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  • 1985-1989  (1,686)
  • 1965-1969  (4,020)
  • 1987  (1,686)
  • 1969  (1,926)
  • 1968  (2,094)
  • General Chemistry  (3,288)
  • Inorganic Chemistry  (2,349)
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  • 1985-1989  (1,686)
  • 1965-1969  (4,020)
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  • 1
    Electronic Resource
    Electronic Resource
    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
    Keywords: Development ; Thyroid “C” cell ; Cat ; Immunohistochemistry ; Calcitonin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00325289
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  • 2
    Electronic Resource
    Electronic Resource
    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
    Keywords: Capillaries ; Tooth pulp ; Tight junctions ; Odontoblasts ; Ultrastructure ; Mineralisation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00572537
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  • 3
    Electronic Resource
    Electronic Resource
    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
    Keywords: Experimental communicating syringomyelia ; Ependyma ; Spinal cord ; Cat ; Scanning electron microscope
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00691097
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  • 4
    Electronic Resource
    Electronic Resource
    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
    Keywords: Off-vertical-axis rotation ; Eye movements ; Vestibulo-ocular reflex ; Optokinetic nystagmus ; Otoliths ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00270685
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  • 5
    Electronic Resource
    Electronic Resource
    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
    Keywords: Contrast gain control ; Lateral geniculate nucleus ; Temporal frequency ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00270692
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  • 6
    Electronic Resource
    Electronic Resource
    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
    Keywords: Ocular dominance ; Plasticity ; Noradrenaline ; Cat ; Visual cortex ; Squint effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00249802
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  • 7
    Electronic Resource
    Electronic Resource
    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
    Keywords: Area 19 ; Sinusoidal grating ; End-zone inhibition ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235978
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  • 8
    Electronic Resource
    Electronic Resource
    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
    Keywords: Postural reflexes ; Unexpected postural perturbations ; Electromyographic activity ; Hindlimb muscles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235976
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  • 9
    Electronic Resource
    Electronic Resource
    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
    Keywords: Corticothalamic feedback ; Binocular rivalry ; Lateral geniculate ; Vision ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00236196
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  • 10
    Electronic Resource
    Electronic Resource
    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
    Keywords: Bradykinin ; Tooth-pulp ; Cortical neuron ; Coronal gyrus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00243318
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  • 11
    Electronic Resource
    Electronic Resource
    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
    Keywords: Preoptic region ; Frontal cortex ; Medial basal hypothalamus ; Electrophysiology ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00270688
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  • 12
    Electronic Resource
    Electronic Resource
    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
    Keywords: Corticopontine collaterals ; Corticotectal neurons ; Cortex ; Cat ; Fluorescent tracers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00269447
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  • 13
    Electronic Resource
    Electronic Resource
    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
    Keywords: Cat ; Electrophysiology ; Lateral geniculate cells ; Signal detection ; Visual latencies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235998
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  • 14
    Electronic Resource
    Electronic Resource
    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
    Keywords: Joint ; Spinal cord ; Pain ; Ascending tracts ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00270680
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  • 15
    Electronic Resource
    Electronic Resource
    Lateral excitation in the cat lateral geniculate nucleus (1987)
    Springer
    Experimental brain research 67 (1987), S. 291-298 
    Details
    ISSN: 1432-1106
    Keywords: Lateral inhibition ; Lateral excitation ; Cat ; Dorsal lateral geniculate nucleus ; GABA ; Silent synapses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00248550
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  • 16
    Electronic Resource
    Electronic Resource
    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
    Keywords: Postural reflexes ; Unexpected postural perturbations ; Electromyographic activity ; Motor control ; Hindlimb muscles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00249792
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    Electronic Resource
    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
    Keywords: Visual cortex ; Ocular dominance columns ; Flat-mount ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00249809
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  • 18
    Electronic Resource
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    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
    Keywords: Joint ; Pain ; Inflammation ; Spinal cord ; Ascending tracts ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00270681
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    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
    Keywords: Entorhinal area ; Current source density ; Olfactory afferents ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00247292
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    Electronic Resource
    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
    Keywords: Ammon's horn ; Hippocampus ; Septum ; Dentate gyrus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00255243
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    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
    Keywords: Binocular interaction ; Lateral geniculate nucleus ; Cat ; Retinal disparity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00248796
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    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
    Keywords: Cat ; Inferior colliculus ; Single cell recording ; Binaural hearing ; Time/intensity trading
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00248803
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    Effects of monocular strobe rearing on kitten striate cortex (1987)
    Springer
    Experimental brain research 68 (1987), S. 525-532 
    Details
    ISSN: 1432-1106
    Keywords: Cat ; Visual cortex ; Stroboscopic exposure ; Monocular experience ; Motion deprivation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00249796
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    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
    Keywords: Medial geniculate body ; Tonotopic organization ; Single unit pairs ; Frequency selectivity ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00247026
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  • 25
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    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
    Keywords: O2-Hb affinity ; Bohr effect interaction ; CO2 Bohr effect ; Fixed acid Bohr effect ; Rabbit ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00585068
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    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
    Keywords: Sacral visceral afferents ; Pelvic nerve ; Urinary bladder ; Urethra ; Colon ; Anus ; Functional properties ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: 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.
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    URL: http://dx.doi.org/10.1007/BF00580280
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    Nucleophile Addition von Triorganozinn-Anionen an Kohlenstoffdisulfid, IX1) Synthese und Komplexierung neuer Triphenylstannandithioester (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1099-1104 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nucleophile Addition von Triorganotin-Anionen on Carbon Disulfide, IX1 - Synthesis and Complexation of Novel Triphenylstannane DithioestersThe known alkyl esters Ph3SnC(S)SR (1: R=Me, 2: R=CH2Ph) and the novel stannyl(methyl) esters (3: R=SnPh3, 4: R=CH2SnPh3) were obtained by the reaction of the dioxane adduct Ph3SnCS2Li · 2 C4H8O2 with appropriate organo(element) halides. As the first derivative of a homologous stannylalkanedithiocarboxylic acid, the 3-(triphenylstannyl)propane dithioester Ph3Sn[CH2]3C(S)SMe (5) was synthesized by Grignard reaction of (3-chloropropyl)triphenylstannane with activated magnesium (addition of anthracene, ultrasound). The new η1-coordinated pentacarbonylchromium and -tungsten complexes LM(CO)5 (1a: L=1, M=Cr; 2a: L=2, M=Cr; 2b: L=2, M=W; 3b: L=3, M=W; 5b: L=5, M=W) were prepared by modification of previously reported methods.
    Notes: Durch Umsetzen des Dioxan-Addukts Ph3SnCS2Li · 2 C4H8O2 mit geeigneten Organo(element)-halogeniden entstehen die bekannten Alkylester Ph3SnC(S)SR (1: R=Me, 2: R=CH2Ph) sowie die neuartigen Stannyl(methyl)ester (3: R=SnPh3, 4: R=CH2SnPh3). Als erstes Derivat einer homologen Stannylalkandithiocarbonsäure stellten wir den 3-(Triphenylstannyl)propandithioester Ph3Sn[CH2]3C(S)SMe (5) durch Grignard-Reaktion von (3-Chlorpropyl)triphenylstannan mit aktiviertem Magnesium (Anthracen-Zusatz, Ultraschall) dar. Durch Modifikation früher beschriebener Methoden erhielten wir die neuen, η1-koordinierten Pentacarbonylchrom- und -wolfram-Komplexe LM(CO)5 (1a: L=1, M=Cr; 2a: L=2, M=Cr; 2b: L=2, M=W; 3b: L=3, M=W; 5b: L=5, M=W).
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200706
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    Reaktionen des Diphenylphosphanoxids mit Organodiboranen(6) - Struktur einer zwitterionischen -POB- -Verbindung1) (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1117-1123 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Diphenylphosphane Oxide with Organodiboranes - Structure of a Zwitterionic -POB- -Compound1)(C6H5)2 (3′a), prepared from diphenylphosphane oxide (C6H5)2P(O)H (1) and activated triethylborane (2a*), reacts with tetraalkyldiboranes(6) (R2BH)2 [R=C2H5: (4a)2; R=C3H7: (4b)2] to form the BH3-addition compounds (C6H5)2P(BH3)OBR2 [R=C2H5: 3′a-BH3], [(C6H5)2P(BH3)O]2BR [R=C2H5: 5a-(BH3)2], and [(C6H5)2P(BH3)O]3B [6-(BH3)3]. The reaction of bis(9-borabicyclo[3.3.1]nonane) (4c)2 with 1 leads to (C6H5)2POBC8H14 (3′c) or 3′c-4c and (C6H5)2PH (7) or (C6H5)2PH-HBC8H14 (7-4c). The crystalline zwitterionic (C6H5)2P(H)OB[OP(BH3)(C6H5)2]3 [1-6-(BH3)3] (X-ray analysis) is isolated from the reaction of 1 with (4a)2.
    Notes: Aus Diphenylphosphanoxid (C6H5)2P(O)H (1) erhält man mit aktiviertem Triethylboran (2a*) das Derivat (C6H5)2POB(C2H5)2 (3′a). Aus 3′a sind mit Tetraalkyldiboranen(6) (R2BH)2 [R=C2H5: (4a)2; R=C3H7: (4b)2] die BH3-Additionsverbindungen (C6H5)2P(BH3)OBR2 [R=C2H5: 3′a-BH3], [(C6H5)2P(BH3)-O]2BR [R=C2H5: 5a-(BH3)2] und [(C6H5)2P(BH3)O]3B [6-(BH3)3] zugänglich. Bis(9-borabicyclo[3.3.1]nona) (4c)2 und 1 reagieren unter Bildung von (C6H5)POBC8H14 (3′c) oder 3′c-4c und (C6H5PH-HBC8H14 (7-4c). Das kristallisierte zwitterionische (C6H5)2P(H)OB[OP(BH3)-
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200708
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    Electronic Resource
    Synthese und Strukturanalyse von 1,2,3,4-Tetrahydrobenzo[g]chinoxalin-5,10-chinonen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1125-1132 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure Analysis of 1,2,3,4-Tetrahydrobenzo[g]-quinoxaline-5,10-quinones2,3-Diamino-1,4-dihydroxynaphthalene reacts with different aromatic aldehydes to give 2,3-disubstituted 1,2,3,4-tetrahydrobenzo[g]quinoxaline-5,10-quinones (1-7). In the course of the reaction a new C-C bond is formed stereoselectively. The yields are in the range of 80%. The corresponding benzoquinoxalinequinone 8 with different substituents in 2- and 3-positions is formed by a two-step preparation. Oxidation of these trans products leads to the benzo[g]quinoxaline-quinones and subsequent catalytic reduction yields the cis isomers. The structures and the configuration of 1 and 9 were determined by X-ray crystallography. The conformations of the new heterocycles are discussed with respect to the results obtained in solid and liquid phase.
    Notes: 2,3-Diamino-1,4-naphthohydrochinon reagiert mit Benzaldehyden unter Cyclisierung und Protonenwanderung stereoselektiv zu 2,3-disubstituierten 1,2,3,4-Tetrahydrobenzo[g]chinoxalin-5,10-chinonen (1-7) (Ausbeuten ca. 80%). Benzochinoxalin-5,10-chinon 8, das in 2- und 3-Stellung unterschiedlich substituiert ist, wird durch eine zweistufige Reaktion erhalten. Die Anordnung der Phenylreste in 2- und 3-Stellung wird für 1 und 9 durch Röntgenstrukturanalysen ermittelt; beide Spezies liegen in trans-Konfiguration vor. Durch Oxidation zu Benzo [g]chinoxalin-chinonen und anschließende katalytische Hydrierung werden cis-Isomere erhalten. Unter Berücksichtigung der Ergebnisse aus den Kristallstruktur- und NMR-Untersuchungen werden verschiedene Konformationen diskutiert.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200709
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    Reaktionen von (Organo)Phosphor-Sauerstoff-Verbindungen mit Diorgano-hydro-boranen1) (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1105-1115 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of (Organo)phosphorus-Oxygen Compounds with Diorgarno-hydro-boranes1)Trialkyl phosphites P(OR)3 [R=CH3 (2a), C2H5 (2b), CH(CH3)2 (2c), C4H9 (2d)] react with tetraalkyldiboranes(6) (R′2BH)2 [R′=C2H5 (1a)2, C3H7 (1b)2] in a temperature-dependent manner between 20 and 130°C to form the trialkyl phosphite-boranes (RO)3P-BHR′2, (RO)3P-BH2R′, and (RO)3P-BH3, which have various stabilities toward alcohols. With bis(9-borabicyclo-[3.3.1]nonane) (1c)2 the easily protolyzed addition compounds are obtained [e.g. 2a-1c, 2c-1c]. - Diorgano phosphites (RO)2P(O)H [R=CH3 (3a), C4H9 (3b), C6H5 (3c), CH2C6H5 (3d)], triorgano phosphates (RO)3PO [R=CH3 (4a), C4H9 (4b), C6H5 (4c), 2-CH3C6H4 (4d)], and the monosaccharide-diphenyl phosphates 4f, 4g, and 4h are reduced by (1a)2 or (1c)2 to give H2, PH3, and insoluble yellow phosphorus compounds, respectively. Phosphoric acid (4e), their derivatives OP(OBR2)3 [R=C2H5 (4ea), R2=C8H14 (4ec)], and phenylphosphonic acid C6H5P(O)-(OH)2 (6) are not deoxygenated at 130°C by (1a)2 to (1c)2. - Diorganophosphinic acids R2P(O)OH [R=C6H5 (5a), c-C6H11 (5b)] and phenylphosphinic acid C6H5(H)P(O)OH (5c) are reduced by (1a)2-(1c)2. Reaction of 5a with (1a)2 leads to the compounds [(C6H5)2P(BH3)O]B(C2H5)2 (8a-BH3), [(C6H5)2P-(BH3)O]BC2H5 [9a-(BH3)2], and [(C6H5)2P(BH3)O]3B [10-(BH3)3]. 5a reacts with (1c)2 under simultaneous formation of (C6H5)2PH (7) or (C6H5)2PH-HBC8H14 (7-1c) and (C6H5)2-POBC8H14 (8c) or (C6H5)2P(OBC8H14)-HBC8H14 (8c-1c). - 6 reacts with tetraethyldiboroxane (11a) to form a mixture of the oligomeric compounds -P(C6H5)(O)OB(C2H5)O]n-(6′a)n.
    Notes: Trialkylphosphite P(OR)3 [R=CH3 (2a), C2H5 (2b), CH(CH3)2 (2c), C4H9 (2d)] reagieren mit Tetraalkyldiboranen(6) (R′2BH)2 [R′=C2H5 (1a)2, C3H7 (1b)2] in Abhängigkeit von der Temperatur (20 bis 130°C) unter Bildung der gegenüber Alkoholen unterschiedlich stabilen Trialkylphosphit-Borane (RO)3P-BHR′2, (RO)3P-BH2R′ und (RO)3P-BH3. Mit Bis(9-borabicyclo-[3.3.1]nonan) (1c)2 erhält man die protolytisch leicht spaltbaren Additionsverbindungen [z.B. 2a-1c, 2c-1c]. - Diorganophosphite (RO)2P(O)H [R=CH3 (3a), C4H9 (3b), C6H5 (3c), CH2C6H5 (3d)], Triorganophosphate (RO)3PO [R=CH3 (4a), C4H9 (4b), C6H5 (4c), 2-CH3C6H4 (4d)] sowie die Monosaccharid-Phosphorsäure-diphenylester 4f, 4g und 4h werden von (1b)2 bzw. (1c)2 unter Bildung von H2, PH3 und/oder unlöslichen, gelben Phosphor-Produkten reduziert. - Phosphorsäure (4e), deren Derivate OP(OBR2)3 [R=C2H5 (4ea), R2=C8H14 (4ec)] und Phenylphosphonsäure C6H5P(O)(OH)2 (6) lassen sich von (1a)2 - (1c)2 bis 130°C nicht desoxygenieren. - Diorganophosphinsäuren R2P(O)OH [R=C6H5 (5a), c-C6H11 (5b)], Phenylphosphinsäure C6H5(H)P(O)OH (5c) werden von (1a)2 bis (1c)2 reduziert. 5a und (1a)2 bilden [(C6H5)2P(BH3)O]B(C2H5)2 (8a-BH3), [(C6H5)2P(BH3)O]2BC2H5) [9a - (BH3)2] und [(C6H5)2P(BH3)O]3B [10-(BH3)3]. Mit (1c)2 reagiert 5a unter gleichzeitiger Bildung von (C6H5)2PH (7) bzw. (C6H5)2PH-HBC8H14 (7-1c) sowie von (C6H5)2POBC8H14 (8c) bzw. (C6H5)2P(OBC8H14)-HBC8H14 (8c-1c). - 6 bildet mit Tetraethyldiboroxan (11a) ein Gemisch oligomerer - [P(C6H5)(O)OB(C2H5)O]n-Verbindungen (6′a)n.
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    URL: http://dx.doi.org/10.1002/cber.19871200707
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    The Vinylogous Tricarbonyl Chromophore. Violerythrine End Groups and Related Six-Membered Ring Compounds. Their synthesis, Conformation, and Investigation by Photoelectron, UV, and NMR Spectroscopy and by Crystal Structure Analysis1) (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1133-1149 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Der vinyloge Tricarbonyl-chromophor. Violerythrin-Endgruppen und verwandte Sechsringverbindungen. Synthese, Konformation, Untersuchung mit Photoelektronen-, UV-, NMR-Spektroskopie und Röntgenstrukturanalyse1)Die Synthese von ungesättigten Fünf- und Sechsringen, 3a, 4, 5b, 5c und 17a, die das Strukturelement des 3-Penten-1,2,5-trions enthalten, wird beschrieben. Diese vinylogen Tricarbonyle werden zusammen mit verwandten Verbindungen auf ihre chromophoren Eigenschaften hin untersucht. Die Konformation in Lösung, insbesondere der Torsionswinkel Ring-Seitenkette, wird mit Hilfe von 3JCH-Kopplungen, NOE-Differenzspektren und Kraftfeldrechnungen abgeleitet. Röntgenstrukturanalysen von 11a, 17a, 18a und 35 liefern die Geometrie im festen Zustand. Die Ionisierungsenergien werden photoelektronenspektroskopisch bestimmt. Zur Berechnung und Interpretation der Absorptionsspektren und der Farbe werden die CNDO/S-CI- und die HAM/3-Methode verwendet.
    Notes: The synthesis of five- and six-membered rings 3a, 4, 5b, 5c, and 17a, containing the structural moiety 3-pentene-1,2,5-trione, is described. The chromophoric properties of these vinylogous tricarbonyls together with related compounds are investigated. The conformation in solution, particularly the torsion angle ring/sidechain, can be derived from measurements of 3JCH coupling constants, NOE difference spectra, and force-field calculations. X-ray structure analyses of 11a, 17a, 18a, and 35 afford geometries in the solid state. Ionization energies are determined by means of photoelectron spectroscopy. The theoretical calculations and interpretation of absorption spectra and colour are carried out using the models CNDO/S-CI and HAM/3.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200710
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    Elementorganische Amin/Imin- Verbindungen, XXVIII1) Polycyclische Phosphor-Stickstoff-Rhenium(I)-Komplexe (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1183-1190 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Element-Organic Amine/Imine Compounds, XXVIII1). - Polycyclic Phosphorus-Nitrogen Rhenium(I) ComplexesThe thermolysis of [(OC)4RE - NR - P(Cl)(NR2) - NR](2), R = SiMe3 affords the tricyclic phosphorus dispiro compound 3, the cubanelike rhenium complex [Re2(CO)6(μ3-NR)4(μ3 -PNR)2] (4) as well as the tetracyclic rhenium complex 5. The attempt to synthesize 3 from RN-P(NR)(NR2)-NR- P(NR)(NR2 (7), R=SiMe3, and [Re(CO)5X] or [(OC)4ReX]2 (X=Cl, Br), gave the ionic species [RN-(RN)(RHN)P-NR-P- NR-SiMe2-NR]⊕ [Re2(CO)6(μX)3]⊖ (6a, X=Cl; 6b, X=Br). 3, 5, and 6a have been characterized by an X-ray structure analysis.
    Notes: Die Thermolyse von [(OC)4Re-NR -P(Cl)(NR2)-NR] (2), R = SiMe3 ergibt die tricyclische Phosphor-Dispiroverbindung 3, den cubanartigen Rheniumkomplex [Re2(CO)6(μ3-PNR)2] (4) sowie den tetracyclischen Rheniumkomplex 5. Beim Versuch, 3 aus RN-P(NR)(NR2)-NR -P(NR)(NR2) (7), R = SiMe3 und [Re(CO)5X] bzw. [(OC)4ReX]2 (X=Cl, Br) herzustellen, bildeten sich die Komplexsalze [RN- (RN)(RHN)P-NR-SiMe2-NR[⊕ [Re2(CO)6(μX)]⊖ (6a, X = Cl; 6b, X = Br). 3, 5 und 6a wurden durch eine Röntgenstrukturanalyse charakterisiert.
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    URL: http://dx.doi.org/10.1002/cber.19871200713
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    Dibenzocycloocten-, Dibenzochalcocin- und Diarenochalconindione (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1151-1173 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dibenzocyclooctene-, Dibenzochalcocine- and Diarenochalconinediones2,2′-Oxybis-, -thiobis-, and -methylenebisbenzoic esters 2a-c react with methyllithium in ether to give low yields of 5H-dibenzo[b,g]chalcocine-5,7(6H)-diones 6a, 7a, and dibenzo[a,d]cyclooctene-5,7(6H,12H)-dione (8), respectively. Very good yields of such heterocycles with oxygen (6a-h, 37), sulfur (7a-h, 38) and selenium (36) as key atom are obtained when diaryl ethers (21, 22, 25), -sulfides (27, 29, 30), and -selenides (33) that contain 2′ -acetyl- (or -propionyl-) and 2-methoxycarbonyl groups are treated with sodium hydride in boiling toluene. Analogously are prepared the dibenz[b,g]oxonine-11,13(6H,12H)-diones 62a-c and 7H-benzo[h]naphtho[1,8-bc]thionine-7,9-(8H)-dione (65) which are expanded by one ring member. In the analogous reaction of a corresponding benzophenone derivative 35, spiro[1H-indene-1,1′(3′H)-isobenzofuran]-3(2H),3′- dione (41) is formed in a tandem reaction. - Under phase transfer conditions the dibenzochalcocinediones 6, 7, 36 and also the corresponding nitrogen cycles 5 react to give mixtures of C-(42-45) and O-alkyl derivatives (46-49). Methyllithium and diisobutylaluminium hydride provide the carbinols 50-54. With bromine and SO2Cl2, respectively, the methylene group is mono- or dihalogenated to the products 56, 57; defined nitration was only possible for the oxacycle 6a.
    Notes: Die 2,2′-Oxybis-, -Thiobis- und -Methylenbisbenzoesäureester 2a-c reagieren mit Methyllithium in Ether in schlechten Ausbeuten zu den 5H-Dibenzo[b,g]chalcocin-5,7(6H)-dionen 6a, 7a bzw. Dibenzo[a,d]cycloocten-5,7(6H,12H)-dion (8). Sehr gute Ausbeuten an derartigen Heterocyclen mit Sauerstoff (6a-h, 37), Schwefel (7a-h, 38) und Selen (36) als Schlüsselatom erhält man bei der Umsetzung von mit 2′-Acetyl- (bzw. -Propionyl-) und 2-Methoxycarbonyl-Gruppen versehenen Diarylethern (21, 22, 25), -sulfiden (27, 29, 30) und -seleniden (33) mit Natriumhydrid in siedendem Toluol. In analoger Weise lassen sich die um ein Ringglied erweiterten Dibenz[b,g]oxonin-11,13(6H,12H)-dion 62a-c und das 7H-Benzo[h]naphtho[1,8-bc]thionin-7,9(8H)-dion (65) herstellen. Bei der analogen Umsetzung eines vergleichbaren Benzophenonderivates 35 wird in einer Tandemreaktion Spiro[1H-inden-1,1′(3′H)-isobenzofuran]-3(2H),3′-dion (41) gebildet. - Unter Phasentransfer-Bedingungen lassen sich die Dibenzochalcocindione 6, 7, 36 sowie die entsprechenden Stickstoffcyclen 5 zu Gemischen von C-(42-45) und O-Alkylderivaten (46-49) umsetzen. Methyllithium bzw. Diisobutylaluminiumhydrid liefern die Carbinole 50-54. Mit Brom bzw. SO2Cl2 werden die an der Methylengruppe mono- oder dihalogenierten Produkte 56, 57 erhalten; definiert nitrieren ließ sich nur der Oxacyclus 6a.
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    URL: http://dx.doi.org/10.1002/cber.19871200711
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    Thiastannacyclohexane (R2SnS)3 und -adamantane (RSn)4S6 Synthesen, Eigenschaften und Strukturen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1175-1182 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thiastannacyclohexanes (R2SnS)3 and -adamantanes (RSn)4S5: Synthese, Properties, and StructuresCyclotristannathianes (4) are obtained from R2SnCl2 (1) and Na2S · 9H2O or (CH3)3SiSSi(CH3)3. Analogously, hexathiatetrastannaadamantanes are prepared from RSnCl3 (2) and the sulfenylating agents mentioned before. The reaction between dimesityltin dichloride (1a) and Na2S · 9H2O depending on the reaction conditions yields either the corresponding dithiadistannacyclobutane (3) or cyclotristannathiane 4a. The structure of the cyclostannathianes 3, 4, and 5 are elucidated by determining the intensity ratio of geminal 119Sn-117Sn couplings. Calculated data are confirmed by experimental values. Additional proof is provided by measuring the change of intensity ratio in the 117Sn-NMR spectrum of 4c. X-ray structure determination proved for (C6F5Sn)4S6 (5g) to have the same geometry as in solution.
    Notes: Cyclotristannathiane (4) werden durch Umsetzung von R2SnCl2 (1) mit Na2S · 9H2O bzw. (CH3)3 erhalten. Analog werden Hexathiatetrastannaadamantane (5) aus RSnCl3 (2) und obigen Sulfenylierungsagentien synthetisiert. Die Reaktion zwischen Dimesitylzinndichlorid (1a) und Na2S · 9H2O führt je nach Reaktionsbedingungen entweder zum entsprechenden Dithiadistannacyclobutan (3) oder zu Cyclotristannathian 4a. Die Konstitutionen der Cyclostannathiane 3, 4 und 5 wurden durch Intensitätsmessungen der geminalen 119Sn-117Sn-Kopplung ermittelt. Berechnete Werte ließen sich experimentell bestätigen. Die Beweisführung wird im Fall von 4c durch die im 117Sn-NMR-Spektrum aufgezeigte Intensitätsveränderung ergänzt. Die an (C6F5Sn)4S6 (5g) durchgeführte Röntgenstrukturanalyse belegt die in Lösung aufgezeigte Geometrie.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200712
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    Zur Synthese perfluorierter Sulfimide, RfN=SO2, und deren Stabilisierung durch tertiäre Amine (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1183-1190 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Element-Orgainc Amine/Imine compounds, XXVII1). - Polycyclic Phosphorus-Nitrogen Rhenium(I) ComplexesThe amine-stabilized sulfimides RN=SO2 Ň7H13 8, 9, and 10 could be obtained by reaction of sulfamoyl chlorides RNH-SO2Cl [R=C6F5 4, (CF3)2CH 5, (CF3)2CHOCO 6] with quinuclidine (7). A direct approach to 8 and 15 was found by oxidation of N-sulfinylamines RN=SO [R=C6F5 12, (CF3)2CF 14] with quinuclidine N-oxide or trimethylamine N-oxide, respectively. The X-ray structure analysis of 8 indicates a doublebond in the N=SO2 group, while the amine is tetrahedrally coordinated in a distance to the sulfur atom longer than a single bond. Additional reaction of N-sulfinylamines or sulfamoyl chlorides are reported.
    Notes: Die aminstabilisierten Sulfimide RN=SO2Ň7H13 8, 9 und 10 konnten durch Reaktion der Sulfamoylchloride RNH-SO2Cl [R=C6F5 4, (CF3)2CH 5, (CF3)2CHOCO 6] mit Chinuclidin (7) erhalten werden. Ein direkter Zugang zu 8 und 15 wurde durch Oxidation der N-Sulfinylamine RN=SO [R=C6F5 12, (CF3)2CF 14] mit Chinuclidin-N-oxid bzw. Trimethylamin-N-oxid gefunden. Die Röntgenstrukturanalyse an 8 weist auf eine Doppelbindung in der N=SO2-Gruppe hin, während das Amin tetraedrisch in einem Abstand zum Schwefelatom koordiniert ist, der länger als einer Einfachbindung entsprechend ist. Weitere Reaktionen von N-Sulfinylaminen bzw. Sulfamoylchloriden werden beschrieben.
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    Aminosäuren, 10 Zur Reaktion von Pyroglutaminsäure-Derivaten mit Thionyl- und Oxalylchlorid (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 55-59 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of N-methyl- and N-benzyl-substituted 5-oxoproline methylesters (1a, b) with thionyl or oxalyl chloride yield N-substituted 5-chloro-2,3-dihydro-1H-pyrrole-2-carboxylic esters. These esters, as α-chloro enamines, undergo further electrophilic reaction in the ß-position by thionyl or oxalyl chloride. Thus, N-substituted bis(pyrrolyl) thioethers 2, bis(pyrrolyl) disulfides 3, and their oxidation products 4,5, and 6 are formed with excess thionyl chloride. N-substituted 5-chloro-4-[chloro(chlorocarbonyl)methyl]-1H-pyrrole-2-carboxylic esters 12 are obtained with oxalyl chloride. Reaction of L-1-benzhydryl-5-oxoproline methylester (L-1c) with thionyl chloride results in the formation of N-unsubstituted bis(pyrrolyl) thioether 9 under comparable conditions.
    Notes: N-Methyl- und N-Benzyl-substituierte 5-Oxoprolin-methylester (1a, b) bilden mit Thionyl- bzw. Oxalychlorid N-substituierte 5-Chlor-2,3-dihydro-1H-pyrrolcarbonsäureester, die als α-Chlor-enamine in ß-Position elektrophil mit Thionylchlorid bzw. Oxalylchlorid weiterreagieren: mit Thionylchlorid zu N-substituierten Bis(pyrrolyl)thioethern 2 und Bis(pyrrolyl)disulfiden 3 sowie deren Oxidationsprodukten 4, 5 und 6, mit Oxalylchlorid zu N-substituierten 5-Chlor-4-[chlor(chlorcarbonyl)methyl]-1H-pyrrol-2-carbonsäureestern 12. Die Umsetzung von L-1-Benzhydryl-5-oxo-prolin-methylester (L-1c) mit Thionylchlorid führt unter vergleichbaren Bedingungen zum N-unsubstituierten Bis(pyrrolyl)thioether 9.
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    Elektroreduktion organischer Verbindungen, 7 Bildung von Monothioacetalen bei der Elektroreduktion von Thioketonen in Alkoholen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 67-70 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thioethers 3 and monothioacetals 4 are obtained on cathodic reduction of thiopivalophenone (2) in alcohols as solvents in the presence of alkylating agents.
    Notes: Bei der kathodischen Reduktion von Thiopivalophenon (2) in Alkoholen als Lösungsmittel in Gegenwart von Alkylierungsmitteln erhält man neben den Thioethern 3 die Monothioacetale 4.
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    Zum Norcaradien-Cycloheptatrien-Strukturproblem (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 79-80 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: LiAlH4 reduction of ketone 1 which adopts a norcaradiene form leads to the alcohol 2. Ketone 1 may also be converted into the alkene 3 using McMurry conditions. Both reactions are accompanied by valence isomerisations to a bi- or tetracycloheptatriene
    Notes: Das als Norcaradien-Isomere vorliegende Keton 1 läßt sich durch Reduktion mit LiAlH4 in den Alkohol 2 und unter McMurry-Bedingungen in das Alken 3 überführen dabei beobachteten wir Valenzisomerisierung zu einem Bi- bzw. Tetra(cycloheptatrein)-System.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200114
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    9,12,22,25-Tetramethoxy[7.7]paracyclophan-4,17-dion:Synthese und Molekülstruktur (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 89-91 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Starting from 1,4-bis-(3-iodopropyl)-2,5-dimethoxybenzene (3) via the reaction to the corresponding bis(1,3-dithian-2-yl) compound 4 and its double alkylation by 3 the 22-membered ring system of 5 was obtained from which 9,12,22,25-tetramethoxy[7.7]paracyclophane-4,17-dione (1) was prepared. The molecular structure of 1 is discussed on the basis of an X-ray analysis.
    Notes: Ausgehend von 1,4-Bis(3-iodpropyl)-2,5-dimethoxybenzol (3) wurde über die Reaktion zu der entsprechenden Bis(1,3-dithian-2-yl)-Verbindung 4 und deren erneute doppelte alkylierung durch 3 das 22-gliedrige Ringsystem von 5 aufgebaut, aus dem 9,12,22,25-Tetramethoxy[7.7]paracyclophan-4,17-dion (1) erhalten wurde. Die Molekülstruktur von 1 wird auf der Grundlage einer Röntgen-Strukturanalyse diskutiert.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200116
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    Synthese, Reaktivität und Struktur von Kupfer-, Silber- und Gold-Komplexen des Typs (C5Me5CS2)M(PR3)n mit einzähnig und zweizähnig gebundenem Dithiocarboxylat-Ligand (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 97-104 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The reactions of (η5-C5Me5)Cu(PR3) (1a - c) and (η1-C5Me5)-Au(PR3) (2a,c) with CS2 lead to insertion of carbon disulfide into the C5Me5 - M bond to the formation of the dithiocarboxyalto complexes (C5Me5CS2)M(PR3)n (3a - c, 4a, c). The silver compound (C5Me5CS2)Ag(PPh3)2 (5) is directly obtained from [AgCl(PPh3)]4, C5Me5Li, and excess CS2. The synthesis of 3 - 5 and (C5Me5CS2)Cu(PMe3)3 (6) can also be achieved almost quantitatively from C5Me5CS2Li, formed in situ from C5Me5Li and CS2 and MCl(PR3)n. By use of methyl iodide instead of MCl-(PR3)n, the ester C5Me5CS2Me (7). is obtained. The results of the X-ray structural analyses of (C5Me5CS2)Cu(PPh3)2 (3a) and (C5Me5CS2)Au(PiPr3) (4c) confirm that the dithiocarboxylato ligand to coordinated via both sulfur atoms to copper but only via one sulfur atom to gold. In solution, compound 6 undergoes a fast PMe3 ligand exchange which has been studied by NMR spectroscopy. The sign of J(PH) of 6 has been determined.
    Notes: Die Reaktionen von (η5-C5Me5)Cu(PR3) (1a - c) und (η1-C5Me5)-Au(PR3) (2a,c) mit CS2 führen zu einer Insertion des Schwefelkohlenstoffs in die C5Me5-Metall-Bindung und zur Bildung der Dithiocarboxylat-Komplexe (C5Me5CS2)M(PR3)n (3a - c, 4a, c). Die Silberverbindung (C5Me5CS2)Ag(PPh3)2 (5) ist direkt aus [AgCl(PPh3)]4, C5Me5Li und überschüssigem CS2 erhältlich. Die Synthese von 3 - 5 und (C5Me5CS2)Cu(PMe3)3 (6) gelingt praktisch quantitativ auch durch Umsetzung von in situ aus C5Me5Li und CS2 gebildetem C5Me5CS2Li und MCl(PR3)n. Bei Verwendung von Methyliodid an Stelle von MCl(PR3)n) entsteht der Ester C5Me5CS2Me (7). Die Ergebnisse der Röntgenstrukturanalysen von (C5Me5CS2)Cu(PPh3)2 (3a) und (C5Me5CS2)Au(PiPr3) (4c) bestätigen, daß der Dithiocarboxylat-Ligand über beide Schwefelatome am Kupfer, jedoch nur über ein Schwefelatome am Gold koordiniert ist. Verbindung 6 unterliegt in Lösung einem raschen PMe3-Ligandenaustausch, der NMR-spektroskopisch untersucht worden ist. Das Vorzeichen der PH-Kopplung von 6 wurde bestimmt.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200118
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    Synthese von 2,6-Diazabicyclo[2.2.2]octan-3,5-dion-Abkömmlingen und 2(1H)-Pyridinonen. - Ein Beitrag zur Regiochemie und Stereospezifität 1,4-Dipolarer Cycloadditionen von Pyridmidinium-4-olaten an elektronenreiche und elektronenarme Alkene (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 109-114 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The pyrimidinium-4-olates of type 1 combine with enol ethers, enamines, ketene acetals, 1,4-dihydro-1,4-epoxynaphtalene, dimethyl fumarate, or dimethyl maleate to produce 2,6-diazabicyclo[2.2.2]octane-3,5-diones 2,3,5,7,9,17 - 19, whereas the reaction of the pyrimide[2.1-b]benzothiazolium-4-olate 13 with 8b or 1,1-bis(dimethylamino)ethene proceeds with formation of the 2(1H)-pyridinone derivative 15. The primary adducts 9a,b fragment thermally into 2(1H)-pyridinones 11a, b. In the example of the reaction of 1a with dimethyl maleate, the stereospecificity is determined.
    Notes: Die Pyrimidinium-4-olate von Typ 1 vereinigen sich mit Enolethern, Enaminen, Keten-acetalen, 1,4-Dihydro-1,4-epoxynaphthalin, Fumarsäure-dimethylester oder Maleinsäure-dimethyl-ester zu 2,6-Diazabicyclo[2.2.2]octan-3,5-dionen 2, 3, 5, 7, 9, 17-19, während das Pyrimido[2,1-b]benzothiazolium-4-olat 13 mit 8b oder 1,1-Bis(dimethylamino)ethen das 2(1H)-Pyridinon-Derivat 15 liefert. Die Primäraddukte 9a, b spalten thermisch in die 2(1H)-Pyridinone 11a, b. Am Beispiel der Umsetzung von 1a mit Maleinsäure-dimethylester wird die Stereospezifität ermittelt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200120
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  • 42
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    Titanium-Mediated Stereoselective Knoevenagel Condensation of Ethyl (Diethoxyphosphoryl)acetate with Aldehydes (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 121-122 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The titanation of the sodium salt of ethyl (diethoxyphosphoryl)-acetate (1) results in a reagent which undergoes a stereoselctive Knoevenagel condensation with aldehydes to form the corresponding trisubstituted olefins 3 having the Z-configuration.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200123
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  • 43
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    Direct Geminal Dimethylation of Aromatic Aldehydes with Dichlorodimethyltitanium (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 123-123 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic aldehydes react specifically with (CH3)2TiCl2 to form the geminal dimethylated products.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200124
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    Niederkoordinierte Phosphorverbindungen, 54 Phosphaalkene durch Cope-Umlagerung (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 125-129 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The styryl-substituted diphosphanes 2a, b are prepared by the reaction of the chlorophosphanes 1a, b with magnesium or tert-butyllithium, respectively. Compound 2b, substituted with bulky residues, gives the racemic form of the phosphaalkene 5 by Cope rearrangement, which is slowly and irreversibly converted into the meso-form.
    Notes: Aus den Chlorphosphanen 1a, b wurden die Styryl-substituierten Diphosphane 2a, b hergestellt. An der mit sperrigen Resten substituierten Verbindung 2b konnte erstmals die Cope-Umlagerung eines Diphosphans zu einem Phosphaalken 5-rac beobachtet werden. Die Racemform wandelt sich irreversibel in die Mesoform von 5 um.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200202
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  • 45
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    Organische Synthesen mit übergangsmetall-Komplexen, 20 Lineare C-Kettenverlängerung von Allenen durch metallinduzierte Allen/Vinylcarben-Umlagerung und regiospezifische Insertion von CO in die M - C-Bindung einer zweikernigen Carbonyleisen-Matrix (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 105-107 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Binuclear carbonyl(1-propene-2,3-diyl)iron complexes 4, regioselectively derived from 1,2-propadienes 1, can be stepwise isomerized at 60°C to give binuclear 1-ferra-1,3-diene complexes 6, which at 130°C further rearrange to give ferracyclopentadienes 7 under formation of a C=C bond by a regiospecific insertion of CO at the higher substituted terminal carbon (but not at the Fe=C bond) of the ferradiene unit.
    Notes: Die von 1,2-Propadienen 1 regioselektiv erhältlichen zweikernigen Carbonyl(1-propen-2,3-diyl)eisen-Komplexe 4 isomerisieren stufenweise bei 60°C unter metallinduzierter 1,2-Wasserstoff-Wanderung zu zweikernigen 1-Ferra-1,3-dienen 6, und diese wiederum bei 130°C zu Ferracyclopentadienen 7 unter Aufbau einer C=C-Bindung durch regiospezifische Insertion von CO am höher substituierten terminalen C-Atom (nicht an der Fe=C-Bindung) der Ferradien-Einheit.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200119
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  • 46
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    Electronic Resource
    (Trimethylsiloxy)maleinsäureanhydrid (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 119-120 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Trimethylsioxy)maleic anhydride (2) can easily be prepared from pyridinium salt 1 and chlorotrimethylsilane. Reaction of 2 with acetone or acetaldehyde affords the diols 3a and 3b.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200122
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    Masthead (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200201
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  • 48
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    1,3-Dithienium- und 1,3-Dithioleniumsalze, VI N,N-Disubstituierte 4-Aminobenzophenone aus 1,3-Dithian- bzw. 1,3-Dithiolan-2-ylium-tetrafluoroboraten (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 135-139 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The 1,3-dithienium- and 1,3-dithiolenium tetrafluoroborates 3 (n=3, 2), respectively, react in good yields with the N,N-dialkylarylamines 4 to give the 2,2-disubstituted cyclic dithio acetals 5, which can be converted after dethioacetalization with HgCl2/HgO into the ketones 7.
    Notes: Die 1,3-Dithienium- bzw. 1,3-Dithiolenium-tetrafluoroborate 3 (n=3, 2) reagieren in guten Ausbeuten mit den N,N-Dialkylarylaminen 4 zu den 2,2-disubstituierten cyclischen Dithioacetalen 5, die sich nach Dethioacetalisierung mit HgCl2/HgO in die Ketone 7 überführen lassen.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200204
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  • 49
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    Niederkoordinierte Phosphorverbindungen, 55 Zur Cope-Umlagerung an 1,3-Diphospha-1,5-hexadienen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 131-134 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chlorophosphane 1 reacts with substituted allyl-Grignard reagents 2a, b to yield the 1,3-diphospha-1,5-hexadienes 3a, 4b. 31P-NMR temperature run of 3a shows dynamic processes, which can be explained by inversion of the trivalent P-atom. Above 40°C 3a undergoes a [3,3′]-phospha-carbon Cope rearrangement to give the thermodynamically stable product 4a. The structures of 3a and 4a are confirmed by X-ray structure analysis.
    Notes: Das Chlorphosphan 1 reagiert mit den substituierten Allyl-Grignard-Reagenzien 2a, b zu 1,3-Diphospha-1,5-hexadienen 3a, 4b. Bei 3a lassen sich 31P-NMR-spektroskopisch temperaturabhängige dynamische Phänomene beobachten, die auf Inversion am Phosphan-Phosphor zurückgeführt werden. Oberhalb von 40°C unterliegt 3a einer [3,3′]-Phospha-Kohlenstoff-Cope-Umlagerung zum thermodynamisch stabileren Produkt 4a. Die Molekülstrukturen von 3a und 4a wurden röntgenographisch bestimmt.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200203
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  • 50
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    Chirale Cluster mit μ3-Alkin- und μ3-Vinyliden-Liganden (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 141-151 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: By reaction of alkyne-bridged dicobalt complexes with Fe2(CO)9 or Fe3(CO)12 alkyne- and vinylidene-bridged clusters of the general type FeCo2(CO)9(μ3-L) were accessible. These and the homologous RuCo2 clusters could be subjected to the reaction types metal exchange and alkyne-vinylidene rearrangement. Combination of both reaction types in the appropriate sequence yielded altogether 16 new hetero trinuclear clusters with μ3-vinylidene ligands. Internal alkynes R2C2 with R=Me, Et, Ph and terminal alkynes HC2R with R=H, Me, t-Bu, Ph were used; the latter were also the precursors of the corresponding vinylidene ligands. The resulting metal frameworks were of the FeCoNi, FeCoMo, FeCoW, RuCoNi, RuCoMo, RuCoW, FeNi2, and FeCo2 types. The alkyne-vinylidene rearrangements on the chiral clusters showed diastereoselectivities between 0 and 100%. The crystallographically determined molecular structure of RuCoWCp(CO)8(μ3-CCH-t-Bu) allows to interprete the diastereoselectivity as not resulting from steric effects.
    Notes: Durch Umsetzung von alkinverbrückten Dicobalt-Komplexen mit Fe2(CO)9 bzw. Fe3(CO)12 wurden alkin- und vinylidenverbrückte Cluster des allgemeinen Typs FeCo2(CO)9(μ3-L) zugänglich. Auf diese und die homologen RuCo2-Cluster ließen sich die Reaktionstypen Metallaustausch und Alkin-Vinyliden-Umlagerung anwenden. Kombination beider Reaktionstypen in der geeigneten Reihenfolge lieferte insgesamt 16 neue Hetero-Dreikerncluster mit μ3-Alkin-Liganden und 29 entsprechende Verbindungen mit μ3-Vinyliden-Liganden. Es kamen interne Alkine R2C2 mit R=Me, Et, Ph und terminale Alkine HC2R mit R=H, Me, t-Bu, Ph zum Einsatz; letztere waren auch die Vorläufer der entsprechenden Vinyliden-Liganden C2HR. Die entstehenden Metallgerüste waren vom FeCoNi-, FeCoMo-, FeCoW-, RuCoNi-, RuCoMo-, RuCoW-, FeNi2- und FeCo2-Typ. Die Alkin-Vinyliden-Umlagerungen auf den chiralen Clustern zeigten Diastereoselektivitäten zwischen 0 und 100%. Die kristallographisch bestimmte Molekülstruktur von RuCoWCp(CO)8(μ3-CCH-t-Bu) läßt sich so interpretieren, daß die Diastereoselektivität nicht auf sterischen Effekten beruht.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200205
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    1,3-Dipolare Cycloadditionen, 92 Reaktionen aliphatischer Diazoverbindungen mit vierfach Acceptorsubstituierten Ethylenen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 153-158 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: In contrast to a literature report, diazomethane and diazoaceticester add to the CC double bond of tetracyanoethylene and ethylenetetracarboxylic ester. The behavior of the 1- and 2-pyrazolines deviates from the rule.
    Notes: Entgegen einem Literaturbericht finden die Cycloadditionen des Diazomethans und Diazoessigsäureesters an die CC-Doppelbindung des Tetracyanethylens und des Ethylentetracarbonsäureesters statt. Das Verhalten der 1- and 2-Pyrazoline zeigt Abweichungen von der Norm.
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    URL: http://dx.doi.org/10.1002/cber.19871200206
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    1,3-Dipolare Cycloadditionen, 93 Überraschungen bei der Umsetzung des 2,3-Dicyanfumarsäure-dimethylesters mit Diazomethan (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 159-169 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The reaction with excess of diazomethane furnished methyl 4-cyano-1-methylpyrazole-5- and-3-carboxylate (2 and 3) as well as the three N-methyl-1,2,3-triazolecarboxylic esters 4-6. A mechanistic study revealed a poly-step sequence. The initial formation of the pyrazoline 8 proceeded normal. Base catalysis effected an equilibration of trans- and cis-2-pyrazoline, 8⇌12, followed by a fragmentation into methyl 4-cyano-3-pyrazolecarboxylate (26) and methyl cyanoformate (32); a 4H-pyrazole is supposed to be the key intermediate. The final products mentioned above emerged from further reaction of 26 and 32 with diazomethane.
    Notes: Die Reaktion mit überschüssigem Diazomethan lieferte 4-Cyan-1-methylpyrazol-5- und-3-carbonsäure-methylester (2 und 3) sowie die drei N-Methyl-1,2,3-triazolcarbonsäure-methylester 4-6. Eine mechanistische Studie brachte eine vielstufige Reaktionsfolge an den Tag. Die einleitende Bildung des Pyrazolins 8 vollzog sich normal. Unter Baseneinwirkung kam es zur Äquilibrierung von trans-2-Pyrazolin 8 mit cis-2-Pyrazolin 12, gefolgt von einer Spaltung in 4-Cyan-3-pyrazolcarbonsäureester (26) und Cyanameisensäureester (32); ein 4H-Pyrazol wird als Zwischenstufe vermutet. Die oben erwähnten Endprodukte entsprangen der Weiterreaktion von 26 und 32 mit Diazomethan.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200207
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    Phosphorverbindungen ungewöhnlicher Koordination, 171) über die Abfangreaktion von Phenylthioxophosphan mit Hexacarbonylbis(cyclopentadienyl)dimolybdän (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1263-1267 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phosphorus compounds with Unusual Cooradination, 171). - On the Trapping Reaction Of Phenylthioxophosphane with Hexacarbonylbnis(cyclopentadienyl)dimolybdenumPhenylthioxophosphane (6) - generated in boiling toluene from endo/exo-10 - reacts under these conditions with hexacarbonylbis(cyclopentadienyl)dimolybdenum (12) to yield the two binuclear molybdenum complexes 13a and 14a. A crystal structural analysis has been performed for 13a. Lawesson's reagent (17) leads under the same conditions with 12 to the analogous complexes 13b and 14b.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200727
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    Masthead (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200801
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    Synthesen, Struktur und Eigenschaften von 1,1-Dialkoxy-2-azapropenylium-Salzen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1271-1279 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses, Structures, and Properties of 1,1-Dialkoxy-2-azapropenylium Salts1,1-Dialkoxy-2-azapropenylium salts 1 were synthesized by alkylation at the oxygen atom of N-methylenecarbamates 4 with trialkyloxonium salts 5, in cases, where steric hindrance makes N-alkylation difficult (4a); otherwise the iminium salts 6 are formed preferentially. A more general synthetic route to the salts 1 is based on the reaction of N-(alkoxymethyl)imidocarbonates 8 with acylium ions (acyl cleavage reaction). The salts are thermally not very stable; phenyl ester derivatives are easily converted into 4H-1,3-benzoxazine derivatives 11. - An X-ray analysis of 1aa shows an allenic structure with orthogonal π systems; for steric reasons the C-N-C bond angle is reduced to ca. 150°. - Quantum mechanical ab initio calculations predict high steric flexibility for the salts 1; in the parent compound (16a) an allenic structure is slightly (2-3 kcal/mol) favored over allylic forms (16d). Thermodynamically more stable are the isomeric iminium salts 6 and 17, respectively. - Depending on the substitution pattern in solution (IR, dynamic NMR spectroscopy) allenic (1a) or allylic (1b) structures are observed.
    Notes: 1,1-Dialkoxy-2-azapropenylium Salze 1 können durch O-Alkylierung am Carbonylkohlenstoff von N-Methylencarbamidsäureestern 4 mit Trialkyloxonium-Salzen 5 erhalten werden, falls eine N-Alkylierung sterisch erschwert ist (4a); andernfalls werden die Iminium-Salze 6 gebildet. Eine allgemeinere Darstellungsmethode für die Salze 1 beruht auf der Umsetzung von N-(Alkoxymethyl)-imidokohlensäureestern 8 mit Acylium-Ionen (Acylspaltung). Die Salze 1 sind thermische nicht sehr beständig Phenylester-Derivate gehen leicht in 4H-1,3-Benzoxazin-Derivate 11 über. - Die Kristallstrukturanalyse von 1aa ergibt eine allenische Struktur mit orthogonalen π-Systemen, wobei der C-N-C-Bindungswinkel auf ca. 150° reduziert ist (sterische Effekte). - Quantenmechanische Ab-initio-Berechnungen sagen hohe sterische Flexibilität der Salze 1 voraus, wobei beim Grundkörper allenische Strukturen (16a) geringfügig (ca. 2-3 kcal/mol) gegenüber allylischen Formen (16d) bevorzugt sind. Thermodynamisch günstiger als die Salze 1 (bzw. 16) sind die isomeren Iminium-Salze 6 bzw. 17. - Je nach Substitutionsmuster beobachtet man in Lösung (IR-, dynamische NMR-Spektroskopie) allenische (1a) oder allylische Strukturen (1b).
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200802
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    Organische Synthesen mit Übergangsmetallkomplexen, 231) Bicyclische 3-Imidazoline aus primären Isocyaniden und Alkenylcarben-Komplexen durch metallinduzierte anomale Insertion einer C=N- in eine α-CH-Bindung des Isocyanids (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1287-1291 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Syntheses via Transition Metal Complexes, 231). - Bicyclic 3-Imidazolines from Primary Isocyanides and Alkenylcarbene Complexes by a Metal-Induced Anomalous Insertion of a C=N- into an α-CH Bond of the IsocyanideAlkenylcarbene complexes 1 react smoothly with one equivalent of methyl- and primary isocyanides 2 to give 1:1 adducts 3, which contain C-alkenyl ketenimine ligands. To these a second molecule of 2 may be added in a [4 + 1] fashion with formation of bis-(imino)cyclopentene complexes 6 or - in a competing reaction path - with induction of a second spontaneous ring closure to 3-imidazoline complexes 4/5 by an insertion of 2 into the α-CH bond of 3. Complexes 4-6 were characterized spectroscopically, the 3-imidazoline complex 4a also by an X-ray analysis. In competition with the addition of 2c to 3c an isomerisation of 3c to the α-alkoxycyanide complex 9a is observed involving an N/Cmigration of the N-allyl group. Steric factors exhibit strong influences on the course of the different competition reactions.
    Notes: Alkenylcarben-Komplexe 1 bilden mit Methyl- bzw. einem primären Isocyanid 2 1:1-Addukte 3, die einen C-Alkenylketenimin-Ligand enthalten. An diesen läßt sich ein zweites Molekül 2 addieren unter [4 + 1]-Cycloaddition zu Bis(imino)cyclopenten- 6 bzw. unter weiterem Ringschluß zu 3-Imidazolin-Komplexen 4/5 durch metallinduzierte Insertion von 2 in eine α-CH2N-Bindung von 3. Die Komplexe 4-6 wurden spektroskopisch, der 3-Imidazolin-Komplex 4a zusätzlich durch eine Kristallstrukturanalyse charakterisiert. Neben einer Addition von 2c an 3c wird eine Isomerisierung von 3c zum α-Alkoxycyanid-Komplex 9a unter N/C-Wanderung des N-Allylrests beobachtet. Sterische Faktoren beeinflussen entscheidend das Zusammenspiel sämtlicher Konkurrenzreaktionen.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200804
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    Arsen als Funktionszentrum und Substituent von Yliden (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1281-1285 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Arsenic as a Functional Center and as a Substituent in YlidesBis(dimethylarsino)-, bis(diethylarsino)-, and bis(diphenylarsino)-methane (1-3) are obtained from Cl2AsCH2AsCl2 and the corresponding Grignard reagents. Through the reaction with MeI or EtI, respectively, 1 and 2 give mono- and bis-quarternary salts 4-7. The former (4, 6) when treated with NaNH2 in liquid ammonia, yield the ylides R3As=CH-AsR2 (R=Me: 8; R=Et: 9), while the latter (5, 7) could not be converted into double-ylides R3As=C=AsR3. 3 affords the ylide MePh2As=CH-AsPh2 (11) via the arsonium salt 10. Treatment of 11 with Ph2AsCl gives MePh2As=C(AsPh2)2 (13) as the product of a transylidation reaction. With MeI only C-alkylation of 11 takes place (to give 14). - Ph2PCH2AsPh2 is the starting material for the synthesis of the (arsinomethyl)phosphonium salt 17 and the ylide MePh2-P=CH-AsPh2 (15). This ylide is also exclusively C-alkylated by MeI (to give 16). Methylation of Ph2PCH2AsPh2 by MeOSO2F yields the diquaternary salt 18, which on reaction with NaNH2/NH3 (liq.) affords the first mixed P/As double-ylide MePh2-P=C=AsPh2Me (19). The ylide Ph3P=C(AsPh2)2)2 (20) is converted into semi-ylidic quaternary salts [Ph3PC(AsPh2)-AsPh2Me]I (21) and [Ph3PC(AsPh2Me)2]I2 (22) by MeI, which are analogues of the tris(phosphonio)methanide salts [(R3P)3C]X2.
    Notes: Bis(dimethylarsino)-, Bis(diethylarsino)- und Bis(diphenylarsino)-methan (1-3) wurden aus Cl2AsCH2AsCl2 und den entsprechenden Grignard-Reagenzien dargestellt. 1 und 2 ergeben mit MeI bzw. EtI die Mono- und Bisquartärsalze 4-7. Aus ersteren (4, 6) entstehen bei Einwirkung von NaNH2 die Arsen-Ylide R3As=CH-AsR2 (R=Me: 8, R=Et: 9). Die Isolierung von Doppel-yliden R3As=C=AsR3 aus 5 und 7 gelang dagegen nicht. Aus 3 ist über das Monoquartärsalz 10 analog das Ylid MePh2-As=CH -AsPh2 (11) zugänglich, aus dem mit Ph2AsCl unter Umylidierung das erste Arsonium-bis(arsino)methylid, MePh2-As=C(AsPh2)2 (13), hervorgeht. 11 wird von MeI am ylidischen C-Atom methyliert (zu 14). - Von Ph2PCH2AsPh2 aus gelangt man mit MeI zum (Arsinomethyl)phosphoniumsalz 17, das mit NaNH2 das Ylid MePh2P=CH - AsPh2 (15) liefert. Auch dieses Ylid wird von MeI nur C-alkyliert (zu 16). Die Quartärisierung von Ph2PCH2AsPh2 mit MeOSO2F führt zum Diquartärsalz 18, aus dem das erste gemischte P/As-Doppel-ylid, MePh2-P=C=AsPh2Me (19), entsteht. Das Ylid Ph3P=C(AsPh2)2 (20) kann mit MeI in die Semi-ylid-Quartärsalze [Ph3PC(AsPh2)-AsPh2Me]I (21) und [Ph3PC(AsPh2Me)2]I2 (22) übergeführt werden, die den Tris(phosphonio)methanid-Salzen [(R3P)3C]X2 entsprechen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200803
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    Organische Synthesen mit Übergangsmetallkomplexen, 251) Cyanoallylierung von Carbenliganden mit Allylisocyaniden durch metallinduzierte N/C-Allylumlagerung intermediärer 3-Aza-1,2,5-hexatrien-Komplexe (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1293-1296 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Syntheses via Transition Metal Complexes, 251). - Cyanoallylation of Carbene Ligands with Ally Isocyanides via Metal-Induced N/C-Allylic Rearrangement of intermediate 3-Aza-1,2,5-hexatriene ComplexesAllyl isocyanides 2 react with (CO)5M=C(OEt)C6H5 (1, M=Cr, W) to give N-allylketenimine/(3-aza-1,2,5-hexatriene) complexes 3 in high yields. In absence of suitable reactants compounds 3 isomerise spontaneously and smoothly already at 0°C via a metalinduced N/C-migration of the allyl group to give 4-pentenenitrile complexes 5, from which the ligand can be disengaged by substitution with pyridine. The regiochemistry of the rearrangement corresponds to the [3,3] type as has been proven by a labeling experiment with α,α-dideuterioallyl isocyanide. In the presence of an alcohol, the reaction of 1 with 2 leads to the formation of competition products resulting from an N/C-rearrangement or the addition of the alcohol to 3, respectively. The competition ratio strongly depends on the type of metal used. The tungsten complex 3b, e.g., at 0°C adds one equivalent of an alcohol to give up to 97% yields of (allylamino)carbene complexes 8b-c, while the corresponding chromium complex 3a rearranges smoothly under these conditions to give 5a only. The addition of alcohols to 3b is reversible: on thermolysis of 8c at 70°C the products of thermal isomerisation of 3b together with a chelate complex 9 are obtained.
    Notes: Durch Addition von Allylisocyaniden 2 an (CO)5M=C(OEt)C6H5 (1, M=Cr, W) erhält man in hohen Ausbeuten N-Allylketenimin-/(3-Aza-1,2,5-hexatrien)-Komplexe 3. Diese isomerisieren in Abwesenheit geeigneter Reaktionspartner spontan und glatt schon bei 0°C unter metallinduzierter N/C-Wanderung des Allylrestes zu 4-Pentennitril-Komplexen 5. Anhand von Markierungsexperimenten mit α,α-Dideuterioallylisocyanid wurde hierfür die Regiochemie einer [3,3]-Umlagerung nachgewiesen. Aus 5 kann der Ligand durch Verdrängung mit Pyridin freigesetzt werden. Bei der Umsetzung von 1 mit 2 in Gegenwart von Alkoholen beobachtet man in Konkurrenz zur N/C-Umlagerung eine Addition des Alkohols an 3. Abhängig vom Metall ergeben sich dabei erhebliche Reaktivitätsunterschiede: der Wolframkomplex 3b z. B. addiert bei 0°C rasch ein äquivalent des Alkohols unter (fast) ausschließlicher Bildung von (Allylamino)carben-Komplexen 8b, c, wohingegen der entsprechende Chromkomplex 3a unter gleichen Reaktionsbedingungen glatt zu 5a isomerisiert. Die Addition von Alkoholen an 3b ist reversibel: bei der Thermolyse (70°C) von 8c erhält man neben einem Chelatkomplex 9 das thermische Isomerisierungsprodukt von 3b.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200805
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    Trimethylsilylcyanid als Umpolungsreagens, XV Intramolekulare Diels-Alder-Reaktion mit Vinylfuranen über die Umpolung von 3-(2-Furyl)acrolein (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 325-329 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: With 3-(2-furyl)acrolein (17) as an example it is demonstrated that umpolung of aldehydes with trimethylsilyl cyanide allows the synthesis of diene-dienophiles (19, 21) for intramolecular Diels-Alder reactions introducing the required protecting group at the same time. In this novel model reaction thermal [4 + 2] cycloaddition finally affords so far unknown tricyclic ketones with one furan ring (25 and 26). This reaction sequence should be useful in natural product synthesis.
    Notes: Am Beispiel von 3-(2-Furyl)acrolein (17) wird gezeigt, daß die Umpolung von Aldehyden mit Trimethylsilylcyanid eine Synthese von Dien-Dienophilen (19, 21) für die intramolekulare Diels-Al-der-Reaktion erlaubt, bei der zugleich die erforderliche Carbonylschutzgruppe eingeführt wird. Thermische [4 + 2]-Cycloaddition erzeugt in dieser neuen Modellreaktion schließlich bisher unbekannte tricyclische Ketone mit einem Furanring (25 und 26). Die Reaktionsfolge dürfte für Naturstoffsynthesen einsetzbar sein.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200312
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    Diagnostic OH 1H-NMR shift differences in syn and anti ß-Hydroxy Ethers (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 331-333 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die relative chemische Verschiebung des OH-Protonen-Signals in den 1H-NMR-Spektren eines Paares diastereomerer ß-Hydroxyether erlaubt eine syn/anti-Zuordnung der relativen Konfiguration. Dies basiert vermutlich auf der Bildung von Strukturen mit intramolekularer Wasserstoff-Brücke. Insofern ist diese Regel auf solche ß-Hydroxyether beschränkt, bei denen nur dieser Typ von intramolekularer H-Brücke ausgebildet werden kann.
    Notes: In a pair of diastereomeric ß-hydroxy ethers the relative 1H-NMR chemical shift of the OH proton is diagnostic for the syn or anti stereostructure. This is probably based on the presence of internally hydrogen-bonded structures. The rule is therefore restricted to those compounds for which only this type of internal hydrogen bonding is accessible.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200313
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    Photoreactions of biacetyl with electron-rich olefins. An extended mechanism (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 307-318 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die Photoreaktionen von Biacetyl (1) mit verschiedenen elektronenreichen Olefinen wurden untersucht. Im allgemeinen bilden sich bei der Bestrahlung mit λ=400-480 nm (nπ*-Anregung von Biacetyl) in Abhängigkeit von der Olefin-Struktur Oxetane und Allylalkohole. Hinweise auf die primäre Bildung eines Exciplexes liefert die ungewöhnliche Abhängigkeit der Geschwindigketiskonstanten der Lumineszenzlöschung von Biacetyl durch die Olefine (log kq) von der freien Bildungsenthalpie des Elektronentransfers (ΔG2). Ein Mechanismus mit einer Exciplex-Zwischenstufe und einem ionischen Photodissoziationsweg gestattet es nach Anpassung der Parameter, die experimentellen Daten gut zu simulieren (log kq/ΔG2-Korrelation). Vollständiger Elektronentransfer wurde als Folgeprozeß bei einigen besonders elektronenreichen Olefinen mit Hilfe der ESR-Spektroskopie bzw. durch Abfangen der Radikalkationen bewiesen. Die Abhängigkeit der Produktquantenausbeuten von der Lösungsmittelpolarität bestätigt die Konkurrenz zwischen Produktbildung und ionischer Photodissoziation. Die bevorzugte Bildung von Allylalkoholen (Reduktionsprodukte) mit starken Donor-Olefinen und die regioselektiv ablaufende Oxetanbildung mit Ketenacetal werden auf der Basis von stark polaren Exciplexen bzw. Kontaktionenpaaren und Zwitterionen als Zwischenstufen diskutiert.
    Notes: The photoreactions of biacetyl (1) with various electron-rich olefins have been investigated. Oxetanes and allyl alcohols are formed upon irradiation with λ=400-480 nm (nπ* excitation of biacetyl) depending on the nature of the olefin. An unusual relationship between the rate constants of luminescence quenching of biacetyl by olefins (log kq) and the free enthalpies of electron transfer (ΔG2) indicate formation of an exciplex first. A reasonable good fit between experimental results of log kq and ΔG2 has been obtained on the basis of a mechanistic model which includes the exciplex intermediate as well as an ionic photodissociation pathway and some empirical adjustment of the parameters. Complete electron transfer as a consecutive process has been proven for some strong electron-donating olefins by means of ESR spectroscopy and scavenging of the radical cations. The solvent dependence of the product quantum yields further confirms the competition between ionic photodissociation and product formation. The preferred formation of allyl alcohols (reduction products) with strong electron-donating olefins and the highly regioselective oxetane formation with ketene acetal are discussed in terms of exciplexes of strong CT character or even contact ion pairs and dipolar intermediates.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200310
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    Das Hydrolyseverhalten zwei- und dreifach mesylierter Hydroxylamine und ihrer Derivate (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 351-354 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The mesylhydroxylamines (CH3SO2)2NOH, (CH3SO2)2NOCH3, CH3SO2N(H)OSO2CH3, CH3SO2N(CH3)OSO2CH3 (1-4) and (CH3SO2)2NOSO2CH3 (5) were treated with basic, neutral, and acidic aqueous solutions. The reaction products were identified. Possible decomposition mechanisms were discussed.
    Notes: Die Mesylhydroxylamine (CH3SO2)2NOH, (CH3SO2)2NOCH3, CH3SO2N(H)OSO2CH3, CH3SO2N(CH3)OSO2CH3 (1-4) und (CH3SO2)2NOSO2CH3 (5) wurden in alkalischer, neutraler und saurer Lösung hydrolysiert. Die Zersetzungsprodukte wurden identifiziert und mögliche Reaktionswege ihrer Entstehung diskutiert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200317
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    Alkyl Shifts in 1,4-Dipoles from Tosyl Iso(thio)cyanate and Imido(thio)carbonates or Isoureas (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 339-344 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die Dipole 3, 13 aus Tosylisocyanat (2a) und Imido(thio)kohlensäureestern 1 (12) geben O → N-Alkyl-Verschiebungen zu (Thio)Allophansäureestern 5 (14). ähnlich führt die Addition von Tosylisothiocyanat (2b) an den Isoharnstoff 24a zum Produkt 28 einer O→S-Methyl-Verschiebung. Ausgehend von 2a und den Imidothiokohlensäureestern 12b,c ergab ein Kreuzungsversuch die vier Produkte 14a-d und bewies so den intermolekularen Verlauf der Umlagerung. Beim Zusammengeben des Isothiocyanats 2b und der Imido(thio)kohlensäureester 1 (12) oder von 2a und der Isoharnstoffe 24a,b bleibt die Reaktion jedoch auf der Stufe der Dipole 8, 19, 25a, b stehen.
    Notes: O→N alkyl shifts are observed in the dipoles 3, 13 from tosyl isocyanate (2a) and imido(thio)carbonates 1 (12) to give (thio)allophanates 5 (14). Similarly, addition of tosyl isothiocyanate (2b) to isourea 24a leads to the product 28 of an O → S methyl shift. A cross-over experiment involving 2a and imidothiocarbonates 12b,c gives the four products 14a-d proving the intermolecular nature of the rearrangement. However, on mixing 2a and isoureas 24a,b or 2b and imido(thio)carbonates 1 (12), the reaction stops at the stage of dipoles 8, 19, 25a,b.
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    URL: http://dx.doi.org/10.1002/cber.19871200315
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    PMO Analysis of Cycloadditions, I Diels-Alder Reactions of 2,3-Bis(methylene)norbornane (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1323-1330 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: PMO-Analyse von Cycloadditionen, I. - Diels-Adler-Reaktionen von 2,3-Bis(methylen)norbornanEine störungstheoretische Methode (PMO) zur Berechnung der Wechselwirkung von Molekülen auf der Basis des semiempirischen MINDO/3-Verfahrens wird auf die Cycloadditionen von 2,3-Bis(methylen)norbornan (1) mit den elektronenarmen Olefinen 2-5 angewendet. Verschiedene Anteile der Wechselwirkungsenergie, von sterischen Effekten, polaren Beiträgen und Orbitalwechselwirkungen stammend, werden analysiert. Die Ergebnisse werden mit dem Programmpaket PERVAL, das für einen IBM AT Personal Computer entwickelt wurde, berechnet und graphisch ausgewertet. Die Reaktivitätssequenz 2 〈 3 〈 4 〈 5 wird auf die dominante HOMODien-LUMODienophil-Wechselwirkung zurückgeführt. Es werden verschiedene Möglichkeiten der Anwendung des Programms PERVAL aufgezeigt.
    Notes: A perturbational molecular orbital (PMO) treatment within the semiempirical MINDO/3 approximation is applied to the cycloadditions of 2,3-bis(methylene)norbornane (1) to electron-deficient olefins (2-5). Different contributions to the interaction energy deriving from steric effects, polar effects, and orbital interactions are analysed. The results, obtained by the program package PERVAL, which is developed for an IBM AT personal computer, are evaluated graphically. The origin of the reactivity sequence 2 〈 3 〈 4 〈 5 is traced back to the HOMOdiene-LUMOdienophile interaction. Various possibilities to interpret the results of PMO calculations are demonstrated.
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    URL: http://dx.doi.org/10.1002/cber.19871200810
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    Diels-Alder-Reaktionen mit 2H-Pyran-2-onen: Reaktivität und Selektivität (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1339-1346 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diels-Alder Reactions with 2H-Pyran-2-ones: Reactivity and Selectivity2H-Pyran-2-ones 1 react with maleic anhydride (2) in a double Diels-Alder reaction to give bicyclo[2.2.2]oct-2-ene-5,6:7,8-tetracarboxylic dianhydrides 5; the syn/syn structure was established. As expected, the reactivity of 1 was increased by electron donor substituents (OR, alkyl) and diminished by electron withdrawing substituents (CO2R). The steric influence of substituents at C-6 also decrease the reactivity of 1. - Methyl propiolate (6) and phenylacetylene (9) react with 1 to form the Diels-Alder products 7 which suffer CO2 elimination to yield methyl benzoates 8 with low and biphenyls 10 with high regioselectivity, respectively.
    Notes: 2H-Pyran-2-one 1 gehen mit Maleinsäureanhydrid (2) eine zweifache Diels-Alder-Reaktion zu Bicyclo[2.2.2]oct-2-en-5,6:7,8-tetracarbonsäure-dianhydriden 5 ein, deren syn/syn-Struktur nachgewiesen wurde. Die Reaktivität von 1 wird erwartungsgemäß durch Donor-Substituenten (OR, Alkyl) erhöht und durch Acceptor-Substituenten (CO2R) verringert; Substituenten in 6-Stellung der α-Pyrone 1 führen infolge ihres sterischen Einflusses zu einer deutlichen Reaktivitätsverminderung. - Aus 1 und Propiolsäuremethylester (6) bzw. Phenylaceylen (9) entstehen über die primären Diels-Alder-Cycloadditionsprodukte 7 unter CO2-Abspaltung isomere Benzoesäure-methylester 8 mit geringer bzw. Biphenyle 10 mit hoher Regioselektivität.
    Additional Material: 11 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200812
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    Darstellung hochsubstituierter Aromaten über Diels-Alder-Reaktionen mit 2H-Pyran-2-onen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1347-1355 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Highly Substitued Benzenes via Diels-Alder Reactions with 2H-Pyran-2-onesThe 2H-pyran-2-ones (α-pyrones) 1 react as dienes in Diels-Alder reactions with acetylene derivatives. The primarely formed cycloadducts immediately aromatize to benzenes by CO2 elimination. Thus, methyl acetylenedicarboxylate (2a) gives dimethylphthalates 3, and methyl acetylenediphosphonate (2b) gives dimethyl 1,2-phenylenediphosphonates 8. The reactions of 1-(dimethylamino)-1-methoxyethene (9) with 1 regioselectively produce N,N-dimethylanilines 10 and isomeric homophthalate derivatives 12. Naphthoquinones 14 could be generated from 1,4-benzoquinone (13) and 1 in the presence of acetic anhydride and Pd/C. Hydroxy-2H-pyran-2-ones 4 react via their trimethylsilyl ether 6 analogously with 2a to give dimethyl (trimethylsiloxy)-phthalates 7 which are easily converted to phenols 5 by acidcatalyzed hydrolysis.
    Notes: Acetylenderivate reagieren mit 2H-Pyran-2-onen (α-Pyronen) 1 als Dien-Komponenten primär zu Diels-Alder-Cycloadditionsprodukten, die sofort unter CO2-Abspaltung zu Benzolderivaten aromatisieren. So werden mit Acetylendicarbonsäure-dimethylester (2a) Phthalsäure-dimethylester 3 und mit Acetylenbis(phosphonsäure-dimethylester) (2b) 1,2-Phenylenbis(phosphonsäure-dimethylester) 8 erhalten. 1-(Dimethylamino)-1-methoxyethen (9) sowie 2,3-Pentadiendisäure-dimethylester (11) bilden mit 1 regioselektiv N,N-Dimethylaniline 10 sowie isomere Homophthalsäure-Derivate 12. Aus 1,4-Benzochinon (13) und 1 entstehen in Gegenwart von Acetanhydrid und Pd/C Naphthochinone 14. Hydroxy-2H-pyran-2-one 4 lassen sich über ihre Trimethylsilylether 6 mit 2a zu den (Trimethylsiloxy)phthalsäure-dimethylestern 7 umsetzen, deren säurekatalysierte Hydrolyse glatt zu den Phenolen 5 führt.
    Additional Material: 13 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200813
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    Blitzvakuumpyrolyse von o-Alkylaryl- und Arylalkylchlorboranen Synthese benzoanellierter Boracycloalkene (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1331-1338 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Flash Vacuum Pyrolysis Of o-Alkyaryl- and Arylalkylchloroboranes. - Synthesis of Benzoannutated Boracycloalkenes The dichloroorganylboranes chosen as pyrolytic starting materials were synthesized upon treatment of the corresponding triorganylboroxines and aryltrimethylsilanes (giving 3, 4) or the tetraorganylstannanes (giving 9-12, 17-20) with boron trichloride. At 700°C the flash vacuum pyrolysis of the dichloro(2-ethylphenyl)boranes 10 and 4 led to 1-boraindanes 21 and 22 selectively. The dichloro-2-tolylborane (9), the B-dimethylamino derivative, and mesitylboranes like 3 were completely stable upon pyrolysis. Pyrolyzing the isopropylphenylborane 12 1,5-elimination exclusively took place yielding 26, while pyrolysis of propylphenylborane 11 led to a mixture of boraindane 29 and boratetraline 30. To exclude such competitive reactions, some arylalkyldichloroboranes were pyrolyzed. At 750°C dichloro(2-methylbenzyl)borane (18) exclusively yielded oligomeric 2-chloro-2-boraindane (31). At 950°C even the pyrolysis of benzyldichloroborane (17) succeeded in a 1,4-elimination reaction yielding the eight-membered 2H-benzoborete dimer 34. The inversion barrier of 34 is ΔG228=10.3 kcal mol-1, determined by NMR spectroscopy. The pyrolysis of the next-higher homologous dichloroorganylborane 19 yielded a boraindane 21 and a noncyclic diorganylborane 38 by a dehydroboration/hydroboration pathway. Both reaction types also took place when pyrolyzing dichloro[2-(2-tolyl)ethyl]borane (20): cyclization under formation of a five-membered ring system 39, formed upon attack of an aromatic C-H bond exclusively, and formation of an open-chain chlorodiorganylborane 40.
    Notes: Die als Pyrolyse-Edukte eingesetzten Dichlororganylborane wurden durch Umsetzung der entsprechenden Triorganylboroxine und Aryltrimethylsilane (zu 3, 4) oder der Tetraorganylstannane (zu 9-12, 17-20) mit Bortrichlorid gewonnen. Die Blitzvakuumpyrolyse der Dichlor(2-ethylphenyl)borane 10 und 4 führte bei 700°C selektiv zu den 1-Boraindanen 21 und 22. Das Dichlor-2-tolylboran (9) war thermisch ebenso stabil wie das B-Dimethylamino-Derivat und Mesitylborane wie 3. Auch bei der Pyrolyse des Isopropylphenylborans 12 trat ausschließlich 1,5-Eliminierung unter Bildung von 26 ein, während die Pyrolyse des Propylphenylborans 11 zu einem Gemisch aus Boraindan 29 und Boratetralin 30 führte. Um derartige intramolekulare Konkurrenzsituationen auszuschließen, wurden Arylalkyldichlorborane pyrolysiert. Dichlor(2-methylbenzyl)boran (18) lieferte bei 750°C ausschließlich oligomeres 2-Chlor-2-boraindan (31). Bei 950°C reagierte sogar Benzyldichlorboran (17) unter 1,4-Eliminierung zu dem achtgliedrigen 2H-Benzoboret-Dimeren 34. Die Inversionsbarriere von 34 wurde NMR-spektroskopisch zu ΔG228=10.3 kcal mol-1 bestimmt. Die Pyrolyse des nächsthöheren homologen Dichlororganylborans 19 lieferte ein Boraindan (21) und ein nichtcyclisches Diorganylboran 38 über eine Dehydroborierungs-/Hydroborierungsreaktion. Beide Reaktionstypen wurden auch bei der Pyrolyse von Dichlor[2-(2-tolyl)ethyl]boran (20) beobachtet: Cyclisierung ausschließlich unter Fünfringbildung (39) durch Angriff einer aromatischen C-H-Bindung und Bildung eines offenkettigen Chlordiorganylborans (40).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200811
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    Reaktivität von Silan- und Germaniminen Me2E=NR (E=Si, Ge)1) (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1357-1368 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Adduct Formation and Reactivity Of Silane- and Germaneimines Me2E=NR (E=Si, Ge)1)Silane- and Germaneimines Me2E= NR (E=Si, Ge; R=silyl), generated as reactive intermediates by thermal [2+3] cycloreversion from [2+3] cycloadducts of Me2E=C(SiMe3)2 or Me2E=NR with silyl azides RN3, combine with reactants a (e. g. NEtMe2) under addition (formation of adducts 7), with a - b [e. g. RO - H, RHN - H, X - SiMe3 (X=Cl, N3, MeO, Me2N), Cl - GeMe3, Cl - SnMe3] under insertion into the a - b bond (formation 13-16), with a=b (e.g. RN=EMe2, O=CPh2) under [2+2] cycloaddition (e. g. formation of 17, 18), with a=b=c (e.g. R′N=N=N) under [2+3] cycloaddition (formation of 19, 20), and with a=b - c - H (e.g. CH2=CR - CH2 - H, O=CMe - CH2 - H) under ene reaction (formation of 21-24). [2+4] cycloaddition of Me2Si=NR with organic 1,3-dienes (e. g. CH2=CR - CR=CH2, cyclopentadiene) is not observed. By comparison with ethenes Me2E=C(SiMe3)2, imines Me2E=NR have greater tendency for insertion and lesser tendency for cycloaddition; by comparison with silaneimines Me2Si=NR, germaneimines Me2Ge=NR are possibly less Lewis acidic.
    Notes: Silan- und Germanimine Me2E=NR (E=Si, Ge; R=Silyl), erzeugt als Zwischenstufen durch thermische [2+3]-Cycloreversion aus den [2+3]-Cycloaddukten von Me2E=C(SiMe3)2 bzw. Me2E=NR mit Silylaziden RN3, reagieren mit Reaktanden a (z. B. NEtMe2) unter Addition (Bildung von Addukten 7), mit a-b [z. B. RO - H, RHN - H, X - SiMe3 (X=Cl, N3, MeO, Me2N), Cl - GeMe3] unter Insertion in die a - b-Bindung (Bildung von 13-16), mit a=b (z. B. RN=EMe2, O=Cph2) unter [2+2]-Cycloaddition (z. B. Bildung von 17, 18), mit a=b=c (z. B. R′N=N=N) unter [2+3]-Cycloaddition (Bildung von 19, 20) und mit a=b - c - H (z. B. CH2=CR - CH2 - H, O=CMe - CH2 - H) unter En-Reaktion (Bildung von 21-24). [2+4]-Cycloaddition von Me2Si=NR mit organischen 1,3-Dienen (z. B. CH2=CR - CR=CH2, Cyclopentadien) wird nicht beobachtet. Verglichen mit den Ethenen Me2E=C(SiMe3)2 zeigen die Imine Me2E=NSiMe3 eine größere Tendenz zur Insertion und kleinere Tendenz zur Cycloaddition; verglichen mit den Silaniminen Me2Si=NR sind die Germanimine Me2Ge=NR wohl weniger Lewis-sauer
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200814
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    Reaktionen mit Diazoazolen, VIII1) Synthesen von Azolo[5,1-d]-1,2,3,5-tetrazin-4(3H)-onen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1375-1395 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Diazoazoles, VIII1). - Syntheses of Azolo [5,1-d]-1,2,3,5,-tetrazin-4(3H-onesAzolo[5,1-d]-1,2,3,5-tetrazin-4(3H)-ones 4 and 5 are formed by cycloaddition reactions of α-diazoazoles 2 with aryl or alkyl isocyanates 3a-p, respectively, as well as with diisocyanates 3q, r (Method A). Alternative syntheses for 4 are presented by diazotization of N-alkyl(aryl)-5-amino-1H-pyrazole-1-carboxamides (6) and subsequent intramolecular coupling (Method B), by coupling of 3-diazo-5-methyl-4-phenyl-3H-pyrazole (2A) with primary amines 11 to give pyrazolyltriazenes 12A, and by their carbonylation reaction (Method C). The lability of azolotetrazinones against bases is exemplified with-methyl-3,8-diphenylpyrazolo-[5,1-d]-1,2,3,5-tetrazine-4(3H)-one (4Aa) in its reaction with hydroxide ions or morpholine.
    Notes: Azolo[5,1-d]-1,2,3,5-tetrazin-4(3H)-one 4 und 5 entstehen durch Cycloaddition von α-Diazoazolen 2 an Aryl- oder Alkylisocyanate 3a-p bzw. an Diisocyanate 3q, r (Methode A). Alternativsynthesen für 4 werden durch Diazotierung von N-Alkyl(Aryl)-5-amino-1H-pyrazol-1-carboxamiden 6 und nachfolgende intramolekulare Kupplung (Methode B) sowie durch Kupplung von 3-Diazo-5-methyl-4-phenyl-3H-pyrazol (2A) mit primären Aminen 11 zu Pyrazolyltriazenen 12A und deren Carbonylierung (Methode C) vorgestellt. Die Basenlabilität der Azolotetrazinone wird am Beispiel des 7-Methyl-3,8-diphenylpyrazolo[5,1-d]-1,2,3,5-tetrazin-4(3H)-ons (4Aa) in dessen Reaktion mit Hydroxidionen oder Morpholin aufgezeigt.
    Additional Material: 9 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200816
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    NMR-spektroskopische Untersuchungen zur Konstitution von Benzyl- und 1-Napthylmethyl-Verbindungen des Titaniums, Zirconiums und Hafniums (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1369-1374 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: NMR Spectroscopic Investigations on the Constitution of Benzyl and 1- Naphthylmethyl Compounds of Titanium, Zirconium, and Hafnium1H- und 13H- spectra of tetrabenzyl compounds (C6H5CH2)4M (M=Ti, Zr, Hf; 1 - 3) and analogous 1-naphtylmethyl derivatives (1-C10H7CH2)4M (M=Ti, Zr, Hf; 4-6) do not show noticable changes in their bonding properties which were postulated on the basis of X-ray structure analyses of 1-3. On exchanging benzyl groups in 1 and 2 against halogen atoms leading to the compounds (C6H5CH2)4 - nMHaln (M=Ti, Zr, Hf; Hal=Cl, Br, I; n=1 - 3; 7-21) the δCH2 values indicate sensitively the alternation of electron density at the metal atoms. In contrast, no alternation of the benzyl group-metal bonds is indicated by the chemical shifts of the phenyl group C and H atoms, but it becomes evident when benzyl groups are substituted by Cp. Whilst in 1 - 3 a η4-coordination of the benzyl groups can be assumed, these groups are η1-bonded in Cp2Ti(CH2C6H5)2 (23) and Cp2Zr(CH2C6H5)2 (25). Furthermore, an alternation of the coordination systems could be proved in case of 3 and 6 in the presence of donor molecules (THF, pyridine).
    Notes: Die 1H- und 13C-NMR-Spektren (T 298 K, C6D6) der Tetrabenzylverbindungen (C6H5CH2)4M (M=Ti, Zr, Hf; 1-3) und der benzylanalogen 1-Napthylmethyl-Derivate (1-C10H7CH2)4M (M=Ti, Zr, Hf; 4-6) lassen keine besonderen Bindungsverhältnisse erkennen, die aufgrund von Röntgenstrukturuntersuchungen bei 1-3 vermutet wurden. Bei einem Austausch von Benzylgruppen in 1 und 2 gegen Halogenatome, d.h. in Verbindungen des Typs (C6H5CH2)4 - nMHaln (M=Ti, Zr, Hal=Cl, Br, I; n=1 - 3; 7-21), zeigt δCH2 empfindlich die veränderte Elektronendichte an den Metallatomen an. Demgegenüber werden aus den chemischen Verschiebungen der Phenyl-C- und -H-Atome keine Veränderungen der Art der Benzyl-Metall-Bindung sichtbar. Diese zeigen sich jedoch beim schrittweisen Austausch von Benzylgruppen gegen Cp-Reste. Während in 1-3 eine η4- Koordination der Benzylreste anzunehmen ist, liegen in Cp2Ti(CH2C6H5)2 (23) und Cp2Zr(CH2C6H5)2 (25) η1-gebundene Benzylgruppen vor. - In Gegenwart von Donorliganden (THF, Pyridin) wird für 3 und 613C-NMR-spektroskopisch ebenfalls eine Änderung der Bindungsart der Organylreste an das Zentralatom nachgewiesen.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200815
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    Diazoverbindungen, 691) 2-(oder 4-)(Diazomethyl)-2-(oder 4-)H-benzopyrane - Synthese durch elektrophile Diazoalkansubstitution und katalytische Zersetzung (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1397-1402 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diazo Compounds, 691) - 2-(or 4-)(Diazomethyl)-2-(or 4-)H-benzopyrans - Synthesis by Electrophilic Diazoalkane Substitution and Catalytic DecompositionElectrophilic diazoalkane substitution of the (diazomethyl)phosphoryl compounds 9a-c with the benzopyrylium tetrafluoroborate 8 yields the 2-[diazo(phosphoryl)methyl]-2H-1-benzopyrans 10a-c and the 4-isomers 11a-c. Lithiated methyl diazoacetate reacts analogously with 8 under formation of 10d and 11d. At the μ-allylpalladium chloride catalyzed decomposition of 10a-d the benzoxepines 14a-d are formed by ring enlargement reaction; 1,2-H shift is responsible for the additional formation of the 2-methylene-2H shift is responsible for the additional formation of the 2-methylene-2H-benzopyrans 15b and c in the case of 10b and c. The catalytic decomposition of 11a-d proceeds exclusively in the sense of an intramolecular [2 + 1] cycloaddition to afford the 3,4-dihydro-2,3,4-metheno-2H-benzopyrans 18a-d. The benzoxepines 14a,d are characterized by photochemical electrocyclic reaction to 19a and b.
    Notes: Elektrophile Diazoalkansubstitution der (Diazomethyl)phosphoryl-Verbindungen 9a-c mit dem Benzopyrylium-tetrafluoroborat 8 liefert die 2-[Diazo(phosphoryl)methyl]-2H-1-benzopyrane 10a-c und die 4-Isomeren 11a-c. Lithiierter Diazoessigsäuremethylester reagiert analog mit 8 unter Bildung von 10d und 11d. Bei der μ-Allylpalladium-chlorid-katalysierten Zersetzung von 10a-d entstehen die Benzoxepine 14a-d durch Ringerweiterungsreaktion; 1,2-H-Verschiebung ist für die zusätzliche Bildung der 2-Methylen-2H-benzopyrane 15b und c im Fall von 10b und c verantwortlich. Die katalytische Zersetzung von 11a-d verläft ausschließlich im Sinne einer intramolekularen [2 + 1]-Cycloaddition zu den 3,4-Dihydro-2,3,4-metheno-2H-benzopyranen 18a-d. Die Benzoxepine 14a,d sind durch photochemische, elektrocyclische Reaktion zu 19a und b charakterisiert.
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    URL: http://dx.doi.org/10.1002/cber.19871200817
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    Übergangsmetall-substituierte Diphosphene, IX1) Synthese und Struktur von metallierten 1,3-Diphospha-2-propanonen. - Carbonylierung von Diphosphenyl-Komplexen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1421-1426 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal-Substituted Diphosphenes, IX1). - Synthesis and Structure of Metalated 1,3-Diphospha-2-propanones. - Carbonylation of Diphosphenyl ComplexesThe diphosphenyl complexes (η5-C5Me5)(CO)2M-P=P-Ar (3) (M=Fe, Ru, Os; Ar=2,4,6-t-Bu3C6H2) react with Fe2(CO)9 to yield adducts such as (η5-C5Me5)(CO)2M[Fe(CO)4]P=P-Ar(4) as well as the 1,3-diphospha-2-propanone complexes [(η5-C5Me5)-(CO)2M-P(CO)PAr]Fe2(CO)6 (5) by catalytic carbonylation of the activated P=P double bond. The structures of 4a and 5a are established by X-ray diffraction studies.
    Notes: Die Diphosphenyl-Komplexe (η5-C5Me5)(CO)2M-P=P-Ar (3) (M=Fe, Ru, Os; Ar=2,4,6-t-Bu3C6H2) reagieren mit Fe2(CO)9 zu Addukten des Typs (η5-C5Me5)(CO)2M[Fe(CO)4]P=P-Ar(4) und den 1,3-Diphospha-2-propanon-Komplexen [(η5-C5Me5)-(CO)2M-P(CO)PAr]Fe2(CO)6 (5). Offensichtlich entsteht 5 aus 3 durch katalytische Carbonylierung der aktivierten P=P-Funktion. Von 4a und 5a wurden Röntgenstrukturanalysen durchgeführt.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200820
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    Synthese, Struktur und einige Reaktionen von Tris- und Tetrakis(diphenylphosphino)allen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1403-1412 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Structure, and Some Reactions of Tris- and Tetrakis(diphenylphosphino)allenesTreatment of the reagent 2, obtained from 1-(diphenylphosphino)-1-propyne (1) and n-BuLi, with Ph2PCl gives high yields of tetrakis(diphenylphosphino)allene (3). On oxidation with H2O2 or Me3SiOOSiMe3, this compound yields the tetraoxide 4a, while with sulfur or selenium the tetrachalcogenides 4b,c are obtained. The allene group is not affected in these processes. In the reaction of 3 with MeLi P - C cleavage occurs to give Ph2PMe and 1,3,3-tris(diphenylphosphino)allenyllithium (5), which is converted into tris(diphenylphosphino)allene (Ph2P)2C=C=CHPPh2 (6) upon hydrolysis. Quaternization with MeI under mild conditions leads to the monoquaternary salts 7 and 8 from 3 and 6, respectively. With excess MeI at higher temperature a phosphonioalkynyl-semiylide salt [(MePh2P)2C-C≡C-PPh2Me]2+ 2 I- (9) is formed from both 3 and 6. The by-product of the P-C cleavage in 3 by MeI is Ph2PMe2+ I-3. - The structures of the allenes 3 and 6 and of the salt 9 have been confirmed by single crystal X-ray diffraction. The Ph2P groups in 3 adopt a similar conformation as found previously for (Ph2P)2C=CH2, with an opposite orientation of the lone pairs of electrons at phosphorus relative to the allene axis. In 6 a rotamer with an approximately symmetrical (“anti”) orientation of the geminal Ph2P groups is present. 9 is found to be another example of semiylidic quaternary salts with a delocalized ylide function.
    Notes: Das aus 1-(Diphenylphosphino)-1-propin (1) mit n-BuLi erhältliche Reagens Ph2P-C≡C-CH2Li(2) ergibt bei der Behandlung mit Ph2PCl hohe Ausbeuten an Tetrakis(diphenylphosphino)allen (3). Diese Verbindung liefert nach Oxidation mit H2O2 oder Me3SiOOSiMe3 das Tetraoxid 4a, mit Schwefel oder Selen die entsprechenden Tetrachalkogenide 4b,c. Die Allengruppierung wird dabei nicht angegriffen. Durch Umsetzung von 3 mit MeLi kommt es zur Spaltung einer P-C-Bindung. Das neben Ph2PMe gebildete 1,3,3-Tris(diphenylphosphino)allenyllithium (5) kann durch Hydrolyse in (Ph2P)2C=C=CHPPh2 (6) verwandelt werden. Bei schonender Quartärisierung mit MeI entstehen aus 3 und 6 die Monoquartärsalze 7 und 8, mit überschüssigem Reagens bei erhöhter Temperatur dagegen als gemeinsames Produkt das Phosphonioalkinyl-semiylid-Salz [(MePh2P)2C-C≡C-PPh2-Me]2+ 2 I- (9). Nebenprodukt der auch hierbei in 3 eintretenden P-C-Spaltung ist Ph2PMe2+ I-3. - Die Strukturen der Allene 3 und 6 sowie des Salzes 9 wurden durch Röntgenbeugungsanalysen an Einkristallen gesichert. Die Ph2P-Gruppen in 3 besitzen ähnliche Konformationen wie im analogen (Ph2P)2C=CH2 mit jeweils entgegengesetzten Orientierungen der freien Elektronenpaare an den P-Atomen zur Allen-Achse. In 6 ist ein Rotameres mit annähernd symmetrischer (“anti”) Orientierung der geminalen Ph2P-Gruppen vorhanden. 9 ist ein weiteres Beispiel für Semiylid-Quartärsalze mit delokalisierter Ylid-Funktion.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200818
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    Alkylation of Position C-5 of Triacetic Acid Lactone by [2,3] Sigmatropic Rearrangement of Sulphonium Ylides (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1413-1419 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkylierung der 5-Stellung von Triessigsäurelacton durch [2,3]-sigmatrope Umlagerung von Sulfonium-YlidenDie Reaktionen von 4-Methoxy-6-(phenylthiomethyl)-2H-pyran-2-onen 4 mit drei verschiedenen Diazoverbindungen unter Kupfer- oder Rhodium-Katalyse liefern entsprechende Sulfonium-Ylide, die durch [2,3]-sigmatrope Umlagerung und nachfolgende Prototropie die Pyrone 6, die an der schwer zugänglichen 5-Stellung funktionalisiert sind, ergeben. Entschwefelung von 6 mit desaktiviertem Raney-Nickel ergibt die Pyrone 17-19. Der Einfluß der experimentellen Bedingungen auf die Konkurrenz von [2,3]-sigmatroper und Stevens-Umlagerung wurde bei der Reaktion von 4-Methoxy-6-(phenylthiomethyl)-2H-pyran-2-on (4a) mit Diazomalonsäure-dimethylester studiert. Zusammen mit den aus [2,3]-sigmatroper und Stevens-Umlagerungen abgeleiteten Verbindungen 6d und 8 wurden noch andere Produkte (9, 10 und 11), die über Sulfonium-Ylid-Gleichgewichtseinstellung und Radikalverknüpfung entstehen, isoliert.
    Notes: Reactions of the 4-methoxy-6-(phenylthiomethyl)-2H-pyran-2-ones 4 with three different diazo compounds under copper or rhodium catalysis give the corresponding sulphonium ylides, which through [2,3] sigmatropic rearrangement and further prototropy afford the pyrones 6, functionalized at the difficutly accessible position C-5. Desulphurations of products 6 with deactivated Raney nickel give the pyrones 17-19. The influence of the experimental conditions on the competition between [2,3] sigmatropic and Stevens rearrangement has been studied for the reaction of 4-methoxy-6-(phenylthiomethyl)-2H-pyran-2-one (4a) and dimethyl diazomalonate. Several products (9, 10, and 11) arising from sulphonium ylides equilibration and radical recombination have been found in addition to the [2,3] sigmatropic and the Stevens rearrangement products 6d and 8.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200819
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    Heterocyclic β-Enamino Esters, 481) Heterocondensed Pyridines by Cycloaddition-Extrusion Sequence of Bi- and Tricyclic 1,3-Oxazinones with N,N-Diethyl-1-propynylamine (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1427-1431 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclische β-Enaminoester, 481). - Heterokondensierte Pyridine durch Cycloaddition-Extrusion-Sequenz bi- und tricyclischer 1,3-Oxazinone mit N,N-Diethyl-1-propinylaminDihalogentriphenylphosphorane überführen die N-benzoylierten 2-Amino-4,5-dihydrofuran- (5b), -pyrrol- (7b), -isoxazol- (9b) und -oxazol-3- oder-4-carbonsäure-ethylester (11b) in die heterokondensierten 1,3-Oxazinone 6, 8, 10 und 12. Mit N,N-Diethyl-1-propinylamin ergeben diese und die bereits beschriebenen 1,3-Oxazinone 1a,b, 2a,b und 3 regiospezifisch in einer Cycloadditions-Extrusions-Sequenz die entsprechenden heterokondensierten Pyridine 13a,b, 14a,b, 15a,b, 16-21, von denen 15b und die 4-Oxonaphthyridine 16, 17 Beispiele für die Insertion des Acetylen-Reagens darstellen.
    Notes: Dihalotriphenylphosphoranes convert the N-benzoylated ethyl 2-amino-4,5-dihydrofuran- (5b), -pyrrole- (7b), -isoxazole- (9b), and -oxazole-3- or-4-carboxylates (11b) into heterocondensed 1,3-oxazinones 6, 8, 10, and 12. Treatment with N,N-diethyl-1-propynylamine of these compounds as well as the already known 1,3-oxazinones 1a,b, 2a,b, and 3 results in a regiospecific cycloaddition-extrusion sequence to afford the corresponding heterocondensed pyridines 13a,b, 14a,b, 15a,b, and 16-21. Of these 15b and the 4-oxonaphthyridines 16, 17 represent examples of insertion of the acetylene reagent.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200821
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    Photochemistry of Heterocycles, 161) Sensitized Photorearrangement of 2,4-Dioxofuro[2,3-d]pyrimidines into 5,7-Diazaspiro[2.5]octanes (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1433-1435 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Short-wavelength triphenylene-sensitized UV irradiation of the furo[2,3-d]pyrimidines 2a-c leads to homolysis and rearrangement with formation of the 5,7-diazaspiro[2.5]octanes 3a-c. Employing the 6,6-dimehtyl derivative 2d, homolysis gives A and subsequent ∊-H abstraction (Norrish-type II) furnishes B ⇄ C; radicalic hydroxylation in 5-position (from THF peroxide) finally leads to 5-hydroxy-2,4,6-trioxo-5-propenylpyrimidine 3d.
    Notes: No Abstract
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200822
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    Carben-analoge Reaktionen der Dehalogenierungsprodukte von Dichlor(diisopropylamino)boran mit Aromaten und 1,2-Dimethoxyethan (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1437-1439 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbene-Analgous Reactions of the Products of Dehalogenation of Dichloro(diisopropylamino)borane with Aromatic Compounds and 1,2-DimethoxyethaneSodium complexes of aromatic compounds in 1,2-dimethoxyethane react with dichloro-diisopropylamino)borane to give compounds formed via carben(oidal) intermediates: From naphthalene 1,2-bis(diisopropylamino)-1,1a,2,8b-tetrahydroborireno[2,3-b][3]benzoborepine (1) is formed. From acenaphthylene 2-(diisopropylamino)-2,3-dihydro-1H-naphtho[1,8-cd]borine (2) and with 1-methylnaphthalene, in addition to 1,2-bis[(diisopropylamino)methoxyboryl]ethyne (3), (diisopropylamino)dimethoxyborane (4) is isolated. 1H-, 11B-, 13C-, 14N-, 15N NMR and MS data are given. For 3 the X-ray structure is reported.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200823
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    Photoelektronenspektrum und elektronische Struktur von 4-Butadiinylmorpholin, einem Amino-substituierten 1,3-Diin (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1441-1443 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photoelectron Spectrum and Electronic Structure of 4-Butadiynylmorpholine, an Amino-Substitued 1,3-DiyneThe PE spectrum of the title compound 1 has been obtained. Based on MNDO calculations, the ionization potentials have been assigned to molecular orbitals of the amino-substituted 1,3-diyne. Besides the n orbitals of the electron lone-pairs of the morpholine ring, there are two pairs of occupied π MOs of the diyne. One pair of π MOs interacts strongly with the n(N) MO, while the other one corresponds to those of unsubstituted butadiyne. MNDO calculations indicate a pyramidal configuration of the nitrogen atom with a rather low inversion barrier.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200824
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    Ethylidenphosphoran-Ethenylfluorphosphoran-(λ5σ4P-λ5σ5P)-Umlagerung (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1445-1446 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ethylidenephosphorane - Ethenylfluorophosphorane (2λ5σ4P-λ5σ5P) Rearrangement2-Methoxy-1,3,2-dioxaphospholane (4) reacts with 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1) to furnish 2-methoxy-2-[2,2,2,-trifluoro-1-(trifluoromethyl)ethylidene]-1,3,2λ 5σ5-dioxaphospholane (6) which rearranges upon standing at ambient temperature to form 2-[2,2-difluoro-1-(trifluoromethyl)ethenyl]-2-fluoro-2-methoxy-1,3,2λ5σ5-dioxaphospholane (7).
    Notes: No Abstract
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200825
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    Schwefeldiimide mit Thioarsinyl- und Selenoarsinyl-Substituenten (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1447-1448 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sulfur Diimdides Containing Thioarsinyl and Selenoarsinyl SubstituentsWhile bis(di-tert-butylphosphino)sulfur diimide, S(N-PtBu2)2 (1a), readily adds both elemental sulfur and selenium below 0°C to give 1: 2 adducts S[N - P(Y)tBu2]2 [Y=S (1b), Se (1b), Se (1c)], the analogous bis(di-tert-butylarsino)sulfur diimide, S(N - AstBu2)2 (2a), is almost unreactive under comparable conditions. However, thioarsinyl sulfur diimide, S[N - As(S)tBu2]2 (2b), can be obtained from K2SN2 and two equivalents of tBu2As(S)Cl. In contrast to sulfur, selenium is slowly attached to the arsino centers of 2a in toluene solution at 25°C to give both the di- and the monoselenium adduct, S[N-As(Se)tBu2]2 (2c) and tBu2As(NSN)As(Se)tBu2 (2d), respectively.
    Notes: No Abstract
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200826
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    Reaction of Cyclic Thioureas with 2-Benzylidenecycloalkanones (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1449-1450 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: BF3. OEt2-catalyzed reaction of cyclic thioureas (1) with 2-benzylidenecycloalkanones (2) afforded tricyclic 1,3-thiazines (3, 4). The progress of the reactions was found to depend on the ring size of both 1 and 2.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200827
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    Katalytische Synthese von 5-Benzylidenhydantoinen aus Alkylisocyanaten und Phenylacetylen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1451-1453 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Catalytic Synthesis of 5-Benzylidenehydantoins from Alkyl Isocyanates and PhenylacetyleneNew 5-benzylidenehydantions 1-4 have been prepared from alkyl isocyanates and phenylacethylene in the presence of various ruthenium clusters as catalyst precursors. All products have been separated into the expected Z and E isomers.
    Notes: No Abstract
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200828
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    Synthese von 1λ6- und 1λ4-1,2,6-Thiadiazinen aus S,S-Dialkylschwefeldiimiden (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1455-1459 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 1λ6- and 1λ4-1,2,6,-Thiadiazines from S,S-Dialkylsulfur Diimides1λ6,2,6-Thiadiazines 4a-h, 1λ4,2,6-Thiadiazines 5a-k, 6a,b, and ring-open products 3a-o are synthesized by reaction of dialkylsulfur diimides 1a-g with ethylene derivatives 2a-h. 1λ6,2,6-Thiadiazines 4h,b,c can be converted into 1λ4,2,6-Thiadiazines 5j, 6a,b under acid catalysis. The ring-open product 3n leads to 1λ6,2,6-thiadiazine 4a when heated with base.
    Notes: No Abstract
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200829
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    Anomer kontrollierte Substitutionsreaktionen mit verschiedenen N-Alkylpyridiniumverbindungen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 735-745 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The results of semiempirical MNDO calculations on bond lengths, heats of formation, and net atomic charges of compounds 6, 7, and 8, which all contain an N-alkylpyridinium moiety (see Table 1), allow general trends to be recognized. These trends allow the prediction of important reactivity characteristics of this series of compounds and were the reason for the synthesis of compounds 9, 24, and 26 and for tests of their usefulness. Specifically, the C1-N2 bond length serves as a useful criterion for the reactivity with nucleophilic partners, especially in combination with thermodynamic data calculated from reactions (3) and (4) (Tables 3 and 4). In 7 and 8, this bond is very long as a consequence of an extreme anomeric effect. This observation is reflected in the (experimentally tested) property of the complexes 9 to split off the pyridine moiety. The Cl atom in 6a does not influence the C1-N2 bond length but it does activate the C1 atom toward nucleophilic attack and can itself function as the leaving group [see eq. (10)]. - A remarkable example, both on the basis of the MNDO results (using the model compound 6i) and from the experimental viewpoint, was observed for the class of compounds 24a. The calculated C1-N2 bond length of 6i (1.563 Å) could be classified as adequate for nucleophilic substitution of the pyridine moiety controlled by the anomeric effect on the basis of experimental tests. Whereas “normal” N-alkylpyridinium salts (e.g. the N-methylpyridinium cation, 6b) are hardly ever attacked in the C1 position, the preparative usefulness of this structural element can now be considerably increased by use of the anomeric effect. This is demonstrated by the synthesis of compounds 5, 9h, 17, and 22 from 9, 25a and 25b from 24a as well as 27a from 26a.
    Notes: Ergebnisse aus semiempirischen (MNDO)-Berechnungen der Bindungslängen, Bildungsenergeien und Überschußladungen solcher Verbindungsklassen 6, 7 und 8, die als gemeinsames Strukturelement einen N-Alkylpyridinium-Molekülteil besitzen (vgl. Tab. 1), lassen allgemeingültige Trends erkennen, mit deren Hilfe wichtige Reaktivitätsmerkmale dieser Reihe vorhergesagt werden können und somit Anlaß zur gezielten Herstellung der Beispiele 9, 24 und 26 und deren erste Verwendungstests waren: Insbesondere die C1-N2-Bindungslänge kann bei Umsetzungen mit nucleophilen Reaktionspartnern - bei zusätzlicher Berücksichtigung der entsprechend Gl. (3) und (4) berechneten thermodynamischen Daten (Tab. 3 und Tab. 4) - als ein zuverlässiges Beurteilungskriterium dienen. Diese Bindung ist in 7 und 8 infolge eines extremen anomeren Effekts sehr lang, ein Befund, der sich in der (experimentell überprüften) Eigenschaft der Komplexe 9, den Pyridiniumteil besonders leicht abzuspalten, widerspiegelt. Das Cl-Atom in 6a ist auf die genannte Bindungslänge ohne Einfluß, es erleichtert jedoch den nucleophilen Angriff auf das C1-Zentrum und kann selbst zur Abgangsgruppe werden [vgl. Gl. (10)]. - Ein sowohl aufgrund der MNDO-Ergebnisse (Berechnung des Modells 6i) als auch aus experimenteller Sicht bemerkenswertes Beispiel manifestiert sich als Konsequenz dieser überlegungen in der Substanzklasse 24a: Die berechneten C1-N2-Bindungslänge von 6i (1.563 Å) konnte durch experimentelle Tests [G1. (9)] als hinreichend für die durch den anomeren Effekt gesteuerte nucleophile Substitution des Pyridiniumteils in 24a klassifiziert werden. Während also “normale” N-Alkyl-pyridiniumsalze (z. B. das N-Methylpyridinium-Kation 6b) kaum an der C1-Position angreifbar sind, kann durch gezielte Ausnutzung des anomeren Effekts das präparative Anwendungsspektrum dieses Strukturelements nunmehr deutlich erweitert werden (hier umrissen durch die Herstellung der Verbindungen 5, 9h, 17 und 22 aus 9, 25a und 25b aus 24a sowie 27a aus 26a).
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200510
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    Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, VIII (Tetrahydrofurfuryl)phosphan-Komplexe von Rhodium(I) mit reaktiven Rhodium-Sauerstoff-Bindungen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 761-767 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The rhodium complexes SbF6 (5a, b) [R=Ph (a), c-C6H11 (b)] are obtained by Cl- abstraction from ClRh(COD)PR2CH2C4H7O (3a, b) with AgSbF6. 3a, b result from [μ-ClRh(COD)]2 (1) and the P,O ligands R2PCH2C4H7O (2a, b). Complex 5b is also formed from [Rh(COD)(THF)2]SbF6 (4) and 2b. As was demonstrated with the cis complexes PF6 (8a, b), the introduction of a second ligand 2a, b succeeds either by COD elimination from [Rh(COD)-(PPh2CH2C4H7O)2]PF6 (6a) or by an one-pot reaction of [μ-ClRh(COE)2]2 (7) with 2a, b and NaPF6. In the presence of excess COD 8a is reversibly transformed into 6a with cleavage of two Rh-O bonds. In contrast to 8a, 8b reacts with hydrogen to give the cis hydrido compound PF6 (9b) with reorientation of the P,O ligands from cis to trans, being only stable in solution under an atmosphere of hydrogen. Upon the oxidative addition of CH3I (13CH3I) to 8b, leading to cis-PF6 (10b and 10′b, respectively), also the kinetic instability of the Rh-O bond is of importance. With cleavage of the Rh-O bond 8a, b react with CO (13CO) to give the trigonal-bipyramidally configurated complexes [(OC)3Rh(PR2CH2C4H7O)2]PF6 (11a, b and 11′a, b, resp.) with trans-arranged P,O ligands. As a result of CO (13CO) elimination and reversible Rh-O bond formation 11b and 11′b (13CO enriched) are tranformed into the trans-P configurated complexes PF6 (12b and 12′b, resp.), showing fluctional behaviour at 20°C in the 31P{1H}-NMR spectrum, regarding the Rh-O bond.
    Notes: Die Rhodium-Komplexe SbF6 (5a, b) [R=Ph (a), c-C6H11 (b)] erhält man durch Cl--Abstraktion aus ClRh(COD)PR2CH2C4H7O (3a, b) mit AgSbF6. 3a, b entstehen aus [μ-ClRh(COD)]2 (1) und den P,O-Liganden R2PCH2-C4H7O (2a, b). Komplex 5b bildet sich auch aus [Rh(COD)-(THF)2]SbF6 (4) und 2b. Die Einführung eines zweiten Liganden 2a, b gelingt, wie mit den cis-Komplexen PF6 (8a, b) gezeigt wird, entweder durch COD-Abspaltung aus [Rh(COD)(PPh2CH2C4H7O)2]PF6 (6a) oder durch Eintopfreaktion von [μ-ClRh(COE)2]2 (7) mit 2a, b und NaPF6. In Gegenwart von überschüssigem COD geht 8a reversibel unter Spaltung von zwei Rh-O-Bindungen in 6a über. Im Gegensatz zu 8a reagiert 8b mit Wasserstoff unter Umorientierung der P,O-Liganden von cis nach trans zur cis-Hydrido- Verbindung PF6 (9b), die nur in Lösung unter H2- Atmosphäre beständig ist. Bei der oxidativen Addition von CH3I (13CH3I) an 8b, die zu cis-PF6 (10b bzw. 10′b) führt, spielt ebenfalls die kinetische Labilität der Rh-O-Bindung eine Rolle. Unter öffnung der Rh-O-Bindung reagieren 8a, b mit CO (13CO) zu den trigonalbipyramidal konfigurierten Komplexen [(OC)3Rh(PR2CH2-C4H7O)2]PF6 (11a, b bzw. 11′a, b) mit trans-ständigen P,O-Liganden. 11 b bzw. 11′b (13CO-angereichert) eliminiert CO (13CO) und geht dabei unter reversibler Rh-O-Knüpfung in den trans-P-konfigurierten Komplex PF6 (12b bzw. 12′b) über, der bezüglich der Rh-O-Bindung bei 20°C im 31P{1H}-NMR-Spektrum fluktuierendes Verhalten zeigt.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200513
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    Reaktion von Dioxomolybdän(VI)-Komplexen mit S-Methylthiocarbazat. Darstellung und Struktur eines Diazenido-Hydrazido-Komplexes mit “side on” gebundenem Hydrazido(1 - )-Liganden (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 783-787 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The reaction of NH2NHC(O)SMe with MoO2(S2CNEt2)2 and MoO2(ONEt2)2 yields the diazenido-hydrazido complexes [Mo(NNC(O)SMe)(NH2NC(O)SMe)(S2CNEt2)2] · CH2Cl2 (2) and [(μ-OMe)Mo(NNC(O)SMe)(NH2NC(O)SMe)(ONEt2)]2 (4), respectively. X-ray structure analysis shows that 2 contains the side-on hydrazido(1 - ) ligand NH2NC(O)SMe, whereas in 4 the same ligand is N,O-chelated. In 2 the Mo - N distances are 213.1(7) and 213.4(5) pm, the N - N distance is 140.4(9) pm. The nitrogen atoms are sp3 hybridized. Possible factors influencing the coordination mode of hydrazido(1 - ) ligands, i.e. side on, end on, or chelating, are discussed.
    Notes: Die Reaktion von NH2NHC(O)SMe mit MoO2(S2CNEt2)2 und MoO2(ONEt2)2 ergibt die Diazenido-Hydrazido-Komplexe [Mo(NNC(O)SMe)(NH2NC(O)SMe)(S2CNEt2)2] · CH2Cl2 (2) bzw. [(μ-OMe)Mo(NNC(O)SMe)(NH2NC(O)SMe)(ONEt2)]2 (4). Röntgenstrukturanalysen von 2 und 4 ergaben, daß der Hydrazido(1 - )-Ligand NH2NC(O)SMe in 2 symmetrisch “side on”, im dimeren 4 dagegen als N,O-Chelat gebunden ist. Die Mo-N-Abstände in 2 betragen 213.1(7) und 213.4(5) pm, der N - N-Abstand 140.4(9) pm. Die Stickstoffatome sind sp3-hybridisiert. Mögliche Faktoren für die “side-on”-, “end-on”-oder chelatartige Koordination von Hydrazido(1 - )-Liganden werden diskutiert.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200516
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  • 87
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    Liquid Chromatography on Triacetycellulose, 14 Chromatographic Separation of Enantiomers and Barriers to Enantiomerization of Axially Chiral Aromatic Carboxamides (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 803-809 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The enantiomers (M) and (P) of a series of similar aromatic carboxamides have been, for the first time, investigated analytically and enriched preparatively by liquid chromatography on triacetylcellulose. Enantiomeric purities (7-99%), specific rotations, and barriers to rotation about the C(sp-C(sp bond (87-120 kJ/mol, Table 5) were determined. These energies are discussed in terms of the size of ortho substituents and of the buttressing effects by meta substituents.
    Notes: Die Enantiomeren (M) und (P) einer Reihe verwandter aromatischer Carbonsäureamide wurden erstmals mittels Flüssigkeits-Chromatographie an Triacetylcellulose analytisch untersucht und präparativ angereichert. Enantiomerenreinheiten (7-99%), spezifische Drehungen und Schwellen der Rotation um die C(sp-C(sp-Bindung (87-120 kJ/mol, Tab. 5) wurden ermittelt. Diese Energiebeträge werden im Hinblick auf den Raumbedarf von ortho-Substituenten und die Stützeffekte durch meta-Substituenten diskutiert.
    Additional Material: 10 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19871200519
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    Metallaheterocumulene, VII α-Bromisocyanid-Komplexe durch Addition von Bromid an kationische 2-Azoniaallenyliden-Komplexe (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 811-814 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The cationic [3,3-bis(tert-butyl)-2-azoniaallenylidene]pentacarbonyl complexes [(CO)5M(CNC(tBu)2)]⊖ AlBr4⊕ (2) [M=Cr (a), W (b)] which are synthesized by the reaction of (CO)5M-[C(OEt)N=C(tBu)2] (1) with AlBr3, react with tetrahydrofuran via addition of Br⊖ to give the isocyanide complexes (CO)5M-C≡N-C(tBu)2Br (3). Under nitrogen at room temperature, 3b decomposes in solution within ca. two hours to give the binuclear diisocyanide complex [(CO)5W-C≡N]2C(tBu)2 (4b). When the same conditions are applied to solutions of 3b in the presence of oxygen or of galvinoxyl 3b is stable. The structure of 4b was confirmed by an X-ray analysis.
    Notes: Die kationischen [3,3-Bis(tert-butyl)-2-azoniaallenyliden]pentacarbonyl-Komplexe [(CO)5M(CNC(tBu)2)⊖ (2) [M=Cr (a), W (b)] - darstellbar durch Umsetzung von (CO)5M[C(OEt)- N=C(tBu)2] (1) mit AlBr3 - reagieren mit Tetrahydrofuran unter Addition von Br⊕ zu den Isocyanid-Komplexen (CO)5M - C≡N-C(tBu)2Br (3). Bei Raumtemperatur zersetzt sich 3b unter Stickstoff in Lösung innerhalb von ca. zwei Stunden zu dem zweikernigen Diisocyanid-Komplex [(CO)5W-C≡N]2C(tBu)2 (4b), in Gegenwart von Sauerstoff oder von Galvinoxyl ist 3b unter ansonsten gleichen Bedingungen stabil. Die Struktur von 4b wurde durch eine Röntgenstrukturanalyse gesichert.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200520
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    Synthesen mit Cyclobutadienen, 17 Bootförmig deformierte Arene: Die Kristall- und Molekülstruktur vic-tri-tert-butylsubstituierter Benzol-, Pyridin- und Phosphinin-Systeme (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 819-824 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The crystal structure of arene 3 and heteroarenes 4, 5 has been determined by X-ray diffraction. Steric overcrowding in the vic-tri-tert-butyl-substituted part of the molecules causes the aromatic rings to deviate strongly from planarity. Unsymmetrical boat conformations are found in all cases (bow and stern angles: 30.1 and 11.6° in 3, 25.5 and 12.9° in 4), the boat in 5 being rather twisted. Compound 3 represents the most strongly deformed non-bridged and non-condensed benzene derivative for which experimental data are available. Phosphinine 5 has the most distorted non-bridged and non-condensed 6π aromatic system known so far.
    Notes: Die Kristallstruktur der Arene bzw. Heteroarene 3, 4 und 5 wurde durch Röntgenbeugung bestimmt. Die mit dem vic-Tri-tert-butyl-Substitutionsmuster verbundene räumliche überfüllung führt zu einer starken Abweichung der aromatischen Ringe von der Planarität. In allen Fällen liegen unsymmetrische Bootkonformationen vor (Bug- und Heckwinkel: 30.1 und 11.6° in 3, 25.5 und 12.9° in 4), wovon die in 5 stark verdrillt ist. Die Verbindung 3 ist das am stärksten deformierte, nichtüberbrückte und nichtkondensierte Benzolderivat, für das bislang experimentelle Strukturdaten vorliegen; das Phosphinin 5 ist der am meisten verzerrte 6π-Aromat dieser Art überhaupt.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200522
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    Desaminierungsreaktionen, 47 Zerfall von 1-(3-Hydroxypropyl)cyclopropandiazonium-Ionen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 847-848 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The diazonium ions 13 have been generated by alkaline cleavage of the analogous nitrosocarbamate 12. The product distribution indicates little participation of the hydroxy group (0.4% 9) while the allyl cation 14 arising from 13 undergoes intramolecular (4.3% 17) as well as intermolecular (75% 16) nucleophilic substitution.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200525
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    Borylierung von Arylsilanen, I Ein allgemeiner, einfacher und selektiver Zugang zu Phenyldihalogenboranen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 853-854 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Upon treatment with trihaloboranes 2b-d the phenyltrimethylsilanes 1, 6, 8, and 10 yield the corresponding phenyldihaloboranes 3, 7, 9, and 11 with high selectivity. Benzylsilanes are not attacked.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200527
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    Synthesen mit Cyclobutadienen, 18 Dewar-Benzole aus Tri-tert-butylcyclobutadiencarbonsäureestern und monoakzeptorsubstituierten Acetylenen - thermische und photochemische Folgereaktionen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 825-838 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The methyl cyclobutadienecarboxylate 1a adds methyl propiolate (2a) to the regioisomeric Dewar benzenes 3a (73%) and 4a (19%). In contrast, the corresponding tert-butyl carboxylate 1b reacts with the same dienophile as well as the acceptor-substituted olefines 2b and c exclusively by formation of the Dewar benzenes 3b-d (68-82%). - Both Dewar benzenes 3a and b are smoothly transformed into the benzenes 5a and b by thermal means. Photolyses of both aromatic compounds do not lead back to 3a and b but produce the Dewar isomers 7a and b, which finally undergo intramolecular [2+2] cycloaddition to give the prismanes 9a and b. A fundamentally comparable reaction sequence can be achieved with 4a (→ 6a → 8a → 9a). Reaction branching is observed on thermolysis of 9b: On the one hand the benzene 5b (54%) accompanied with 10% of the Dewar benzene 7b, on the other hand a 1:1 mixture of the aromatic compounds 6b and c is obtained. - Photochemically the Dewar benzenes 3a and b can directly be converted into the prismanes 10a and b (97 and 86%, respectively). Prismane/prismane isomerization (10 → 16) succeeds as a consequence of a thermal (10a,b → 12a,b) as well as of two light-induced reaction steps (12a,b → 14a,b and 14a,b → 16a,b). In an analogous way, the prismane 11 is received from 4a and then transformed into the isomer 16 via 13 and 15. As a special feature of the thermolysis of 11 the formation of 12a has to be noted, a reaction which is explained by the benzvalene intermediate 25. - The crystal structure analysis of 10b shows an evident influence of only one of both carbonyl groups (methylester) onto the prismane skeleton. This is manifested by two long, vicinal [C1-C2 1.579(3) and C1-C6 1.567(3) Å] and a short distal three-membered ring bonds [C2-C6 1.528(3) Å]. Furthermore, the C1-C4 bond [1.506(4) Å] is shortened relative to the C2-C3 distance [1.553(3) Å], whereas the C5-C6 bond [1.594(3) Å] is prolonged by the strong repulsion of both tBu groups.
    Notes: Der Cyclobutadiencarbonsäure-methylester 1a addiert Propiolsäure-methylester (2a) zu den regioisomeren Dewar-Benzolen 3a (73%) und 4a (19%). Dagegen entstehen aus dem entsprechenden tert-Butylester 1b und dem gleichen Dienophil sowie den akzeptorsubstituierten Olefinen 2b und c ausschließlich die Dewar-Benzole 3b-d (68-82%). - Thermisch gehen die beiden Dewar-Benzole 3a und b glatt in die Benzole 5a und b über. Photolysen der Aromaten führen nicht zu 3a und b zurück, sondern zu den Dewar-Isomeren 7a und b, die schließlich intramolekulare [2+2]-Cycloaddition zu den Prismanen 9a und b eingehen. Mit 4a läßt sich eine grundsätzlich vergleichbare Reaktionsfolge realisieren (→6a →8a →9a). Reaktionsverzweigung beobachtet man bei der Thermolyse von 9b: Einerseits erhält man das Benzol 5b (54%) neben 10% Dewar-Benzol 7b, andererseits ein 1:1-Gemisch aus den Aromaten 6b und c. - Photochemisch lassen sich die Dewar-Benzole 3a und b direkt in die Prismane 10a und b (97 bzw. 86%) umwandeln. Prisman/Prisman-Isomerisierung. (10 → 16) gelingt als Folge eines thermischen (10a,b → 12a,b) sowie zweier lichtinduzierter Reaktionsschritte (12a,b → 14a,b und 14a,b → 16a,b). Entsprechend läßt sich aus 4a das Prisman 11 gewinnen und dann über 13 und 15 in das Isomer 16 umwandeln. Als Besonderheit der Thermolyse von 11 ist die Bildung von 12a zu vermerken, dessen Entstehen über die Benzvalen-Zwischenstufe 25 erklärt wird. - Die Kristallstrukturanalyse von 10b zeigt einen deutlichen Einfluß nur einer der beiden Carbonylgruppen (Methylester) auf das Prismangerüst. Er äußert sich in zwei langen, vicinalen [C1-C2 (1.579(3) und C1-C6 1.567(3) Å] und einer kurzen distalen Dreiringbindung [C2-C6 1.528(3) Å]. Dar über hinaus ist die C1-C4-Bindung [1.506(4) Å] relativ zum C2-C3-Abstand [1.553(3) Å] verkürzt, während die C5-C6-Bindung[1.594(3) Å] durch die starke Abstoßung der beiden tBu-Gruppen verlängert ist.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871200523
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    Silylierte Aminophosphonium-Salze und Aminophosphonium-methylide (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 789-794 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The reaction of the aminophosphonium methylides (Et2N)3P=CH2, Me(Et2N)2P=CH2, (Me2N)3P=CH2, or Me(Me2N)2P=CH2 (1a-d) with the chlorosilanes Me3SiCl and (t-Bu)2SiCl2, resp., yield silylated phosphonium salts 2a-d (Scheme 1). Treatment of these with strong base (KH/THF) or transylidation using a second equivalent of the ylide 1a-d affords the silylated ylides (Et2N)3P=CHSiMe3, Me(Et2N)2P=CHSi(t-Bu)2Cl, and Me(Me2N)2P=CHSi(t-Bu)2Cl (3a-c,c′,d). Attempts for further dehydrohalogenation of the latter to give species R3P=C=SiR′2 were unsuccessfull. Instead, treatment of 3d with t-BuLi/TMEDA yielded the cyclic ylide (4) whose structure was determined by single crystal X-ray diffraction. Addition of HCl (in Et2O) to 4 gives the corresponding phosphonium salt Cl (5). - For reason of comparison, the ylides Me3P=CH2, (i-Pr)3P=CH2, and Ph3P=CH2 (1e-g) were also converted (via silylated phosphonium salts) into ylides Me3P=CHSiR3, (i-Pr)3P=CHSiR3, and Ph3P=CHSiR3, where R3=(t-Bu)2Cl and (t-Bu)MeCl (3e-g). 3f can also be converted into an endocyclic ylide (6), whereas 3g, on standing in THF solution, yields the double ylide [Ph3P=C - Si(t-Bu)2]2 (7) with exocyclic ylide functions. NMR data are presented for all new ylides.
    Notes: Aus den Aminophosphonium-methyliden (Et2N)3P=CH2,Me(Et2N)2P=CH2, (Me2N)3P=CH2 oder Me(Me2N)2P=CH2 (1a-d) entstehen bei der Reaktion mit den Chlorsilanen Me3SiCl bzw. (t-Bu)2SiCl2 die silylierten Phosphoniumsalze 2a-d (Schema 1). Durch die Einwirkung starker Basen (KH/THF) oder durch Umylidierung mit einem weiteren äquivalent Ylid 1a-d werden daraus die silylierten Ylide (Et2N)3P=CHSiMe3, Me(Et2N)2P=CHSi(t-Bu)2Cl und Me(Me2N)2P=CHSi(t-Bu)2Cl (3a-c,c′,d). Eine weitere Dehydrohalogenierung der beiden letzteren Ylide zu den kumulierten Systemen R3P=C=SiR′2 gelingt nicht. Statt dessen wird bei der Einwirkung von t-BuLi/TMEDA auf 3d das cyclische Ylid (4) gebildet, dessen Struktur durch Einkristall-Röntgenbeugung gesichert wurde. 4 ergibt mit HCl in Et2O das korrespondierende Phosphoniumsalz (5). - Zu Vergleichszwecken wurden aus Me3P=CH2, (i-Pr)3P=CH2 und Ph3P=CH2 (1e-g) über die silylierten Phosphoniumsalze auch die Silyl-Ylide Me3P=CHSiR3, (i-Pr)3P=CHSiR3 und Ph3P=CHSiR3 mit R3=(t-Bu)2Cl und (t-Bu)MeCl (3e-g) dargestellt. Aus 3f konnte mit t-BuLi/TMEDA wieder ein endocyclisches Ylid (6) erhalten werden. 3g ergibt beim Lagern in THF-Lösung das Doppelylid [Ph3P=C - Si(t-Bu)2]2 (7) mit exocyclischen Ylidfunktionen. Für alle neuen Ylide werden NMR-spektroskopische Daten vorgelegt.
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    URL: http://dx.doi.org/10.1002/cber.19871200517
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    Ein weiterer erfolgloser Versuch, Tetra-tert-butylethylen herzustellen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 871-872 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rather than providing the title compound 5 the reaction of tetraacetylethene (3) with excess dimethyltitanium dichloride (4) leads to 2,2,4,4,6,6,8,8-octamethyl-3,7-dioxabicyclo[3.3.0]octl(5)-ene (10). The mechanism of formation of this tetramethylated product is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200532
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    Mono- und dimetallierte Cyclobutendione mit Molybdän-, Wolfram-, Mangan- und Rheniumcarbonylen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 889-893 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The nucleophilic substitution of chloride in dichlorocyclobutenedione by carbonylmetallates gives the μ-(3,4-dioxo-1-cyclobutene-1,2-diyl) complexes LnM(C4O2)MLn 1 [MLn=Re(CO)5, Mn(CO)5, W(CO)3(η5-C5H5)] and the μ-(2-chloro-3,4-dioxo-1-cyclobuten-1-yl) complexes LnM— [MLn = Mn(Co)5, W(CO)3(η5-C5H5), Mo(CO)3(η5-C5H5)], respectively. The structure of the dirhenium complex (OC)5Re(C4O2)Re(CO)5 (1a) was determined by X-ray diffraction. The Re-C bonds are slightly shortened with respect to single bonds, Re-C=2.18(1)/2.17(1)Å [monoclinic, P21, a=7.031(1), b=11.532(1), c=11.418(1)Å, β=105.54(1)°, V=891.95Å3, dcalc=2.727 g/cm3 for Z=2, Rw=0.031 for 252 refined parameters and 3539 observables with I ≥ 2.0σ(I)].
    Notes: Die nucleophile Substitution von Chlorid in Dichlorcyclobutendion durch Carbonylmetallate liefert die μ-(3,4-Dioxo-1-cyclobuten-1,2-diyl)-Komplexe LnM(C4O2)MLn 1 [MLn=Re(CO)5, Mn(CO)5, W(CO)3(η5-C5H5)] bzw. die μ-(2-Chlor-3,4-dioxo-1-cyclobuten-1-yl)-Komplexe LnM— [MLn = Mn(Co)5, W(CO)3(η5-C5H5), Mo(CO)3(η5-C5H5)]. Nach der Röntgenstrukturanalyse des Dirhenium-Komplexes (OC)5Re-(C4O2)Re(CO)5 (1a) sind die Re-C-Bindungen gegenüber Einfachbindungen leicht verkürzt, Re-C=2.18(1)/2.17(1)Å [monoklin, P21, a=7.031(1), b=11.532(1), c=11.418(1)Å, β=105.54(1)°, V=891.95Å3, dber=2.727 g/cm3, Z=2, Rw=0.031 für 252 verfeinerte Parameter und 3539 Observablen mit I ≥ 2.0σ(I)].
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200604
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    Übergangsmetall-Silyl-Komplexe, 18 Hydrido-Silyl- und Bissilyl-Komplexe des Eisens mit verbrückenden oder chelatisierenden Diphosphinoethan-Liganden (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 879-887 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complexes [mer-(CO)3Fe(H)SiR3]2(dppe) (1) (dppe=Ph2PCH2-CH2PPh2), [mer-(CO)3Fe(SiR3)2]2(dppe) (2), (CO)2(dppe)Fe(H)-Sir3 (3), and (CO)2(dppe)Fe(SiR3)2 (6) are synthetized by several routes: by photochemical reaction of dppe-substituted iron carbonyls with HSiR3, by thermal reaction of (CO)4Fe(H)SiR3 or (CO)4Fe(SiR3)2 with dppe, or by exchange of the silyl groups. The dinuclear complexes 1 and 2 can be converted to the mononuclear complexes 3 and 6. The choice of the most suitable method of preparation depends essentially on the nature of the silyl ligand. Bissilyl complexes (2 or 6) are only obtained if SiR3=SiCl3 or SiMeCl2. In solution the complexes 3 are fluxional. In the crystalline state 3d (SiR3=SiMe3) shows a distorted octahedral geometry. The silyl group has trans orientation to one of the phosphorus atoms and cis to the hydride ligand, which in turn is trans to one of the carbonyls.
    Notes: Komplexe [mer-(CO)3Fe(H)SiR3]2(dppe) (1) (dppe=Ph2PCH2CH2PPh2), [mer-(CO)3Fe(SiR3)2]2(dppe) (2), (CO)2(dppe)Fe(H)-SiR3 (3) und (CO)2(dppe)Fe(SiR3)2 (6) können nach mehreren Methoden synthetisiert werden: durch photochemische Umsetzung von dppe-substituierten Eisencarbonylen mit HSiR3, durch thermische Umsetzung von (CO)4Fe(H)SiR3 oder (CO)4Fe(SiR3)2 mit dppe oder durch Silylgruppenaustausch. Die zweikernigen Komplexe 1 und 2 lassen sich in die einkernigen Komplexe 3 und 6 umwandeln. Die Wahl der jeweils günstigsten Darstellungsmethode hängt entscheidend von der Art des Silylrestes ab. Bissilyl-Komplexe (2 oder 6) werden nur mit SiR3=SiCl3 oder SiMeCl2 erhalten. Die Komplexe 3 sind in Lösung fluktuierend. Im kristallinen Zustand ist 3d (SiR3=SiMe3) verzerrt oktaedrisch koordiniert, der SiMe3-Rest steht trans zu einem der Phosphoratome und cis zum Hydrid-Liganden, welcher seinerseits trans zu einem der Carbonyle angeordnet ist.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200603
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    Komplexe mit einem pentakoordinierten Kohlenstoffatom, III Goldverbindungen von (η5 -Cyclopentadienyl)(η5-2, 3-dihydro-1H-1, 3-diborol-2-yl)metall-Komplexen (Metall=Co, Rh) (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 911-914 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: In the cobalt and rhodium sandwich complexes 2b and 3a the acidic hydrogen at C-2 is substituted by the isolobal Au-PPh3 group with formation of the dinuclear complexes 4b and 5a. Spectroscopic data and the X-ray structure determination of 4b establish the pentacoordination at the C-2 atom. In the NMR spectra of 5a3JPRh=12 Hz is observed.
    Notes: In den Cobalt- und Rhodium-Sandwichkomplexen 2b und 3a wird der acide Wasserstoff an C-2 durch die isolobale Au - PPh3-Gruppe unter Bildung der Zweikernkomplexe 4b und 5a ersetzt. Spektroskopische Daten und die Röntgenstrukturanalyse von 4b belegen die Pentakoordination am C-2-Atom. In 5a wird NMR-spektroskopisch 3JPRh=12 Hz beobachtet.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200608
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  • 98
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    Reaktionen mit Aziridinen, 41 Hoch regioselektive (anomale) Ringöffnung von 1-Benzoyl-2,2-dimethylaziridin durch einfache Nitril-Anionen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 855-857 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anions 3a-e of the acetonitriles 2a-e cleave the aziridine ring of 1-benzoyl-2,2-dimethylaziridine (1) at the tertiary Catom (abnormal opening) and provide in this way good yields of the 4-(benzoylamino)-3,3-dimethylbutyronitriles 5a-e and of the 2-(benzoylimino)pyrrolidine 7a, respectively. Positional isomers could not be detected.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200528
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  • 99
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    Beiträge zur Chemie des Bors, 185 Reaktionen von Metallcarben-Komplexen mit (tert-Butylimino)- (2,2,6,6-tetramethylpiperidino)boran (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 863-865 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [2 + 2] Cycloaddition of the aminoiminoborane 1 with Cp2-Ti=CH2 yields a blue 1-aza-2-bora-4-titanacyclobutane derivative 2. In contrast, Fischer carbenes (CO)5M = C(OMe)Me (M=Cr, W) react in a complex way to produce 1 · M(CO)5 (4), tmpB(NHCMe3)OMe (5), and the borylated acetylene derivative 6.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200530
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  • 100
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    Masthead (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200601
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