated in longitudinal sections. The clefts contain a specialized connective tissue with elastic and collagen fibrils. The connective tissue compartment of fibers and matrix separating individual inner core lamellae is unique, in that it contains extremely thin collagen fibrils measuring approximately 15 nm in diameter. The diameter of collagen fibrils increases as the cleft is approached. Here the fibrils resemble typical endoneural collagen.
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  • 38
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    Cell & tissue research 253 (1988), S. 95-103 
    ISSN: 1432-0878
    Keywords: Pacinian corpuscle ; Axonal spines ; Axonal extreme tip ; Inner core lamella ; Basal lamina-like material ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The present report is the second of two studies re-evaluating the cytological characteristics of Pacinian corpuscles. The extreme tip of the axon of a Pacinian corpuscle has been identified and is quite different from the previously described ultraterminal region. The latter is the site where the inner core lamellae begin to terminate and is characterized by a smooth axolemma. The extreme tip lacks inner core lamellae directly abutting the axolemma and is instead characterized by the presence of many axonal spines projecting into a matrix of basal lamina-like material. The extreme tip of the axon thus resembles the organization of the axolemma facing the clefts of the inner core. The axonal spines at the cleft and extreme tip are proposed as a site of restricted current flow due to the tight apposition of inner core lamellae to the axolemma of X-axis. The hemiinner cores thus could restrict current flow to the cleft. These anatomical specializations could represent both a source and a sink for K+ ions during mechano-electric transduction and account in part for the exquisite sensitivity of Pacinian corpuscles to complex pressure waves.
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  • 39
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    European archives of oto-rhino-laryngology and head & neck 245 (1988), S. 321-324 
    ISSN: 1434-4726
    Keywords: Otoliths ; Middle ear pressure ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The influence of varying middle ear pressure on the otolith system was investigated in anesthetized cats. Extra-axonal recordings of action potentials were performed in the vestibular nerve fibers and in the neurons in the lateral vestibular nucleus that responded to lateral or anteroposterior steadystate tilt. Positive or negative pressure was applied to the ipsilateral middle ear during the recordings. Seventy-three percent of the fibers and 63% of the neurons responded to changes in the middle ear pressure. These response rates were higher than those previously reported on the units innervating semicircular canals. Findings suggest that the otolith organs are more sensitive to changes in the middle ear pressure than are the semicircular canals. The units responding to lateral tilt were more sensitive to middle ear pressure than those that responded to anteroposterior tilt. Displacement of endolymph caused by pressure changes in the middle ear was considered to have affected the activities of hair cells in otolith organs.
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  • 40
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoisomeric Sinensiaxanthins and Sinensiachromes: Separation and Absolute ConfigurationThe so-called sinensiaxanthins and sinensiachromes, important apocarotenols from various fruits, have been separated into 2 and 4 stereoisomers, respectively, and their absolute configurations have been determined: (3S,5R,6S)-5,6-epoxy-5,6-dihydro-10′-apo-β-carotene-3,10′-diol (2), its (9Z)-stereoisomer 7, the (8R)- and (8S)-epimers of (3S, 5R)-5,8-epoxy-5,8-dihydro- 10′ -apo-β-carotene-3, 10′-diol (4 and 5), and their (9Z)-stereoisomers 3 and probably 6. Thus, sinensiaxanthins are cleavage products from (Z/E)-isomeric antheraxanthins or violaxanthins (scission at C(9′)-C(10′)) and sinensiachromes analogously from mutatoxanthins or auroxanthins.
    Additional Material: 4 Ill.
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  • 41
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantioselective Saponification of Diacetates of 2-Nitro-1,3-propanediols by Pig-Liver Esterase and Preparation of Enantiomerically Pure Derivatives of 2-Nitro-allylic Alcohols (Chiral Multiple-Coupling Reagents)The reproducible enantioselective saponification of open-chain and cyclic diacetates of meso-2-nitro-1,3-propanediols (see 4b-13b) with pig-liver esterase (PLE) gives monoacetates (see 4c-l3c) of 〉 95% enantiomeric excess. The Re enantiotopic acetate group appears to be saponified preferentially, as proved by the X-ray crystal structure analysis of three camphanoates 4d, 6d, and 7d. Elimination of H2O or AcOH from the hydroxy acetates thus available gives derivatives of nitro-allylic alcohols (see 20-24, 27, and 29) which are subjected to diastereoselective Michael additions or SN2′ substitutions.
    Additional Material: 4 Ill.
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  • 42
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 72-76 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new pterocarpinoids, sphenostylin A, B, C, and D (1-4), have been isolated from the CHCl3 extract of the root bark of Dolichos marginata ssp. erecta (Leguminosae) by preparative liquid chromatography. The structures have been established by spectroscopic methods (UV, 1H-NMR, 13C-NMR, EI-MS, DCI-MS, CD) and chemical transformations. The isolated compounds showed weak antifungal activity against Cladosporium cucumerinum.
    Additional Material: 1 Tab.
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  • 43
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homophthalic acid (1) undergoes reaction with 1,2-, 1,3-, and 1,4-diamines to give condensed 1(2H)-isoquinolinones like 2, 4, 13, and 25, which exhibit marked enamine character. These are attacked by electrophiles at the N or C terminus. Some notable reactions of imidazoisoquinolone 2 are those with maleic and acrylic acids to form the tetracycles 48 and 51, respectively. With propiolic acid, 5 underwent an interesting reaction to form the benzimidazonaphthyridine 53. An equally interesting behaviour was elicited from 2 in its reaction with formaldehyde, when in addition to the expected methylene-bridged molecule 59, the novel spiro derivative 60 was formed by the dimerisation of a presumed azadiene intermediate 63.
    Additional Material: 2 Ill.
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  • 44
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 120-123 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1H- and 13C-NMR data of the dimeric anhydride 1 of 2,3-O-isopropylidene-β-D-ribofuranose are reported together with the 1H-NOE values. The data show that the products of the polymerization of 1,5-anhydro-2,3-O-isopropylidene-β-D-ribofuranose are α- and β-D-ribofuranans and not an α-D-ribofuranan and a β-D-ribofuranan and a β D ribo-pyranan as claimed before [2] [3].
    Additional Material: 3 Tab.
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  • 45
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,6-Diphenylpyridine forms, as twofold-deprotonated, terdentate ligand, complexes with Pt(II) and Pd(II), having two adjacent five-membered metallocycles. As mono-deprotonated, bidentate ligand, it forms cis-bis-complexes having a chirality axis. Pt(II) complexes undergo thermal and photochemical oxidative addition reactions, yielding stable Pt(IV) compounds. Pd(II) complexes yield substitued 2,6-diphenylpyridine in photochemical reactions.
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  • 46
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 168-194 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability to incorporate alkyl, alkenyl, aryl, and heteroatomic groups into substrates for the silicon-directed Nazarov cyclization and their subsequent reactions has been investigated. In general, most of the groups are compatible with the conditions for the cyclization and do not interfere even when directly attached to the divinyl ketone. The influence of substituents on the rate of the cyclization has been addressed and is consistent with a simple mechanistic picture. O- and N-Containing functions are tolerated except when attached to the α-vinyl C-atom of the divinyl ketone. The diastereoface-directing effect of a fused cyclobutane is discussed.
    Additional Material: 7 Tab.
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  • 47
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 1:1 mixture of the racemic trans- and cis-1-p-menthene-3,8-diols ((±)-3 and (±)-4, resp.) was readily prepared in 3 steps starting from 3-methyl-2-cyclohexen-1-one. The relative configuration of the diols, purified via the corresponding cyclocarbonates, was assigned by 1H-NMR spectroscopy and found to be at variance with tentative claims in the literature. Optically active samples of 3 and 4 were prepared by resolution of the racemates with (R)-1-phenylethylamine. The absolute configuration of the resulting diols was determined by chemical correlation with standards of known absolute configuration.
    Additional Material: 4 Tab.
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  • 48
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 224-236 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Enantiomerically Pure, α-Alkylated Lysine, Ornithine, and Tryptophan DerivativesThe imidazolidinones 9 and 10 as well as the oxazolidinone 18a were prepared in several steps by known methods from lysine and ornithine with an overall yield of ca. 20%. After double deprotonation with LDA, the corresponding dianionic derivatives could be diastereoselectively alkylated with electrophiles (MeI, C6H5CH2Br, C6H5CHO, CH3CHO). Acid hydrolysis led to the two enantiomeric 2-methyl- and 2-benzyllysines and to the enzyme inhibitor (S)-2-methylornithine. Several α-alkylated tryptophan derivatives were obtained through alkylation of the heterocycles derived from various amino acids with 1-(tert-butyloxycarbonyl)-3-(bromomethyl)indole (26). Alkaline hydrolysis of the five-membered auxiliary ring of 30b followed by treatment with HCl afforded (S)-2-methyltryptophan (31).
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  • 49
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogenation of Flavylium Salts: Formation of Heptacyclic compounds; X-Ray Crystal Structure of 2-[10b,10c,16,16a-Tetrahydro-16,16a-dimethyl-10b,16-methylene-5aH-di[1]benzopyrano[4,3-b:3′,4′ -c; 2,3:2′,3′][1]benzoxepin-5a-yl]phenolThe hydrogenation of flavylium salts 1 either by catalytic reduction or by chemical reduction afforded the unexpected heptacyclic compound 2, the structure of which was determined by X-ray analysis. The latter was confirmed by 1H-NMR and mass spectra.
    Additional Material: 2 Ill.
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  • 50
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational Analysis of Tripeptide Models: The Influence of α,α-disubstituted α-Amino Acids on the Secondary Structure. X-Ray Analysis and Conformational Energy CalculationsThe X-ray analysis of tripeptide Z-Ile-Val(2-Me)-benzocaine (1f) reveals the presence of a type-III β-turn. Moreover, MMP2 calculations on tripeptides, e.g. Z-Ile-Aib-benzocaine (1c), Z-Ile-D-Val(2-Me)-benzocaine (1g), Z-Ile-Gly(2,2-Pr2)-benzocaine (1h), Z-Ile-Gly-benzocaine (1a), and 1f, fit well into the frame of NMR and CD investigations. They allow considerations on the relative stability of different types of β-turns depending on the peptide sequence, e.g. the kind of α,α-disubstituted amino-acid moieties.
    Additional Material: 4 Ill.
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  • 51
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 292-297 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of (-)-(R)-Nephthenol and (-)-(R)-Cembren AStarting for L-serine,(-)-(R)-nephthenol((-)-2) and (-)-(R)-cembren A((-)-3) were synthesized.
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  • 52
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single crystals of the N,N,N′,N′-tetramethylethylenediamine (TMEDA) complex 6 of the title compound have been isolated. Compound 6 decomposes in the crystalline state above -20°. From the bond lengths and angles obtained by X-ray crystal-structure analysis (data collected at -70°), compound 6 is best described as a (E)-1-(tert-butylthio)-1-lithio-2-butene with the double bond acting as an additional ligand on lithium (unsymmetrical allylic group). The S-atom is in a cisoid arrangement in a common plane with the four C-atoms of the butenyl system. The t-Bu group and the Li-atom are located above and below this plane. The structure is discussed with respect to the reactivity of 6 (α/γ reactivity). The gross structure is reproduced surprisingly well by an ab initio SCF MO calculation of the model lithiopropene-1-thiol 7(HS instead of t-BuS, CH2 instead of CHCH3, no solvation of Li). The prominent difference is the symmetry of the allyllic moiety in the calculated structure.
    Additional Material: 6 Ill.
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  • 53
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Note on the Synthesis of an Optically Active ACE Inhibitor with Amino-oxo-benzazepine-1-alkanoic-Acid Structure by Means of an Enantioconvergent Crystallization-Based ResolutionAn enantioselective synthesis of the potent angiotensin-converting enzyme inhibitor (1′S,3S)-3-[(1′-(ethoxy-carbonyl)-3′-phenylpropyl)amino]-2,3,4,5-tetrahydro-2-oxo-1H-1-benzazepine-1-acetic acid hydrochloride (3) is described which user a crystallization-based resolution of a racemic amino intermediate with concomitant racemization of the unwanted enantiomer.
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  • 54
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 363-368 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polycyclopentanes as Steroid AnalogaThe synthesis of linearly annellated pentaquinanes from a readily available triquinane is reported.
    Additional Material: 1 Tab.
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  • 55
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 395-403 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of an Optically Active Penem Intermediate by Asymmetric AmidoalkylationThe amidoalkylation of an optically active, cationic glycine derivative with methyl acetoacetate furnishes an intermediate 10a (Scheme 2) that is transformed in six steps to the optically active, silyl-protected 4-acetoxy-3-(1-hydroxyenthyl)-2-azetidinon 18a, a well known intermediate in penem synthesis.
    Additional Material: 3 Tab.
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  • 56
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically pure 5,6-dimethylidenebicyclo[2.2.1]hept-2-yl derivatives have been prepared. The sign of the Cotton effects associated with lowest-energy transition of 2-(dicyanomethylidene)-((-)-(1S,4S)-15), (E)-2-(methoxyimino)-((+)-(1S,4S)-16), (Z)-2-(methoxyimino)-5,6-dimethylidenebicyclo[2.2.1]heptane ((-)(1S,4S)-17), and 2,3,5-trimethylidenebicyclo[2.2.1]heptane ((-)-(1R,4S)-18) is opposite to the chirality constituted by the coupling of the electric transition moments of the two homoconjugated π-chromophores (Kuhn-Kirkwood dipole-coupling mechanism). When the substituents at C(2) are not π-functions, no general rule can be retained for the chiroptical properties of the 5,6-dimethylidenebicyclo[2.2.1]hept-2-yl systems as shown for dimethyl acetal (-)-(1S,4S)-19, ethylene acetal (+)-(1R,4R)-20, exo and endo methyl ethers (+)-(1R,2S,4R)-21 and (+)-(1R,2R,4R)-22, and for spirol[5,6-dimethylidenebicyclo[2.2.1]heptane-2.2'-oxiranes](-)-(1S,2S,4S)-23 and (-)-(1S,2S,4S)-24.
    Additional Material: 2 Ill.
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  • 57
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: About forty novel phenyl benzoates also incorporating a trans-1,4-disubstituted cyclohexane ring and a chiral centre have been prepared. The dependence of the liquid-crystal transition temperatures of this new class of compounds on lateral substituents, diverse central linkages, chain lengths, and position of the chiral centre has been studied systematically. The synthesis and liquid-crystal transition temperatures of these new compounds are described in detail.
    Additional Material: 7 Tab.
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  • 58
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    Helvetica Chimica Acta 71 (1988), S. 486-492 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [4 + 2] Cycloadditions of α,β-Unsaturated Hydrazones to Pyridine-2,3-dicarboximides via 1-(Dimethylamino)-1,4-dihydropyridine DerivativesThe [4 + 2] Cycloaddition of α,β-unsaturated hydrazones of type 1 (1-aza-1,3-butadienes) with 2-halogenomaleimides 4 affords 1,4-dihydropyridines 6 which, after treatment with an acid, yield highly substituted pyridine-2,3-dicarboximide derivatives 7 (Scheme 1).
    Additional Material: 3 Tab.
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  • 59
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    Helvetica Chimica Acta 71 (1988), S. 498-501 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation (λ 〉 340 nm) of the title compound 2a in t-BuOH affords 3,3,10,10-tetramethyl-2,8-dioxatricyclo-[4.3.2.01,6]undecane-5,9-dione (3) via photoextrusion of 2-methylpropene and subsequent photocycloaddition of 2a to the alkene. The same regioisomer 3 is formed selectively and in much higher yields on irradiating 2a in the presence of excess 2-methylpropene. Irradiation of 3 (λ = 300 nm) in t-BuOH in the presence of the same alkene gives a 6:1 mixture of spirooxetanes 7a and 7b but not α-cleavage products. In 2-propanol, 2a is photoreduced to a 2:1 mixture of diastereoisomeric hydrodimers 9.
    Additional Material: 1 Tab.
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  • 60
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Helvetica Chimica Acta 71 (1988), S. 602-608 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A General Synthesis for Mono-C-Functionalized TetrazamacrocyclesA new synthesis, under usual conditions of concentration, medium, and temperature, of a series of mono-C-functionalized tetraazamacrocycles is given. The method may easily be generalized. The new procedure allows the modification of the length of the side-chain or the size of the cavity by choosing fitted staring materials. The key intermediate has a tosylated linear side-chain susceptible to be transformed into a large variety of functional groups.
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  • 62
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomerically pure methyl 5-bromo-5-deoxy-2,3-O- isopropylidene-β-D- (D-5b) and -β-l-ribofuranoside (l-5b) have been derived from (-)-(1R,2S,4R)-2-exo-cyano-7-oxabicylo[2.2.1]hept-5-en-endo,-yl (1′S)-camphanate (1) and (+)-(1S,2R,4S)-2-exo-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-endo-yl(1′R)-camphanate (2), respectively, in 5 synthetic steps and 28% overall yield. Hydrolysis of D-5b and L-5b afforded methyl 2,3-O isopropylidene-β-D-ribofuranoside (D-5a) and methyl 2,3-O-isopropylidene β-L-ribofuranoside (L-5a), respectively. The intermediate (+)-(1R,4R,5R,6R) 5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-7) and its enantiomer(-)-7 were also obtained enantiomerically pure by resolution of (=)-7 by the Johnson-Zeller method. In bothe approaches, the chiral auxiliaries ((-)- and (+)-camphanic acids, or (+)-(S)-N,S-dimethyl-S-phenylsulfoximide) were recovered at an early stage of the synthesis.
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  • 63
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Solvolysis Mechanism of cis - and trans-2-Arylcylopentyl p-Toluenesulfonates. The Step: 1-Deuterium Isotope Effects, Basic Salt Effects, and Special Salt EffectWe have studied the first step of the solvolysis of cis and trans-2-arylcyclopentyl p-toluenesulfonates in HCOOH, AcOH, and EtOh. All substrates show a high kinetic 1-deuterium isotope effect (kH/kD(1) 〉1.15). This fact indicates that first step leads to classical intimate ion-pair Which dissociates to a solvet-separated ion-pair, without participation either of solvent, the 2-aryl group, or a H-atom at C(2). The slight influence of added basic ions on reaction rate allows us to exclude any direct solvent attack on the covalent substrate even in the most favorable case, i.e. ethanolysis of 2-(p-nitrophenyl)cylopentyl-p-toluenesulfonates. Furthermore, solvent-separated ion pair formation is indicated by the special salt effect induced by LiClO4.
    Notes: No abstract.
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  • 64
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    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optically active (4S,8S)-4, 8-bis(hydroxymethyl)-1,5,7-triazabicyclo[4.4.0]dec-5-ene ((S,S)-1) has been synthesized in nine steps from L-asparagine with a total yield of 5.1%. Similarly, the enantiomer (R,R)-1 has been prepared from D-asparagine. (S,S)- and (S,S)-1 are representative examples of rigid and functionalized bicyclic guanidine systems and constitute useful intermediates in the construction of chiral selective anion-receptor molecules.
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  • 66
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and antifungal activity of a novel series of 3-aryl-5-[(aryloxy)alkyl]-3-[(1H-imidazol-1-yl)-methyl]-2-methylisoxazolidines and related compounds, are discussed. The synthesis of the title compounds was accomplished via a 1,3-dipolar cycloaddition of α-substituted ketonitrones with l-alkenyl phenyl ethers (Scheme 2 and 3). The compounds were evaluated for in vitro antifungal activity in solid agar cultures against a broad variety of yeast and systemic mycoses and dermatophytes. While antifungal activity was evident throughout the series, in general, derivatives having halogen atom(s) in either or both aryl rings demonstrated the highest potency, especially against Trichophyton rubrum and Candida albicans. The dichloro analog 20 (PR 967-248) was found to possess the most useful activity. Its minimum inhibitory concentration (MIC) values ranged between 0.2 and 2.0 μg/ml, as compared to 0.2-20.0 μg/ml for the standard drug ketoconazole (4).
    Additional Material: 1 Ill.
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  • 67
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    Helvetica Chimica Acta 71 (1988), S. 742-748 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Olefins with captodative substitution are reactive dienophiles in Diels-Alder reactions with normal and inverse electron demand. This is shown for reactions of 2-(tert-butylthio)acrylonitrile (1) with various dienes and heterodienes, e.g. 1,3-cyclohexadiene, hexachloro-1, 3-cyclopentadiene, acrolein, methacrolein, and methyl vinyl ketone (Schemes 2 and 3). In case of the hetrodienes, 3,4-dihydro-2H-pyrans are formed beside small amounts of tetrahydrothiophenes; however, with methyl vinyl ketone, both reaction pathways are equally followed. The high reactivity of captodative olefins in Diels-Alder reactions are rationalized on the basis of Sustmann's FMO model under consideration of Viehe's concept of captodative substitution of alkenes.
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  • 68
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    Helvetica Chimica Acta 71 (1988), S. 783-787 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel rearrangement of 2(5H)-furanones is described. When refluxed in aq. Ethanolic solution in the presence of excess KOH, the 2,5-dihydro-2-oxofuran-3-carboxamides 6 underwent a novel rearrangement to the corresponding 4,5-dihydro-4-oxo-2-(phenylamino)-3-furancarboxylic acids 1 in moderate-to-excellent yields.
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  • 69
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    Helvetica Chimica Acta 71 (1988), S. 788-807 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Short Total Syntheses of (±)-Sativene and (±)-cis-SativenediolOur approach to (±)-sativene (7) and (±)-cis-sdtivenediol (9) involves: (a) reaction of 3-methylbutanoyl chloride with Et3N/cyclopentadiene to give the endo-isopropyl-ketone 1 (here improved to 71%), (b) NBS bromination of 1 to a 5:1 mixture (87%) of the bromo-ketones 2 and 3, (c) NFD-reaction sequence initiated by the attack of 1,2-butadienyl titanate (complex of 15, obtained from 2-butine) on 2/3 to afford 52% of the brexenone derivative 4 (along with 8% of its epimer 16), (d) addition of dibromomethane to 4 forming 63% of the diene-alcohol 5 (along with 13% of the diene-carbaldehyde 38), and (e) carbenoid ring-expansion with MeLi applied to 5 resulting in 41% the diene-ketone 6 (along with 15% of a 1:3 mixture of the diene-ketones 32 and 33). Wolff-Kishner reduction of 6 led to 81% of (±)-sativene (7), when enough O2 was present, but to 97% of the diene 8 in the strict absence of O2. (±)-cis-Sativenediol (9) was obrained (86%) by OsO4 hydroxylation of 8. The brexenone derivatives 4 and 16 (6:1, 50%) were also produced when the NFD-reaction sequence was applied to the isomeric bromo-ketone mixture 13/13 (1:3). The latter was obtained by NBS bromination of 10, which in turn was available by base epimerization of 1, followed by destructive removal of unreacted 1 by repeated gas-flow thermolysis. An analogous (less convenient) route to (±)-sativene (7) passed through a series of dihydro compounds (the ene series) it started with the methylidene-ketone 36, which was the product (97%) of a partial hydrogenation of 4. Addition of dibromomethane to 36 led t 62% of the methylidene-alcohol 39 (along with a little tetracyclic ether 40). Carbenoid ring expansion of 39 with MeLi afforded ca. 42% of the methylidene-ketone 41 (along with 7% of the methylidene-ketone 43 or, under slightly different condition, along with 9% of the methylidene-ketone 42 and 10% of the methylidene-carabaldehyde 44). The methylidene-alcohol 39 and the methylidene-ketone 43 were also obtained by partial hydrogenation of 5 and 33, respectively. Wolff-Kisher reduction converted 41 into (±)-sativene (7 99%); the same conditons applied to 42 afforded only ca. 8% 7 (along with three other hydrocarbons, one of them (ca. 21%) probably being (±)-copacamphene (45)). In the diene series, the two succeeding reactions (4→5 and 5→6) competed with the same side reaction, a rearrangement leading to the brendene-aldehyde 38. In the ene series, the corresponding dihydro-by-product 44 was found in the reacton 39→41, but not during 36→39. These side reactons could largely be suppressed by keeping the reaction temperature low. An explanation is proposed.
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  • 70
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    Helvetica Chimica Acta 71 (1988), S. 859-866 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the bromo-substituted naphthalene 1 with the alkanethiolate anions 2a-b and arenethiolate 2c in tetraglyme gave the corresponding 1-naphythyl thio-ethers 3a-c. Thio-ethers 3a-c were oxidized to the corresponding sulfones 4a-c with m- chloroperoxybenzoic acid. The reaction of the dichloro-substituted anthracene 5a with 2b gave the disubstutution product 6a. The reaction of 9-bromoanthracene 5c with the alkanethiolate 2b gave 6b, whereas the reaction of 5c with the arenethiolate 2c gave a mixture of substitution product 6c and anthracene 7. The observation of the formation of both 6c and 7 is explained by the competition between substitution (SnAr) and electron-transfer (ET) mechanisms. Consistent with this interpretation, the reaction of the monochloro-substituted 5b, which has a higher-energy σ* orbital, with 2c gave 6c without the formation of 7. Zn/KOH in tetraglyme was shown to reduce the aryl halides 5b-c and thio-ether 6c to 7.
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  • 71
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    Helvetica Chimica Acta 71 (1988), S. 876-880 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Decarboxythamnolic AcidThe total synthesis of the meta-depside decarboxythamnolic ( = 3-[(3-formyl-2-4-dihydroxy-6-methyl-phenyl)oxy]-2-hydroxy-6-methoxy-4-methylbenzoic acid; 25) by the biomimetic condensation of the substituted β-orcinol units 9 and 22 is described.
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  • 72
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diets supplemented with astaxanthin and canthaxanthin, respectively, and a control diet without carotenoid additions, were fed to 1½-year-old Atlantic salmon (Salmo salar, L.) for one year. The integuments were investigated as to their quantitative and qualitative carotenoid composition. Astaxanthin and canthaxanthin deposited in the skin amounted to 20 and 14% of the total carotenoids only. Seventy % must be considered as metabolites of astaxanthin and canthaxanthin and 10% as basic xanthophylls also present in the control groups. Astaxanthin apparently underwent the following metabolic pathway: astaxanthin→idoxanthin→adonixanthin→zeaxanthin→zeaxanthin 5,6-epoxides. Reduction of the 4′-carbonyl group was stereospecific leading to the (4′R)-idoxanthin. Canthaxanthin was obviously converted to β,β-carotene via 4′-hydroxyechinenone, echinenone, and 4-hydroxy-β,β-carotene.
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  • 73
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    Helvetica Chimica Acta 71 (1988), S. 1210-1219 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four highly oxygenated polyphenols 1-4, have been isolated from the stem bark of Cordia goetzei Gürke (Boraginaceae) and their structures elucidated by a combination of one- and two-dimensional (including COLOC) NMR spectroscopic techniques, mass spectroscopy, and chemical methods. The first new compound, cordigone (1), is a tetrahydrofuran derivative and the second one, cordigol (2), a furobenzopyran derivative. The benzofurans 3 and 4 are orange pigments, responsible for the coloration of the stem bark of the tree. All four polyphenols are fungicidal against cladosporium cucumerinum.
    Additional Material: 3 Tab.
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  • 74
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    Helvetica Chimica Acta 71 (1988), S. 1191-1198 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Base-modified octanucleotides derived from d(G1-G2-A-A-T-T-C-C-) (11) but containing 8-aza-7-deaza-2′-deoxyguanosine (2) instead of 2′-deoxyguanosine (1) have been prepared by solid-phase synthesis employing P(III) chemistry. Isobutyrylation of 2, followed by 4, 4′-dimethoxytritylation and subsequent phosphitylation yielded the methyl or the cyanoethyl phosphoramidites 6a or 6b, respectively. They were used as building blocks in automated DNA synthesis. The resulting octanucleotides 12-14 containing 2 showed increased Tm values compared to the parent oligomer 11. The oligomers 11-14 were employed as sequence-specific probes in endo-deoxyribonuclease Eco RI oligonucleotide recognition. Whereas displacement of dG-2 (enzymic cleavage site of 11) abolished phosphodiester hydrolysis, replacement of dG-1 enhanced the cleavage rate compared to 11.
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  • 75
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title complexes have been derived from tricarbonyl [(1R,4S,5S,6R,)-C,5,6,C-η-(5,6-dimethylidenebicyclo[2.2.2]oct-2-ene)]iron (1.). The crystal structure and absoulte configuration of (+)-tricarbonyl (1S,2S,4R,5R,6S)-C,5,6,C,-η-(5,6-dimethylidenebicyclo[2.2.2]oct-2-yl p,-bromobenzoate)]iron ((+)-6) determined by X-ray diffrac-tion studies proved earlier attribution of the relative configuration (endo us. exo,) of the tricarbonyliron moieties in complexes 1 and 2 of 5,6-dimethylidenebicyclo[oct-2-ene. The structure of (+)-6 confirms the absolute configuration derived earlier from circular-dichroism spectra of 5,6-dimethylidenebicyclo[2.2.2]oct-2-yl esters and 5,6-dimethylidenebicyclo[2.2.2]octan-2-one.
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  • 76
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The [2 + 2] Photocycloaddition of 2-(trimethylsilyloxy)-1,3-butadiene to a number of 2-cycloalkenones proved to be quite a general reaction leading to good yields of the cycloadducts (Table). This finding is surprising since dienes, in general, are better known as quenchers of enone triplets rather than as photochemical reactants. Both the high substrate concentrations, which can be employed in these cycloadditions, and the remarkable regio and stereoselectivity of the processes qualify them as valuable for syntheses. In a first application, the photoproducts 1a, b were transformed in three steps into a viable precursor 4 of the pentalenolactone-G and -H antibiotics.
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  • 77
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexes trans-[PtXY(2] (X = H or Me; Y = OMe, OCHO, CO2H, and BH4; 2 = 2,11-bis{bis[3-(trifluoromethyl)phenyl]phosphinomethyl}benzo[c]phenanthrene) were prepared, and their decompositions to trans[PtHX(2)] were studied. Some binuclear hydrido-bridged complexes, e.g.[(2)HPt(μ-H)PtH(2)]+, were also obtained. The preparation of complexes trans-[PtHX(28)2] (X = H or Me, 28 = bis[3-(trifluoromethyl)phenyl]benzylphosphine) is also reported. The X-ray crystal structure of trans-[PtHCl1)] (1 = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene) was carried out.
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  • 78
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    Helvetica Chimica Acta 71 (1988), S. 1005-1010 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The near-infrared luminescence of singlet oxygen (1O2) has been measured in order to determine the efficiency of 1O2 quenching by two carotenoid compounds, β-carotene and canthaxanthin. 1H-Phenalen-1-one and rose bengal have been used as photosensitizers in those steady-state luminescence experiments. Stern-Volmer analysis of the 1O2 luminescence in solutions of CCl4 and CD3OD, containing different concentrations of the carotenoids, has shown a very efficient quenching by canthaxanthin. The rate constants are about a factor of 2 below the diffusion limited values for the given solvents, confirming earlier results in benzene. In comparison, the efficiency of 1O2 quenching by β-carotene is slightly lower than that by canthaxanthin in non-polar solvents and is reduced by an order of magnitude in CD3OD, due to the aggregation of this quencher.
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  • 79
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    Helvetica Chimica Acta 71 (1988), S. 1035-1041 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of 3-azetidinones with different N-substituents and their transformation to 3-ethylideneazetidines has been studied in relation with a projected synthesis of 3-ethylideneazetidine-2-carboxylic acid (= polyoximic acid; 1). The stable crystalline 3-azetidinone hydrochloride (18), obtained by hydrogenolysis of the known 1-(diphenylmethyl)-3-azetidenone (4), is described for the first time, From this key intermediate, 3-oxoazetidine-derived amides, exemplified by benzamide 12,urethanes (e.g. 17), and ureas (e.g. 20) can be prepared in good yield (Scheme 3). The olefination of 3-azetidinones with alkylidene(triphenyl)phosphoranes is a perparatively useful process only for derivatives with a pyramidal N-atom, e.g. the diphenylmethyl derivative 4, and not for the amide 12 or the urethane 17 (Scheme 4). 3-Alkylidene-azetidines with an amide N-atom should, therefore, be prepared by exchange of the N-substituent after the introduction of the double bond.
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  • 80
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption spectra, luminescence spectra, and luminescence lifetimes of the isomeric [M(bph)(bpy)] and [M(phpy)2] complexes M = Pt(II) or Pd(II), bph2- = 1,1′-biphenyl-2,2′-diyl dianion, phpy- = 2-phenylpyridine-2′-yl anion, and bpy = 2,2′-bipyridine have been investigated and compared with those of [M(bpy)2]2+ complexes and of the free protonated ligands H2bph, Hbpy+, and Hphpy. In the absorption spectra, the region below 320 mm is dominated by ligand-centered (LC) transitions, whereas metal-to-ligand charge transfer (MLCT) transitions are responsible for the bands present in the near UV/VIS region. The MLCT bands move to higher energies on replacing Pt with Pd and in going from [M(bph)(bpy)] to the [M(phpy)2] isomer. For the mixed-ligand complexes, evidence for both M → bph2- (at higher energies) and M → bpy bands is found. The structured luminescence observed at 77 K shows lifetimes of 4.0 and 1.1 μs for [Pt(phpy)2] and [Pt(bph)(bpy)], respectively, and 480 and 250 μs for the analogous Pd complexes. On the basis of the energy and lifetime data, the luminescence of the Pt(II) complexes is assigned to the lowest triplet MLCT excited state, whereas for the Pd complexes the luminescent state is thought to result from a mixture of MLCT and LC triplet levels.
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  • 81
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    Helvetica Chimica Acta 71 (1988), S. 1108-1115 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of tri-heteroleptic complex of Ru(II) with diimine ligands is describe. Ten compounds [Ru(R2bpy) (biq) (L)][PF6]2 (R = H, CH3); L = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (Me2bpy), 2,2′-bipyrimidine (bpm), 2,2′-biisoquinoline (biiq), 1,10-phenanthroline (phen), dipyrido[3,2-c:2′,3′-e]pyridazine (taphen), 2,2′-biquinoline (biq), 6,7-dihydrodipyrido[2,3-b:3,2-j][1,10]-phenanthroline (dinapy), 2-(2[pyridyl)quinoline (pq), 1-(2-pyrimidyl)pyrazole] (pzpm), 2,2′-biimidazole (H2biim) are characterized by elemental analysis, electronic and 1H-NMR spectroscopy. The relative photosustitution rates of biq in MeCN are given at three temperatures.
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  • 82
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    Helvetica Chimica Acta 71 (1988), S. 1177-1190 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal Generation and Reactions of (Benzylthio)-and (Arylthio)-Substituted Nitrile YlidesThermolysis of 4-(benzylthio)- and 4-(arylthio)-1,3-oxazol-5(2H)-ones 6, at 110-155° in the presence of dipolarophiles with activated C≡C, C=C, C=O, C=S, and N=N bonds, led to 5-membered cyclo-adducts and CO2 (cf. Schemes 3, 5-7). Heating 6a and 6c in the presence of ethyl propiolate yielded ethyl quinoline-3-carboxylate (19) and ethyl pyridine-3-carboxylate(22), respectively (cf. Scheme 8). These results are rationalized on the basis of the intermediate formation of thio-substituted nitrile ylides of type 7 (cf. Scheme 2), which undergo regioselective 1,3-dipolar cycloadditions with reactive dipolarophiles. In the absence of such a dipolarophile, the nitrile ylides isomerize via a [1,4]-H shift to give 2-aza-1,3-butadienes of type 20. The latter are trapped in a Diels-Alder reaction with ethyl propiolate (cf. Scheme 8).
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  • 83
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    Helvetica Chimica Acta 71 (1988), S. 1220-1227 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tautomerisation between proxibarbal (I) and the two diastereoisomers of valofan, IIX and IIY, was investigated in aqueous solutions, and various rate and equilibrium caonstants were calculated by compartmental analysis. The proportion of I at equilibrium was found to increase with pH, and indeed, the two equilibrium constants are linear functions of pH. In contrast, the equilibrium-concentratio ratio of IIY/IIX was close to 63:37 and remained constant in the pH range investigated. The rate constants were also determined as a function of temperature, allowing calculation of the tehrmolynamic parameters. Under physiological conditions, the difference in free energy favouring I vs. IIX and IIY is 6.7 and 5.4KJ · mol-1, respectively.
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  • 84
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthess of 6,7,8,9-tetramethylidene-2-oxabicyclo[3.2.2]nonan-3-one (12), 6,7,8,9-tetramethylidene-2-azatricyclo[3.2.2]nonan-3-one (13), and (1RS,5SR,6RS,7SR)-6,7-bis(chloromethyl)-8,9-dimethylidene-2-oxabicyclo-[3.2.2]nonan-3-one (14) are presented. The rate constants of the two successive Diels-Alder additions of a given dienophile to 12 and 13 were nearly the same. Lewis-acid-catalyzed Diels-Alder addition of methyl vinyl ketone to 14 gave adduct 39 with high regio- and stereoselectivity. Lewis acids isomerized 39 into(1RS,5RS,6SR,7SR,11RS)-6,7-bis(chloromethyl)-3-oxo-2-oxatricyclo[7.4.0.01,5]tridec-8-en-11-yl methyl ketone (40) whose structure was determined by single-crystal X-ray crystallography. Heating 39 with CsF/Cs2CO3 in DMF/HMPT gave (1RS,5RS,11RS)-6,7-dimethylidene-3-oxo-2-oxatricycl. [7.4.0.01,5]tridec-8-en-11-yl methyl ketone (42). The exocyclic butadiene moiety of triene 42 added to methyl propynoate and 2,3-didehydroanisole with good regioselectivity giving polysubstituted anthracenyl and naphthacenyl derivatives, respectively.
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  • 85
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparative Chromatographic Resolution of Synthetically Useful Cyclic AcetalsRacemic cyclic acetals derived from aldehydes and glycine, glycolic acid, thioglycolic acid, formylacetic acid, and acetoacetic acid (oxazolidinones 4-13, dioxolanones 14, 15, oxathiolanone 16, dioxinones 17-23) are resolved by preparative high-pressure liquid chromatography on silica gel coated with the polymer from N-acryloylphenylalanine ethyl ester (Chiraspher®). The separation factors α range from1,1 to 2,4. Use of a Prepbar®-chromatography system allows injection of several grams at a time. The enantiomeric acetals thus obtained are fully characterized. First application to amino-acid synthesis are mentioned.
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  • 86
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the electron-transfer reaction between racemic or optically active [Co(bamap)H2O]+ and optically active Fe2+ complexes of the three new pentadentate ligands bamap, alamp, and valmp has been investigated. All the reacting species show C2 symmetry. With respect to aquo-Fe2+, the reaction rate for the Fe2+ complexes is enhanced by a factor of 104 to 105, and the observed kΔΛ/kΛΛ ratio is 1.0, 1,9, and 1.2, respectively. In all cases where stereoselectivity is observed, the reaction is faster between the complexes of opposite absolute configuration (ΔΛ or ΛΔ) than between species with the same configuration (ΛΛ or ΔΔ). The stereoselectivity effects are discussed of the basis of the structure of the transition state and the interatomic distances between the two metal centers at the moment of electron transfer.
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  • 87
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    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 88
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    Helvetica Chimica Acta 71 (1988), S. 1399-1405 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Epoxidation of (-)-(1R,2R,4R)-2-endo-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-exo-yl acetate ((-)-5) followed by saponification afforded (+)-(1R,4R,5R,6R)-5,6-exo-epoxy-7-oxabicyclo[2.2.1]heptan-2-one ((+)-7). Reduction of (+)-7 with diisobutylaluminium hydride (DIBAH) gave (+)-1,3:2,5-dianhydroviburnitol ( = (+)-(1R,2R,3S,4R,6S)-4,7-dioxatricyclo[3.2.1.03,6]octan-2-ol; (+)-3). Hydride reductions of (±)-7 were less exo-face selective than reductions of bicyclo[2.2.1]heptan-2-one and its derivatives with NaBH4, AlH3, and LiAlH4 probably because of smaller steric hindrance to endo-face hydride attack when C(5) and C(6) of the bicyclo-[2.2.1]heptan-2-one are part of an exo oxirane ring.
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  • 89
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    Helvetica Chimica Acta 71 (1988), S. 1483-1490 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new phenlypropanoid glycoside has been isolated from the methanolic extract of the aerial parts of Stachys lavandulifolia (Lamiaceae), lavandulifolioside (1). On the basis of chemical and spectral data the structure of the new compound 1 has been elucidated as β-(3,4-dihydroxyphenyl)ethyl O-α-L-arabinopyranosyl-(1→2)-α-L-rhamnopyranosyl-(1→3)-4-O-caffeoyl-β-D-glucopyranoside.
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  • 90
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    Helvetica Chimica Acta 71 (1988), S. 1498-1501 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical cation of 2,3-diazabicyclo[2.2.2]oct-2-ene (1), generated by γ-rays in a CF2ClCFCl2 matrix, has been fully characterized by its hyperfine data with the use of ESR, ENDOR, and TRIPLE resonance spectroscopy. The isotropic coupling constants for \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{\relbar}\kern-4pt {.} }}$\end{document} are +3.14 mT for the two 14N Nuclei in the azo group, -0.336 mT for the two protons at the bridgehead C atoms, and +151 and +0.135 mT for the sets of four exo- and four endo-protons, respectively. MO calculations indicate that these values are consistent with an electron removal from an orbital represented by the antibonding combination (n_) of the lone-pair atomic orbitals at the two N atoms. The corresponding radical anion \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{\relbar}\kern-4pt {.} }}$\end{document} is persistent in fluid solution and its hyperfine data, combined with MO calculations, point to an electron uptake into the antibonding π orbital (π*) of the azo group. It is, thus, reasonable to classify \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{+}\kern-4pt {.} }}$\end{document} as a σ and \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\scriptstyle {{\relbar}\kern-4pt {.} }}$\end{document} as a π radical.
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  • 91
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient synthesis of chiral semicorrin ligands is described (see 6-9, Schemes 2 and 3). Both enantiomers are readily obtained in enantiomerically pure form starting either from D-or L-pyroglutamic acid (1). Semicorrins of this type possess several features that make them attractive ligands for enantioselective control of metal-catalyzed reactions. Their structure is characterized by C2 symmetry, a conformationally rigid ligand system, and two stereogenic centers adjacent to the coordination sphere. In a metal complex, the two substituents at the stereogenic centers shield the metal atom from two opposite directions and, therefore, are expected to have a pronounced effect on the stereochemical course of a reaction occurring in the coordination sphere. The structure of these two substituents can be easily modified in a variety of ways. A series of (semicorrinato)copper(II) complexes (see 10-14, Scheme 4) has been prepared, and in one case (14), the three-dimensional structure has been determined by X-ray analysis (Fig. 1).
    Additional Material: 2 Ill.
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  • 92
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solid-liquid phase-transfer glycosylation (KOH, tris[2-(2-methoxyethoxy)ethye]amine ( = TDA-1), MeCN) of pyrrolo[2,3-d]pyrimidines such as 3a and 3b with an equimolar amount of 5-O-[(1,1 -dimethylethyl)dimethylsilyl]-2,3-O-(1-methylethylidene)-α-D-ribofuranosyl chloride (1) [6] gave the protected β-D-nucleosides 4a and 4b, respectively, stereoselectively (Scheme). The β-D-anomer 2 [6] yielded the corresponding α-D-nucleosides 5a and 5b with traces of the β-D-compounds. The 6-substituted 7-deazapurine nucleosides 6a, 7a, and 8 were converted into tubercidin (10) or its α-D-anomer (11). Spin-lattice relaxation measurements of anomeric ribonucleosides revealed that T1 values of H—C(8) in the α-D-series are significantly increased compared to H—C(8) in the β-D-series while the opposite is true for T1 of H—C(1′). 15N-NMR data of 6-substituted 7-deazapurine D-ribofuranosides were assigned and compared with those of 2′-deoxy compounds. Furthermore, it was shown that 7-deaza-2′deoxyadenosine ( = 2′-deoxytubercidin; 12) is protonated at N(1), whereas the protonation site of 7-deaza-2′-deoxyguanosine (20) is N(3).
    Additional Material: 4 Ill.
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  • 93
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 94
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1616-1621 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Group-IV-A phthalocyanines with four crown ether substituents have been prepared from 4′,5′-dicyanobenzo(15-crown-5), 4′,5′-diiminoisoindolino(15-crown-5), or metal-free phthalocyanine and the corresponding metal salts. The axial ligands of dichloro[tetra(15-crown-5)phthalocyaninato]silicon or -tin have been converted into dihydroxy derivatives by hydrolysis in aqueous Et3N. The catalytic effect of H2O-free CaC12 in quinoline is used for the polycondensation of dihydroxysilicon-phthalocyanine to cofacially arrayed polymers. The thermal stability of group-IV-A-metal phthalocyanines is confirmed by the higher initial decomposition points (290-440°) compared to those of the corresponding transition-metal phthalocyanines.
    Additional Material: 2 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1659-1660 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O-Labelled carbon monoxide was prepared on the gram scale from enriched water and acetals of norborn-2-en-7-one(= bicyclo[2.2.1]hept-2-en-7-one) in almost quantitative yields and without isotopic dilution.
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  • 96
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dimethyl acetals 4 of (E)-2,4-pentadienal and of (E,E)- and (E,Z)-2,4-hexadienals undergo regio- and stereospecific cycloaddition reactions with in-situ-generated acylnitroso dienophiles 5a and 5b, leading thereby to the corresponding dihydrooxazines 7a-d and 8c-d. cis-Glycolization of these latter adducts stereospecifically gave the dihydro derivatives 9a-d and 10d which, after sequential hydrogenolysis, deacetalization, and instant cyclization, led to the aminodeoxyribose derivatives 17a, 17f, and 18, and to the amino-dideoxyallose compounds 17c and 17h. These piperidino-deoxysugar derivatives exhibit a strong anomeric effect, i.e. OH—C(1) is always axial, which is explained in terms of a nN(π)-σ*(C—OH) orbital compression, as compared to the less pronounced one in the more classical pyranose series.
    Additional Material: 8 Tab.
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  • 97
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1681-1688 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3 Dipolar Cycloaddition of Aromatic Nitrile Ylides and Nitrile Oxides with Cyanogen and DiazocyanidesNitril ylides 2 generated from the imidoyl chlorides 1 react with cyanogen and aryldiazocyanides to 2,5(4)-dia-ryl-1H-imidazole-4(5)-carbonitriles 3a,b or 5(4)-(arylazo)-2,4(5)-diaryl-1H-imidazoles 4a and 2,3,5-triaryl-2,3-dihydro-1H-1,2,4-triazole-1-carbonitriles 5a-f, respectively (Scheme 1). Reactions of benzonitrile oxides 7 with these dipolarophiles lead to 3,3′-diaryl-5,5′-bi[1,2,4]oxadiazoles 8a-c or 3-aryl-5-(arylazo)-1,2,4-oxadiazoles 9a-j (Scheme 2).
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  • 98
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses of the Spermidine Alkaloids (±)-Inandenin-10-ol, Inandenin-10-one, and (±)-OncinotineNew syntheses of the title compounds using two-ring-enlargement reactions are described. Starting from the aldehyde 1, the corresponding 4′-aza derivative 15 could be obtained by reductive amination with the appropriate and protected spermidine derivative 14 (Scheme 4). Enlargement of the carbocyclic ring in 15 by five members gave, after further transformations, the hydroxylactam 18. Transamidation of 18, the second ring-enlargement step, led to (±)-inandenin-10-ol (7;22.9% overall yield) and, after oxidation, to inandenin-10-one (8; 22.5%, overall yield). (±)-Oncinotine 6 was synthesized by two pathways (Scheme 6): protection of the terminal NH2 group by treatment with the Nefkens reagent and replacement of the OH group by Cl gave 24, which by thermal transamidation followed by direct ring closure led to the oncinotine derivative 26. The same intermediate could be obtained in higher yield via 28 by oxidation and protection of 18 followed by transamidation and reductive ring closure. Treatment of 26 with hydrazine finally gave (±)-oncinotine 6 in 15.9% overall yield.
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  • 99
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 1824-1839 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diastereoselective Alkylation 3-Aminobutanoic Acid in the 2-PositionThe enantiomerically pure 3-aminobutanoic acids (R)- and (S)-6 are readily available by preparative HPLC separation of the two diastereoisomers 5 obtained from addition of (S)-phenethylamine to methyl crotonate and subsequent hydrogenolysis (Scheme 2). (S)-Methyl 3-(benzoylamino) butanoate ((S)-3) is also available by enzymatic kinetic resolution with pig-liver esterase. The N-benzyl- and N- benzyloxycarbonyl derivatives rac3,8, and 9 of 3-aminobutanoates are doubly deprotonated with LDA and alkylated or aminated in high selectivity (17 examples, relative topicity like; see Tables 1 and 2). The configuration of three of the products is assigned (Schemes 4-6), and in four cases, the free α-substituted β-amino acid is prepared by acidic hydrolysis (see Table 3). It is shown that the doubly lithiated β-amino-acid derivative is solubilized, and its reactivity may be strongly influenced by the presence of 3 equiv. of LiCl.
    Additional Material: 3 Tab.
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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