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  • Digitale Medien  (6.530)
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  • Digitale Medien  (6.530)
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  • 2025-2025
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  • 2015-2019
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  • 1
    Digitale Medien
    Digitale Medien
    Prenatal development of the cat thyroid: immunohistochemical demonstration of calcitonin in the “C” cells (1987)
    Springer
    Anatomy and embryology 177 (1987), S. 51-54 
    Details
    ISSN: 1432-0568
    Schlagwort(e): Development ; Thyroid “C” cell ; Cat ; Immunohistochemistry ; Calcitonin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The presence of calcitonin in the cat thyroid was studied immunohistochemically in a series of gland development. the first positive cells are to be found on the 38th day of gestation, i.e. 1–2 days after level nine of ontogenetic development has been reached. The cytoplasm of these cells form only a narrow border round the nucleus. With advancing development the bumber of calcitonin-positive and its amount increases. From approximately the 50th day of prenatal development, the initially diffusely scattered, solitary calcitonin-positive cells are gradually replaced by groups of cells, which begin to occupy a characteristic position in relation to the follicular epithelium. The largest quantity of calcitonin-positive cells is found in foetuses about to be born. In non-pregnant adult cats, the incidence of immunohistochemically calcitonin-reactive cell is more sporadic and their distribution in the lobes of the thyroid is uneven.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00325289
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  • 2
    Digitale Medien
    Digitale Medien
    An investigation of pulp capillaries and tight junctions between odontoblasts in cats (1987)
    Springer
    Anatomy and embryology 177 (1987), S. 131-138 
    Details
    ISSN: 1432-0568
    Schlagwort(e): Capillaries ; Tooth pulp ; Tight junctions ; Odontoblasts ; Ultrastructure ; Mineralisation ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The relative roles of capillaries and odontoblasts in the process of dentinogenesis and in pulp reactions to trauma and pathology are not clear. Contributing to the problem is the paucity of information on odontoblast —capillary relationships and tight junctions between odontoblasts. Using light microscopy the capillaries have now been examined in semithin transverse sections of perfusion fixed teeth at different positions in the long axis from the apical foramina to the pulp horns. Odontoblastic capillaries were prominent in the coronal and middle regions of canines and present at the same levels of incisors. In the pulp horns and just coronal to the pulp horns capillaries were all subodontoblastic but near the apex there were also a few odontoblastic capillary profiles. Transmission electron microscopy on ultrathin sections revealed that a high proportion of middle and coronal odontoblastic capillary profiles were fenestrated but subodontoblastic profiles coronal to the pulp horns were the most fenestrated. In a search for tight junctions in ultrathin sections some typical strands were observed between odontoblasts. The difficult of obtaining the latter evidence was explained by the cellular arrangement of the odontoblasts which differed markedly from an ideal parallel, apically coplanar arrangement. The results question the possibility that there is a direct exchange of materials between pulp capillaries and dentine in teeth of limited growth and provide a baseline for future experiments to test the permeability of the odontoblast layer.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00572537
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  • 3
    Digitale Medien
    Digitale Medien
    Structural alterations in the spinal cord during progressive communicating syringomyelia. An experimental study in the cat (1987)
    Springer
    Acta neuropathologica 72 (1987), S. 248-255 
    Details
    ISSN: 1432-0533
    Schlagwort(e): Experimental communicating syringomyelia ; Ependyma ; Spinal cord ; Cat ; Scanning electron microscope
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary A hydrocephalic-hydromyelic condition was induced in adult cats by causing the closure of the lateral apertures with intracisternal injections of kaolin. After displaying the symptoms characteristic of increased intracranial pressure, which lasted about 10–14 days but varied somewhat in intensity from animal to animal, the cats recovered. From approximately the 2nd post-operative week onward, a distended central canal was revealed by ventriculography; subsequently cavities developed in the tissue of the cord that communicated with the canal. Most cavities were located dorsal to the canal. The surfaces of the distended canal and the cavities showed that in ventral areas the ependyma streched but remained intact, whereas in dorsal areas it ruptured, exposing the nerve fibers to the cerebrospinal fluid (CSF). In cats which had been hydrocephalic for up to 2 years the walls of the cavities were covered by gliotic scar tissue; the nerve fibers were no longer exposed directly to the CSF.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00691097
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  • 4
    Digitale Medien
    Digitale Medien
    Vestibular and optokinetic eye movements evoked in the cat by rotation about a tilted axis (1987)
    Springer
    Experimental brain research 66 (1987), S. 522-532 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Off-vertical-axis rotation ; Eye movements ; Vestibulo-ocular reflex ; Optokinetic nystagmus ; Otoliths ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Horizontal and vertical eye movements were recorded from cats in response to either a) off-vertical axis rotation (OVAR) at a range of velocities (5–72 deg/s) and a range of tilts (0–60 deg) or b) horizontal (with respect to the cat) optokinetic stimulation (10–80 deg/s), also around a range of tilted axes (0–60 deg). The responses to stopping either of these stimuli were also measured: post-rotatory nystagmus (PRN) following actual rotation, and optokinetic after nystagmus (OKAN) following optokinetic stimulation. The response found during OVAR was a nystagmus with a bias slow-phase velocity that was sinusoidally modulated. The bias was dependent on the tilt and reached 50% of its maximum velocity (maximum was 73±23% of the table velocity) at a tilt of 16 deg. The phase of modulation in horizontal eye velocity bore no consistent relation to the angular rotation. The amplitude of this modulation was roughly correlated with the bias with a slope of 0.13 (deg/s) modulation/(deg/s) bias velocity. There was also a low-velocity vertical bias with the slow-phases upwardly directed. The vertical bias was also modulated and the amplitude depended on the bias velocity (0.27 (deg/s) modulation/ (deg/s) bias velocity). When separated from the canal dependent response, the build up of the OVAR response had a time constant of 5.0±0.8 s. Following OVAR there was no decline in the time constant of PRN which remained at the value measured during earth-vertical axis rotation (EVAR) (6.3±2 s). The peak amplitude of PRN was reduced, dependent on the tilt, reaching only 20% of its EVAR value for a tilt of 20 deg. When a measurable PRN was found, it was accompanied by a slowly-emerging vertical component (time constant 5.4±2s) the effect of which was to vector the PRN accurately onto the earth horizontal. OKN measured about a tilted axis showed no differences in magnitude or direction from EVAR OKN even for tilts as large as 60 deg. OKAN following optokinetic stimulation around a tilted axis appeared normal in the horizontal plane (with respect to the animal) but was accompanied by a slowly emerging (time constant 4.1±2 s) vertical component, the effect of which was to vector the overall OKAN response onto the earth horizontal for tilts less than 20 deg. These results are compared with data from monkey and man and discussed in terms of the involvement of the velocity storage mechanism.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00270685
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  • 5
    Digitale Medien
    Digitale Medien
    Expression of “retinal” contrast gain control by neurons of the cat's lateral geniculate nucleus (1987)
    Springer
    Experimental brain research 66 (1987), S. 589-596 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Contrast gain control ; Lateral geniculate nucleus ; Temporal frequency ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary This paper describes the temporal tuning of cells in the lateral geniculate nucleus of the cat (27 X cells, 51 Y cells) and how this changes with stimulus contrast. Drifting sinusoidal gratings of optimal spatial frequency were presented at 7 temporal frequencies (0.5, 1, 2, 4, 8,16 and 32 Hz) and 4 contrasts (10, 20, 40, 80%). For some cells response growth at all temporal frequencies was proportional to changes in contrast. Thus, their temporal tuning functions, on log-log axes, were displaced vertically with increasing contrast. This shift also largely characterizes the response to low temporal frequencies of the other neurons studied. For these other cells, however, responses to high temporal frequencies grew disproportionately large with increasing contrast generally causing their tuning functions to change shape. Typically the peaks of these functions shifted to higher frequencies at higher contrasts. Most of the X cells studied displayed behavior of the first type, while Y cells usually followed the second pattern. This qualitative impression was confirmed quantitatively. Cubic spline functions were fit to the temporal tuning functions obtained at different contrast levels and the peaks of the curves were extracted. X and Y cells preferred similar temporal frequencies at low contrast levels (X mean=8.1 Hz; Y mean=8.4 Hz) but Y cell values were significantly higher at higher contrasts (80%) (X mean= 12.0 Hz; Y mean=16.8 Hz). These contrast-dependent changes in the temporal characteristics of geniculate cells resemble those described for retinal ganglion cells by Shapley and Victor (1978 and subsequent). Thus, the gain control behavior of geniculate cells probably reflects the temporal properties of their retinal inputs with relatively little modification.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00270692
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  • 6
    Digitale Medien
    Digitale Medien
    Reduced binocularity in the noradrenaline-infused striate cortex of acutely anesthetized and paralyzed, otherwise normal cats (1987)
    Springer
    Experimental brain research 68 (1987), S. 593-605 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Ocular dominance ; Plasticity ; Noradrenaline ; Cat ; Visual cortex ; Squint effect
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary In anesthetized and paralyzed cats, the normal alignment of the visual axes is disturbed by paralysis of the eye muscles. Thus, the separation between paired receptive fields of binocular cells in visual cortex is increased (paralysis squint). This increased separation is normally tolerated by the majority of visuocortical cells, about 80% of them being binocularly driven (Hubel and Wiesel 1962). It was shown previously that neuronal plasticity in visual cortex can be enhanced in both normal adult cats (Kasamatsu et al. 1979) and kittens (Kuppermann and Kasamatsu 1984) by intracortical microinfusion of noradrenaline (NA). In the present study we tested whether the usual range of disparity produced by the paralysis squint is sufficient to induce ocular dominance changes in visual cortex of adult cats when the neuronal plasticity is enhanced by NA. NA was continuously infused into visual cortex throughout the experiments. The period of the paralysis squint varied from experiment to experiment between 9 and 47 h. We found: (1) These short periods were sufficient to produce a marked reduction in the proportion of binocular cells. (2) The proportion decreased linearly with increasing the duration of the squint period at a rate of 0.17 per 10 h up to about 22 h. (3) At longer durations the average binocularity remained at about 0.30 and could not be further reduced in the present paradigm. (4) The binocularity seemed to decrease with increasing separation of paired receptive fields. (5) Binocularity increased again toward the normal value after optical correction of the squint. (6) The amount of increased binocularity was linearly correlated with the duration of the period after the squint correction. (7) The binocularity increased at a rate of 0.18 per 10 h, reaching the normal value in less than 30 h. We thus concluded that if visuocortical plasticity is maintained at a high level through the continuous infusion of NA it is possible to change the ocular dominance distribution in the mature visual cortex by manipulations of the alignment of the visual axes even in the acutely anesthetized and paralyzed condition.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00249802
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  • 7
    Digitale Medien
    Digitale Medien
    Receptive field properties of cells in area 19 of the cat (1987)
    Springer
    Experimental brain research 65 (1987), S. 549-558 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Area 19 ; Sinusoidal grating ; End-zone inhibition ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary We have recorded extracellularly from single cells in area 19 of the cat for the purpose of providing a quantitative description of response characteristics. A prominent feature of this area is a high incidence of cells that are end-stopped. Drifting sinusoidal gratings were used to determine spatial and temporal characteristics of the discharge region. In addition, we have conducted independent tests to characterize end zones of receptive fields. When a grating patch was used to stimulate the discharge region alone, all of the cells showed a band-pass spatial frequency tuning characteristic. The optimal spatial frequency ranged from 0.1 to 1.13 cycles/deg, and the distribution had a peak at 0.4 cycles/deg. The bandwidth at half peak amplitude ranged widely from 0.7 to 3.3 octaves (mean 2.0 octaves). When gratings were also presented to the end zones, responses to stimulation of the central region were suppressed. The surround was phase-insensitive in that the relative phase between the grating in the two regions generally did not affect the strength of the suppression. To determine spatial characteristics of the end-zone inhibition, the spatial frequency of the end-zone grating was changed while that for the central pattern was fixed. All cells showed a bandpass characteristic for end-zone inhibition, but in each case, the tuning width was broader than that for excitation. The mean spatial frequency bandwidth of end-zone inhibition was 2.7 octaves. The peak of the inhibition generally coincided with the peak of the excitatory spatial frequency tuning of the discharge center. Considered together, these results show that neurons in area 19 share common properties with those in areas 17 and 18, but they exhibit phase-insensitve end-zone inhibition more frequently.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00235978
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  • 8
    Digitale Medien
    Digitale Medien
    Automatic postural responses in the cat: responses of proximal and distal hindlimb muscles to drop of support from a single hind- or forelimb (1987)
    Springer
    Experimental brain research 65 (1987), S. 527-537 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Postural reflexes ; Unexpected postural perturbations ; Electromyographic activity ; Hindlimb muscles ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Cats respond to drop of the support from beneath a single limb with the “diagonal stance response” (Coulmance et al. 1979). They load the limbs on the diagonal opposite to the one containing the dropped limb and unload the third supporting limb in the diagonal containing the dropped limb. Characteristic biomechanical delays in limb motion and in vertical force changes imposed upon the limbs are observed. These delays range from 30 to 45 ms, depending upon the location of the dropped limb. This study describes the kinematics of the “diagonal stance response” and the activation of selected agonist-antagonist muscle pairs acting on the joints of the hindlimb during the response. Proximal and distal hindlimb muscles respond to perturbations in groups that are appropriate to the vertical forces imposed upon the limb. When the hindlimb containing the recording electrodes is loaded by drop of the contralateral hindlimb or the ipsilateral forelimb medium latency (25–45 ms) EMG responses occur in the extensors. This response serves to stiffen the limb against the increased vertical force of loading. A similar response is observed when the hindlimb is reloaded after being dropped. In this case, however, short latency responses precede the medium latency responses in muscles that are passively stretched by the limb drop. When drop of the diagonal forelimb unloads the hindlimb containing the electrodes, medium latency responses are observed in the distal hindlimb flexors, which indicates that the unloading is evoked in part by active lifting of the limb. In most cases, the medium latency responses precede or are coincident with the changes in force imposed on the limb, suggesting that the observed responses are centrally programmed.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00235976
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  • 9
    Digitale Medien
    Digitale Medien
    Neuronal dynamics in the visual corticothalamic pathway revealed through binocular rivalry (1987)
    Springer
    Experimental brain research 66 (1987), S. 10-20 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Corticothalamic feedback ; Binocular rivalry ; Lateral geniculate ; Vision ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Single unit activity was recorded from principal cells in the A-laminae of the cat dorsal lateral geniculate nucleus (dLGN). A steady state pattern of afferent activation was induced by presenting a continuously drifting square wave grating of constant spatial frequency to the eye (the dominant eye) that provided the excitatory input to the recorded cell. Intermittently, a second grating stimulus was presented to the other, nondominant, eye. In most neurones nondominant eye stimulation led to inhibition of relay cell responses. The latency of this suppressive effect was unusually long (up to 1 s) and its intensity and duration depended critically on the similarity between the gratings that were presented to the two eyes. Typically suppression was strongest when the gratings differed in orientation, direction of movement and contrast and when the nondominant eye stimulus was moving rather than stationary. Ablation of visual cortex abolished these long latency and feature-dependent interferences. We conclude that the visual cortex and the corticothalamic projections are involved in the mediation of these interocular interactions. We interpret our results as support for the hypothesis that corticothalamic feedback modifies thalamic transmission as a function of the congruency between ongoing cortical activation patterns and afferent retinal signals.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00236196
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  • 10
    Digitale Medien
    Digitale Medien
    Responses of bradykinin sensitive tooth-pulp driven neurons in cat cerebral cortex (1987)
    Springer
    Experimental brain research 66 (1987), S. 435-439 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Bradykinin ; Tooth-pulp ; Cortical neuron ; Coronal gyrus ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The properties of single cortical neurons responding to electrical stimulation of the tooth-pulp and to intrapulpal application of bradykinin were studied in the cat. The activities of tooth-pulp driven neurons (TPNs) were recorded from the middle and anterior parts of the coronal gyrus of the cerebral cortex. Bradykinin-sensitive tooth-pulp driven neurons (BK-TPNs) were located in layer IV of area 3b of the anterior part of the coronal gyrus. These neurons had a large cutaneous oro-facial receptive field and received a nociceptive input from the facial skin as well as from the tooth-pulp. The BK-TPNs had a higher threshold and longer latency to electrical stimulation than TPNs insensitive to bradykinin (non BK-TPNs). These findings suggest that BK-TPNs in this cortical area may be involved in sensory processing of noxious information from trigeminal regions.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00243318
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  • 11
    Digitale Medien
    Digitale Medien
    Responses of cat preoptic neurons to stimulation of the medial frontal cortex and the medial basal hypothalamus (1987)
    Springer
    Experimental brain research 66 (1987), S. 555-564 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Preoptic region ; Frontal cortex ; Medial basal hypothalamus ; Electrophysiology ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Responses of single preoptic neurons to electrical stimulation of the medial frontal cortex, the mediobasal hypothalamus (MBH) and the medial forebrain bundle (MFB) were recorded in anaesthetised cats. Single pulse stimulation of the medial frontal cortex orthodromically drove 96 otherwise quiescent preoptic neurons, which were found more frequently in the dorsal preoptic region, inhibited 53% of the spontaneously active preoptic neurons and excited 16%. Testing of cortically influenced preoptic neurons with MBH or MFB stimulation resulted in antidromic invasion of 6% (MBH) and 9% (MFB). Convergence of orthodromic inputs from medial frontal cortex and MBH was detected in 78% of spontaneously active preoptic neurons, and three-way convergence including input from MFB was noted in 17% of neurons tested with all stimulators. Some cortex-responsive neurons were found to also respond to vaginal or anal probing, paw squeezing and haemorrhage. The role of this input to the preoptic region from medial frontal cortex remains to be elucidated, but may include neuroendocrine, behavioural and homeostatic functions.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00270688
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  • 12
    Digitale Medien
    Digitale Medien
    Branching cortical neurons in cat which project to the colliculi and to the pons: a retrograde fluorescent double-labeling study (1987)
    Springer
    Experimental brain research 67 (1987), S. 1-15 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Corticopontine collaterals ; Corticotectal neurons ; Cortex ; Cat ; Fluorescent tracers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The fluorescent double-labeling technique has been used to determine whether the corticopontine and the corticotectal fibers in the cat are derived from two different sets of neurons or whether they are derived from branching neurons which distribute collaterals to the pontine grey and the colliculi. After unilateral DY.2HCl injections in the pontine grey and FB injections in the ipsilateral colliculi, large numbers of FB-DY.2HCl double-labeled neurons were present in the cortex of the ipsilateral hemisphere. However, the labeled neurons in its rostral part may have represented pyramidal tract neurons which were labeled retrogradely because their fibers descended through the DY.2HCl injection area. Therefore, also DY.2HCl injections were made in the pyramid (i.e. caudal to the pons) and the cortical pyramidal tract area, containing the retrograde DY.2HCl-labeled neurons, was delineated. In the rest of the experiments only the DY.2HCl-labeled neurons in the caudal two thirds of the hemisphere (outside the pyramidal tract area) were taken into account because only these neurons could, with confidence, be regarded as corticopontine neurons. In some anterograde HRP transport experiments the trajectories of the corticotectal and the corticopontine fibers were visualized. On the basis of the findings the DY.2HCl injections in the pontine grey were placed such that they could not involve any of the corticotectal fibers passing from the cerebral peduncle to the colliculi. Thus artifactual doublelabeling of cortical neurons was avoided. However, also under these circumstances many double-labeled neurons were present in the caudal two thirds of the hemisphere. This led to the conclusion that in the cat a large proportion of the corticopontine neurons in the caudal two thirds of the hemisphere represent branching neurons which also distribute collaterals to the colliculi. The parietal (anterior part of the lateral gyrus, middle and posterior suprasylvian gyri) and the cingulate areas together contained three quarters of all labeled corticopontine neurons outside the pyramidal tract area. In the parietal areas roughly 25% of them were double-labeled and in the cingulate area 14%. However, in the visual areas 18 and 19 a much larger percentage (30–60%) was doublelabeled. In a recent study from our laboratory it was found that in the cat the pyramidal tract fibers distribute an abundance of collaterals to the pontine grey. Therefore, a large proportion of all corticopontine connections in this species appear to be established by branching neurons which also distribute fibers to other cell groups in the brain stem and the spinal cord.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00269447
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  • 13
    Digitale Medien
    Digitale Medien
    Detection latencies of X and Y type cells of the cat's dorsal lateral geniculate nucleus (1987)
    Springer
    Experimental brain research 65 (1987), S. 703-706 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Cat ; Electrophysiology ; Lateral geniculate cells ; Signal detection ; Visual latencies
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The latencies of visually-evoked responses from X- and Y-type neurons of the cat's dorsal lateral geniculate nucleus were measured in a manner that takes account of the inherent variability of discharge in these cells. Latencies measured in this way vary from trial to trial in one cell (and also between cells) by tens to as much as hundreds of milliseconds. This variability in the time for generation of reliable responses suggests that the much emphasized conduction advantage of the Y pathway plays a minor role in the detection of visual stimuli by the cat.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00235998
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  • 14
    Digitale Medien
    Digitale Medien
    Convergent inputs from articular, cutaneous and muscle receptors onto ascending tract cells in the cat spinal cord (1987)
    Springer
    Experimental brain research 66 (1987), S. 479-488 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Joint ; Spinal cord ; Pain ; Ascending tracts ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary 1.Responses were recorded from 160 ascending tract cells in segments L4 to L6 of the spinal cord in chloralose anaesthetized, spinalized cats. The tract cells were identified by antidromic activation following stimulation of pathways in the lateral and ventral funiculi at the level of the spinal cord transection at the thoracolumbar junction. Axonal conduction velocities ranged from 9 to 114 m/s. 2. A sample of 152 of the neurones examined could be subdivided according to the distribution of their receptive fields into 49 cells activated just from receptors located in skin (“s” cells), 17 neurones excited by receptors in deep tissues (“d” cells), 15 units with a convergent input from receptors in skin and deep tissues (“sd” cells), and 25 neurones with a convergent input from the knee joint and either skin (“sj” cells), deep tissues (“dj” cells) or both (“sdj” cells). No receptive fields could be demonstrated for the remaining 46 neurones. 3. “S” and “sj” cells were found almost exclusively in the dorsal horn, whereas many “d”, “sd”, “sdj” and “dj” units were in the ventral horn. Almost all of the cells that lacked receptive fields were in the ventral horn or intermediate grey. 4. Ninety-one of 158 cells (56%) demonstrated no background activity. Of these, 43 cells (27%) lacked receptive fields. Many of the silent neurones were in the ventral horn, but some were in the dorsal horn. Of 25 cells having knee joint input, 18 (72%) had background activity. 5. All of the neurones that had a receptive field in the knee joint also had a convergent input from receptors in other tissues. In 3 cases, there was a receptive field in the skin over the foot (“sj” cells). For 16 cells, receptive fields included not only the knee joint but also skin and deep tissue (“sdj” cells). Usually, the cutaneous receptive field was near the knee joint, but sometimes it was remote, such as on the foot. The deep receptive fields were chiefly in the muscles of the thigh and/or leg. For 6 “dj” cells, the receptive fields included not only the knee joint but also deep fields like those of “sdj” cells. 6. Cutaneous receptive fields were classified as “low threshold” (cells excited best by innocuous intensities of mechanical stimulation), “wide dynamic range” (cells activated by weak mechanical stimuli, but the best responses were to noxious stimuli) or high threshold (innocuous stimuli had little effect, but noxious mechanical stimuli produced a vigorous discharge). Similarly, stimulation of the knee joint with weak mechanical stimuli could excite some neurones, while others could be activated by weak or strong articular stimuli but were excited best by noxious stimuli, and still other neurones were activated by knee joint stimuli only if the intensity was noxious. 7. In several instances, contralateral receptive fields were noted. These were generally in deep tissue or in the knee joint. 8. It was concluded that many of the responses to articular stimulation of the spinal cord ascending tract cells examined in this study could have been mediated by the fine afferent fibres that supply the knee joint. Although further work will be required to determine which particular ascending tracts transmit nociceptive information concerning the knee joint, it can be proposed that many of the responses demonstrated here were likely to play a role in either joint pain of in triggering responses associated with joint pain.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00270680
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  • 15
    Digitale Medien
    Digitale Medien
    Lateral excitation in the cat lateral geniculate nucleus (1987)
    Springer
    Experimental brain research 67 (1987), S. 291-298 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Lateral inhibition ; Lateral excitation ; Cat ; Dorsal lateral geniculate nucleus ; GABA ; Silent synapses
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Visual responses were elicited by global phase reversal stimuli in cells of the cat dorsal lateral geniculate nucleus (dLGN) after small retinal lesions had been centered on each receptive field. After acute lesions of different sizes exclusively lateral inhibition was found. When GABAergic inhibition was blocked by continuous microiontophoretic application of bicuculline lateral excitation emerged in dLGN cells partially deafferented by small and medium size acute retinal lesions, but not in those affected by large lesions. This indicates the presence of excitatory retinal inputs at the periphery of the dLGN cell dendrites which are normally suppressed by strong, long-ranging lateral inhibitory processes. After chronic deafferentation, the remaining excitatory inputs increase in effectiveness and lateral excitation is seen without blockade of inhibition. The maximal lateral spread of excitation (300 μm) in the dLGN is distinctly smaller than the extent of lateral inhibition (1000 μm).
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00248550
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  • 16
    Digitale Medien
    Digitale Medien
    Automatic postural responses in the cat: responses of distal hindlimb muscles to paired vertical perturbations of stance (1987)
    Springer
    Experimental brain research 68 (1987), S. 477-490 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Postural reflexes ; Unexpected postural perturbations ; Electromyographic activity ; Motor control ; Hindlimb muscles ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The active components of the quadrupedal diagonal stance response to rapid removal of the support from beneath a single limb were studied in cats to further define the mechanisms that trigger and generate the response. We recorded EMG activity from lateral gastrocnemius and tibialis anterior muscles in awake, behaving cats while they stood on an hydraulic posture platform. By dropping the support from beneath a single limb, we evoked the diagonal stance response, with its characteristic changes in vertical force and EMG patterns. As the animal responded to this drop, a second perturbation of posture was then presented at intervals of 10 to 100 ms following the first. This second perturbation, which consisted of dropping the support from beneath the two limbs that were loaded as a result of the initial limb drop, made the first response biomechanically inappropriate. The EMG responses observed in both muscles during paired perturbations were triggered by the somatosensory events related to the perturbations. Muscle responses that were appropriate for the first perturbation always occurred with amplitudes and latencies similar to control trials. This was true even when the second perturbation occurred 10–20 ms after the first, that is, when this perturbation either preceded or was coincident with the response to the initial limb drop. The EMG responses that were normally associated with the second perturbation were delayed and/or reduced in amplitude when the time interval between perturbations was short. As the inter-perturbation interval was lengthened beyond 60–100 ms, however, EMG responses to the second perturbation were unaffected by the occurrence of the first perturbation. When the hindlimb containing the recording electrodes was dropped as part of the second perturbation, a myotatic latency response was observed in tibialis anterior. The amplitude of this response to the second perturbation was greater than controls when this displacement was presented during the period between initiation of the first perturbation and execution of the response to it. When the second displacement was presented after execution of the first response began, the amplitude of the myotatic response was reduced below control levels. While the results do not preclude the possibility that these “automatic” postural responses are segmental or suprasegmental reflexes, they support the hypothesis that the active component of the response to drop of the support beneath a single limb is centrally programmed and that the appropriate response can be riggered very rapidly by the somatosensory information signalling the perturbation.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00249792
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  • 17
    Digitale Medien
    Digitale Medien
    The pattern of ocular dominance columns in flat-mounts of the cat visual cortex (1987)
    Springer
    Experimental brain research 68 (1987), S. 661-666 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Visual cortex ; Ocular dominance columns ; Flat-mount ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Ocular dominance (OD) columns in the cat visual cortex were visualized with autoradiography after intravitreal injection of (3H)proline. Extending previous studies, a flat-mount technique was applied that enabled the analysis of the distribution of label throughout extensive regions of the visual cortex without requiring reconstructions from serial sections. OD-columns were confined to layer IV and consisted of isolated patches and short bands. The latter were parallel to each other and regularly spaced, the main trajectory being orthogonal to the 17/18 border. This pattern of the geniculo-cortical terminals was similar in the hemispheres ipsi- and contralateral to the injected eye. The mean periodicities of the OD-bands were virtually identical in the two hemispheres of the same animal: 850 μm and 830 μm in cat D1 and 770 μm and 800 μm in cat D2. However, the ipsilateral OD-columns appeared smaller, more heavily labeled and more sharply delineated than the contralateral columns.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00249809
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  • 18
    Digitale Medien
    Digitale Medien
    Enhancement of the responses of ascending tract cells in the cat spinal cord by acute inflammation of the knee joint (1987)
    Springer
    Experimental brain research 66 (1987), S. 489-499 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Joint ; Pain ; Inflammation ; Spinal cord ; Ascending tracts ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary 1. Recordings were made from 16 ascending tract cells in the spinal cords of anaesthetized, spinalized cats before and after an acute arthritis was produced by injection of kaolin and carrageenan into the knee joint. 2. The responses tested routinely were to passive flexion of the knee, an innocuous movement. In some cases, responses to other movements were also tested, and changes in background discharge rates were monitored. 3. Control recordings for a period of 1 h or in 3 cases of 3 h indicated that the responses to flexion were reasonably stationary. 4. Four tract cells that initially showed little or no response to flexion of the knee joint developed large responses within 1 to 2 h after inflammation of the joint. 5. Another 9 cells were tested that had responses to flexion of the knee joint prior to inflammation. In 6 cases, inflammation produced enhanced static or transient responses. In 2 cases, the effect of flexion was initially inhibitory or variable, but after inflammation these cells showed large excitatory responses. In the other case, inflammation had no effect. Background discharges were increased by inflammation in 6 of these 9 cells. 6. The effect of inflammation of the knee joint was tested on 3 tract cells that had no clearly defined receptive field in the knee. In 1 case, a response developed to knee flexion after acute inflammation was produced. In the other 2 cases, there were initially responses to knee flexion, but these were unchanged by inflammation. 7. Two of the cells tested had bilateral receptive fields in or around the knee joints. Inflammation of one knee joint enhanced the responses to flexion of the same but not of the contralateral knee in one case but greatly increased the responses to flexion of both knees in the other case. 8. Injections of prostaglandin (PGE2) caused an enhancement of the responses to knee flexion beyond that caused by inflammation in 5 of 7 cases. One cell whose responses to flexion of the knee were unaffected by inflammation showed inhibitory responses to prostaglandin injections into the inflamed knee joint. 9. The effects of inflammation on the responses of ascending tract cells of the spinal cord appear to serve as a useful neural model of the events responsible for the development of arthritic pain.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00270681
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  • 19
    Digitale Medien
    Digitale Medien
    Synaptic organization of olfactory inputs and local circuits in the entorhinal cortex: a current source density analysis in the cat (1987)
    Springer
    Experimental brain research 67 (1987), S. 615-622 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Entorhinal area ; Current source density ; Olfactory afferents ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The distribution of the olfactory afferents within the ventrolateral part of the entorhinal cortex (EC) was studied by means of field potentials evoked by stimulation of the olfactory bulb (OB) and the olfactory cortex (PPC). Depth profiles of the field potentials evoked by OB or PPC stimulation were studied using current source density analysis. After OB or PPC stimulation an early superficial sink-deep source configuration was found, which some time later reversed into a superficial source-deep sink. Both OB and PPC activated mainly the superficial dendrites of the cells of layers II and III. In layers II and III evidence for strong recurrent inhibition was found, using double pulse stimulation. The results indicate that there exists a common basic design of the synaptic organization of the olfactory areas of the base of the brain extending to the EC.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00247292
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  • 20
    Digitale Medien
    Digitale Medien
    Direct projections from Ammon's horn to the septum in the cat (1987)
    Springer
    Experimental brain research 68 (1987), S. 179-188 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Ammon's horn ; Hippocampus ; Septum ; Dentate gyrus ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Direct projections from Ammon's horn to the septum were studied in the cat by the anterograde tracing method after injecting WGA-HRP (wheat germ agglutinin-horseradish peroxidase conjugate) into Ammon's horn. The results were further confirmed by the retrograde WGA-HRP method after injecting WGA-HRP into the septum. Pyramidal neurons in fields CA1, CA2 and CA3 were observed to send their axons ipsilaterally to the lateral septal nucleus; the septal parts of the hippocampus sent projection fibers to the dorsomedial portions of the lateral septal nucleus via the medial aspects of the subcallosal fornix, while the hippocampal regions successively more proximal to the temporal pole sent projection fibers to progressively more ventrolateral portions of the lateral septal nucleus via more lateral aspects of the subcallosal fornix. It was also found that the septal parts of fields CA1, CA2 and CA3 sent projection fibers bilaterally to the dorsomedial aspects of the lateral septal nucleus. Field CA4 appeared to send projection fibers only sparsely, if at all, to the medial septal nucleus. The rudimentary parts of the hippocampal formation, taenia tecta and indusium griseum, were found to have reciprocal ipsilateral connections with the dorsal portions of the lateral septal nucleus.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00255243
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  • 21
    Digitale Medien
    Digitale Medien
    Binocular interaction in the dorsal lateral geniculate nucleus of the cat (1987)
    Springer
    Experimental brain research 68 (1987), S. 305-310 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Binocular interaction ; Lateral geniculate nucleus ; Cat ; Retinal disparity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary We have investigated binocular interaction in the dorsal lateral geniculate nucleus (LGN) of the cat. Neurons were recorded extracellularly during visual stimulation with sinusoidal gratings which were presented at different interocular phases (disparities). The large majority of cells (91%) exhibited some type of binocular interaction. For 75% and 16% of the total number of cells, the binocular interaction was inhibitory or facilitatory, respectively. For the remaining 9% of cells, no interaction was evident. In marked distinction from visual cortex, the facilitatory and inhibitory interactions in the LGN are independent of the relative interocular phase of the patterns. Neurons in the LGN are therefore insensitive to the stereoscopic depth cue, retinal disparity.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00248796
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  • 22
    Digitale Medien
    Digitale Medien
    Processing of interaural time and intensity differences in the cat inferior colliculus (1987)
    Springer
    Experimental brain research 68 (1987), S. 379-392 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Cat ; Inferior colliculus ; Single cell recording ; Binaural hearing ; Time/intensity trading
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary 1. Binaural neurones were recorded in the central nucleus of the cat inferior colliculus and were stimulated with tone and noise bursts. Closed field sound systems were used to produce independent interaural time (ITD) and intensity (IID) differences. Particular attention was paid to high frequency (above 2 kHz) cells. 2. Three main types of binaural neurone were found: High frequency excitatory-inhibitory neurones (EI cells), excited by input from the contralateral ear and inhibited by ipsilateral input, high frequency excitatory-excitatory cells (EE cells), excited by inputs from either ear and low frequency cells sensitive to interaural phase differences (IPD cells). 3. The EI cells had characteristics similar to those of IE cells in the contralateral lateral superior olive. They were sensitive to envelope ITDs (most cells) and IIDs (all cells) favouring the contralateral ear. The response of these cells increased with increasing contra lead ITDs or contra loud IIDs up to values well outside the physiological range. 4. Low frequency binaural cells were sensitive to interaural phase differences (IPDs). The peak response was often in the contralateral physiological range and the response was unaffected by IIDs. 5. Many high frequency EE cells were sensitive to envelope ITDs. These units were relatively unaffected by IID. Although the ITD sensitivity of these cells was generally less than that of the IPD cells, the peak response of the ITD curve was also often in the contralateral physiological range. 6. Some of the high frequency EI and EE cells were sensitive to ongoing time differences (OTDs) in white noise signals, i.e. they showed ITD response curves to carrier only shifted noise bursts. 7. The EI cells often showed recovery from inhibition at large ipsilateral lead. This tendency was increased as the sound pressure level on the inhibitory side was lowered and by the use of click stimuli. Similarly, cycles of suppression could be seen to follow excitation in some EE cells. The time course of these effects was in the order of hundreds of μs. 8. Binaural characteristics (degree of ITD, IID or OTD sensitivity) showed considerable interunit variation within each cell type. These variations were also affected by signal type (tone or noise bursts) and did not appear to be correlated with best frequency, nature of the tuning curve or PSTH type. We suggest that the time course of the inhibitory and excitatory effects at each unit (and its interaction with the signal type) determines the type of ITD response and that this time course varies from cell to cell.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00248803
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  • 23
    Digitale Medien
    Digitale Medien
    Effects of monocular strobe rearing on kitten striate cortex (1987)
    Springer
    Experimental brain research 68 (1987), S. 525-532 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Cat ; Visual cortex ; Stroboscopic exposure ; Monocular experience ; Motion deprivation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Monocular deprivation in kittens does not lead to an ocular dominance shift in striate cortex if the visual stimuli do not contain contours. In the present study we sought to find out whether an ocular dominance shift is produced if the visual environment does contain contours but is devoid of motion. Six kittens were reared with one eye occluded in a visual environment that was lit only by the light of a stroboscope (2 flashes per sec). Exposure was started at 5–6 weeks of age after dark-rearing from birth and extended until 8–12 weeks of age for 8 h per day. The rest of the time was spent in total darkness. Thus, the animals were completely deprived of vision in one eye, while the other eye experienced only stationary flashing contours. Single units in area 17 of these animals were studied and compared to normally reared cats. In all six animals ocular dominance was clearly shifted towards the eye with strobe experience. The ocular dominance shift showed, however, the following interdependencies with other parameters: neurones that responded to stationary flashing test stimuli were nearly always dominated by the strobe eye; neurones that responded only to moving bars or edges remained binocular. In the normal control animals the ocular dominance distribution was similar for both groups of cells. Track analysis according to cortical lamination revealed that neurones in infragranular layers consistently showed a weaker OD shift towards the strobe eye than neurones in supragranular layers (including layer 4). Response latencies to stationary flashing stimuli were significantly shorter in the strobe-reared animals than in the normal controls. Orientation tuning was normal in all animals. Directional tuning was reduced after monocular strobe experience, but not by the same amount as described after binocular strobe rearing. The present results demonstrate that monocular visual experience reduced to stationary flashing contours is sufficient to produce on ocular dominance shift in striate cortex. This adds further support to existing notions about the role of nervous activity for changes in cortical connections. Cortical responses to afferent stimulation and the resulting correlated activation of pre- and postsynaptic neurones seem to be a prerequisite for a stabilization of synaptic connections.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00249796
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  • 24
    Digitale Medien
    Digitale Medien
    Tonotopic organization in the medial geniculate body (MGB) of lightly anesthetized cats (1987)
    Springer
    Experimental brain research 69 (1987), S. 24-42 
    Details
    ISSN: 1432-1106
    Schlagwort(e): Medial geniculate body ; Tonotopic organization ; Single unit pairs ; Frequency selectivity ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary In the medial geniculate body (MGB) of nitrous oxide anesthetized cats, the pars lateralis (PL) was the only nucleus to show a clear topographic arrangement of its neurons according to their characteristic frequency (CF). When compared to barbiturate anesthetized cats (Imig and Morel 1985a), the tonotopic organization in PL appeared less strict and was characterized by a significant local CF disparity. Furthermore, the degree of tonotopic organization varied along the rostrocaudal axis of the nucleus: it was lower in its caudal than in its rostral half. In the pars ovoidea, the rostral half of the pars magnocellularis (PM) and the suprageniculate nucleus, CF sequences and quantitative evaluations of the tonotopicity indicated the presence of some degree of tonotopic organization which was lower than in PL. No such organization was observed in the caudal part of PM nor in the ventrolateral nucleus, while in the dorsal nucleus, the proportion of toneresponding units was too low for a significant analysis.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00247026
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  • 25
    Digitale Medien
    Digitale Medien
    The effects of CO2 and fixed acid on the O2-Hb affinity of rabbit and cat blood (1987)
    Springer
    Pflügers Archiv 408 (1987), S. 451-457 
    Details
    ISSN: 1432-2013
    Schlagwort(e): O2-Hb affinity ; Bohr effect interaction ; CO2 Bohr effect ; Fixed acid Bohr effect ; Rabbit ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The action of respiratory and metabolic acid-base disturbances on the O2-Hb affinity was studied in rabbits and cats. Blood samples of both species were exposed to in vitro pH-changes, which were either achieved by variation ofPCO2 (2.8–8.3 kPa) at constant lactic acid concentration, or by addition of lactic acid (5–14 mmol·l−1) at constantPCO2. ThePO2 at halfsaturation (P50) and the Hill'sn were determined from O2-Hb dissociation curves (ODC) in a range between 20 and 80% SO2. Under standard conditions (T=331 K,PCO2=5.33 kPa, pH=7.4), the average P50 value was 4.66±0.05 kPa in rabbits, that is slightly higher than reported by others, and 5.17±0.03 kPa in cats. The average values of Hill'sn were 2.91±0.02 and 2.95±0.03 for rabbits and cats, respectively. When plasma pH was varied by CO2, the resulting classical CO2 Bohr factor φCO2=ΔlgP50/ΔpH50 was distinctly higher in cats (−0.560±0.006,n=25) than in rabbits (−0.504±0.014,n=22), although in the latter species being even higher than reported elsewhere. Concomitant metabolic acidosis did not significantly affect φCO2, but shifted the P50 at a given plasma pH to lower values. Substitution of lactic acid with equimolar amounts of sodium lactate left both φCO2 and P50 unchanged. When plasma pH was varied by lactic acid (LA), the resulting fixed acid Bohr factors φLA were similar for cats (−0.420±0.016,n=21) and rabbits (−0.427±0.010,n=18), and not influenced by additional respiratory acidosis. Concomitant respiratory acidosis, however, shifted the P50 at a given plasma pH to higher values. The deviation of lgP50 from that under standard conditions (lgP50st) induced by both, respiratory and metabolic acid-base changes, can generally be expressed by Eqs. (1) or (2) (1) $$1gP_{50} - 1gP_{50} st = \varphi CO_2 \left( {pH - 7.4} \right) - \left( {\varphi CO_2 - \varphi LA} \right) \cdot \left[ {pH\left( {LA} \right) - 7.4} \right]$$ (2) $$1gP_{50} - 1gP_{50} st = \varphi LA\left( {pH - 7.4} \right) + \left( {\varphi CO_2 - \varphi LA} \right) \cdot \left[ {pH\left( {CO_2 } \right) - 7.4} \right].$$ Thereby, the first term considers the total pH-deviation, irrespective of its origin, and the second term represents the metabolic (1) or the respiratory (2) correction. For practical use and within the physiological range of plasma pH (7.2–7.6), φCO2 and φLA are assumed to be additively linked and to be independent of pH. Once these factors are determined for a given species, together with the buffer capacity for CO2, they provide sufficient data to estimate fairly accurately the position of the ODC. This is particularly important for in vivo conditions where respiratory and metabolic acid-base disturbances often occur simultaneously.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00585068
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  • 26
    Digitale Medien
    Digitale Medien
    Responses of sacral visceral afferents from the lower urinary tract, colon and anus to mechanical stimulation (1987)
    Springer
    Pflügers Archiv 410 (1987), S. 296-303 
    Details
    ISSN: 1432-2013
    Schlagwort(e): Sacral visceral afferents ; Pelvic nerve ; Urinary bladder ; Urethra ; Colon ; Anus ; Functional properties ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The discharge characteristics of sacral visceral afferents supplying the urinary bladder, urethra, colon and anus to mechanical stimuli were analyzed in the anaesthetized cat. The stimuli used were passive distension (urinary bladder, colon), isovolumetric contraction (urinary bladder), movements of the urethral catheter and mechanical shearing stimuli (mucosal skin of the anal canal). (1) In total 245 afferent units which projected in the pelvic nerve were isolated from the sacral dorsal roots. From one of the following organs, urinary bladder, colon, urethra and anus 117 afferent units were activated. By these stimuli from the bladder, urethra and anus 122 afferent units could not be activated, and as far as tested also not from the colon; in 6 afferent units the classification was unclear. (2) Afferent units from the urinary bladder and the colon responded consistently to passive distension of the respective organ. The units from the urinary bladder showed graded responses at intraluminal pressures of about 10–70 mm Hg and responded also to isovolumetric contractions of the organ. The thresholds of the units from the bladder to passive distension and contraction varied from about 5 to 20 mm Hg intravesical pressure. (3) The afferent units from the urethra and the anus did not react or showed some weak phasic and irregular responses to distension and contraction applied to the urinary bladder or to distension of the colon. They were consistently excited by low threshold mechanical stimulation of the urethra and anus, respectively. (4) The axons from the bladder, urethra and anus were presumably myelinated (conduction velocity above 2 m/s) and conducted at 10.3±6.1 m/s (n=34, mean±SD), 26.3±9.3 m/s (n=13) and 9.5±5.1 m/s (n=37), respectively. The axons from the colon conducted at about 0.5 to 16 m/s (n=20), 13 of them conducting at less than 2 m/s. About 75% of the axons which could not be activated by mechanical stimulation of the visceral organs were presumably unmyelinated (conduction velocity below 2 m/s). (5) Some ongoing activity was found in 9 out of 26 afferent units from the anus but, with one exception, the afferent units from the bladder, urethra and colon were silent. (6) It is concluded that the pelvic afferent units from the urinary bladder, urethra, colon and anus consist of distinct populations with characteristic response patterns. There is no indication from this investigation that the urinary bladder is supplied by sacral afferents which are only recruited at high intravesical pressures during passive distension and isovolumetric contractions and which are possibly associated with pain.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00580280
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  • 27
    Digitale Medien
    Digitale Medien
    Complexes of 2,2′,2″-Nitrilotriphenol. Part 1. A Study of Bimolecular Nucleophilic Substitution at the Boron Atom (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 499-510 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The tetradentate ligand 2,2′,2″-nitrilotriphenol forms a boron complex III with an intramolecular, transannular N→B dative bond of 1.68 Å in a strained tricyclo[3.3.3.0]undecane chelating system. The complex reacts with nitrogen bases L, such as pyridine, quinuclidine and others, to form complexes III-L, in which the intramolecular B-N bond is replaced by one between B and the external nucleophile. In solution, this displacement reaction is reversible. It was studied by temperature-dependent NMR spectroscopy. The resulting reaction and activation parameters suggest that the reaction is a bimolecular nucleophilic substitution (SN2).
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700303
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  • 28
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    Digitale Medien
    Complexes of 2,2′,2″-Nitrilotriphenol. Part 3. Crystal and Molecular Structures of Three Aluminium Complexes (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 520-533 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Crystal and molecular structures of three Al(III) complexes of the tripod ligand 2,2′,2″-nitrilotriphenolate (I) are presented. They all show 5-coordinate Al in approximately trigonal bipyramidal geometry, with an external nucleophile X occupying the second axial position. X is OH- in[Al(I)(OH)]-[Hquin]+ (quin = quinuclidine), N in [Al(I)(py)] (py = pyridine), and one of the O-atoms of a second molecule in the dimeric [(Al(I))2]. Correlated variations in the axial bond lengths of the trigonal bipyramid are observed: [(Al(I))2]: Al-Nint. = 2.094 Å, Al-Oext. = 1.850 Å; [Al(I)(py)]: Al-Nint. = 2.153 Å, Al-Next., = 1.992 Å; [Al(I)(OH)]-: Al-Nint. = 2.278 Å, Al-Oext. = 1.765 Å. They are interpreted in terms of a dissociative reaction path at the Al(III) centre.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700305
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  • 29
    Digitale Medien
    Digitale Medien
    Molluscicidal Saponins from Swartzia madagascariensis DESVAUX (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 570-576 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The phytochemical investigation of the dried fruits of Swartzia madagascariensis (Leguminosae) afforded the five triterpenoid saponins 1-5. They were shown to be glucuronides of oleanolic acid and of gypsogenin by chemical and spectral means (FAB-MS, 13C-NMR, GC/MS). One of the isolated compounds, identified as 3-O-[O-α-L-rhamnopyranosyl-(1→3)-(β-D-glucopyranosyluronic acid)]oleanolic acid, was responsible for the high molluscicidal activity of Swartzia madagascariensis fruits against the schistosomiasis-transmitting snails Biomphalaria glabrata and Bulinus globosus.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700309
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  • 30
    Digitale Medien
    Digitale Medien
    The Hydrolysis of Ethyl 1-Methyl-2,4-cyclopentadiene-1-carboxylate by Nonenzymatic and Enzymatic Methods. Carbon-Carbon vs. Carbon-Oxygen Bond Cleavage (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 587-592 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The title ester 5 is shown to undergo C-C bond cleavage under the conditions of basic ester hydrolysis (KOH/EtOH) with formation of potassium ethyl carbonate (6) and the tautomeric methylcyclopentadienes 7 and 8. In contrast, porcine liver esterase (PLE, EC 3.1.1.1) cleanly hydrolyses 5 to give the isolable 1-methyl-2,4-cyclopentadiene-1-carboxylic acid (13). The latter undergoes thermal dimerization with conservation of the geminal-substitution pattern. The configuration of the Diels-Alder adduct 17 is ascertained by it photochemical transformation into bishomocubane dicarboxylic acid 12, easily distinguished by its C2 symmetry. Under the conditions of acid-catalyzed hydrolysis, dimerization of ester 5 and polymerization prevail, unless low acid concentration is used. The dimer 9 of 5 has one ester function that is reluctant to undergo basic hydrolysis.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700311
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  • 31
    Digitale Medien
    Digitale Medien
    Potassium Carboxylates by Direct Carbonylation of Potassium Alkoxides (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 593-599 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction of the K+ alkoxide of linalool (1) in benzene with CO at 425-440 bar and 120-130° for 12-30 h gave the K+ salt of 2,6-dimethyl-2-vinyl-5-heptenoic acid (4a) in a ca. 25% yield based on ca. 65% converted alkoxide. Reaction of the [K+ ⊂ 18-crown-6] alkoxide of 1 with CO at 50-55 bar and 40° for 90-140 h gave a mixture containing mainly the [K+ ⊂ 18-c-6] salts of 4a (ca. 62%) and of the homogeranic acids 3a and 6a (together ca. 27% of the mixture) in a ca. 35% combined yield based on 50-60% converted alkoxide. The uncomplexed or complexed K+ alkoxide of (S)-1 gave, with ca. 85% net retention, the K+ salt of (S)-4a. Reaction of the [K+ ⊂ 18-c-6] alkoxide of geraniol (2) with CO at 50 bar and 40° for 65-70 h gave myrcene (10) and geranyl formate (11) in a ca. 40-50% yield each based on ca. 85% converted alkoxide. Reaction of the [K+ ⊂ 18-c-6] alkoxide of 3-pentyl-1,4-pentadien-3-ol (14) at 50 bar and r.t. for 70 h gave a mixture of the [K+ ⊂ 18-c-6] salts of 2-pentyl-2-vinyl-3-butenoic acid (15a) (67%) and the 4-pentyl-2,4-hexadienoic acids 18a and 19a (together 23% of the mixture) in a ca. 90% combined yield based on ca. 65% converted alkoxide.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700312
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  • 32
    Digitale Medien
    Digitale Medien
    Synthesis and Copper(I) Complexes of a Series of 9- to 13-Membered N3 Macrocycles (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 680-689 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Eight cyclic triamines with ring sizes between 9 and 13 were synthesized by the p-toluenesulfonate method. The open-chain triamines bis(2-aminoethyl)amine (dien) and bis(3-aminopropyl)amine (diprop) were used as starting materials. In some cases, the corresponding dimeric cyclic hexaamines have been isolated and characterized as major by-products. The complexation of Cu(I) by the triamines has been studied potentiometrically in CH3CN/H2O. All ligands L form ternary complexes [Cu(CH3CN)L]+. The corresponding association constants vary between 1011 and 107, decreasing with increasing ring size. In addition, complexes [Cu(CH3CN)yLH]2+, y = 1 or 2, are found as less important species with maximum concentrations of 7 to 50%.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700318
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  • 33
    Digitale Medien
    Digitale Medien
    The Microstructure of Selective Palladium Hydrogenation Catalysts Supported on Calcium Carbonate and Modified by Lead (Lindlar Catalysts), Studied by Photoelectron Spectroscopy, Thermogravimetry, X-Ray Diffraction, and Electron MicroscopyThe following abbreviations and acronyms are used in the text: B. e. : Binding energy [eV], BET: Brunauer-Emmett-Teller (method of surface-area determination by physisorption of N2), AES: Auger electron spectroscopy, XPES: X-ray photoelectron spectroscopy, UPES: Ultraviolet photoelectron spectroscopy, ISS: Ionscattering spectroscopy, UHV: Ultrahigh vacuum (10-5 Pa), FTIR: Fourier-transform IR spectroscopy, TGA: Thermal gravimetric analysis, XRD: X-ray diffraction, XDA: Energy dispersive microanalysis, SEM: Scanning electron microscopy, TEM: Transmission electron microscopy, FWHM: Full width at half maximum. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 627-679 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A detailed analysis of the system Pd + Pb on CaCO3 is presented. This system known as Lindlar catalyst is used for selective hydrogenations of C≡C bonds to C=C bonds. It was found to consist of seven distinct chemical phases. Essential ingredients are solid solutions of hydrogen and oxygen in Pd. The latter phase enables the metal particles to be attached to the support via an orientational relationship calcite (113)∥Pd + O (111). The addition of Pb neither changes the micromorphology of the disk-shaped Pd particles nor does it modify the electronic structure of Pd as studied by chemisorption experiments. The addition of Pb seems to block certain active sites and, thus, to enhance the selectivity. The support was found to be a multi-domain mixture of calcite and aragonite with domain sites of several hundred Å. The free surface of the pore-free solid is covered by a calcium-hydroxide carbonate. This phase as well as several other Pb phases seem to represent only spectator materials. Verification of this as well as finding the correlation between structure and function of the various components requires a kinetic analysis which is outside the scope of this paper. It is demonstrated that a variety of analytical techniques is required to unravel the complex nature of such a ‘simple' catalyst’ as it is Pd on CaCO3.
    Zusätzliches Material: 36 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700317
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  • 34
    Digitale Medien
    Digitale Medien
    Verapliquinones: Novel Diprenylquinones from an Aplidium sp. (Ascidiacea) of Ile-Verte Waters, Brittany (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 621-626 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An Aplidium sp. (Ascidiacea), collected in French Atlantic waters near the Ile Verte, is shown to contain verapliquinone B (2) and verapliquinone D (6) as the first examples of linear diprenylquinones of the neryl type, besides their respective isomers 1 and 5 of the geranyl type.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700316
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  • 35
    Digitale Medien
    Digitale Medien
    Fe(II)-Induced Fragmentation Reaction of γ-Hydroperoxy-α,β-enones. Part 1. Synthesis of 13(14→8)-abeo-Steroids (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 701-716 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Some steroidal analogues embodying the hitherto unknown 13(14→8)-abeo skeleton have been synthesized by Fe(II)-induced rearrangement (tandem β-fission/reductive alkylation) of 14α-hydroperoxy-7-en-6-ones. The configurational assignment was made by thorough analysis of NMR spectra; the structure of one of the products was unambiguously assessed by X-ray single-crystal analysis.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700320
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  • 36
    Digitale Medien
    Digitale Medien
    Light-Induced, Thermal, and Acid-Catalyzed π-Skeletal Rearrangements of Five-Ring-Annelated HeptalenesPresented in part by H.-J.H. in a lecture at the ETH in Zürich, 1985. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 742-759 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It is shown that, upon irradiation in CDCl3 solution, 5,6,8,10-tetramethylheptalene-1,2-dicarboxylic anhydride (6) rearranges to its double-bond-shift (DBS) isomer 7 in an equilibrium reaction (Scheme 2). The isomer 7 is DBS stable at -50°. At ca. 30°, a thermal equilibrium with 97.8% of 6 and 2.2% of 7 is rapidly established. Similarly, the ‘ortho’-anhydrides 9 and 11 (Schemes 4 and 5) can be rearranged to their corresponding DBS isomers 12 and 13, respectively. Whereas 12 is DBS stable at 30° (at 100° in tetralin, 94.0% of 9 are in equilibrium with 6.0% of 12), the i-Pr-substituted isomer 13 is already at 30° in thermal equilibrium with 11 leading to 98.7% of 11 and 1.3% of 13. It is shown by rearrangement of diasteroisomeric ‘ortho’-anhydrides of known relative and absolute configuration (Scheme 6) that the DBS in such five-ring-annelated heptalenes occurs with retention of the configuration of the heptalene skeleton as already established for other heptalene compounds. It is found that the DBS process may also take place under acid catalysis (e.g. HCl/CH3OH), thus yielding 9 from 12 (Scheme 9). The ‘ortho’-anhydrides 21 and 23 (Scheme 10) which are isomeric with 9 and 11 (Scheme 3) undergo rapid DBS' already at room temperature. The thermal equilibrium 21⇄22 consists of 18% of 21 and 82% of 22 at 30° and that of 23⇄24 of 17% of 23 and 83% of 24 at -30°. From these equilibrium mixtures, the pure DBS isomer 22 can be obtained by crystallization. Again, these rapid DBS' occur with retention of configuration of the heptalene skeleton (Fig. 4).
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700323
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  • 37
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    Digitale Medien
    Synthese und NMR-Spektren von Nonafulven sowie Vergleich mit 10-PhenylnonafulvenHerrn Prof. Dr. Hans Nitschmann zum 80. Geburtstag gewidmet52. Mitt. über Fulvene, Fulvalene; 51. Mitt. [1]; Kurzmitt. [2]. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 862-880 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and NMR Spectra of Nonafulvene and Comparison with 10-PhenylnonafulveneExperimental procedures for the reaction of cis,cis,cis,trans-cyclononatetraenide (ccct-CNT-; see 4) with bromomethyl acetate (1a, R = H, X = Br) to give (cyclononatetraenyl)methyl acetate (5a; 84% yield) as well as for the base-induced elimination of HOAc from 5a to give nonafulvene (6a; 44% yield) are described. Spectroscopic as well as chemical evidence for 6a and 6b is presented. An approximate high-field-NMR analysis of 6a and 6b has been completed. The results are in favour of a fast interconversion of the type 6A⇄6B (Scheme 4), and supported by the MNDO-optimised geometry of 6a. The first X-ray analysis of a cyclononatetraene (i.e. of 5b) has been accomplished: 5b is a polyolefinic molecule with largely alternating bond lengths and with a nine-membered ring deviating strongly from planarity.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700327
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  • 38
    Digitale Medien
    Digitale Medien
    Field-Desorption Mass Spectra of Fern Phloroglucinols Containing Three to Six Ring ConstituentsDedicated to the late Prof. Peter Brown (12.IX.1938-15.III.1981), Dept. of Chemistry, Arizona State University, Tempe, Arizona 08521, U.S.A., Whose premature death was a great loss to his friends and collegues. The last letter which we received from him (November 15, 1980) contained the first FD mass spectra of five relatively large fern phloroglucinols which he had successfully analyzed. Two of these spectra, in which no thermal rearrangement and /or fragmentation was observed, are reproduced in this article (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 881-893 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It has been previously shown that the structural analysis of the title compounds by electron-impact ionization (EI)mass spectrometry is complicated by extensive, if not complete, thermal rottlerone-type rearrangement and/or fragmentation reactions. The use of a ‘softer’ ionization technique such as field desorption (FD) is, therefore, required in order that these compounds may be characterized in terms of their molecular size and composition. In this report, the FD mass spectra of typical representatives of this class of compounds are described along with the attempted suppression of undesirable thermal reactions by the optimization of the emitter temperatures.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700402
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  • 39
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    Digitale Medien
    Structures and Electrical Properties of Some New Organic Conductors Derived from the Donor Molecule TMET (S,S,S,S,-Bis(dimethylethylenedithio) tetrathiafulvalene) (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 942-953 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Crystal structures and electrical properties of radical-cation salts of the chiral organic donor TMET (S,S,S,S,-bis-(dimethylethylenedithio)tetrathiafulvalene) are described. Two structural types, 2:1 with octahedral anions Pf-6, AsF-6, SbF-6, I-3 (incommensurate), and 3:2 with tetrahedral anions BF-4, CIO-4, ReO-4 are observed. Resistivity measurements between 2 and 298 K indicate that the 3:2 types are organic metals, while the other compounds are semiconductors. (TMET)3(CIO4)2 is metallic down to about 120 K at ambient pressure and remains metallic down to 2 K at 8 kbar.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700405
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  • 40
    Digitale Medien
    Digitale Medien
    Bildung tricyclischer Thietan-Derivate durch intramolekulare(2+2)-Cycloaddition (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 992-994 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Formation of Thietane Derivatives via Intramolecular (2+2) CycloadditionOn irradiation, the two 4-vinyl-1,3-thiazole-5(4H)-thiones 1a, b, synthesized from thiobenzoic acid and the corresponding 3-amino-2H-azirines 2a,b, undergo an intramolecular (2+2)-cycloaddition reaction of the C=S and C=C bonds to give the tricyclic thietane derivatives 3a,b.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700409
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  • 41
    Digitale Medien
    Digitale Medien
    Photochemical Synthesis of 2-Alkylidene-1,3-cyclocalkanediones. Preliminary Communication (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 995-996 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Photolysis (λ = 254 nm) of 4-(tert-butyl)-4,6,7,8-tetrahydro-7,7-dimethy-2H-1-benzopyran-2,5(3H)-dione (3a) in t-BuOH affords 2-(2,2-dimethylpropylidene)-5,5-dimethyl-1,3-cyclohexanedione (1a) in 80% yield via homolysis of the lactone O—CO bond and subsequent ketene elimination.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700410
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  • 42
    Digitale Medien
    Digitale Medien
    Some Cyclic Oligopeptide with S2n Symmetry (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1012-1016 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Some cyclic oligopeptides formed by an equal number of alternating D- and L-amino-acid residues have been synthesized by using the hydrochloride of the open-chain peptide acid as precursor and the mixed-anhydride condensation method. The cyclic oligopeptides (tetra-, hexa-, and octavaline, hexaleucine, and hexaphenylalanine) form very stable H-bonded structures (IR-amide band at 3270-3290 cm-1) which are insoluble in common organic solvents. In CF3COOH/CDCI3 (25°), they yield 1H-NMR spectra snowing the expected equivalency of the various amino-acid residues.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700413
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  • 43
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    Digitale Medien
    Strukturaufklärung ungewöhnlicher Umlagerungsprodukte von S-(1-Alkenyl)sulfoximiden mit Hilfe der Stossaktivierungsmassenspektrometrie (CAD-MS) (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1041-1049 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Structure Determination of Unusual Rearrangement Products of S-(1-Alkenyl)sulfoximides by Collisionally Activated Dissoication Mass Spectrometry (CAD-MS)The Molecular ions of s-(l-alkenyl)--N-(p-tolyl)sulfoximides 1 are transformed into the N(phenylsufenyl)sulfonamides 3+ by a 1,2-migration of the alkenyle group to the O-atom of the sulfoximide function followed by a 2,3-sigmatropic rearrangement. The structure of the production e has been unambiguouslydetermined by the CAD method, showing the identity of the ion e (m/z368) obtained from 1a and from 4a.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700416
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  • 44
    Digitale Medien
    Digitale Medien
    Reaktionen von 1,2-Bis(trimethylsilyl)iminen mit Selen-und Tellur-halogeniden (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1076-1078 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions of 1,2-Bis(trimethylsilyl)imines with Selenium and Tellurium HalogenidesThe reactions of benzil-bis(trimethylsily)imine and phenanthrene-9,10-bis(trimethylsilyl)imine with SeOCl2, SeCl4 and TeCl4 are described.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700420
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  • 45
    Digitale Medien
    Digitale Medien
    Remote Tricarbonyl(diene)iron Substituent Effect on Ester Heterolysis. The Solvolyses of 5,6,7,8-Tetramethylidenebicyclo[2.2.2]oct-2-yl Methanesulfonate and of its Tricarbonyliron Mono- and Dinuclear ComplexesPart of Ph.D. thesis of J.-C. Zwick, Ecole Polytechnique Fédérale de Lausanne, 1987. Part of this work has been presented at the Fall Meeting of the Swiss Chemical Society in Bern, Oct. 10, 1986. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1079-1094 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Buffered acetolyses and hydrolyses of 5,6,7,8-tetramethylidenbicyclo[2.2.2]oct-2-yl methanesulfonate (17), of its ‘syn-endo’ (18), ‘syn-exo’ (19), ‘anti-endo’ (20), ‘anti-exo’ (21) tricarbonyliron complexes and of its ‘anti-exo,syn-endo’ (22) and ‘anti-endo,syn-exo’ (23) bis(tricarbonyliron) dinuclear complexes have been investigated (product analysis and kinetics). In contract with the solvolyses of the uncomplexed mesylate 17, the solvolyses of the complexed esters can be highly chemo- and stereoselective. The nature of the products (non-rearranged bicyclo[2.2.2]oct-2yl vs. rearranged bicyclo[3.2.1]oct-2-yl derivatives) depends on the relative configuration of the tricarbonyl(diene)iron moieties and on the medium. The rates of solvolyses of 17 are only slightly affected by complexation of one or both s-cis-butadiene units with Fe(CO)3 groups, except in the cases where the diene moiety ‘anti’ with respect to the mesylate is complexed onto its ‘endo’ face (20,23). In these cases, significant rate-retardation effects are observed, consistent with the inductive effect of the Fe(CO)3 substituent. Such retardation effects are overwhelmed by competing accelerating homoallylic participation by uncoordinated ‘anti’ -diene moieties (18,19) or, as in the case of the ‘anti-exo’-Fe(CO)3 complexes 21 and 22, by possible direct metal participation to the ionization process.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700421
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  • 46
    Digitale Medien
    Digitale Medien
    Synthetic Models of the Active Site of Cytochrome P-450. 1st Communication. The Synthesis of a Doubly-Bridged Iron(II)-Porphyrin Carrying a Tightly Bound Thiolate LigandPresented in part at the ‘Gordon Research Conference’ on the ‘Chemistry and Biology of Pyrroles’, New Hampshire, 27.7.-1.8.86 (W.-D.W.), and at the ‘Swiss Chemical Society’ meeting, Bern, 10.10.86 (B.S.). (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1173-1193 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The doubly-bridged iron(II)-tetraphenylporphyrin derivative 6, carrying a sterically fixed S- ligand in the ‘proximal’ position and the substrate at the ‘distal’ site, was synthesised as an enzyme model for cytochrome P-450. Compound 36, the CO complex of 6, displays a split Soret band (403 and 457 nm) similar to the native cytochrome P-450.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700425
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  • 47
    Digitale Medien
    Digitale Medien
    Stereoselektive Alkylierung an C(α) von Serin, Glycerinsäure, Threonin und Weinsäure über heterocyclische Enolate mit exocyclischer DoppelbindungZughörige Kurzmitteilungen: [1] (Weinsäre) [2] (Threonin) [3] (Serin) [4] (Glycerinsäure).Siehe auch die Diskussionen in den vor kurzem erschienenen Übersichtsartikeln [5][6]. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1194-1216 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Steroselective Alkylation at C(α) of Serine, Clyceric Acid, Threonine, and Tartaric Acid Involving Heterocyclic Enolates with Evocyelic Double BondsThe chiral, non-racemic title acids are converted to methyl dioxolane-(cf. 13), oxazoline-(4) and oxazolidinecarboxylates (cf. 9). Deprotonation by Li(i-Pr) 2N at dry-ice temperature gives solutions of the lithium enolates A-D With exocyclic enolate double bonds. These are stable crough with respect to β-elimination (Scheme 1) to be alkylated with or without cosolvents such as HMPA or DMPU The products are formed in good to excellent yields and, with the exception of the tartrate-derived acetonlde (see Scheme 2), with diastereoselectivities above 90%. While the tartrate-and threonine-derived enolates (A and B, resp.) are chiral due to the second stereogenic center of the precursors, the serine- and glyceric-acid-derived enolates (Aand B, resp.) are chiral due to the second sterogenic center of the precursors, the serine-nd glyceric-acid-derived enolates are non-racemic due to a tert butyl-substituted (pivalaldehyde-derived) acetal center (C and D, resp.). The products of alkylation can be hydrolyzed to give α-branched tartaric acid (Scheme 2), allothreonine (Scheme 3), serine (Scheme 4), and glyceric-acid derivatives (Scheme 5) with quaternary stereogenic centers. The configurations of the products are determined by NOE-NMR measurements and by chemical correlation. These show that the dioxolane-derived enolates A and D are alkylated preferentially from that face of the ring which is already substituted (‘syn’-attack), while the dihydrooxazol-and oxazolidine-derived enolates B and C are alkylated from the opposite face (‘anti’-attack). The ‘syn’-attack is postulated to arise from strong folding of the heterocyclic ring due to electronic repulsion between the enolate π-system and non-bonding electron pairs on the heteroatoms (see Scheme 6).
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700426
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  • 48
    Digitale Medien
    Digitale Medien
    Novel Synthesis of Agaritine, a 4-Hydrazinobenzyl-Alcohol Derivative Occurring in Agaricaceae (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1261-1267 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The 4-hydrazinobenzyl alcohol (3 was prepared (58%)) by diiobutylaluminiumhydride reduction of methyl 4-hydrazinobenzoate (4), whereas LiA1H4 or LiBh4 reduction of4 proceeded further to yield (via intermediate 3) (4-tolyl)hydrazine (5). The alcohol 3 was stable under O2-free conditions and exhibited no tendency to eliminate H2O, neither thermally nor with H+ catalysis. Oxidation of 3 with SeO2 yielded 4-(hydroxymethyl)benzine-diazonium ion (8), identified by its azo coupling product 9 with 2-naphthol. Condensation of 3 with 1-benzyl 5-Hydrogen N-(benzyloxycarbonyl)-L-glutamate (10) in presence of dicyclohexylcarbodiimide afforded 81% of N2-(benzyloxycarbonyl)-L- glutamic acid 1-(benzyl-ester) 5-{2-[4-(hydroxymethyl)phenyl]hydrazide} (11) which upon controlled hydrogenolysis (quinoline-sulfur-poisoned Pd/C catalyst) gave 82% of L-Glutamic acid 5-{2-[4-(hydroxymethyl)phenyl] hydrazide} (1), i. e. agaritine, a metabolite of Agaricus bisporus. Without poisoning of the catalyst, hydrogenolysis of (11) yielded L-glutamic acid 5-[2-(4-tolyl)hydrazide] (12).
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700505
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  • 49
    Digitale Medien
    Digitale Medien
    The Solid and Solution Conformations of (±)-Corycavine (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1482-1486 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The crystal structure of corycavine, a protopine-type alkaloid, has been determined by X-ray analysis. A conformational feature observed is the existence of a strong electrostade interaction between the N- and C-atom at a distance of 2.618 Å. Such an interaction stabilizes the 10-membered ring conformation of the structure. Analyses of NMR spectra indicate that corycavine has the same conformation in solution as in the crystal state.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700605
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  • 50
    Digitale Medien
    Digitale Medien
    Dimethylformamide-Exchange Mechanism on Some First-Row Divalent Transition-Metal IonsPart 33 of the series ‘High-Pressur NMR Study’. Part 32: [1].Taken in part from the diploma work of C. Cossy, Université de Lausanne, 1983.This work was presented in part at the 24th International Conference on Coordination Chemistry, Athens, Greece, August 1986. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1516-1525 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effect of temperature on the dimethylformamide exchange on Mn(DMF)2+6 and Fe(DMF)2+6 has been studied by 13C- and 17O-NMR, respectively, yielding the following kinetic parameters: k298 equals; (2.2±0.2). 106 S-1, ΔH≠ = 34.6 ± 1.3 kJ mol-1, ΔS≠ = -7.4 ± 4.8 J K-1mol-1 for Mn2+ and K298 = (9.7 ± 0.2).105 S-1, Delta;H≠ = 43.0 ± 0.9 kJ mol-1, ΔS≠ = + 13.8 ± 2.8 J K-1mol-1 for Fe2+. The volumes of activation, ΔV≠ in cm3mol-1, derived from high-pressure NMR on these metal ions, together with the previously published activation volumes for Co2+ and Ni2+ (+2.4 ± 0.2 (Mn2+), +8.5 ± 0.4 (Fe2+) +9.2 ± 0.3 (Co2+), + 9.1 ± 0.3 (Ni2+)) give evidence for a dissociative activation mode for DMF exchange on these high-spin first-row transition-metal divalent ions. The small positive ΔV≠ value observed for DMF exchange on Mn2+ seems to indicate that a mechanistic changeover also occurs along the series, (probably from Id to D), as for the other solvents previously studied (Ia to Id, for H2O, MeOH, MeCN). This changeover is shifted to the earlier elements of the series, due to more pronounced steric crowding for dimethylformamide hexasolvates.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700608
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  • 51
    Digitale Medien
    Digitale Medien
    Two New Antifungal Naphthoxirene Derivatives and their Glucosides from Sesamum angolense WELW (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1551-1557 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two novel naphthoxirene derivatives 1 and 2 their glucosides 3 and 4 have been isolated from the root bark of Sesamum angolense Welw. (Pedaliaceae) by preparative liquid chromatography. The structure of 1 was established by X-ray diffraction analysis. The identities of the other naphthcxirenes were deduced by spectroscopic (IR, UV, 1H-NMR, 13C-NMR, EI-MS, DCI-MS) and chemical methods (oxidation, acid and enzymatic hydrolysis). Compounds 1-3 exhibited antifungal activity. Naphthoxirene 1 was, in addition, cytotoxic to human colon carcinoma cells.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700613
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  • 52
    Digitale Medien
    Digitale Medien
    On Negative Birefringence in Water-in-Oil Microemulsions (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1531-1536 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The occurrence of a negative birefringence in water-in-oil (W/O) microemulsions has been substantiated and analyzed. The analysis is based on the well-established aqueous nanodroplet model of W/O microemulsions. In the particularly investigated water/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/aliphatic oil systems, the AOT monolayer exhibits a negative induced intrinsic birefringence, which is brought about by the pronounced polarizability of the alkyl moiety of the AOT molecule approximately perpendicular to the direction of its permanent dipolement.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700610
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  • 53
    Digitale Medien
    Digitale Medien
    Erratum (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 2246-2246 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700829
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  • 54
    Digitale Medien
    Digitale Medien
    Mitteilungen - Communications (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 2305-2306 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700830
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  • 55
    Digitale Medien
    Digitale Medien
    Herstellung und Charakterisierung in Membranen von Ionophoren mit Selektivität fü Natrium-Ionen (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 153-157 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Preparation of Neutral Sodium-Selective Ionophores and their Characterization in Membrane ElectrodesDifferent ionopbores based on N,N′-dibenzyl-N,N′-diphenyl-1,2-phenylenedioxydiacetamide (1) have been prepared by substitution of the aromatic ring carrying the ether O-atoms. Substituents of widely different electronegativity (CH3, CH3O, CHO, CN NO2, Br) do not relevantly influence the ion selectivity.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700119
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  • 56
    Digitale Medien
    Digitale Medien
    Complexes of 3,3′-Oxybis[(diphenylphosphino)methylbenzene] with Ni(II), Pd(II), Pt(II), Rh(I), and Ag(I). How Important is Backbone Rigidity in the Formation of trans-Spanning Bidenatate Chelates?? (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 158-170 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The bidentate diphosphine ligand, 3,3′-oxybis[(dipenylphosphino)methylbenzene] (1) forms monomeric, trans-square-planar complexes MX2(1) (M = Ni, Pd, Pt; X = Cl-, Br- I-, and, in part, N3-, NCS-, CN-, NO3-) as well as Pt(H)Cl(1), Pt(H)Br(1), and RhCl(CO)(1). Polymeric species have been observed with substitutionally inert metal centres: trans-[PtCl2(1)]2 and cis-[PtCl2(1)]n (mean value of n ≈ 4-5) 31P-NMR, and selected IR and UV/VIS parameters are reported. Ligand 1 shows a marked preference for trans-spanning and monomeric chelate formation, despite its various degrees of freedom of internal rotation in the lignad backbone. The readily available ligand 1 as well as analogues with other donor atoms, therefore, appear useful in most potential applications of trans-spanning chelate ligands. The crystal structure of AgCl(1)·0.5 (CH3)2C=O·0.39 C6H12 (space group C2/c,a = 21.02 Å, b = 14.57 Å, c = 24.79 Å, β = 99.77°, V = 7531.4 Å3, Z = 8) confirms the presence of three-coordinate Ag(I), with a coordination intermediate between a trigonal-planar and a T-shaped geometry (P-Ag-P = 145.61(8)°).
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700120
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  • 57
    Digitale Medien
    Digitale Medien
    Aza-2-dienes-1,3. Partie 5. Préparation de N-aminoimidazoles, 3H-pyrroles, triazolo[1,2,4][1,5-a]pyrazines et imidazo[1,2-a]pyrazines (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 187-195 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 2-Aza-1,3-dienes. Access to N-Aminoimidazoles, 3H-Pyrroles, [1,2,4]Triazolo[1,5-a]pyrazines, or Imidazo[1,2-a]pyrazinesNucleophilic attack of 5-(dialkylamino)-2-aza-1,3-diene-1,1-dicarbonitriles (or their 1-methoxycarbonyl analogous) by hydrazines or hydrazdes gives substituted N-aminoimidazoles, [1,2,4]triazolo-[1,5-a]pyrazines, or α-dihydrazino derivatives. With α-amino esters (or analogous), imidazo[1,2-a]pyrazines are produced. Addtion of cyanide anions occurs also with formation of substituted 3H-pyrroles. Structures and rationalisation of this nucleophilic attack are discussed.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700123
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  • 58
    Digitale Medien
    Digitale Medien
    Syntheses of Tetrahydrolipstatin and Absolute Configuration of Tetrahydrolipstatin and Lipstatin (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 196-202 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Lipstatin (1), a natural product, and tetrahydrolipstatin (2) are pancreatic lipase inhibitors. Non-stereoselective and partially stereoselective syntheses of 2 are used to establish the absolute configuration of tetrahydrolipstatin and lipstatin.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700124
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  • 59
    Digitale Medien
    Digitale Medien
    Ring-Open Analogues of Adenine Nucleoside. Aminoacyl Derivatives of Cyclo- and Acyclo-Nucleosides (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 219-231 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of acyclic analogues of ribo- and deoxyribonucleosides is described. These compounds (Table 3) are both poor substrates and poor inhibitors of adenosine deaminase. The synthesis of dinucleotides from these analogues is also described, and the activity along with the inhibitory properties of some of them are studied against deaminase enzyme. These nucleotides are resistant to degradation by phosphodiesterases. HCl impregnated on silica gel is an excellent reagent for the preparation of the chloromethyl ether precursors of acyclo-nucleosides. A general and rapid procedure is developed for the preparation and isolation of the 5′-aminoacyl derivatives of robo- and arabinonucleosides. Quinoline has a marked effect on aminoacylations without racemization. Compounds 35a, b possess remarkable antiviral effects in vitro. A procedure is also developed for the conversion of acyclo-ribonucliosides 13e, f to acyclo-deoxyribonucleosides 11e, f.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700127
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  • 60
    Digitale Medien
    Digitale Medien
    Functionalisation of saturated hydrocarbons. Part 9Part 8:[1].. Oxidation of patchouli alcohol by the ‘gif system’: Isolation and organoleptic properties of three new ketonic derivativesDedicated to Prof. Vlado Prelog on the occasion of his 80th birthday (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 273-280 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oxidation of patchouli alcohol (1) using the ‘Gif system’ afforded as major isolated products three new ketonic derivatives 16-18. The structures of these compounds were established by spectral techniques including 2D-NMR. Ketones 16-18 display interesting organoleptic properties.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700202
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  • 61
    Digitale Medien
    Digitale Medien
    Synthese von ω-(5-Oxo-1-cyclopentenyl)alkansäure-methylestern aus 2-Nitrocycloalkanonen (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 315-320 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis of Methyl ω-(5-Oxo-1-cyclopentenyl)alkanoates Starting from 2-NitrocycloalkanonesA convenient synthesis of methyl ω-(5-oxo-1-cyclopentenyl)alkanoates 1 is described. 2-Nitrocycloalkanones 2 are converted to 2-(3,3-dimethoxypropy1)-2-nitrocycloalkanones 4. Treatment of 4 with MeOH/MeONa led to the ring-opened nitronates 5 which underwent a Nef reaction to form the corresponding oxo derivatives 6. Partial hydrolysis of followed by base-catalyzed aldol reaction gave the desired products in high yields.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700207
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  • 62
    Digitale Medien
    Digitale Medien
    Cyclobut-2-enones from Alkynes via Dichlorocyclobut-2-enonesIn part taken from the Ph.D. thesis of A.A.A., University of Zürich, 1986. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 321-328 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The [2 + 2]-cycloaddition of dichloroketene (prepared in situ from CCl3COCl and Zn(Cu)) with three alkynes 1a-c to form 2,3-dimethyl-(2a), 2,3-diethyl-(2b) and 3-butyl-4,4-dichlorocyclobut-2-enone (2c) proceeds rapidly in the absence of POCl3. The primary products 2a-c rearrange in situ to the 2,4-dichlorocyclobut-2-enones 3a-c under the influence of ZnCL2 produced during the reaction. ZnCl2 converts both 2a and 3a into a 4:6 equilibrium mixture of the two; this isomerization does not occur with LiCl. The Cl-atoms of both 2a, b and 3a, band of 2c may reductively be removed with Zn(Cu) in AcOH/pyridine to afford the alkylcyclobutenones 4a-c. Without pyridine, this reduction gives ca. 1:1 mixtures of the double-bond isomers 4 and 5 in low yields. The cyclobutenones 2c and 4c may be deuterated by CD3COOD in the presence of pyridine. D-Atom is introduced into 2c at C(4) and at C(γ), and into 4c at C(2) and C(4). A mechanism for this deuteration is considered, which does not involve a cyclobutadienolate 7, but rather a cyclobutenolate of type 8. The reductions of 2 and 3 to 4 might also pass through the same type of intermediate 8.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700208
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  • 63
    Digitale Medien
    Digitale Medien
    3-(Dimethylamino)-2,2-dimethyl-2H-azirin als α-Aminoisobuttersäure(Aib)-Äquivalent: Cyclische Depsipeptide durch direkte Amid-CyclisierungVorläufige Mitteilung s. [1]; vgl. auch [2]. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 329-338 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 3-(Dimethylamino)-2,2-dimethyl-2H,-azirine as an α-Aminoisobutyric-Acid (Aib) Equivalent: Cyclic Depsipeptides via Direct Amid CyclizationIn MeCN at room temperature, 3-(dimethylamino)-2,2-dimethyl-2H-azirine (1) and α-hydroxycarboxylic acids react to give diamides of type 8 (Scheme 3). Selective cleavage of the terminal N,N-dimethylcarboxamide group in MeCN/H2O leads to the corresponding carboxylic acids 13 (Scheme 4). In toluene/PhSH, phenyl thioesters of type 11 are formed (see also Scheme 5). Starting with diamides 8, the formation of morpholin-2,5- diones 10 has been achieved either by direct amide cyclization via intermediate 1,3-oxazol-5(4H)-ones 9 or via base-catalyzed cyclization of the phenyl thioesters 11 (Scheme 3). Reaction of carboxylic acids with 1, followed by selective amide hydrolysis, has been used for the construction of peptides from α-hydroxy carboxylic acids and repetitive α-aminoisobutyric-acid (Aib) units (Scheme 4). Cyclization of 14a, 17a, and 20a with HCI in toluene at 100° gave the 9-, 12-, and 15-membered cyclic depsipeptides 15, 18, and 21, respectively.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700209
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  • 64
    Digitale Medien
    Digitale Medien
    Synthese von 2-Hydeoxy-3-methyl-2-hexen-4-olid (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 369-374 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis of 2-Hydroxy-3-methyl-2-hexen-4-olidThe title compound 13a, a substance used in food-flavoring, was synthesized in 89% overall yield, starting from methyl 2-hydeoxy-3-butenoate (3a). The key step in this transformation is the isomerization of the C=C bond in 3a which yielded methyl 2-oxobutanoate as an intermediate. The latter underwent a self-condensation yielding 2-hydroxy-4-(methoxycarbonyl)-3-methyl-2-hexen-4-olid (11a), which, after hydrolysis and decarboxylation, gave 13a. In addition, the syntheses of five other compounds related to 13a are reported.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700214
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  • 65
    Digitale Medien
    Digitale Medien
    Triaziridine 7. Mitteilung6. Mitteilung: [1].. Stabile pyramidale Konfigurationen an den Stickstoff-Atomen von Dialkyl-und Trialkyl-triaziridinen (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 381-389 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Stable Pyramidal configurations at the Nitrogen Atoms of Dialkyl-and Trialkyl-triaziridinesStereochemical features of the recently synthesized nine samples of di- and trialkyl-triaziridines, namely the 1,3-cyclopentylen-(series a) and the two stereoisomers of the diisopropyl derivatives (series b and c), containing as the third substituent an H-atom (2), a CH3 group (3)or a CH2OH group (4), were elaborated on the basis of the 1H-, 13C-, and 15N-NMR spectra. The three N-atoms of the saturated N3-homocycle were found to be stable to pyramidal inversion in all cases. According to their NMR spectra, 2-4 of the series a and b possess twofold symmetry (Cs), while 2-4 of series c are asymmetric. Thus, series c has the trans-configuration at N(2)/N(3) and, consequently, the cis-configuration at N(1)/N(2), while series a and b have the cis-configuration at N(2)/N(3) and -since the all-cis-arrangement is excluded-the trans-configuration at N(1)/N(2). The asymmetry of the trans-configurated 2c turned into twofold symmetry (C2), when a little CF3COOH was added. The 1H- and 13C-NMR data of series b and c of our alkyl-triaziridines exhibit a shielding effect, according to which there are two types of i-Pr groups, i-Pr(a) and i-Pr(b). They differ in the NMR signals of the H- and the C-atoms of their CH groups: the H-atoms of i-Pr(a) are more deshielded by 0.75-1.111 ppm and its C-atoms are more shielded by 10.0-160.0 ppm as compared to the corresponding atoms of i-Pr(b). i-Pr(a) is cis (on the N3-homocycle) to a large substituent (such as i-Pr, Me, CH2OH) and to a lone pair, while i-Pr(b)is cis only to a small (H) or to no substituent and to one or two lone pairs. An analogous effect appears in the NMR signals of the CH3 and CH2OH groups at N(1) of 3 and 4 in the series b and c.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700216
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  • 66
    Digitale Medien
    Digitale Medien
    Synthese eines Nickel(II)-B,C,D-hexadehydrocorrinats durch (A→D)-CyclisierungKurzmitteilung: [1].Professor Dr. Gerhard Quinkert zum 60. Geburtstag gewidmet (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 402-411 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis of a Nickel(II) B,C,D-Hexadehydrocorrinate by (A→D)-Ring ClosureThe B,C,D-hexadehydrocorrin of type 10 fills a gap in the corrin family whose members can occur at different oxidation levels. We report here on the synthesis of a correspondingly protected secocorrin 23 and its convenient cyclization to 10
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700219
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  • 67
    Digitale Medien
    Digitale Medien
    Studies on the Biosynthesis of Tabtoxin (Wildfire Toxin). Origin of the Carbonyl C-Atom of the β-Lactam Moiety from the C1-Pool (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 412-422 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Re-isolation of Pseudomonas tabaci strain NCPPB 2730 from its host, the tobacco plant, led to an activation of the bacteria in order to produce the β-lactam dipeptide tabtoxin (Wildfire toxin, 1). Incorporation of several 14C-labelled amino acids as well as L-[methyl-13C]methionine, L-[1,2-13C2]- and L-[3,4-13C2]aspartate, rac -[1,2-13C2]glycerol, and [1,2-13C2]acetate into isotabtoxion (2) demonstrated that the building blocks of tabtoxin (1) are L-threonine, L-aspartate, the Me group of L-methionine and a C2-unit derived from the C3-pool (Fig. 3). The Me group of L-methionine provides the carbonyl C-atom of the β-lactam moiety. These findings represent a novel pathway in β-lactam biosynthesis. Mechanistic aspects with respect to the β-lactam ring formation are discussed. A biradical 16 is proposed as an intermediate during the cyclization of a N-formyl-α-amino ketone 15.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700220
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  • 68
    Digitale Medien
    Digitale Medien
    Mitteilungen - Communications (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 488-491 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700229
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  • 69
    Digitale Medien
    Digitale Medien
    On the Purported Structure of Cyclodeca[1,2,3-de: 6,7,8-d′e′]dinaphthalene (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 480-487 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of the bis(sulfonium salt)7 in a solution of Na2CO3 in H2O/EtOH yielded three main products 8-10. The spectroscopic data of 8 were identical to those which led Mithcell and Sondheimer to assign them to cyclodeca[1,2,3-de: 6,7,8-d′e′]dinaphthalene (3). Our investigations show, however, that the correct structural assignment leads to the structure of 7,7a-dihydrodibenzo[de,mn]naphthacene (8).
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700228
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  • 70
    Digitale Medien
    Digitale Medien
    Masthead (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987) 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700101
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  • 71
    Digitale Medien
    Digitale Medien
    Mehrstufige Redoxsysteme. XLIX. MitteilungXLVIII. Mitteilung:[1]. Mit π-Systemen substituierte 1,3-Dimethylidencyclobutane: Synthese und Eigenschaften (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 929-941 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Multistep Redox Systems. 1,3-Dimethylidenecyclobutanes Substituted by π-Syntheses and PropertiesAs potential redox systems 1,3-dimethylidenecyclobutanes are synthesized in which the ‘exo’-methylidene group participates in a cyclopentadienyl (typeC4)or cycloheptatrienyl (type A5) system. Benzo-annellated systems are also described. The formation of the C=C bond by the reaction of thioketones (3 and 31) with diazo compounds is extended to extended to 1,6,7,21, and 24, which so far had not been employed. In some cases, intermediate thiiranes can be isolated (e.g.4) which are smoothly transformed into the target compounds of types C4 and A5 by extrusion of sulfur. The new C=C bonds may be introduced stepwise, thereby allowing the synthesis of unsymmetrically substituted 1,3-dimethylidenecyclobutanes (e.g. 20 and 35). Reduction of by Na does not produce bicyclobutanes but compounds 43 and 44 with one dihydrofulvene unit.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700404
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  • 72
    Digitale Medien
    Digitale Medien
    Verecynarmin A, a Novel Briarane Diterpenoid Isolated from Both the Mediterranean Nudibranch Molluse Armina maculata and its Prey, the Pennatulacean Octocoral Veretillum cynomorium (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 984-991 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The briarane diterpenoid verecynarmin A (=(-)).(8R,9S,11R,12aR,4Z,6Z)-11,12-epoxy-8,8a,9,10,12,12a,13-octahydro-1,5,8a,12-tetramethylbenzo[4,5]cyclodeca[1,2-b]furan-9-yl acetate; ((-)-1) is shown to be contained in both the Mediterranean nudibranch mollusc Armina maculata(RAFINESQUE) and its prey, the pennatulacean octocoral Veretillum cynomorium(PALLAS). The structure is mainly solved by 1D-NMR, 2D-NMR, and NOE studies of (-)-1. However, the relative configurations at the epoxide and angular methyl centres, as well as the preferred conformation, are established by shift-reagent and NOE studies of diol(-)-4 obtained by epoxide-ring opening of (-)-1 with LiA1H4. The absolute configuration is established via deacetylation of (-)01 followed by Horeau's esterification.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700408
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  • 73
    Digitale Medien
    Digitale Medien
    Oxidationsreaktionen methyl-substituierter 2,1,3-Benzothiadiazole und 2,1,3-Benzoselenadiazole mit Selen-dioxid (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 997-1000 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oxidation Reactions of Methyl Substituted 2,1,3-Benzothiadiazoles and 2,1,3-Benzoselenadiazoles with Selenium DioxideThe synthesis 5-8 by oxidation of 4-methyl-(1),5-methyl(2), 5,6-dimethyl-2,1,3-benzoselenadiazole (3), and 5,6-dimethyl-2,1,3-benzothiadiazole (4), respectively, with selenium dioxide as well as their spectroscopic properties are described.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700411
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  • 74
    Digitale Medien
    Digitale Medien
    Steric Effects on Reaction Rates. Part IX. Force-Field Parameters for Bridgehead and Rigid Tertiary Carbenium Ions (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1017-1024 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Molecular-mechanics calculations for strain of carbenium ions are tested using Bentley's unified reactivity scale for bridgehead solvolysis as reference. Excellent correlations are obtained for solvolytic bridgehead reactivity with the calculated steric-energy difference (ΔEst) between substrate (R—H or R—OH) and cation (R+). After adjustment of appropriate force-field parameters, the approach is successfully extended to the rigid, but planar cations derived from structures 15-20; however, the general set of parameters cannot be applied to highly strained systems such as the cation formed from 17. With all of the 18 sets of parameters tested, the 2-endo-norbornyl derivative 16, is adequately correlated, while the exo isomer 15 exhibits enhanced reactivity by a factor of ca. 102 to 103.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700414
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  • 75
    Digitale Medien
    Digitale Medien
    Complexes of 2,2′,2″-Nirtilotriphenol. Part IV. Cage Compounds with Phosphorus(III) and Phosphorus(V) (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1063-1069 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The ligand 2,2′,2″-nitrilotriphenol reacts with P(III) and P(V) compounds to form corresponding phosphorus complexes. Syntheses and NMR data of 2,2′,2″-nitrilotriphenyl phosphite (II), 2,2′,2″-nitrilotriphenyl phosphate (III) and of a hydrolysis product of II, 2,2′-[N-(2-hydroxyphenyl)imino]diphenly phosphonate (IV), are reported, as well as crystal structures of II and IV. Phosphite II shows a bicycloundecane framework; no NċPinteraction is present. The phosphonate IV shows two coordinated and one dangling phenol group; the N-atom does not interact with the P-atom. Strong acids protonate II as well as III to form cations: in these, NMR evidence indicates coordination of the N-atom to the P-atom.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700418
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  • 76
    Digitale Medien
    Digitale Medien
    Octacarbonyldicoblat-Inauced (1,3) H Shits in 1-Methylallenecarboxylates and Allenic LactonesDedicated to Professor Dr. André S. Dreiding (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1070-1075 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The allenecarboxylates 1a,b and allenic lactones 4a,b undergo thermally induced (1,3) H Shifts in the presence of Co2(CO)8. The non-isolated 1,3-dienes 2a,b react further affording the Diels-Alder Adducts 3a,b Scheme 1 in high yields. These adducts were not formed in the case of the 2-vinybutenolides 5a,b. On irradiationin the presence of Co2(CO)8 or Mn2(Co)10, the studied allenes reacted in a different manner, yielding either cyclization products 7 and 8 (Scheme 3) or products 9 and 10, formed via H abstracton and solvent addition (Schemes 4 and 5).
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700419
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  • 77
    Digitale Medien
    Digitale Medien
    Brominations of Cyclic Acetals from α-Amino Acids and α- or β-Hydroxy Acids with N-Bromosucinimide (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1104-1114 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The preparation of novel electrophilic building blocks for the synthesis of enantiomerically pure compounds (EPC) is described. Thus, the 2-(tert-butyl)dioxolanones, -oxazolidinones, -imidazolidinones, and -dioxanones obtained by acetalization of pivalaldehyde with 2-hydroxy-, 3-hydroxy-, or 2-amino-carboxylic acids are treated with N-bromosuccinimide under typical radical-chain reaction conditions (azoisobuytyronitril/CCl4/reflux). Products of bromination in the α-position of the carbonyl group of the five-membered-ring acetals are isolated or identified (2, 5, and 8; Scheme 1). The dioxanones are converted to 2H, 4H-dioxinones under these conditions (12, 14, 15, 21, and 22; Schemes 2 and 3). The products can be converted to chiral derivatives of pyruvic acid (methylidene derivatives 3 and 6) or of 3-oxo-butanoic and -pentanoic acid (16 and 23). The mechanism of the brominations is interpreted. The conversion of serine to enactiomcrically pure dioxanones 26-28 (Scheme 4) is also discussed.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700423
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  • 78
    Digitale Medien
    Digitale Medien
    Addendum (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1229-1229 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700428
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  • 79
    Digitale Medien
    Digitale Medien
    Mitteilungen - Communications (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1230-1231 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700429
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  • 80
    Digitale Medien
    Digitale Medien
    Enzyme-Catalyzed Hydrolysis of Some Functionalized Dimethyl MalonatesPresented at the meeting of the Swiss Chemical Society, Berne, October 10, 1986. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1250-1254 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A method is described for the preparation of (+)-(R)-methyl hydrogen 2-(tert-butoxymethyl)-2-methyl-malonate (5e) in synthetically useful amounts from readily available starting material.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700503
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  • 81
    Digitale Medien
    Digitale Medien
    Diels-Alder-Reaktionen von 2,4-Bis{[(tert-butyl)dimethylsilyl]oxy}-3-aza-1,3-pentadien mit HeterodienophilenTeil der geplanten Dissertation von U. R. [1]. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1255-1260 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Diels-Alder Reactions of 2,4-Bis{[(tert-Butyl)dimethylsilyl]oxy}-3-aza--1,3-pentadien with HeterodienophilesThe 2,4-bis{[(tert-butyl)dimethylsilyl]oxy}-3-aza-1,3-pentadien(2) reacts via the Diels-Alder adducts 3, 6a-c, and 8a, b, which cannot be isolated, giving the triazines 4, 7a-c, and the oxadiazines 9a, b. The hydrolysis of 4 in MeOH affords the N-acetyl-acetamid derivative 5. The formula of 9a is proven by an X-ray-structure analysis.
    Notizen: No. Abstract.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700504
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  • 82
    Digitale Medien
    Digitale Medien
    Zwei weitere Iridoid-glycoside und ein Monoterpen-glycosid aus Sambucus ebulus L. (Caprifloiaceae). 3. Mitteilung über die Inhaltsstoffe der Zwergholunderwurzel (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 91-101 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New Iridoid Glycosides and a Monoterpene Glycoside from Sambucus ebulus L. (Caprifloiaceae)From the roots of Sambucus ebulus L., two novel valeriana-type ester iridoid glycosides, 6′-O-apiosylebuloside (1) and 7,7-O-dihydroebuloside (3), along with the open-chain monoterpene glycoside 5 were isolated. Their structure elucidation is based mainly on one- and two-dimensional NMR methods. 1H,1H-COSY experiments permitted complete assignment of signals arising from the disaccharide unit in 1. Biogenetically, 3 seems to represent the equivalent of loganin in the valeriana-type series of iridoid glycosides.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700111
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  • 83
    Digitale Medien
    Digitale Medien
    Synthese von ‘D-Isothreonin’ und ‘L-Alloisothreonin’ aus L-Alanin (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 116-120 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis of ‘D-Isothreonine’ and ‘L-Alloisothreonine’ Starting from L-AlanineStarting from L-alanine, ‘D-isothreonine’ ( = (2R, 3S)-3-amino-2-hydroxybutanoic acid) and ‘L-alloisothreonine’ ( = (2S, 3S)-3-amino-2-hydroxybutanoic acid) were synthesized.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700113
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  • 84
    Digitale Medien
    Digitale Medien
    Oxidative Breaking of Long-Chain Acetylenic Enol Ethers of Glycerol of the Marine Sponges Raspailia pumila and of Model Compounds with Aerial Oxygen (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1400-1411 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The raspailynes (novel long-chain enol ethers of glycerol having the enol ethers double bond conjugated in sequence, to an acetylenic and an olefinic bond, isolated from the North-East-Atlantic sponges Raspailia pumila and R. ramosa) are stable under normal hydrolytic conditions for enol ethers. In contrast, when their solutions are evaporated, these lipids such as raspailyne Bl (=(-))-3-[(1Z,5Z)-(tetradeca-1,5-dien-3-ynyl)oxy]-1,2-propanediol;(--2) rapidly react with aerial O2 under normal laboratory-daylight conditions, with rupture of the C=C enol ether bond to give 1-O-formylglycerol (3) and an aldehyde (such as tridec-4-en-2ynal(4) from (-)-2). This reaction must be caused by triplet O2, since thermally generated singlet O2 has no effect on (-)-2 in solution. That the mere presence of an enol-ether moiety conjugated to an acetylenic group is responsible for such a behaviour is demonstrated with the model compounds 1-methoxypentadec-1-en-3-yn-5-ol (6a) and its 5-O-acetyl or 5-O-tetra-hydropyranyl derivatives 6b and 6c, respectively. Resistance to both hydroytic conditions and singlet O2 of these compounds is thought to arise from electron depletion at the enol-ether C(beta;) atom by the acetylenic group. Plausible reaction pathways for enol-ether bond rupture in these compounds by aerial O2 are outlined.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700521
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  • 85
    Digitale Medien
    Digitale Medien
    Catalytic Intramolecular Palladium-Ene Reactions. Preliminay CommunicationPresented at the ‘4th IUPAC-Symposium on Organometallic Chemistry Directed towards Organic Synthesis’ (OMCOS IV), July 28, 1987, Vancouver, Canada. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1477-1481 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Pd(dba)2[dba = dibenzylideneacetone]/PPh3-or Pd(PPh3)4-catalyzed cyclizations of acetoxy-dienes 2 → 3 and 10 → 11 gave 1-vinyl-2-methylidene-subsituted cyclopentances and cyclohexanes in high yield, consistent with a palladium-ene/β-elimination mechanism (D → E → F, Scheme 2). The efficient and highly stereoselective cyclizations 7 → 7 and 8 → 9 illustrate intramolecular allylpalladium insertions into 1,2-dialkyl-, trialkyl-, trialkyl-, and cyclic alkenes followed by elimination of the exocyclic β-H giving 1,2-divinylcyclopentanes. These new olefin insertions proceed faster in AcOH (compared to THF) and occur preferentially cis relative to the Pd (13 → 14 → 15).
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700604
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  • 86
    Digitale Medien
    Digitale Medien
    Drug-induced modifications of the immune response part 9Part8: [1]4-(Arylamino)-2,5-dihydro-2-oxo-N-(trans-2-phenylcycolopropyl)furan-3-carboxamides as Novel Antiallergic Compounds (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1526-1530 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis and antiallergic activity of a series of 4-(arylamino)-2,5-dihydro-2-oxo-N-(trans-2-phenyl-cyclopropyl)furan-3-carboxamides 10 are described. Treatment of N-substituted 2-amino-4,5-dihydro-4-oxofuran-3-carboxylic acids 9 with chlorooxobis(2-oxo-1,3-oxazolidin-3-yl)phosphorus (2) and an appropriate aromatic amine in the presence of Et3N, resulted in a novel 3(2H)-furanone-→2(5H)-furanone rearrangement that led to the facile preparation of the new amides 10. The latter exerted a potent antiallergic activity when tested in the dermal vascular permeability and active anaphylaxis assays in rats. The most active compound 10b inhibited the action of serotonin, histamine, and bradykinin by 94, 92, and 100%, respectively, when administered intraperitoneally to rats at doses of 100 mg/kg. The present series of 10 represents a novel class of antiallergic agents.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700609
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  • 87
    Digitale Medien
    Digitale Medien
    Notiz über die Verwendung von 3-(Arylsulfonyl)-2-cycloalkenonen als 2-Cycloalkinon-Synthese-Equivalente (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1537-1539 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Note on the Use of 3-(Arylsulfonyl)-2-cycloalkenones as Synthesis Equivalents of 2-Cycloalkynones3-(Arylsulfonyl)-2-cyclopentenones and 3-phenylsulfonyl-2-cyclohexnone undergo Diels-Alder reactions with cyclopentadiene. Elimination of arylsulfinic acid leads to products, which would have been obtained directly from a Diels-Alder reaction of 2-cyclopentynone or 2-cyclohexynone.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700611
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  • 88
    Digitale Medien
    Digitale Medien
    Inhibition of Electron-Hole Recombination in Substitutionally Doped Colloidal Semiconductor Crystallites (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1596-1604 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The subtitutional doping of 120-Å- sized TiO2 Particles with Fe(III)ions has a profound effect on the charge carrier recombination time in this colloidal semiconductor. In undoped particles, the mean lifetime of an electronhole pair is ca. 30 ± 15 ns. Doping with 0.5% Fe(III) drastically augments the charge-carrier lifetime which is extended to minutes or hours. The slow character of the recombination dynamics in Fe(III)-doped colloids was confirmed by laser photolysis using the characteristic optical of electrons in TiO2 to monitor the time course of the reaction. EPR studies showed the Fe(III) ions to enter the host lattice on Ti(IV) sites, charge compensation taking place through the formation of oxygen vacancies. Valence-band holes produced under band-gap excitation react with these centers it the bulk forming Fe(IV), the conduction band electrons being trapped by Ti(IV) at the particle surface. Presumably, the spatial separation of the trapped electron and hole sites inhibits their recombination.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700617
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  • 89
    Digitale Medien
    Digitale Medien
    The Radical Anions of 1,2-diphenylcyclohexene and Structurally Related Compounds. Conformational ESR and ENDOR studies (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1558-1568 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ESR, ENDOR, and TRIPLE resonance studies have been performed on the radical anions of 1,2-diphenylcyclohex-1-ene (4), 1,2-di(perdeuteriophenyl)cyclohex-1-ene ((D10)4) the trans-configurated 3,4-diphenyl-8-oxabicyclo[4.3.0]non-3-ene (5) and its 2,2,5,5-tetradeuterio derivative (D4)5, and 2,3-diphenyl-8,9,10-trinorborn-2-ene (6). The spectra of \documentclass{article}\pagestyle{empty}\begin{document}$ 4^{- \atop \dot{}} $\end{document} exhibit strong temperature dependence along with a specific broadening of ESR hyperfine lines and proton ENDOR signals. The coupling constant, which bears the main responsibility for these features, is that of the β-protons in the quasi-equatorial positions of the cyclohexene ring, and the experimental findings are readily rationlized in terms of relatively modest conformational changes without invoking the inversion of the half-chair form. The hyperfine data for the β-protons in \documentclass{article}\pagestyle{empty}\begin{document}$ 5^{- \atop \dot{}} $\end{document} closely resemble the corresponding low-temperature values for \documentclass{article}\pagestyle{empty}\begin{document}$ 4^{- \atop \dot{}} $\end{document}, However, the ‘unusual’ features observed for \documentclass{article}\pagestyle{empty}\begin{document}$ 4^{- \atop \dot{}} $\end{document} are absent in the ESR and ENDOR spectra of \documentclass{article}\pagestyle{empty}\begin{document}$ 5^{- \atop \dot{}} $\end{document}, because the half-chair conformation of the cyclohexene ring in \documentclass{article}\pagestyle{empty}\begin{document}$ 5^{- \atop \dot{}} $\end{document} is deprived of its flexibility. Although the boat form of this ring in \documentclass{article}\pagestyle{empty}\begin{document}$ 6^{- \atop \dot{}} $\end{document} is also rigid, the spectra of \documentclass{article}\pagestyle{empty}\begin{document}$ 6^{- \atop \dot{}} $\end{document} are temperature-dependent, due to an interconversion between two propeller-like conformations of the phenyl groups. The pertinent barrier is 30 ± 5 kJ·mol-1. An analogous interconversion presumably takes place in \documentclass{article}\pagestyle{empty}\begin{document}$ 4^{- \atop \dot{}} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ 5^{- \atop \dot{}} $\end{document} as well, but, unlike \documentclass{article}\pagestyle{empty}\begin{document}$ 6^{- \atop \dot{}} $\end{document}, it is not amenable to experimental study.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700614
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  • 90
    Digitale Medien
    Digitale Medien
    Synthesis and Formation of Ironcarbonyl Complexes of 3′,3′-Dimethyl-2,3,5,6-tetramethylidenespiro[bicyclo[2.2.1]heptane-7,2′-oxirane]. Single-Crystal and Molecular Structure of syn,exo2,3-anti,endo5,6-trans-μ-[(1r,2r,3s,4s,5s,6r)-c,2,3,c-η:c,5,6,c-η-(3′,3′-dimethyl-2,3,5,6,-tetramethylidenespiro[bicyclo[2.2.1]heptane-7,2′-oxirane])]bis(tricarbonyliron)Interaction between non-conjugated chromophores, Part 27. Part 26, see [1]. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1638-1648 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The 3′,3′-dimethyl-2,3,5,6-tetramethylidenespiro[bicyclo[2.2.1]heptane-7,2′-oxirane] (3) was derived from 6,6-dimethylfulvene and maleic anhydride. Its reaction with 1 equiv. of ethylenetetracarbonitrile (TCNE) was not regioselective and gave a 1:1 mixture of the corresponding monoadducts 10 and 11. The rate constants of the Diels-Alder additions of 10 and 11 to TCNE were significantly smaller than that of the reaction 3 + TCNE. Monocomplexation of 3 with Fe2(CO)9 was highly exo-face selective giving a mixture of the corresponding monocomplexes 12(anti-exo) and 13(syn-exo). The latter were complexed with Fe2(CO)9 in a non-stereoselective fashion, giving mixtures of the dicomplexes 14(anti-exo, syn-endo), 15(anti-exo,syn-exo), and 16(anti-endo, syn-exo). Exchange of the CO ligands was a faster process for the endo-Fe(CO)3 moieties than for the exo-Fe(CO)3 moieties. Line-shape analysis of the 13C-NMR spectrum of 15 established that one of the exo-Fe(CO)3 groups in 15 rotates ca. 3 times as fast as the other Fe(CO)3 group at 40°. The structure of the anti-endo, syn-exo dicomplex 16 was determined by single-crystal X-ray diffraction studies.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700621
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  • 91
    Digitale Medien
    Digitale Medien
    New Antifungal Chromenyl Ketones and their Pentacyclic Dimers from Hypericum revolutum VAHLPresented in part at the 34th Annual Congress on Medicinal Plant Research, Hamburg, FRG, 22-27 September, 1986. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1694-1702 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two new 2H-1-benzopyranyl ketones 1 and 2 and three new pyrano[3,2-c: 4,5,6-d′ e′]di[1]benzopyrandiyl diketones 3, 4a/4b, and 5 have been isolated from the leaves and twigs of Hypericum revolutum VAHL (Guttiferae). The structure of 3 (hyperevoline) was established by X-ray analysis as 1,1′-[1,13,13a,13b-tetrahydro-5,8,10-trihydroxy-2,2,6,9,13,13-hexamethyl-2H, 7aH-pyrano[3,2-c:4,5,6-d′e′]di[1]benzopyran-4, 11-diyl]bis[2-methyl-1-propanone]. The structures of the isolated compounds were established by spectroscopic (UV, IR, EI-MS, 1H- and 13C-NMR) and chemical (acetylation and acidic dimerization) methods.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700705
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  • 92
    Digitale Medien
    Digitale Medien
    Mammalian Alkaloids: Configurations of Optically Active Salsoline- and 3′,4′-Dideoxynorlaudanosoline-1-carboxylic AcidsSalsoline and norlaudanosoline are well known alkaloids, and these names will be used in the General Part (for systematic names, see Expert. Part). The systematic name for salsoline is 1-methyl-7-methoxy-1,2,3,4-tetrahydroisoquinolin-6-ol and that for norlaudanosoline, also named tetrahydropapaveroline, is 1-(3′,4′-dihydroxybenzyl)-1,2,3,4-tetrahydroisoquinoline-6,7-diol. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1721-1731 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis of the optical isomers of (±)-methyl 6,7-dimethyl-3′,4′-dideoxynorlaudanosoline-1-carboxylate ((±)-2) was accomplished by reaction of (±)-2 with (+)-(R)-1-phenylethyl isocyanate, separation of the urea diastereoisomers (-)-4A and (+)-4B, and alcoholysis of the ureas in refluxing BuOH. Optically active isoquinoline-carboxylates 2A,B and hydantoins 8A,B isolated were characterized. The absolute configuration of the reaction products was established by X-ray analysis of the optically active hydantoin (+)-8A. Hydrolysis of the methyl isoquinolinecarboxylates 2A,B with 48% HBr soln. at reflux afforded the desired optically active 3′,4′-dideoxynorlaudanosoline-1-carboxylic acids 1A,B required for enzyme-inhibition studies. Details of the X-ray diffraction analysis of (+)-methyl salsoline-1-carboxylate hydrobromide ((+)-11A·HBr) prepared earlier are included. CD spectra of (+)-(S)-methyl 6,7-dimethyl-3′,4′-dideoxynorlaudanosoline-1-carboxylate hydrobromide ((+)-2A. HBr) and (-)-(R)-methyl salsoline-1-carboxylate hydrochloride ((-)-11B·HCl) confirmed the assignment of their (S)- and (R)-configurations, respectively.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700707
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  • 93
    Digitale Medien
    Digitale Medien
    Determination of the Quantum Yield of Intersystem Crossing of Rose Bengal (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1760-1773 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The quantum yield of intersystem crossing (Φisc) of a sensitizer is related to the quantum yield of singlet-oxygen production (Φ(1O2)) by the efficiency of the energy transfer (ϕet) and is an important parameter in the evaluation of potential applications of sensitized photo-oxidations. Using two different laser photolysis techniques, the energy-transfer method and the partial saturation method, Φisc of rose bengal has been determined in MeOH and in aqueous solutions. The results confirm that with Φisc(H2O) = 1.05(± 0.06) and Φisc(MeOH)=0.90(±0.08), the generally assumed relation Φisc · ϕet = Φ(1O2), with ϕet = 1, cannot be maintained any longer (Φ(1O2, H2O) = 0.75 and Φ(1O2, MeOH) = 0.76). During these experiments, a second intermediate has been observed which is produced from the triplet state of rose bengal and, stabilized in a anionic micellar solution, has been shown to be the radical cation of the sensitizer. The efficiency of the electron transfer has been evaluated from transient absorption and bleaching recordings, and it seems conclusive to attribute the results to the difference between Φisc and Φ(1O2).
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700712
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  • 94
    Digitale Medien
    Digitale Medien
    ‘Face-to-Face’-Benzo-anellierte homologe Hypostrophene. Synthesen, Röntgenstrukturanalysen und PE-Spektren (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1816-1842 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ‘Face-to-Face’ Benzo-anellated Homologous Hypostrophenes. Syntheses, X-Ray-Structure Analyses and PE Spectra‘Face-to-face’ Benzo-anellated homologous hypostrophenes (series M), of interest as substrates for [6 + 6]-photocycloaddition reactions, have been synthesized. From X-ray structural analyses of 13b and 13c shortest C—C distances of 2.80(2.76)/2.71 Å and interorbital angles (ω) of 129° (128°)/130° between the benzene rings have been determined. The PE spectra are discussed in the context of transannular π,π interactions.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700718
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  • 95
    Digitale Medien
    Digitale Medien
    Formation and Structure of the Phosphoranyl Radical Derived from 1,2-Phenylene Phosphorochloridate: a Solid-State ESR Study (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1897-1904 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The crystal structure of 1,2- phenylene phosphorochloridate has been determined. X-Ray irradiation of these crystals, at low temperature, leads to the formation of a radical exhibiting hyperfine structure with P and Cl nuclei. The corresponding ESR tensors are obtained, and they show that this radical is a phosphoranyl radical adopting a slightly distorded σ* structure. The same species could be produced in frozen solution, its hyperfine tensors are, then, more in accordance with a trigonal-bipyramid structure. The effects of the host matrix on the stabilization of the structure of phosphoranyl are investigated.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700724
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  • 96
    Digitale Medien
    Digitale Medien
    Isolierung und Strukturaufklärung von 36 Diterpenoiden aus Trichomen von Plectranthus edulis (VATKE) T.T. AYE (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1911-1929 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Isolation and Structure Elucidation of 36 Diterpenoids from Leaf-Glands of Plectranthus edulis (VATKE) T.T. AYEAnalysis of the polar diterpenoids from the yellow glands of the title plant from Kenya and Abyssinia led to the identification of several novel abietanoids. Main compound is the known edulon A (40), a 5(4→3) abeo-abietane. Minor compounds include 6 different royleanones, 15 spirocoleons, 3 vinylogous quinones, 8 acylhydroquinones (as their 6,7-dioxo compounds or the tautomeric disophenols), 2 naphthaquinones (as the 1,10-seco-abietanoids), and deacetyledulon A. The known coleon-A-lactone (37) now has also been found in Plectranthus edulis. The intermediacy of the γ-enollactol 44, combined with a leaving group on C(3) is postulted to explain the biogenesis of the unusual 4H-5-oxaaceanthrylen skeleton of edulon A.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700726
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  • 97
    Digitale Medien
    Digitale Medien
    Synthesis of trans-10,11-Dihydro-10,11-dihydroxy-5H-dibenz[b,f]azepine-5-carboxamide, a Major Metabolite of Carbamazepine (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1955-1962 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The stereoselectivity of the reduction of 5-carbamoyl-10,11-dihydro-11-oxo-5H-dibenz[b,f]azepine-10-yl acetate (6), prepared in two steps from 10,11-dihydro-10-oxo-5H-dibenz[b,f]azepine-5-carboxamide (4), has been studied. Among the reagents used, diisobutylaluminum hydride (DIBAH) was found to give the highest trans/cis diol ratio. This allowed the preparation of the important trans-diol metabolite 3 of carbamazepine (1).
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700730
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  • 98
    Digitale Medien
    Digitale Medien
    Are the known Δ2-cephems inactive as antibiotics because of an unfavourable steric orientation of their 4α-carboxylic group? Synthesis and biology of two Δ2-cephem-4β-carboxylic acids (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1967-1979 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two representatives of the yet unknown type of Δ2-cephem-4β-carboxylic acids were prepared. Contrarily to the prediction based on the activity model of Cohen, both acids proved inactive as antibiotics. Possible reasons for this discrepancy are briefly discussed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700732
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  • 99
    Digitale Medien
    Digitale Medien
    Isolierung von 10′-Apo-β-carotin-10′-ol und (3R)-10′-Apo-β-carotin-3,10′-diol (Galloxanthin) aus Rosenblüten. 5. Mitteilung über Rosenfarbstoffe1. bis 4. Mitt., s. [1-4]. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1988-1993 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Isolation of 10′-Apo-β-carotene-10′-ol and (3R)-10′-Apo-β-carotene-3,10′-diol (Galloxanthin) from Rose FlowersThe novel (all-E)-10′-apol-β-carotene-10′-ol (2) and (all-E,3R)-10′-apo-β-carotene-3,10′-diol (5) have been isolated from petals of one yellow species and various whitish or yellow blend varieties of rose cultivars. Each (all-E)-compound is accompanied by a (Z)-isomer, probably the (9Z)-isomer. Diol 5 proved to be identical with galloxanthin, an apo-10′-carotenol previously isolated from the retina of chicken.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700803
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  • 100
    Digitale Medien
    Digitale Medien
    Nucleotides. Part XXVI.Part XXV: [1].. A new synthesis of 9-(′-D-ribofuranosyl)uric acid and its 5′-monophosphateDedicated to Professor Morio Ikehara, Osaka University, Osaka, Japan (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 210-218 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Syntheses for 9-(β-D-ribofuranosyl)uric acid (16) and its 5′-monophosphate 14 have been achieved starting from guanosine and applying the 2-(p-nitrophenyl)ethyl group for protection of the aglycon moiety as well as the phosphate function. A more efficient and direct approach to 14 uses O6, O8-dibenzyl protection and phosphorylation by the Yoshikawa procedure. The various protected intermediates have been characterized by spectroscopic means and elemental analysis.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700126
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