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  • 1
    ISSN: 1432-1432
    Schlagwort(e): Carcinoembryonic antigen ; Evolution ; Gene family ; Human ; Rat ; Synonymous substitutions ; Silent molecular clock ; Evolutionary trees
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary Various rodent and primate DNAs exhibit a stronger intra- than interspecies cross-hybridization with probes derived from the N-terminal domain exons of human and rat carcinoembryonic antigen (CEA)-like genes. Southern analyses also reveal that the human and rat CEA gene families are of similar complexity. We counted at least 10 different genes per human haploid genome. In the rat, approximately seven to nine different N-terminal domain exons that presumably represent different genes appear to be present. We were able to assign the corresponding genomic restriction endonuclease fragments to already isolated CEA gene family members of both human and rat. Highly similar subgroups, as found within the human CEA gene family, seem to be absent from the rat genome. Hybridization with an intron probe from the human nonspecific cross-reacting antigen (NCA) gene and analysis of DNA sequence data indicate the conservation of noncoding regions among CEA-like genes within primates, implicating that whole gene units may have been duplicated. With the help of a computer program and by calculating the rate of synonymous substitutions, evolutionary trees have been derived. From this, we propose that an independent parallel evolution, leading to different CEA gene families, must have taken place in, at least, the primate and rodent orders.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Virchows Archiv 415 (1989), S. 259-263 
    ISSN: 1432-2307
    Schlagwort(e): Transthyretin ; Human ; Fetus ; In situ hybridization ; Immunocytochemistry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Five human fetuses at mid-term (16–20 weeks) and one with a gestational age of 8 weeks were investigated. The cellular localization of transthyretin (TTR)-mRNA in different organs was demonstrated by in situ hybridization with a35S-labelled, single-stranded RNA probe. Immunoreactive TTR (TTR-IR) was localized with a monoclonal antibody to TTR. In all fetuses, choroid plexus epithelial cells demonstrated intense labelling for TTR-mRNA as well as strong TTR-IR. Hepatocytes, on the other hand, showed weak in situ labelling and weak or, in some cases, non-demonstrable TTR-IR. In all mid-term fetuses, but not in the 8 week fetus, TTR-mRNA and TTR were also expressed in pancreatic endocrine A-cells. The degree of in situ labelling in these A-cells was moderate, whereas that of TTR-IR was strong. Despite negative findings for TTR-mRNA in the gut and the kidney, endocrine cells of the gut and epithelial cells of the renal proximal convoluted tubules showed TTR-IR in some of the fetuses. The investigation provides evidence for TTR synthesis in the human fetal choroid plexus, liver and endocrine pancreas. However, further studies are required to demonstrate TTR synthesis in the gut and the kidney.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1434-0879
    Schlagwort(e): Androgen ; Receptor ; cDNA ; Structure ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The androgen receptor in several species (human, rat, calf) is a monomeric protein with a molecular mass of 100–110kDa. The steroid binding domain is confined to a region of 30 kDa, while the DNA-binding domain has the size of approx. 10 kDa. A 40 kDa fragment containing both the DNA and steroid binding domain displayed a higher DNA binding activity than did the intact 100 kDa molecule. cDNA encoding the major part of the human androgen receptor was isolated. The cDNA contains an open reading frame of 2,277 bp but still lacks part of the 5′-coding sequence. Homology with the progesterone and glucocorticoid receptor was about 80% in the DNA binding domain and 50% in the steroid binding domain. The present data provide evidence that the androgen receptor belongs to the superfamily of ligand responsive transcriptional regulators and consists of three distinct domains each with a specialized function.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Urological research 17 (1989), S. 317-324 
    ISSN: 1434-0879
    Schlagwort(e): Human ; Renal cell carcinoma ; Established cell lines ; Epithelial
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary We have established three new cell lines of human renal cell carcinoma (RCC), designated as SMKT-R-1, SMKT-R-2 and SMKT-R-3. These cell lines were derived from a primary lesion of the tumor or a tumor initially xenotransplanted in nude mice. These cell lines have maintained a stable growth in vitro for more than a year. They also exhibited characteristics showing a lack of contact inhibition of cells, colony formation in soft agarose and tumor formation in nude mice by a xenotranaplantation of cells, all of which suggested an epithelial origin. The tumors produced in nude mice by the innoculation of cell lines were demonstrated by light an electron microscopy tobe derived from RCC. The doubling time of these cell lines were 180.0 h, in SMKT-R-1, 56.4 h in SMKT-R-2 and 55.7 h in SMKT-R-3. The cell lines were aneuploid in their chromosomal analysis, and SMKT-R-2 and SMKT-R-3 also had three and two marker chromosomes, respectively. The different biological characters of these cell lines from the others so far established would be of benefit in the future study of human RCC.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 79 (1989), S. 200-204 
    ISSN: 1432-0533
    Schlagwort(e): Alcohol ; Brain ; Neuronal counts ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Neuronal loss from the frontal superior cortex of the brains of alcoholics has recently been documented. In addition to this, a reduction in the mean neuronal area was also seen in the frontal and motor cortices. This suggested a regional specificity of neuronal damage in the brains of alcoholics. Further quantitation of other cortical regions of the same cases as used in the above study has been performed. The frontal cingulate and temporal cortices were examined and there was found to be no significant alteration in the number of neurons when compared to a control population. There was, however, a significant reduction in the mean size of the neuronal soma in the frontal cingulate cortex (P 〈 0.05). These data support the hypothesis of regional variations in the severity of cerebral cortical damage in alcoholism with shrinkage of neurons in most regions examined but neuronal loss only in the superior frontal gyrus.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Anatomy and embryology 180 (1989), S. 577-582 
    ISSN: 1432-0568
    Schlagwort(e): Sphincter urethrae muscle ; Morphogenesis ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The morphogenesis of the sphincter urethrae muscle was studied in human ontogeny. Muscles of 65 embryos and fetuses, 7 newborns, 3 children and 3 adults of both sexes were examined histologically and by means of microdissection. Three developmental stages can be recognized in terms of morphogenetic events, histogenesis and development of sexual dimorphism. In the sexually indifferent stage (up to approximately 50 mm crown-rump length), the sphincter urethrae primordium is formed by a shallow arch apposed only to the ventrolateral wall of the urethra. The primordium extends from the level of the urogenital diaphragm up to the vesicourethral transition. It consists of a condensation of mononuclear cells. Myotubes appear in fetuses of 30 mm crown-rump length. During the second stage (until birth) sexual dimorphism develops in conjunction to the formation of the prostate and vagina. In this stage, the sphincter urethrae muscle fibres gradually extend to the posterior wall of the urethra. At the same time cranially situated muscle fibres project to the lateral wall of the prostate, whereas in females caudally located muscle fibres attach to the lateral wall of the vagina. In this way the sphincter achieves the sexually distinct form. The definitive arrangement develops in the third morphogenic stage (after birth), in which a complete muscle ring is formed by encircling the urethra in the infraprostatic part in males and in the upper, larger part of the sphincter in females. The sphincter urethrae muscle is located inside the sling of the puborectalis muscle in both sexes, but no muscle fibres connect them to one another. A part of the puborectal muscle fibres orginates from the connective tissue plate lying on the ventral face of the sphincter in the level of the bladder neck. From this arrangement it can be suggested that fibres of the puborectalis muscle participate in the ensurence of urinary continence.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    International journal of biometeorology 33 (1989), S. 238-245 
    ISSN: 1432-1254
    Schlagwort(e): Birth interval ; Infertility ; Season ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geographie , Physik
    Notizen: Abstract Questionnaires of birth dates of family members (13 404 families in total) were analyzed in order to examine the effects of delivery season of a baby on the subsequent birth interval. Deliveries at maternal age of 20–34 years were used. In 1921–1935, the mothers who had been delivered of a baby in August–October showed the shortest (30.62 months geometric mean) and those in February–April the longest (34.05 months) non-last intervals, with a highly significant difference among the four delivery seasons (P〈0.001, Kruskal-Wallis test,n=5678). Although the intervals were abruptly prolonged just before the last birth, the above difference was also consistent in the last intervals. When seasonal distributions of last and non-last births were compared, last births tended to be concentrated in the summer half of a year (P〈0.05) in 1921–1935. In 1951–1965, overall geometric mean of the interval shortened to 28.44 months, and the length of intervals did not differ appreciably according to the season of preceding delivery. Deliveries in late summer (August–October) in 1921–1935, therefore, were associated with increased risk of termination of reproduction, on one hand, but a lowered chance of prolongation of the subsequent interval, on the other hand. Possible environmental factors are discussed to explain this apparently paradoxical phenomenon.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 76 (1989), S. 510-518 
    ISSN: 1432-1106
    Schlagwort(e): Heteronymous Ia facilitation ; Presynaptic inhibition ; Reciprocal inhibition ; Monosynaptic reflex ; Voluntary movement ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Variations of presynaptic inhibition in heteronymous Ia fibres projecting to soleus motoneurones were studied during the first 250 ms of phasic voluntary isometric contractions of the antagonist tibialis anterior muscle in human subjects. During the first 60–80 ms of TA e.m.g activity, presynaptic inhibition was often more marked than at rest, but not in all experimental sessions. After 60–80 ms, presynaptic inhibition was always increased compared to rest and to the onset of TA e.m.g. activity. A “rebound” in femoral nerve induced Ia facilitation was often observed between 90–150 ms. The early increase in presynaptic inhibition was widespread and non specific since it was observed at the onset of extensor carpi radialis contractions of maximal strength. The “rebound” in heteronymous Ia facilitation was interpreted as a relative decrease in presynaptic inhibition to which nonspecific suprasegmental and cutaneous effects contributed. The late increase in presynaptic inhibition in Ia fibers to soleus motoneurones was considered as reciprocally inhibiting the Sol H-reflex, thus counteracting the phasic stretch of the antagonist muscle during TA contraction.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 77 (1989), S. 349-360 
    ISSN: 1432-1106
    Schlagwort(e): Electroencephalogram ; Pattern evoked potentials ; Face stimuli ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary In three different experimental series, electroencephalographic responses evoked by changes in pictorial patterns were recorded in 29 adult human subjects (19 females, 10 males). Quantitative data evaluation for the evoked responses from electrodes T5, T6, Cz, Pz (10–20 system) was performed. The stimuli were projected to a 4 × 6 degree binocularly viewed field. The patterns changed within 6 ms every 2.5–4.5 s according to a random program. Paradigm (1): Identical line drawings of a face, a tree and a chair were used, either black on white (P-stimuli) or white on black (N-stimuli); in each set altogether 160 slides appeared in semi-random order. At Cz and Pz a prototypical EEG-response evoked by face stimuli was found exhibiting 3 prominent peaks, very similar for P-stimuli and N-stimuli. A P150 maximum was especially pronounced in the responses to face stimuli but absent in the evoked potentials aroused by chair or tree stimuli. The difference curves (face-chair, face-tree, chair-tree) supported the hypothesis of “face-responsive” components in these responses. Paradigm (2): 4×6 degree slides (black and white photographs) of 54 different human faces, 53 different vases and 53 different pairs of shoes were projected as in paradigm (1), but instruction to the subjects on a supposed post-test memory task raised their attention during the recordings. “Face-responsive” components (an early N 140–160, P 210–240, N 300) were more marked in female than in male subjects, and again most pronounced at electrode Cz. Paradigm (3): When a recognition task was included in paradigm (2) — 9 out of 192 items were memorized 20 minutes before the recording session — essentially the same evoked potentials were obtained as in (2), but an additional late positive wave (450–600 ms) appeared in the responses to all stimuli. We assume that the “face-specific” components — a designation which is used cautiously considering the limited number of non-face stimuli — do not originate in the temporo-occipital cortical face region, but in limbic structures (amygdala, hippocampus) deep in the temporal lobe or in the gyrus cinguli. In the present study no significant hemispheric differences (T5, T6) in the evoked responses were found (all stimulus categories), but such differences are known to appear with highly schematic face stimuli.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 77 (1989), S. 437-441 
    ISSN: 1432-1106
    Schlagwort(e): Local cerebral perfusion ; Visual stimuli ; Functional cerebral changes ; Cerebral autoregulation ; Transcranial Doppler ultrasonography ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Isotope tracer methods for measuring regional cerebral blood flow or metabolism do not provide data on the dynamics of the fast adjustment of local cerebral blood flow. Measuring intracranial flow patterns of the posterior cerebral artery by means or 2 MHz pulsed transcranial Doppler ultrasonography demonstrated that detailed dynamic effects of various visual patterns on local cerebral perfusion can be recorded, and that visual stimuli of different complexity as well as the strategy of stimulus perception cause distinct flow velocity changes in the occipital cortex involved in information processing. This type of on-line analysis may become a powerful tool for detecting fast autoregulatory mechanisms in relation to purely functional cerebral changes.
    Materialart: Digitale Medien
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  • 11
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 78 (1989), S. 139-146 
    ISSN: 1432-1106
    Schlagwort(e): Fast arm movements ; Motor programme generation ; Internal representation ; Movement trajectory ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary We have studied fast arm movements in response to double-step stimuli in two-dimensional space. In a previous paper we found that such movements did not start in the direction of the first or the second target, but in a direction between the two targets. The initial movement direction was found to depend in a continuous fashion on the inter-stimulus interval and on the reaction time. Therefore we concluded that the internal representation of a discrete target displacement is a gradually shifting internal target, moving from the first to the second target location. In this paper we investigate whether the arm movements also show a modification of the trajectory during the movement. An inter-stimulus interval of 100 ms was chosen, because then the initial movement direction is the same as in the response to a single-step displacement. We found that on average double-step trajectories deviate significantly from their original trajectory within 60 ms, and in some cases even within 30 ms of the start of the movement. We conclude that a motor programme is centrally modified according to a changed target location. We hypothesize that the generation of the motor programme starts after the target presentation, and that the activation levels for the appropriate muscles are continuously adjusted to move the hand in the direction of the current internal representation of the target.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 78 (1989), S. 193-202 
    ISSN: 1432-1106
    Schlagwort(e): Evoked potentials ; Face responses ; Temporal cortex ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Evoked potentials were recorded to the separate tachistoscopic presentation of a variety of faces and other simple and complex visual stimuli. A positive potential of 150–200 ms peak latency which responds preferentially, but not exclusively, to faces was identified in 8 out of 9 subjects. This potential, best recorded from midline central and parietal electrodes, was evoked by all face stimuli, including photographs, outline drawings, and fragmentary figures. Changes in stimulus size and other parameters which do not affect the clarity of the face, generally had little effect on the peak amplitude. Stimulus changes such as face inversion, reversing the contrast polarity of photographic images, and selectively removing particular facial features, produced a marked increase in latency but often only slight attenuation of this peak. These response properties correspond well with those reported for face-related single cells in the temporal cortex of the rhesus monkey. The scalp distribution of this face-responsive peak also appears consistent with bilateral sources in the temporal cortex.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 78 (1989), S. 557-566 
    ISSN: 1432-1106
    Schlagwort(e): Posture and stance ; Biped ; Quadruped ; EMG ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary This study investigated the effect of initial stance configuration on automatic postural responses in humans. Subjects were tested in both bipedal and quadrupedal stance postures. The postural responses to horizontal translations of the supporting surface were measured in terms of the forces at the ground, movement of the body segments, and electromyographic (EMG) activity. Postural responses to the same perturbations changed with initial stance posture; these responses were biomechanically appropriate for restoring centre of mass. A change in stance configuration prior to platform movement led to a change in both the spatial and temporal organization of evoked muscle activation. Specifically, for the same direction of platform movement, during bipedal stance muscles on one side of the lower limb were activated in a distal to proximal sequence; during quadrupedal stance, muscles on the opposite side of the lower limb were activated and in a proximal to distal sequence. The most significant finding was an asymmetry in the use of the upper limbs and the lower limbs during postural corrections in quadrupedal stance. Whereas antagonists of the upper limb were either co-activated or co-inhibited, depending on the direction of translation, lower limb antagonists were reciprocally activated and inhibited. Human subjects in a quadrupedal stance posture used the lower limbs as levers, protracting or retracting the hips in order to propel the trunk back to its original position with respect to the hands and feet. Postural responses of the subjects during quadrupedal stance were remarkably similar to those of cats subjected to similar perturbations of the supporting surface. Furthermore, the same predominance of lower limb correction is characteristic of both species, suggesting that the standing cat is a good model for studying postural control in humans.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 78 (1989), S. 575-587 
    ISSN: 1432-1106
    Schlagwort(e): Limb movements ; Visuomotor behaviour ; Visually guided reaching ; Prism adaptation ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The present study examined the kinematics of unrestricted reaches to prismaticallydisplaced targets. The kinematic analysis allowed us (1) to document how and where in the reach adjustments were made to compensate for the prismatic displacement, (2) to detail the changes that occur in the characteristics of reaches during the course of adaptation to the prisms, and (3) to look at the effects of providing information (or not) to the subject about the presence and nature of the prismatic distortion. The experiment differed from classic studies of prism adaptation in that subjects were permitted full visual feedback of their moving limb at all times, and entire reaching movements were recorded in addition to terminal errors. Experimental subjects were tested either with large-displacement prisms of the sort typically used in such experiments (20 diopters) or with small-displacement prisms (5 diopters) the properties of which went undetected in uninformed subjects. By using small displacements, it was possible to examine the process of visuomotor recalibration directly, free of contamination by “conscious” correction strategies. There were no differences in the terminal accuracies of the reaches made by subjects in any of the conditions. The availability of visual feedback allowed subjects to place their finger accurately on the target, despite the fact that in some cases their vision was displaced by as much as 11.4° to the right. When the entire reach was examined, however, it was found that the amount of curvature in the path increased when large or small diopter prisms were unexpectedly introduced, with the subjects showing large deviations to the right. This rightward deviation was corrected in the final approach with a larger terminal correction. On some occasions, nonetheless, corrections were observed very early in the course of the reaching movement and appeared to be part of a natural process of trajectory finetuning. Uninformed subjects exposed to either large or small prismatic displacements also showed evidence of adaptation through an increased number of on-line corrections which compensated for a tendency to reach into the side of space opposite to the direction of the displacement (a “negative aftereffect” in the path of the reach). Moreover, when questioned after the experiment, it became clear that uninformed subjects exposed to small prismatic displacements had apparently failed to detect any visual displacement whatsoever. Taken together, these results suggest that visuomotor recalibration can take place “automatically” without feedback from terminal errors and without the use of conscious strategies. In fact, making subjects aware of the distortion by providing them with explicit information about the prisms led to reduced levels of adaptation. These “informed” subjects showed more smoothly generated reaches during prism exposure, while post-exposure reaches showed less evidence of a negative aftereffect. In fact, postexposure reaches of subjects informed of the presence of the 5 diopter prismatic displacement were indistinguishable from reaches of control subjects.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 78 (1989), S. 613-623 
    ISSN: 1432-1106
    Schlagwort(e): Reciprocal inhibition ; Vibration reflex ; Spinal cord ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Reciprocal inhibition of the voluntarily contracting wrist extensor (extensor carpi radialis, ECR) evoked by proprioceptive afferent input from the flexor (flexor carpi radialis, FCR), was studied in healthy human subjects. Vibration of the FCR tendon was used to elicit Ia-dominated afferent discharge whilst inhibition of ECR was assessed as the reduction in asynchronous, on-going EMG. A small early phase of inhibition (I1) was evident in 25% of trials. The latency (ca. 25 ms) of this component suggested that it was mediated by an Ia oligosynaptic, possibly ‘classical’ disynaptic, inhibitory pathway. A later and apparently separate phase of reduced activity (12, ca. 40 ms) was, however, far more consistently observed (96% of trials) and of greater magnitude. The 12 component was usually followed, some 20 ms later, by a phase of elevated activity (El, 72% trials). Reductions in simultaneously recorded net extensor torque commenced at about 60 ms following the onset of flexor tendon vibration, i.e. some 20 ms after the main I2 EMG component. These mechanical responses must have almost exclusively resulted from reciprocal inhibition of extensor EMG since vibration of the relaxed FCR evoked minimal excitatory flexor activity. The reflex pattern, in any individual subject, was relatively unaffected by altering the duration of the vibration train between one and nineteen cycles (125 Hz). This suggests that the entire response complex resulted largely from the initial afferent volley. The sizes of both the I1 and I2 reductions in ECR activity increased with increasing voluntary extensor contraction so that their depths remained constant proportions of background EMG. Very similar results were obtained when reciprocal inhibition of FCR was produced by vibration of the belly of ECR. Thus, reciprocal inhibition between wrist muscles is mainly expressed as a rather stereotyped, short duration reduction in EMG whose depth is determined by the pre-existing level of motor activity. Some functional implications of this form of reflex behaviour are discussed.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 77 (1989), S. 31-38 
    ISSN: 1432-1106
    Schlagwort(e): Area 17 ; Area 18 ; Neurons ; Glia ; Human ; Aging
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The numerical density of neurons and glial cells was estimated in visual area 18 of the adult human cerebral cortex and compared with that of area 17. Blocks of areas 17 and 18 came from the same brains and this allowed the comparison of 1) neuronal and glial numerical densities through the whole cortical depth with calculation of the neuron/glia ratio, 2) neuronal and glial numbers under one square millimeter of cortical surface, and 3) neuronal numerical densities in three groups of identified layers. The mean neuronal density is approximately 40000 neurons/mm3 in area 17 and 31500/m3 in area 18. The mean glial density is around 27000/mm3 in area 17 and 32000/mm3 in area 18. This gives a neuron/glia ratio of approximately 1.5 in area 17 and of 1.0 in area 18, but the total cellular density is similar in both areas. There are about 90000 neurons and 64000 glial cells under one square millimeter of cortical surface in area 17, and some 73000 neurons and 74000 glial cells in area 18. The higher neuronal density in area 17 is found through the whole depth of cortex and does not seem to be more pronounced in layer IVc of area 17 compared to layer IV in area 18 than in the groups of layers II–III and V–VI.
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 78 (1989), S. 301-308 
    ISSN: 1432-1106
    Schlagwort(e): Motor cortical stimulation ; Cortico-spinal conduction ; Trunk muscles ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Percutaneous electrical stimulation of the motor cortex was used to activate rapidly conducting corticofugal pathways to human abdominal muscles. Following cortical stimulation the response latencies for the abdominal muscles were similar to those for limb muscles which are a similar distance from the motor cortex. Cortically evoked responses recorded from the abdominal muscles had the same latency and similar amplitude during several voluntary tasks including expiration, expulsive manoeuvres and trunk flexion. Responses could also be evoked when the chemical drive to breathe was increased by rebreathing. In addition, the properties of the cortical projection to muscles of the abdominal wall were directly compared with those of the projection to the intrinsic muscles of the hand. The latencies of responses in abdominal muscles and intrinsic muscles of the hand were measured during static contractions over a range of strengths in the same subjects (0–100% maximal voluntary contraction, MVC). For both muscle groups, cortically evoked muscle responses of minimal latency occurred when background contractions reached 10–20% MVC with responses of maximal amplitude at 60% MVC. The variability in latency of fifty consecutive responses were similar for the two muscle groups. Furthermore, post-stimulus time histograms for 4 rectus abdominis motoneurones revealed a brief initial excitatory peak of 1.15ms duration (range 0.96–1.34ms) following cortical stimulation. The characteristics of this peak are the same as reported for motoneurones of intrinsic hand muscles. These findings demonstrate a powerful rapidly conducting pathway from the motor cortex to the human abdominal muscles. This pathway has many of the same properties as the monosynaptic corticospinal projection to the distal muscles of the upper limb.
    Materialart: Digitale Medien
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  • 18
    Digitale Medien
    Digitale Medien
    Springer
    Experimental brain research 78 (1989), S. 309-314 
    ISSN: 1432-1106
    Schlagwort(e): Optokinetic nystagmus ; Stereoscopic vision ; Eye movements ; Binocular disparity ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary It was previously proposed that a linkage between the optokinetic system and the stereoscopic system in higher mammals serves to allow these animals to selectively stabilize those parts of the visual scene which lie in the plane of convergence as the animals move forward in a three dimensional world (Howard and Ohmi, 1984). A new procedure is now described by which OKN gain can be measured as a function of the binocular disparity of the stimulus. With vergence locked on a vertical line, the gain of the slow phase of vertical optokinetic nystagmus (OKN) was recorded in four human subjects as the binocular disparity (stereo depth) of the moving display was changed from-3° to + 3°. The gain of OKN was found to be inversely proportional to binocular disparity. Evidence for cells in the visual cortex, MT and MST that are sensitive both to visual motion and binocular disparity is reviewed. It is argued that the activity of cells responsive to direction of motion and zero disparity selectively augments OKN and that this enables humans to stabilize the images of parts of the scene in the plane of regard while ignoring competing motion signals arising from other distances.
    Materialart: Digitale Medien
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  • 19
    ISSN: 1432-2072
    Schlagwort(e): Benzodiazepines ; Memory ; Implicit memory ; Knowledge memory ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The effects of 0.2 mg/kg orally administered diazepam and of a placebo on explicit memory, implicit and knowledge memory were assessed using a free recall task, a word-stem completion task and two category-generation tasks. Twenty four healthy volunteers took part in this double-blind study. Diazepam impaired explicit but not implicit memory. The drug also spared knowledge memory. Explicit memory was linked with the diazepam-induced sedation and with the self-rated affective load of to-be remembered words, but implicit memory was not. The diazepam-induced dissociation between explicit and implicit memory supports the notion of two distinct forms of memory and reproduced the dissociation observed in organic amnesia.
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    Psychopharmacology 98 (1989), S. 51-55 
    ISSN: 1432-2072
    Schlagwort(e): Human ; Marijuana ; THC ; Titration ; Selfadministration
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The role of marijuana delta-9-tetrahydrocannabinol (THC) content in controlling marijuana smoking behavior was examined in ten regular marijuana smokers. Each subject was allowed to self-administer marijuana of low, medium or high THC content freely over a 30-min period. Each potency of marijuana was color coded, and subjects smoked each potency on five separate occasions to provide the opportunity for them to learn from prior exposures the relative potencies of each marijuana type. Total intake of marijuana smoke during each session was estimated by measuring the post-smoking increase in expired air carbon monoxide (CO) level. Measures of marijuana effect included heart rate and standardized subjective effects scales. There were no differences among the three potencies of marijuana in post-smoking CO boost, and all measures that were sensitive to marijuana showed a clear dose response. Tolerance was observed over the course of the study to the heart-rate increasing effect of marijuana. These results indicate that subjects failed to regulate their intake of marijuana smoke in response to substantial (4-fold) changes in marijuana THC content.
    Materialart: Digitale Medien
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Psychopharmacology 98 (1989), S. 113-119 
    ISSN: 1432-2072
    Schlagwort(e): Ethanol ; Cumulative dosing ; Drug preference ; Human ; Individual differences
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Preference for ethanol versus a placebo was assessed in 12 normal volunteers using a cumulative dosing preference test. The test consisted of four sampling sessions followed by three choice sessions. During the sampling sessions subjects received either five cumulating oral doses of ethanol (0.1g/kg per dose) or equal volumes of placebo, at 15-min intervals. Subjective and observer-rated drug effects, psychomotor performance, drug liking ratings, and breath ethanol levels were measured at regular intervals. During choice sessions, subjects first chose which of the two substances (drug or placebo) they wished to take and ingested one unit dose. Then, at 15-min intervals throughout the session, they could ingest up to ten additional unit doses of the same substance (i.e., up to 1.1 g/kg ethanol). On average, the subjects chose the ethanol-containing beverage on 75% of the choice sessions, and they self-administered a mean total dose of 0.8g/kg per session. Subjects varied in the amount of ethanol ingested on choice sessions, and the amount they chose was related to their subjective responses to the drug during sampling. Subjects who chose the most ethanol reported experiencing stimulant-like effects from the ethanol, whereas the subjects who chose ethanol less frequently and ingested lower doses reported primarily sedative-like effects from the drug. The results demonstrate that the cumulative dosing procedure can be used effectively to evaluate drug preferences and dose preferences in normal volunteers.
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  • 22
    Digitale Medien
    Digitale Medien
    Springer
    Archives of toxicology 63 (1989), S. 351-355 
    ISSN: 1432-0738
    Schlagwort(e): Erythrocytes ; Human ; Methyl chloride ; Glutathione S-transferases
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Erythrocyte cytoplasm of rats, mice and humans was incubated in head space vials with methyl chloride and the decline in concentration of the substance monitored as a parameter of metabolism. The production of S-methylglutathione was controlled by tlc. Rats, mice, bovines, pigs, sheep and rhesus monkeys showed no conversion of methyl chloride in erythrocyte cytoplasm. About 60% of the human blood samples showed a significant metabolic elimination of the substance (conjugators), whereas about 40% did not (non-conjugators). The production of S-methylglutathione indicated enzymatic metabolism of the substance by glutathione S-transferases. In literature, a “major” and “minor” form of human erythrocyte glutathione S-transferase has been described. The results indicate that the “minor” form is probably responsible for the unique metabolism of methyl chloride in human erythrocytes.
    Materialart: Digitale Medien
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Archives of toxicology 63 (1989), S. 427-431 
    ISSN: 1432-0738
    Schlagwort(e): Glutathione transferase ; Human ; Nasal mucosa
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Glutathione transferase (GST) was investigated with 1-chloro-2,4-dinitrobenzene as substrate in tissues speciments of human nasal mucosa. The average ±(SD) of GST activity in the cytosol was 76.8 ±21 nmol/min/mg with a range of 47–113. Using affinity chromatography and isoelectric focusing, the isozymes of GST from human nasal mucosa have been purified and characterized. On the criteria of isoelectric point, substrate specificities, apparent subunit molecular weight, sensitivity to characteristic inibitors and immunological properties the major GST purified (about 85% of total activity) can be identified as class pi GST. Although a limited amount of class alpha GST was expressed by human nasal mucosa, no class mu isoenzymes was noted. In addition, we have also identified a GST subunit that cannot be related to any of three major classes of human GST.
    Materialart: Digitale Medien
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  • 24
    ISSN: 1432-0878
    Schlagwort(e): Periodontal ligament cells ; Alveolar bone cells ; Autologous serum ; Cementum ; Dentin ; Cell culture ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary Recent studies have accomplished the establishment of a collagenous fiber-fringe matrix upon dental root surfaces in vitro. The present study was undertaken to follow the development of such a matrix in vitro and to test the possible effects of root surface treatments upon this matrix. Periodontal ligament cells, 0.1 to 0.2-mm thick dental root discs, and alveolar bone cells were derived after extraction from four partially erupted third molars and the accompanying interradicular bony septa of 1 male patient. Autologous serum was obtained by venipuncture. Cultures were initiated by delivering a 1-ml suspension of 50000 tritiated thymidine-labeled periodontal ligament cells and 50000 alveolar bone cells onto each of 42 culture sets. The following day, demineralized or non-demineralized root discs treated with autologous serum, fibronectin or complete medium were placed in pairs, separated by a 0.1–1.0 mm gap, upon the initial cell layer. Representative cultures were terminated after 2, 3, 4, 5 and 6 weeks, and processed for light- and electron microscopy, morphometric analysis and autoradiography. An outstanding feature of the early cultures (2, 3 and 4 weeks) was a patchwise, random distribution of matrix making a precise developmental study impossible, although collagen fibrils were produced within the first 2 weeks. Some 3-week cultures already demonstrated a mature fiber-fringe characterized electron-microscopically as oriented, densely packed collagen fibrils closely abutting the cementum-lined root discs. The treatments (including autologous serum) used in this study had no appreciable morphologic or morphometric effect upon the fiber-fringe formed. Because none of the cultures in the present or past studies have demonstrated a true cementoid matrix, this model may not be suitable for the in-vitro study of cementum formation.
    Materialart: Digitale Medien
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  • 25
    ISSN: 1432-0878
    Schlagwort(e): Atrial natriuretic peptide ; Receptors ; Autoradiography ; Heart ; Endocardium ; Rat (Sprague-Dawley) ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary The distribution of binding sites for atrial natriuretic peptide in cardiac ventricles of several mammalian species, including rat and human, was determined by in vitro autoradiography. The results revealed a unique anatomic localization of atrial natriuretic peptide binding sites to endomural vessels (Thebesian vessels), which communicate directly with the ventricular chambers. Digital image analysis indicated that these vascular channels possessed binding site densities comparable to those of the renal glomeruli a major target site for circulating atrial natriuretic peptide. In contrast, no specific labeling of branches of the coronary arteries and veins was detected. The discrete localization of atrial natriuretic peptide binding sites to this “primitive” cardiac circulatory system allows speculation as to the role of this hormone in the regulation of endocardialcirculation during cardiac development, normal ventricular function, and in coronary insufficiency.
    Materialart: Digitale Medien
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 256 (1989), S. 27-34 
    ISSN: 1432-0878
    Schlagwort(e): Kidney ; Endothelium ; Monocyte ; Von Willebrand factor ; Immunohistochemistry ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary To clarify the structural base of immune response occurring in the kidney, we investigated the antigenic and functional properties of vascular endothelial cells. Peritubular capillary endothelial cells exhibited the same immuno-histochemical characteristics (OKM5-positive, HLA-DR-positive, Factor VIII/von Willebrand factor antigen-negative, Interleukin 1-positive) as a peripheral blood macrophage subset capable of presenting soluble antigens and triggering the autologous mixed lymphocyte reaction. On the other hand, endothelial cells of glomerular capillary loops, considered to be involved in blood coagulation, were OKM5-negative, HLA-DR-positive, Factor VIII/von Willebrand factor antigen-positive, Interleukin 1-positive. Thus the results of this study suggest that vascular endothelial cells in different anatomic compartments of the kidney express surface antigens heterogenously and may play different roles in the immune reaction.
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 256 (1989), S. 183-190 
    ISSN: 1432-0878
    Schlagwort(e): Testis ; Spermatogonia, dislocation ; Compartmentation, pattern ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary The pattern of compartmentation of the seminiferous epithelium was investigated, using a lanthanum tracer technique, in human testicular biopsies of adult infertile men (age 27 to 44 years), where dislocation of spermatogonia from the basal lamina occurred. Spermatogonia type A and B were found in a two-or three-layered arrangement, in aberrant locations throughout the seminiferous epithelium, and in intratubular positions associated with fragments of Sertoli cell cytoplasm. Tracer impregnation was found around spermatogonia in a multilayered arrangement, indicating the extension of the basal compartment in a luminal direction. Single spermatogonia within the second or third layer of the seminiferous epithelium were regularly found to be surrounded by tracer. The junctional complex between the lateral membranes of adjacent Sertoli cells was devoid of tight junctions. Tracer penetration around spermatogonia in a more luminal position was prevented by intact Sertoli cell junctional complexes; tracer was also absent from intraluminal located spermatogonia associated with cytoplasmic fragments of Sertoli cells. The luminal extension of the basal compartment associated with the dislocation of spermatogonia clearly differs from the pattern of compartmentation during the movement of primary spermatocytes within undisturbed epithelium. There is a strong incidence of elevated serum levels of folliclestimulating hormone (〉7 U/l), indicating a suppression of Sertoli cell function; this may be the cause for the dislocation of spermatogonia and the changes of compartmentation.
    Materialart: Digitale Medien
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  • 28
    ISSN: 1432-0878
    Schlagwort(e): Oesophagus ; Gut sphincters ; Gut peptides ; Neuropeptides ; Gut nerves ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary The intramural distribution of vasoactive intestinal polypeptide (VIP), substance P, somatostatin and mammalian bombesin was studied in the oesophago-gastro-pyloric region of the human gut. At each of 21 sampling sites encompassing this entire area, the gut wall was separated into mucosa, submucosa and muscularis externa, and extracted for radioimmunoassay. VIP levels in the mucosa were very high in the proximal oesophagus (1231±174 pmol/g, mean±SEM) and showed varied, but generally decreasing concentrations towards the stomach, followed by a clear-cut increase across the pyloric canal (distal antrum: 73±16 pmol/g, proximal duodenum: 366±62 pmol/ g); consistent levels were found in submucosa and muscle (200–400 pmol/g) at most sites, the stomach again showing lower concentrations. By contrast, substance P was present in small amounts as far as the proximal stomach, but sharply increased across the pyloric canal, especially in mucosa and submucosa (distal antrum: 20±6.5 and 5.5±1.3 pmol/g; proximal duodenum: 62±8.5 and 34±11 pmol/g, respectively). Somatostatin concentrations were very low in the mucosa of the oesophagus and stepwise increased in the cardiac, mid-gastric and pyloric mucosa (cardia: 224±72 pmol/g; distal antrum: 513±152 pmol/g; proximal duodenum: 1013±113 pmol/g); concentrations in the submucosa and muscularis were generally low, with the exception of antrum and duodenum. Mammalian bombesin was comparatively well represented throughout the oesophageal muscularis (5–8 pmol/g), but most abundant in the stomach in all layers (oxyntic mucosa: 24±2.7 pmol/g; submucosa: 20±5.7 pmol/g; muscle: 28±5.0 pmol/g). In conclusion, a distinct differential distribution of the four peptides studied was revealed, indicating a diffuse, but highly differentiated peptide-containing innervation of the proximal human gut.
    Materialart: Digitale Medien
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  • 29
    ISSN: 1432-0878
    Schlagwort(e): Follicular dendritic cells ; B-lymphocytes ; Follicular structure ; Immunohistochemistry ; Cell culture ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary The morphological and phenotypical features of multicellular complexes formed by follicular dendritic cells and lymphocytes (FDC-LC) isolated from human hyperplastic tonsils and adenoids are described. FDC-LC obtained with this procedure were morphologically and immuno-phenotypically heterogeneous. In one type of FDCLC, probably obtained from germinal centers, the lymphocytes exhibited ultrastructural features of centroblasts and centrocytes. In a second type, likely derived from follicular mantles, the enclosed lymphocytes were small in size and characterized by a condensed chromatin pattern. Similar heterogeneity was observed by immuno-phenotypical analysis, which revealed a prevalence of IgD+, CD3-, MT2+ small lymphocytes in a high proportion of FDC-LC. Both types of FDC-LC contained desmoplakin immunoreactivity in a typical punctate pattern corresponding to intercellular junctions when tested with a specific antibody. These findings confirm the importance of FDC in maintaining the follicular structure and also suggest that the different zones forming lymphoid follicles (mantle zone and germinal center) are formed by lymphocytes gathered in single “domains” by cytoplasmic processes of FDC. These domains have strong resistance to mechanical stress, such as that used in isolation procedures. FDC-LC have also been maintained as organized multicellular clusters for short periods (more than 48 h) in agarose gel cultures.
    Materialart: Digitale Medien
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  • 30
    ISSN: 1432-0878
    Schlagwort(e): Epididymis ; Intermediate filaments ; Coexpression ; Cytokeratin ; Vimentin ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary The anatomical distribution of cytokeratins and vimentin was investigated by means of immunohistochemistry in the human epididymis. Epithelial cells of the ductuli efferentes and the corpus epididymidis were positive for cytokeratins and vimentin. The expression of epithelial vimentin decreased toward the cauda epididymidis, whereas cytokeratins remained unchanged. The epithelium of the ductus deferens was negative when antibodies against vimentin were used. With monoclonal antibodies to individual cytokeratins, the presence of cytokeratins 7, 8, 18, and 19 was demonstrated histochemically throughout the epithelium of the epididymis. Monoclonal antibodies specific for cytokeratin 17 allowed immunohistochemical differentiation between the ductuli efferentes and the ductus epididymidis.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 255 (1989), S. 215-224 
    ISSN: 1432-0878
    Schlagwort(e): Transglutaminase ; Immunocytochemistry ; Induction ; Tissue compartments ; Tissue integrity ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary Tissue transglutaminase is an intracellular enzyme without established physiological function. Biochemically it can be detected in all organs, but no systematic in situ localization has been carried out so far. Here we report the immunohistochemical localization of transglutaminase in human tissues using an affinity purified, monospecific anti-human transglutaminase antibody. It is shown that the widespread organ distribution of the enzyme is the consequence of its occurrence in ubiquitous cell types such as endothelium and smooth muscle cells. Some organ-specific cell types express the enzyme constitutively (mesangial cells, renomedullary interstitial cells, thymic subcapsular epithelium, colonic pericryptal fibroblasts), while in others it seems to be induced either by external stimuli (epithelium of the female breast) or as part of their differentiation/maturation program (developing nephrons, enterocytes of the small intestine). The presence of tissue transglutaminase can be demonstrated in derivatives of all germ layers and in the trophoblast. The functional implications of these findings are presently unknown; however, based on its distribution the role of this enzyme in compartmentation and preservation of tissue integrity against stress may be suggested.
    Materialart: Digitale Medien
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 255 (1989), S. 149-153 
    ISSN: 1432-0878
    Schlagwort(e): Goormaghtigh cells ; Granular cells ; Renin synthesis ; Juxtaglomerular apparatus ; Pseudo-Bartter syndrome ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary It is difficult to distinguish between Goormaghtigh cells (G-cells) and media cells of the glomerular arterioles at the border of the Goormaghtigh cell field. Consequently, it has been unclear whether renin-positive G-cells are normally present and also whether renin-producing cells are recruited from the pool of renin-negative G-cells upon stimulation of the renin-angiotensin system (RAS). In the present study, immunohistochemical and electron-microscopic experiments have been carried out on serially sectioned kidney biopsies from four patients with pseudo-Bartter syndrome. The results strongly suggest that with longlasting stimulation of the RAS all renin-negative (“secretory resting”) G-cells are ultimately converted into renin-producing granular cells.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 255 (1989), S. 631-639 
    ISSN: 1432-0878
    Schlagwort(e): Periodontal ligament cells ; Alveolar bone cells ; Cementum ; Cell culture ; Regeneration ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary Human periodontal ligament cells have been shown to produce a new fibrous attachment at the surface of scaled dental root discs in vitro. The purpose of this investigation was to answer the question whether cells derived from human alveolar bone would enhance this attachment. Three partially erupted third molars were extracted and collected from one female patient and used for harvesting periodontal ligament cells as well as for cutting 0.3 mm dental root discs. Cells derived from alveolar bone were obtained by enzymatic digestion of bone chips harvested after extraction of wisdom teeth from three additional patients. Experimental cultures were prepared by seeding 1.0 × 106 suspensions of periodontal ligament cells onto five Puropor-200 filters. The following day, root disc pairs were placed on the cell layer, leaving a gap (interdental space) of 0.1–0.3 mm. Five days later, all cultures received equal aliquots of alveolar bone cells. The cultures were terminated and processed for microscopic and morphometric evaluation after 56, 112 and 124 days. All cultures demonstrated a dense fiber-fringe attachment along most of the cementum-lined surfaces of root discs. Adjacent to other root-disc surfaces, cells were surrounded by halos of their collagenous product. Mean diameters of collagen fibrils for the 56-, 112- and the two 124-day cultures were 64.6, 48.9 and 62.6 nm, respectively. Compared to results obtained in this system with periodontal ligament cells alone (Bernstein et al. 1988), the fiber fringe in this experiment was denser, composed of collagen fibrils with a larger diameter, and maintained for longer duration in culture. These findings support the hypothesis that cells from the alveolar bone participate, as a normal component of the periodontal ligament, in the maintenance and repair of periodontal ligament attachment.
    Materialart: Digitale Medien
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  • 34
    ISSN: 1432-0878
    Schlagwort(e): Placenta ; Immunoglobulin G ; Endocytosis ; Immunohistochemistry ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary Endogenous immunoglobulin-G was localised in ultrathin frozen sections of human term placenta by use of an indirect immuno electron-histochemical methodology. Immunoreactivity of endogenous IgG to rabbit anti-human immunoglobulin-G antibody was visualised by use of protein-A — colloidal gold complex. Gold marked the syncytiotrophoblast in both coated and uncoated regions of the apical plasmalemma, in vesicles and multivesicular bodies, and in vesicles near the basal plasmalemma. Immunoreactivity was also seen in the interstitial space between the trophoblast and the fetal endothelial layer as well as in various types of vesicles within the endothelial cells. No immunoreactivity was seen in the intercellular clefts of the endothelium. The pattern of localisation observed is consistent with receptor-mediated uptake of immunoglobulin-G into the syncytiotrophoblast of the human placenta followed by release into the interstitial space and then vesciular transport through the endothelium.
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  • 35
    Digitale Medien
    Digitale Medien
    Springer
    European journal of applied physiology 58 (1989), S. 405-410 
    ISSN: 1439-6327
    Schlagwort(e): Human ; Exercise Transitions ; Anaerobic threshold ; Metabolic alkalosis ; Metabolic acidosis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The purpose of this study was to determine the effect of altered metabolic acid-base status on the changes in ventilation in the transition from heavy exercise above anaerobic threshold to rest. Seven subjects ingested, in a randomized and blind manner, either NaHCO3 or CaCO3 (placebo) at a dose of 300 mg · kg−1 body mass and ran on a treadmill for five minutes (90% $$\dot V_{{\text{O}}_{{\text{2max}}} } $$ and above anaerobic threshold) on ten different occasions. Changes in minute ventilation in the exercise transitions were studied by starting and stopping the treadmill abruptly with a remote switch. The fast increase in ventilation at the start of exercise was not accompanied by a corresponding fast drop in ventilation at the end of exercise (P≪0.001) and the effects of chemicals on these changes were not significantly different (P〈0.05). A single-component exponential model, without a time delay, was used to determine the time constants of off-transitional decay in ventilation for the two chemicals in each subject. Parametric and non-parametric statistical tests revealed that the time constants were not as significantly different as the venous pH measurements which were significantly higher with NaHCO3 (P≪0.001). The results indicate that the absence of fast change in ventilation at the end of heavy exercise is not due to lactic acidosis and the consequent slow ventilatory changes in the off-transition of heavy exercise are at least partly mediated by non-humoral factors such as a central neural reverberatory mechanism.
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    European journal of applied physiology 58 (1989), S. 666-673 
    ISSN: 1439-6327
    Schlagwort(e): Electromyography ; Fatigue ; Human ; Isokinetic ; Muscle ; Shoulder flexion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Peak torque, work, mean power and electromyographic (EMG) activity were recorded for each of 150 repeated isokinetic maximal shoulder flexions (45°–90°) in 23 healthy females. From the EMG signals of trapezius, deltoid, infraspinatus and biceps brachii the mean power frequency and the signal amplitude were determined in real time. The mechanical output showed a steep decrease during the first 40 contractions, followed by a plateau maintained until the end. In all muscles, except the biceps brachii, significant decreases in mean power frequency occurred during the first 40 contractions, showing a tendency to stabilize around the same absolute frequency value. Signal amplitude increased in the trapezius, the deltoid and the infraspinatus, but was constant in the biceps brachii. For some individuals rather high EMG activity was recorded in the muscles during the time the arm was supposed to be passively extended to the starting position, and this was found to be associated with lower strength and endurance levels. Longitudinal analyses showed that the mean power frequencies correlated better than the signal amplitudes with the three mechanical variables. The results suggest that the initial steep decrease in mechanical performance and mean power frequency is caused by fatiguing of type 2 motor units.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    European journal of applied physiology 59 (1989), S. 303-309 
    ISSN: 1439-6327
    Schlagwort(e): Electromyography ; Fatigue ; Female ; Human ; Muscle
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary Knowledge of the strength, endurance and coordination of the shoulder muscles during dynamic contractions in healthy women would contribute to the understanding of symptoms in that part of the body in patients with myalgia. Twenty clinically healthy women performed single maximal forward shoulder flexions at four different angular velocities (0.57–3.14 rad·s−1). The same subjects also took part in two endurance tests (at angular velocities of 0.57 and 2.09 rad·s−1, respectively) consisting of 150 repeated maximal shoulder flexions. Electromyographic activity (EMG) was registered from four shoulder flexors using surface electrodes. Work was used as the mechanical variable. During the endurance tests subjects rated their perception of fatigue in the shoulder muscles. Work and the amplitude of the EMG signals decreased with angular velocity. The mean power frequency of the EMG was constant in the span of angular velocities investigated. During the endurance tests, work and the mean power frequency decreased during the initial 40–60 contractions followed by stable levels. The relative work level was higher at 2.09 than at 0.57 rad·s−1. Greater relative increases of the signal amplitudes of EMG occurred at 2.09 than at 0.57 rad·s−1. The EMG activity between the flexions (during the supposed passive extension) was higher at 2.09 than at 0.57 rad·s−1. Such a high activity was associated with a low mechanical performance at 2.09 rad·s−1. It is suggested that the initial sharp decreases in work and in mean power frequency reflect the fatiguing of the fast twitch motor units. Dynamic work consisting of continuous activity could predispose to muscle complaints.
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  • 38
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 19-24 
    ISSN: 0009-2940
    Schlagwort(e): Bis(diorganoboryl)chalcogenides ; Pyrazaboles ; Pyrazoles ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Neuartige Substituierte B2ElVIN2 HeterocyclenDie Bis(diorganoboryl)chalkogenide (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], und (R2B)2Se [R2 = 1,5-C8H14 (7)] reagieren mit Pyrazol (Pz) und dessen Derivaten 3-Methylpyrazol (3-MePz) und Indazol (benzo-Pz) in hohen Ausbeuten (65-92%) zu stabilen 1:1-Additionsverbindungen [z. B. 2 (El = O), 4 (El = O), 6 (El = S), 8 (El = Se)]. 1H-, 13C-, 11B-NMR-Spektren und Röntgenstrukturanalysen (von 2 und 6) zeigen eine Grundstruktur mit einem zentralen B2ElN2-Heterocyclus (El = O, S, Se). Die Reaktion von 2 mit R2BH und die Thermolyse von 4 führen zu den dimeren 1-Pyrazolylboranen 9a bzw. 9b.
    Notizen: The bis(diorganoboryl) chalcogenides (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], and (R2B)2Se [R2 = 1,5-C8H14 (7)] react with pyrazole (Pz) and its derivatives 3-methylpyrazole (3-MePz) and indazole (benzo-Pz) to form in high yields (65-92%) stable 1:1 adducts [e.g. 2 (El = O), 4 (El = O), 6 (El = S) and 8 (El = Se)]. 1H-, 13C-, 11B-NMR spectra and X-ray analyses (of 2 and 6) show a basic structure with a central B2ElN2 (El = O, S, Se) heterocycle. The reaction of 2 with R2BH and the thermolysis of 4 give the dimeric 1-pyrazolylboranes 9a and 9b, respectively.
    Zusätzliches Material: 3 Ill.
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  • 39
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 31-36 
    ISSN: 0009-2940
    Schlagwort(e): Mercury - mercury contacts ; Naphthalenediylmercury compounds ; Organomercury compounds ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Extremely Short Mercury-Mercury Contacts in peri-Dimercurated Naphthalene Compounds1-Naphthylmercury chloride (1) and 1,8-naphthalenediylbis(mercury chloride) (2) were prepared from the corresponding naphthyllithium precursors and HgCl2 in ca. 80% yield. In an alternative route, 2 can be obtained from 1,8-naphthalenediyldiboric acid anhydride and HgCl2 in 85% yield. The structure of 2·DMSO has been determined by X-ray diffraction methods. The lattice contains discrete adducts in which the two mercury atoms are bridged by the DMSO oxygen atom. The HgCl moieties are bent away from each other through distortions of the naphthalene framework and of the C—Hg—Cl axes, which results in a Hg ‥ Hg distance of 3.102(1) Å. - Symmetrization of 2, induced by treatment with NaI in aqueous ethanol, affords bis(μ-1,8-naphthalenediyl)dimercury (3). In the X-ray structure determination of this compound the shortest „non-bonding“ Hg·Hg contact reported in the literature has been detected: Hg1··Hg2 = 2.797(1) Å. The molecule also shows distortions in the naphthalene framework and in the C—Hg—C axes [C—Hg—C = 173.3(5)°].
    Notizen: 1-Naphthylquecksilberchlorid (1) und 1,8-Naphthalindiylbis-(quecksilberchlorid) (2) werden aus den zugehörigen Naphthyllithium-Verbindungen und HgCl2 mit ca. 80% Ausbeute erhalten. Alternativ kann 2 auch aus 1,8-Naphthalindiyldiborsäureanhydrid und HgCl2 gewonnen werden (Ausbeute 85%). Von 2·DMSO wurde die Kristallstruktur bestimmt. Es liegen diskrete Addukte vor, in denen die beiden Hg-Atome durch das O-Atom des DMSO überbrückt werden. Die HgCl-Einheiten sind durch Verzerrungen im Naphthalingerüst, durch Winkelung der Achsen C—Hg—Cl und durch deren Auslenkung aus der Naphthalinebene voneinander weggebogen, so daß ein Hg·· Hg-Kontakt von 3.102(1) Å resultiert. - 2 symmetrisiert sich bei der Einwirkung von NaI in wäßrigem Ethanol unter Bildung von Bis(μ-1,8-naphthalindiyl)diquecksilber (3). Bei der Strukturanalyse dieser im Kristall zentrosymmetrischen Verbindung wurde der bisher kürzeste „nichtbindende“ Hg··Hg-Kontakt von 2.797(1) Å gefunden. Auch in 3 sind die C—Hg—C-Achsen abgewinkelt [C—Hg—C = 173.3(5)°], und das Naphthalingerüst ist verzerrt.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 40
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 59-61 
    ISSN: 0009-2940
    Schlagwort(e): N-Butyl-N′-dansylthiourea ; Complexing agent, fluorescent ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: N-Butyl-N′-dansylthiourea as Fluorescent Broad-Band Complexing AgentN-Butyl-N′-dansylthiourea (2) [dansyl = 5-(dimethylamino)-1-naphthylsulfonyl] is obtained by the reaction of dansylamide (1) with butyl isothiocyanate. The compound is a stable, fluorescent complex agent for a broad spectrum of metal ions. The UV spectra and fluorescence of the ligand and some metal complexes are discussed. The fluorescence of the dansyl group is strongly affected by metal ions.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 41
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 83-94 
    ISSN: 0009-2940
    Schlagwort(e): Enaminecarbaldehydes ; Enamino ketones ; hetero Diels-Alder reaction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese und Struktur von Enaminecarbaldehyden und Enamino KetonenDie Synthese der Enamincarbaldehyde 1a-s und 17a-c sowie der Enamino-Ketone 2a-k und deren N-Acyl-Derivate 19a-k und 21-t mit Elektronenacceptor-Substituenten an C-2 bzw an der CO-Gruppe wird beschrieben. Kondensation von 2-Formyl-3-oxopropansäure-methylester (13) mit Ammoniak und den Aminen 14b-s ergab die Enamincarbaldehyde 1a bzw. 1b-s in einer Ausbeute von 72-93%. Die Enamincarbaldehyde 17 konnten durch Formylierung von 15 mit dem gemischten Ameisensäureessigsäureanhydrid erhalten werden. Die Synthese der Enamino-Ketone 2a-k erfolgte mit einer Ausbeute von 61-97% durch Kondensation von Ammoniak und Aminen mit den Enolethern 24a-f, die durch Umsetzung reaktiver Acylchloride 23 mit Ethylvinyl-ether dargestellt wurden. Die für hetero-Diels-Alder-Reaktionen benötigten N-Acyl-Derivate 19a-k und 21-t wurden durch Acylierung des Enamincarbaldehyds 1a und der Enamino-Ketone 2a-k gebildet.
    Notizen: The synthesis of enaminecarbaldehydes 1a-s and 17a-c as well as enamino ketones 2a-k, and their N-acyl derivatives 19a-k and 21-t with electron accepting substituents at C-2 and at the CO group, respectively, is described. Condensation of methyl 2-formyl-3-oxopropanoate (13) with ammonia and the amines 14b-s gave the enaminecarbaldehydes 1a and 1b-s, respectively, in 72-93% yield. The enaminecarbaldehydes 17 were obtained by formylation of 15 with acetic formic anhydride. The synthesis of the enamino ketones 2a-k was accomplished in 61-97% yield by reaction of ammonia and amines with the enol ethers 24a-f, which were formed by treatment of reactive acyl chlorides 23 with ethyl vinyl ether. The enaminecarbaldehyde 1a as well as the enamino ketones 2a-k could be acylated to give 19a-k and 2l-t, respectively, which can be used in the hetero Diels-Alder reaction.
    Zusätzliches Material: 1 Ill.
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  • 42
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 119-122 
    ISSN: 0009-2940
    Schlagwort(e): Bis(phosphonium) salts ; Pyridylphosphonium salts, tri-n-butyl- and triphenyl- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Chemistry of Triphenyl-(or Tri-n-butyl-)pyridylphosphonium salts, 2. - 2,4-Pyridinediylbis(phosphonium) Salts2,4-Pyridinediylbis(phosphonium) salts 1 react with nucleophiles to give 4-substituted products 6-8. Under radical reaction conditions the 5-position in 1a is attacked to yield 9. sodium azide transforms 1a into 8. This salt is used as starting material for 11. The removal of the phosphonium groups in 1 and in the resulting products can be carried out selectively.
    Notizen: 2,4-Pyridindiylbis(phosphoniumsalze) 1 lassen sich mit nucleophilen Reaktionspartnern in die 4-substituierten Produkte 6-8 überführen. Unter radikalischen Bedingungen wird selektiv die 5-Position in 1a unter Bildung von 9 angegriffen. Nach Umsetzung mit Natriumazid entsteht zunächst das Salz 8, das als Ausgangsverbindung für 11 dient. Die Substitution der Phosphoniumgruppen aus den Edukten 1 und Produkten kann selektiv durchgeführt werden.
    Materialart: Digitale Medien
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  • 43
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 145-149 
    ISSN: 0009-2940
    Schlagwort(e): Cycloalkenes, 1-methyl- ; Ozonolysis ; Peroxyhemiacetals, cyclic ; Rubber, natural ; Tetrahydrofurans, 2-hydroperoxy- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Ozonolyses of 1-Methylcyclopentene, 1-Methylcyclobutene, 5-Hexen-2-one and Natural Rubber in the Presence of MethanolOzonolyses of 1-methylcyclopentene (8a) and of 1-methylcyclobutene (8b) in methanol proceeded in each case in the two possible directions. The resulting methoxyperoxides 13 and 14 afforded the corresponding peroxyhemiacetals 15 and 19 by intramolecular reactions of the OOH with the corresponding carbonyl groups. Ozonolysis of 1-methylcyclobutene (8b) additionally gave the corresponding ozonide 17b and 2-hydroperoxy-5-methoxy-2-methyl-as well as 5-hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b and 18b). The mode of formation of these hydroperoxy compounds has been elucidated by ozonolyses of 5-hexen-2-one (25) and of natural rubber (28) in the presence of methanol.
    Notizen: Ozonolysen von 1-Methylcyclopenten (8a) und von 1-Methylcyclobuten (8b) in Methanol verliefen jeweils nach beiden möglichen Spaltungsrichtungen. Die dabei gebildeten Methoxyhydroperoxide 13 und 14 ergaben durch intramolekulare Reaktionen der OOH- mit den Carbonylgruppen die entsprechenden Peroxyhalbacetale 15 bzw. 19. Bei der Ozonolyse von 1-Methylcyclobuten (8b) wurden zusätzlich das entsprechende Ozonid 17b sowie 2-Hydroperoxy-5-methoxy-2-methyl- und 5-Hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b und 18b) gebildet. Die Bildungsweise dieser Hydroperoxy-Verbindungen wurde durch Ozonolysen von 5-Hexen-2-on (25) und von Naturkautschuk (28) im Beisein von Methanol aufgeklärt.
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  • 44
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 169-174 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis of New 3-substituted PyrrolesThe synthesis of 3-alkyl- (4), 3-(ω-bromoalkyl)- (5), 3-iodo- (6), 3-formyl- (9a), 3-acetyl-1-(triisopropylsilyl)pyrrole (9b), of 2-[1-(triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(triisopropylsilyl)-3-pyrrolecarboxylic acid (8), and 7-[1-(triisopropylsilyl)-3-pyrrolyl]heptanoic acid (10) as well as the desilylation of these products to the corresponding 3-substituted pyrroles 11 is described. Intermediates in these syntheses are 1-(triisopropylsilyl)pyrrole (1), 3-bromo- (2), and 3-lithio-1-(triisopropylsilyl)pyrrole (3).
    Notizen: Die Synthese von 3-Alkyl- (4), 3-(ω-Bromalkyl)- (5), 3-Iod- (6), 3-Formyl- (9a) und 3-Acetyl-1-(triisopropylsilyl)pyrrol (9b), von 2-[1-(Triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(Triisopropylsilyl)-3-pyrrolcarbonsäure (8) und 7-[1-(Triisopropylsilyl)-3-pyrrolyl]heptansäure (10) sowie die Desilylierung dieser Produkte zu den entsprechenden 3-substituierten Pyrrolen 11 wird beschrieben. Zwischenstufen der Darstellung sind 1-(Triisopropylsilyl)pyrrol (1), 3-Brom- (2) und 3-Lithio-1-(triisopropylsilyl)pyrrol (3).
    Zusätzliches Material: 1 Ill.
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  • 45
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 46
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 223-230 
    ISSN: 0009-2940
    Schlagwort(e): Gold(I) silyl complexes ; Transition-metal silyl complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Transition-Metal Silyl Complexes, 26. - Gold(I) Silyl ComplexesComplexes of type L-Au-SiR3 with L = PR′3 or PhNC and SiR3 = Si(aryl)3, Si(SiMe3)3, or SiPh2Me are prepared by reaction of L-Au-Cl with LiSiR3. Depending on L and R, their stability decreases, in the order R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Reaction of R′3P-Au-CH3 or R′3P-Au-OAc with HSiR3 does not yield silyl complexes. However, using chlorinated silanes like HSiR2Cl, CH3/Cl or OAc/Cl exchange takes place. The Mössbauer spectrum of MePh2P-Au-SiPh3 (6) and NMR- and IR-spectroscopic investigations show that silyl groups act as strong σ donors towards the gold atom. MePh2P-Au-SiPh3 (6) and MePh2P-Au-Si(SiMe3)3 (7) have been characterized by X-ray structure analyses [Au—Si 235.4(4) and 235.6(2) pm]. The Au-Si bond in MePh2P-Au-SiPh2Tol (5) is cleaved by X2 (X = Cl, Br, I), HCl or MeI, but not by H2O or MeOH.
    Notizen: Komplexe des Typs L-Au-SiR3 mit L = PR′3 oder PhNC und SiR3 = Si(aryl)3, Si(SiMe3)3 oder SiPh2Me wurden durch Umsetzung von L-Au-Cl mit LiSiR3 dargestellt. Ihre Stabilität sinkt in Abhängigkeit von L und R in der Reihenfolge R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Umsetzung von R′3P-Au-CH3 oder R′3P-Au-OAc mit HSiR3 ergibt keine Silyl-Komplexe, bei Verwendung chlorierter Silane, HSi-R2Cl, findet lediglich CH3/Cl- bzw. OAc/Cl-Austausch statt. Das Mößbauer-Spektrum von MePh2P-Au-SiPh3 (6) sowie NMR- und IR-spektroskopische Untersuchungen zeigen, daß Silylreste als starke σ-Donor-Liganden gegenüber dem Goldatom wirken. MePh2P-Au-SiPh3 (6) und MePh2P-Au-Si(SiMe3)3 (7) wurden durch Röntgenstrukturanalysen charakterisiert [Au—Si 235.4(4) und 235.6(2) pm]. Die Au—Si-Bindung in MePh2P-Au-SiPh2 Tol (5) wird durch X2 (X = Cl, Br, I), HCl oder MeI, nicht aber durch H2O oder MeOH gespalten.
    Zusätzliches Material: 2 Ill.
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  • 47
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 245-252 
    ISSN: 0009-2940
    Schlagwort(e): Germylenes ; Germanium nitrogen compounds ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Reactions of Germylenes with Azides: Iminogermanes, Azidogermanes, Tetrazagermoles and HexaazadigermadispirododecanesGermylenes, X2Ge, stabilized by steric blocking and/or incorporation into five-membered ring systems, react with azido compounds YN3 depending on the steric requirements of the substituents X and Y to give iminogermanes, X2Ge=NY (1, 2) azidogermanes X2Ge(N3)NY2 (6-8) tetrazagermoles, X2Ge(— NY — N =)2 (10-16), and hexaazadigermadispirododecanes, [(— NR — CH2 — CH2 — NR —)Ge(μ-NY -)]2 (17, 18). NMR (1H, 13C, 14N, 15N, and 29Si), MS data, and X-ray structure analyses of the compounds 8, 9, 16, and 18 are reported.
    Notizen: Durch sterische Blockierung und/oder Einbau in fünfgliedrige Ringsysteme stabilisierte Germylene, X2Ge, reagieren mit Azidoverbindungen, YN3, in Abhängigkeit von der Raumerfüllung der Substituenten X und Y zu Iminogermanen X2 Ge=NY (1, 2), Azidogermanen, X2Ge(N3)NY2 (6′8), Tetrazagermolen, X2Ge-(-NY-N=)2 (10-16), bzw. Hexaazadigermadispirododecanen, [(—NR—CH2—CH2—NR— )Ge(μ-NY-)]2 (17, 18). NMR-(1H, 13C, 14N, 15N und 29Si), MS-Daten und Röntgenstrukturanalysen für die Verbindungen 8, 9, 16 und 18 sind angegeben.
    Zusätzliches Material: 4 Ill.
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  • 48
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 271-277 
    ISSN: 0009-2940
    Schlagwort(e): Chalcogenogermanes, (trifluoromethyl)- ; Disilaselenanes ; Germachalcogenanes, bis(trifluoromethyl)- ; Germanes, (trifluoromethyl)- ; Germatranes, (trifluoromethyl)- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: (Trifluormethyl)germanes, III. - Preparation of New (Trifluormethyl)germanium Chalcogene CompoundsStarting with the dihalogenobis(trifluoromethyl)germanes (CF3)2-GeX2 (X = Cl, or I), halogen-chalcogen exchange leads to corresponding chalcogen derivatives of the general type [(CF3)2GeE]n (6, 7) (E = O, NH, S, or Se). The resulting compounds differ in their degree of polymerisation. [(CF3)2GeO]x and the corresponding sesquioxane [(CF3)GeO1, 5]x are highly polymeric, quite in contrast to the corresponding germathianes and -selenanes. The crystal structure of [(CF3)2GeO]x (6a) was determined by X-ray single crystal diffraction. The reaction of CF3GeCl3 with triethanolamine results in the formation of 1-(trifluoromethyl)germatrane (13). Disilaselenane (10) reacts at low temperatures with chloro-(trifluoromethyl)germanes (CF3)nGeCl4-n under retention of one Si—Se bond to give (CF3)nGe(SeSiH3)4-n (11) and H3SiCl. Compounds with n = 3 and 2 could be isolated. Exchange of iodine by ECF3 takes place with iodogermanes (CF3)nGeI4-n and Hg(ECF3)2 (E = S, Se) with formation of a complete series of (trifluoromethyl)(trifluoromethylchalcogeno)germanes (CF3)nGe-(ECF3)4-n (3, 5).
    Notizen: Durch Halogen-Chalkogen-Austauschreaktionen an (CF3)2)GeX2 (X = Cl, I) wurden Bis(trifluormethyl)germachalkogenane [(CF3)2GeE]n (6, 7) E = O, NH, S, Se) von unterschiedlichem Oligomerisierungsgrad erhalten. Die Germoxane [(CF3)2GeO]x und (CF3GeO1,5)x sind im Gegensatz zu den homologen Germathianen und -selenanen polymer, wobei die Struktur von [(CF3)2GeO]x (6a) durch eine Kristallstrukturanalyse ermittelt wurde. Durch Umsetzung von CF3GeCl3 mit Triethanolamin wird 1-(Trifluormethyl)germatran (13) erhalten. Disilaselenan (10) reagiert bei tiefen Temperaturen mit den Chlor (trifluormethyl)-germanen (CF3)nGeCl4-n monofunktionell unter Erhalt einer Si—Se-Bindung zu (CF3)nGe(SeSiH3)4-n (11) und H3SiCl, von denen die Verbindungen mit n = 3 und 2 isoliert werden konnten. Reaktionen der Iodgermane (CF3)nGeI4-n(1) mit Hg(ECF3)2) (E = S, Se) führen unter Substitution des Iods gegen die ECF3-Gruppen zur vollständigen Reihe der (Trifluormethyl)(trifluormethylchalkogeno)germane (CF3)nGe(ECF3)4-n (3, 5).
    Zusätzliches Material: 3 Ill.
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  • 49
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 291-292 
    ISSN: 0009-2940
    Schlagwort(e): (Phthalocyaninato)copper complex, substituted with crown ethers ; Alkali metal extraction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A soluble (phthalocyaninato)copper(II) complex containing eight symmetrical benzo-15-crown-5 substituents, namely {2,3,9,10,16,17,23,24-octakis[[benzo-15-crown-5)-4′ -yl]oxymethyl]phthalocyaninato}copper(II) (2) from 1,2-bis{[benzo-15-crown-5)-4′-yl]oxymethyl}-4,5-dibromobenzene (1) and CuCN in quinoline or pyridine was synthesized. The crown-ether groups in 2 were shown to prefer intramolecular complexation with alkali metal ions.
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  • 50
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 463-466 
    ISSN: 0009-2940
    Schlagwort(e): C—C Rotation ; Sterical hindrance by SF5 groups ; Rotational barriers ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Sterical Hindrance of the C—C Rotation by two SF5 GroupsAddition of SF5Cl to SF5CH=CF2 gives products carrying two SF5 groups on one carbon atom. As a consequence, C—C single bond rotation is strongly hindered. The highest rotational barrier observed is 61.7 kJ mol-1, rotational isomers are hence detectable at room temperature.
    Notizen: Die Addition von SF5Cl an SF5CH=CF2 ergibt Produkte, die zwei SF5-Gruppen an einem Kohlenstoff tragen. In diesen kommt es zu einer starken Hinderung der Rotation um die C—C-Einfachbindung. Die höchste Rotationsbarriere wird mit 61.7 kJ mol-1 gefunden, d. h. Rotationsisomere sind bei Raumtemperatur getrennt nachweisbar.
    Zusätzliches Material: 4 Ill.
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  • 51
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 467-472 
    ISSN: 0009-2940
    Schlagwort(e): Tetracarbonylchromium complexes ; 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine derivatives ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis, Structure, and Reactions of 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine DerivativesThe 1,2,3,6-tetrahydro-1,2,3,6-diphosphadiborine derivatives 3a and 3b are obtained by cyclocondensation of 1,2-bis[chloro(dialkylamino)boryl]ethenes 2 and 1,2-dipotassium 1,2-di-tert-butyldiphosphanediide. As in the case of 2,5-dihydro-1H-1,2,5-phosphadiborole derivatives 1 the temperature-dependent 1H-NMR spectra of 3b exhibit a lowered barrier of inversion at phosphorus. The X-ray structure analysis of 3b shows, that the six-membered C2B2P2 ring is nonplanar and the P atoms are coordinated pyramidally. Attempts to substitute the dialkylamino groups at the boron atoms of 3a and 3b with HCl·Et2O or tBuLi lead to cleavage of the B—P bonds. Reaction between 3a or 3b and Cr(CO)3(MeCN)3 does not result in the formation of tricarbonylchromium complexes but of tetracarbonylchromium complexes 6a and 6b with pentahapto-bonded ligands 3a and 3b.
    Notizen: Die 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborin-Derivate 3a und 3b entstehen durch Cyclokondensation aus 1,2-Bis[chlor(dialkylamino)boryl]ethenen 2 und 1,2-Dikalium-1,2-di-tert-butyldiphosphandiid. Die Temperaturabhängigkeit der 1H-NMR-Spektren von 3b dokumentiert wie bei 2,5-Dihydro-1H-1,2,5-phosphadiborol-Derivaten 1 eine erniedrigte Phosphor-Inversionsbarriere. Die Röntgenstrukturanalyse von 3b zeigt, daß der C2B2P2-Sechsring im Kristall nicht eben ist und daß die P-Atome pyramidal koordiniert sind. Versuche zur Substitution der Dialkylaminogruppen an den Boratomen von 3a und 3b mit HCl·Et2O oder tBuLi führen zur Spaltung der B—P-Bindungen. Die Umsetzung von 3a bzw. 3b mit Cr(CO)3(MeCN)3 ergibt keine Tricarbonylchrom-Komplexe, sondern die Tetracarbonylchrom-Komplexe 6a bzw. 6b, in denen die Liganden 3a und 3b pentahapto gebunden sind.
    Zusätzliches Material: 7 Tab.
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  • 52
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Organic Synthesis via Transition Metal Complexes, 34. - Novel Formation of C=C Bonds by Condensation of Acid Amides with Carbene Complexes Involving an Insertion of C2 Units into M=C BondsCarben complexes LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] and acid amides RCH2CONMe2 2 undergo a novel condensation reaction in presence of POCl3/Et3N to give alkenyl aminocarbene complexes 3. The reaction involves an insertion of a C2 unit of 2 into the M=C bond of 1 to give a C=C bond. It can be achieved with open-chain and cyclic amides like N-methyl-2-pyrrolidone (8). the structures of the complexes have been determined spectroscopically. A mechanism of the reaction is suggested.
    Notizen: Carbenkomplexe LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] lassen sich mit Säureamiden RCH2CONMe2 2 und POCl3/Et3N zu Alkenyl-Aminocarben-Komplexen 3 kondensieren. Dabei wird eine C2-Einheit von 2 in die M=C-Bindung von 1 eingeschoben und eine C=C-Bindung neu geknüpft. Die Reaktion gelingt mit offenkettigen und cyclischen Amiden wie N-Methyl-2-pyrrolidon (8). Die Strukturen der Komplexe wurden spektroskopisch ermittelt und Vorschläge zur Deutung des Reaktionsablaufs gemacht.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 53
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 711-714 
    ISSN: 0009-2940
    Schlagwort(e): Azulenes ; 1,6-Methano[10]annulenes ; 1,2,4,5-Tetrazine ; [4 + 2] Cycloadditions, „inverse“ ; Pyridazines, annulated ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Azulene and 1,6-Methano[10]annulene as Dienophiles in the Diels-Alder Reaction with 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazineThe LUMO-diene-controlled [4 + 2] cycloadditions of azulene (2) and 1,6-methano[10]annulene (14) with the electron-deficient s-cisfixed diazadiene system of 3,6-bis(trifluoromethyl)-1,2,4,5-tetrazine (1) are described. Contrary to expectation, 1 reacts under unusually mild conditions with 2 (or its valence tautomer 3) to yield the adduct 4 which after N2 elimination rearranges to the benzo[f]phthalazine 11. The Diels-Alder reaction of 1 with 14 (or its valence tautomer 13) leads to the annulated dihydropyridazines 15 and 16, which can be dehydrogenated by silver(I) oxide to the methano-bridged aromatic cyclodecapyridazine 17 and the olefinic phthalazino[5,6-f]phthalazine 18, respectively. Besides, the methano-bridged cyclodeca[d]pyridazine 24 is prepared.
    Notizen: LUMO-Dien-kontrollierte [4 + 2]-Cycloadditionen von Azulen (2) und 1,6-Methano[10]annulen (14) an das elektronenarme, s-cis-fixierte Diazadiensystem von 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazin (1) werden beschrieben. Wider Erwarten reagiert 1 unter ungewöhnlich milden Bedingungen mit 2 (oder dessen Valenztautomerem 3) zum Addukt 4, das nach N2-Eliminierung und nachfolgender Umlagerung das Benzo[f]phthalazin 11 liefert. Die Diels-Alder-Reaktion von 1 mit 14 (oder dessen Valenztautomer 13) führt zu den beiden anellierten Dihydropyridazinen 15 und 16, die mit Silber(I)-oxid zu dem Methano-überbrückten aromatischen Cyclodecapyridazin 17 bzw. dem olefinischen Phthalazino[5,6-f]phthalazin 18 dehydriert werden können. Daneben wird das Methano-überbrückte Cyclodeca[d]pyridazin 24 dargestellt.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 715-719 
    ISSN: 0009-2940
    Schlagwort(e): Alkyne ; Carbene ; Cycloisomerization ; Pyrolysis ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Über die thermische Cycloisomerisierung langkettiger Alkylacetylene in der GasphaseDie thermische Cycloisomerisierung einiger Alkylacetylene wurde in einem Laborrohrreaktor aus Quarzglas untersucht. 1-Hexin (1) wird dabei durch 1,2-H-Verschiebung und 1,5-C,H-Insertion des intermediär gebildeten Pentylidencarbens (vgl. Schema 1) in 3-Methyl-1-cyclopenten (5) umgelagert. 5-Methyl-1-hexin (2) reagiert analog; es entsteht 3,3-Dimethyl-1-cyclopenten (6). Im Gegensatz zur Bildung von in 3-Stellung methylierten Cyclopentenen aus 1-Alkinen ensteht aus 2-Hexin (3) 1-Methyl-1-cyclopenten (7). Offenbar ist die Acetylen-Vinyliden-Umlagerung nicht auf 1,2-H-Verschiebung beschränkt. Der Mechanismus der Cycloisomerisierung von Alkylacetylenen wird durch Untersuchungen mit D-markierten Alkinen bestätigt. Die Ergebnisse lassen den Schluß zu, daß die Cycloisomerisierung ohne weiteres mit dem überwiegend nach einem Radikalketten-Mechanismus verlaufenden thermischen Zerfall konkurrieren kann.
    Notizen: The thermal cycloisomerization of some alkylacetylenes was investigated in a tubular quartz reactor. At 570°C 1-hexyne (1) rearranges to 3-methyl-1-cyclopentene (5) with a selectivity of about 27 by a reaction sequence including an acetylene-vinylidene rearrangement and 1,5-C,H insertion of the intermediately formed alkylidenecarbene species. 5-methyl-1-hexyne (2) behaves analogously forming 3,3-dimethyl-1-cyclopentene (6), while 2-hexyne (3) provides 1-methyl-1-cyclopentene (7) indicating that the acetylene-vinylidene rearrangement is obviously not restricted to 1,2-H shifts. The mechanism of the cycloisomerization of alkylacetylenes is investigated by means of D-labeled parent alkynes. The results show that the unimolecular cycloisomerization via alkylidenecarbenes obviously can be an important channel despite the dominance of a radical chain course.
    Zusätzliches Material: 1 Ill.
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  • 55
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 745-748 
    ISSN: 0009-2940
    Schlagwort(e): Flash Pyrolysis ; Matrix IR spectroscopy ; Photolysis ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Methoxy- und AminoisocyanatMethoxyisocyanat (1) kann durch Photolyse von Azidoameisensäure-methylester (3) oder Pyrolyse von N-Methoxycarbonyl-O-methylhydroxylamin (4) dargestellt werden. Aminoisocyanat (2) ist auf ähnliche Weise durch Photolyse von Carbamoylazid (12) und Pyrolyse von Carbazinsäure-methylester (13) oder 3,4-Diaminofurazan (14) zugänglich. Die IR-Spektren von 1 und 2, aufgenommen in einer Argon-Matrix bei 10 K, werden diskutiert.
    Notizen: Methoxyisocyanate (1) can be prepared by photolysis of methyl azidoformate (3) or pyrolysis of N-methoxycarbonyl-O-methyl-hydroxylamine (4). Aminoisocyanate (2) is similarly formed on photolysis of carbamoyl azide (12) and pyrolysis of either methyl carbazate (13) or 3,4-diaminofurazan (14). The infrared spectra of 1 and 2 in an argon matrix at 10 K have been measured, and some of their properties are discussed.
    Zusätzliches Material: 1 Ill.
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  • 56
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 749-752 
    ISSN: 0009-2940
    Schlagwort(e): Matrix isolation ; Photochemistry ; Theoretical vibrational spectra ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Infrarot-Spektren und Photochemie von Isodiazen und seinen deuterierten IsotopomerenDie Matrixisolation von Aminoisocyanat eröffnet einen neuen ergiebigen Weg zur Darstellung von Isodiazen (Aminonitren). Damit ist es möglich geworden, nicht nur sein IR-Spektrum eindeutig festzulegen und mit Hilfe von ab-initio-Rechnungen zu interpretieren, sondern auch seine Photochemie zu untersuchen.
    Notizen: The matrix isolation of aminoisocyanate opens a new efficient route for the preparation of isodiazene (aminonitrene). Its infrared spectrum can now, with the help of ab initio calculations, be interpreted, and its photochemistry can be studied.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 57
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 795-796 
    ISSN: 0009-2940
    Schlagwort(e): Thiochalcones ; Thienylchalcones ; Fries rearrangement ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Four new thienylchalcones (1, 4, 5, and 6) were synthesized by condensing hydroxy-nitroacetophenones with 2-thiophene and 3-thiophenecarboxaldehydes in the presence of dilute NaOH.
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  • 58
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 767-779 
    ISSN: 0009-2940
    Schlagwort(e): Molecular twisting ; cis-9,10-Dihydronaphthalenes, persubstituted ; Valence isomerizations ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Valence Isomerizations, 17. - Persubstituted cis-9,10-Dihydronaphthalenes and their Valence IsomerizationsThe tricyclic diester 10 is available from 2-butyne in a six-step synthesis with an overall yield of 10%. Thermolysis of 10 gives the bicyclic diester 11 which upon UV irradiation yields 12 as the first persubstituted cis-9,10-dihydronaphthalene. X-ray analysis of 12 shows the molecule considerably twisted along the central bond. In addition, the planes of the ester groups are at an angle of approximately 60° to the „planes“ of the six-membered rings so that conjugation of the diene systems with the carbonyl functions is virtually interrupted, an effect which is reflected by the unusual spectroscopic properties of 12. The same structural features can be found in decamethyl-cis-9,10-dihydronaphthalene (16). When heated slightly, 12 is converted to the tetracyclic valence isomer 34. On reduction of 12 with diisobutylaluminum hydride both, dihydronaphthalene dicarbinol 25 as well as its unexpected positional isomer 26, are formed depending on the reaction conditions. Etherification of the reduction products with CH2N2/Et2O—BF3 furnishes a mixture of the three isomeric bis(methoxymethyl) compounds 31, 32 and 33. They can be separated by chromatography in the cold, but revert to the mixture of the three isomers at room temperature. We consider diradical 38 to be the intermediate of this intriguing valence isomerization.
    Notizen: Der tricyclische Diester 10 ist in sechs Stufen in einer Gesamtausbeute von 10% aus 2-Butin zugänglich. Thermolyse von 10 liefert den Bicyclus 11, bei dessen UV-Bestrahlung das erste persubstituierte cis-9,10-Dihydronaphtalin 12 gebildet wird. Eine Röntgenstrukturanalyse von 12 beweist die starke Verdrillung des Moleküls um die zentrale Bindung. Die Ebenen der Ester-Gruppen stehen ungefähr in einem 60°-Winkel zu den Sechsring-„Ebenen“, so daß die Konjugation der Dien-Systeme mit den Carbonyl-Funktionen praktisch unterbrochen ist, ein Effekt, der sich in den ungewöhnlichen spektroskopischen Eigenschaften von 12 widerspiegelt. Analoge Strukturmerkmale gelten auch für das Decamethyl-cis-9,10-dihydronaphthalin (16). Bicyclus 12 wandelt sich bei leichtem Erwärmen in den valenzisomeren Tetracyclus 34 um. Reduktion von 12 mit Diisobutylaluminiumhydrid gibt je nach den Reaktionsbedingungen das Dihydronaphthalindicarbinol 25 bzw. das unerwartete Stellungsisomere 26. Veretherung der Reduktionsprodukte mit CH2N2/Et2O—BF3 liefert ein Gemisch der drei isomeren Bis(methoxymethyl)-Verbindungen 31, 32 und 33, die chromatographisch in der Kälte trennbar sind, aber schon bei Raumtemperatur wieder das Gemisch der drei Isomeren zurückbilden, wobei das Diradikal 38 als Zwischenprodukt dieser erstaunlichen Valenzisomerisierung anzunehmen ist.
    Zusätzliches Material: 2 Ill.
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  • 59
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 803-808 
    ISSN: 0009-2940
    Schlagwort(e): Bismuth organic compounds ; Fluorinated aromatic rings ; Square pyramidal bismuth ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Structures of Pentaarylbismuth CompoundsPentaarylbismuth compounds were synthesized by the known reaction Ar3BiX2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2. Whenever possible they were characterized by single-crystal X-ray structure determination. In two cases almost ideal square-pyramidal geometry was found, in a third case there were two different molecules in the unit cell, both again with square-pyramidal geometry. None of these novel bismuth pentaaryls exhibit the deep coloration and the dichroism of Bi(C6H5)5.
    Notizen: Pentaarylbismut- Verbindungen wurden durch die bekannte Reaktion BiAr3X2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2 hergestellt und, soweit möglich, durch Röntgenbeugung an Einkristallen strukturell untersucht. In zwei Fällen erwies sich die Struktur als nahezu ideal quadratisch-pyramidal, in einem dritten Fall wurden zwei unterschiedliche Moleküle im Kristall gefunden, die aber beide wiederum quadratisch-pyramidal sind. Keines der hier vorgestellten neuen Bismutpentaaryle zeigt die tiefe Färbung und den Dichroismus von Bi(C6H5)5.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 60
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 533-535 
    ISSN: 0009-2940
    Schlagwort(e): Free radicals ; Triphenylmethyl radicals ; ESR measurements ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Sterically Hindered Free Radicals, XIX. - Stable 4,4′,4″-Trisubstituted Triphenylmethyl RadicalsThe title radicals (4-R—C6H4)3C. (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, have been prepared, the latter four for the first time, and the ESR spectra have been recorded. aoH, amH, and apR are listed. The intensities of the ESR signals remain constant within the accessible range of -30 to + 100°C. Within this range these radicals are kinetically stable and do not dimerize like other trityls by, e.g., α,p-, α,o-, α,α -recombinations.
    Notizen: Die Titelradikale (4-R—C6H4)3C· (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, wurden dargestellt, davon die vier letzten erstmalig, und mittels ESR-Spektroskopie vermessen. aoH, amH und apR werden angegeben. Die ESR-Signale bleiben im gesamten zugänglichen Temperaturbereich - 30 bis + 100°C in ihrer Intensität unverändert. Daraus folgt, daß alle diese Radikale im genannten Temperaturbereich kinetisch stabil sind, also nicht wie andere Trityle zu Dimerisierungen, etwa α,p-, α,o-, α,α-, neigen.
    Zusätzliches Material: 1 Tab.
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  • 61
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 523-531 
    ISSN: 0009-2940
    Schlagwort(e): Dicyclopenta-s-indacene ; 2-Osxa[3.3.3]propellane derivatives ; Pentalene derivatives ; [3.3.3]Propellane-3,7-dione ; Weiss reaction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Novel Products in the Weiss Reaction of 1,2-Cyclopentanedione. Improved Preparation of [3.3.3]Propellane-3,7-dioneThe reaction of 1,2-cyclopentanedione (1c, 9) with the 3-oxoglutarate 4 in methanol/water in the presence of sodium bicarbonate followed by hydrolysis and decarboxylation of the product mixture affords the oxa[3.3.3]propellane ester 11c in addition to the [3.3.3]propellanedione 6c. The alkali enolates of 4 react with 9 in boiling methanol to yield the yellow, poorly soluble alkali dihydropentalenolates 12M and the [3.3.3]propellane tetraester 5c, which on hydrolysis and decarboxylation yields 53% of 6c. The dihydropentalenol 12H equilibrates with the tautomeric β-oxodiester 13, the proportion of which increases with solvent polarity. In methanol solutions, 12H and 13 add diastereoselectively forming the dicyclopenta-s-indacene tetraester syn-14, which is derived from a novel pentacyclic ring system. The configuration of syn-14 is determined by X-ray diffraction analysis. The mechanisms of formation are discussed for 11c, 12M, and syn-14.
    Notizen: Nach Umsetzung von 1,2-Cyclopentandion (1c, 9) mit dem 3-Oxoglutarsäureester 4 in Methanol/Wasser in Gegenwart von Natriumhydrogencarbonat, saurer Hydrolyse und Decarboxylierung des Produktgemischs erhält man neben dem [3.3.3]Propellandion 6c den Oxa[3.3.3]propellanester 11c. Die Alkali-Enolate von 4 reagieren mit 9 in siedendem Methanol zu den gelben, schwer löslichen Dihydropentalenolaten 12M und dem [3.3.3]Propellantetraester 5c, der nach Hydrolyse und Decarboxylierung 53% 6c ergibt. Das Dihydropentalenol 12H liegt im Gleichgewicht mit dem tautomeren β-Oxodiester 13 vor, dessen Anteil mit der Polarität des Lösungsmittels zunimmt. In Methanol addieren sich 12H und 13 diastereoselektiv und bilden den Dicyclopenta-s-indacentetraester syn-14, der sich von einem neuartigen, pentacyclischen Ringsystem ableitet. Die Konfiguration von syn-14 wird durch Röntgenstrukturbestimmung aufgeklärt. Die Mechanismen der Bildung von 11c, 12M und syn-14 werden diskutiert.
    Zusätzliches Material: 2 Ill.
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  • 62
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 553-559 
    ISSN: 0009-2940
    Schlagwort(e): Amino acids ; Diastereoselective addition ; 1-(Methacryloyl)proline derivatives ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Amino Acids, 15. - Diastereoselective Addition of Thiocarboxylic Acids to 1-(Methacryloyl)proline and-prolinol DerivativesThiocarboxylic acids 6 add to 1-(methacryloyl)-substituted proline and prolinol derivatives stereoselectively to give the 1-[3-(acylthio)-2-methylpropionyl]proline and -prolinol derivatives 7,7′ and 9. The less soluble (2S,2′R)-diastereomers are obtained in optical yields ≥ 98% by digestion of the crude products, the configuration of which was determined by acid hydrolysis of (2S,2′R)-7,7′ to (R)-3-mercapto-2-methylpropionic acid [(R)-8]. The stereoselectivity of the additions may be explained by a sevenmembered ring intermediate with an intramolecular H bridge, to which the S-nucleophiles add preferentially to give the compounds with the (2′R)-configuration.
    Notizen: Thiocarbonsäuren 6 addieren stereoselektiv mit hohen optischen Ausbeuten an 1-(Methacryloyl)-substituierte Prolin- und Prolinol-Derivate zu den 1-[3-(Acylthio)-2-methylpropionyl]prolin-und -prolinol-Derivaten 7,7′ und 9. Durch Digerieren der Rohprodukte mit Diethylether werden die schwerer löslichen (2S,2′R)-Diastereomeren in optischen Ausbeuten ≥98% erhalten, deren Konfiguration durch Acidolyse von (2S,2′R)-7,7′ zu (R)-3-Mercapto-2-methylpropansäure [(R)-8] bewiesen wurde. Die Stereoselektivität der Additionen wird über einen Siebenring mit intramolekularer H-Brücke als Zwischenstufe, an die Schwefelnucleophile bevorzugt unter Bildung der (2′R)-Konfiguration addieren, gedeutet.
    Zusätzliches Material: 10 Tab.
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  • 63
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 545-551 
    ISSN: 0009-2940
    Schlagwort(e): Amino acids ; Diastereoselective addition ; 1-Acryloylproline esters ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Amino Acids, 14. - Diastereoselective Addition of Benzenesulfenyl Chloride to 1-Acryloylproline Esters(S)-Proline esters (S)-1 react with acryloyl chloride (2) to give 1-acryloylproline esters (S)-3 in good yields. Addition of benzenesulfenyl chloride (6) to (S)-3 at -95°C in dichloromethane results in 1-[2-chloro-3-(phenylthio)propionyl]proline esters (2S,2′R/2S,2′S)-7. The diastereoselectivity of the addition depends on the conformer ratio 3′/3″ of the starting material (S)-3. The diastereomers are separated by MPLC. Configuration at C-2′ of the resulting main products (2S,2′S)-7 was proved by independent synthesis. The diastereoselectivity of the addition of 6 to (S)-3 is interpreted to result from formation of a complex of the benzenesulfenyl cation with the proline ester group and subsequent electrophilic addition to a thiiranium intermediate B with (2S,2′R) configuration; the (2S,2′S) diastereomeric adduct 7 then results by nucleophilic attack of chloride at C-2′ under ring opening.
    Notizen: Die 1-Acryloylprolinester (S)-3 werden durch N-Acylierung der Prolinester (S)-1 mit Acryloylchlorid (2) in guten Ausbeuten hergestellt; sie addieren Benzolsulfenylchlorid (6) bei -95°C in Dichlormethan mit hoher Diastereoselektivität zu 1-[2-Chlor-3-(phenylthio)propionyl]prolinestern (2S,2′R/2S,2′S)-7, die mittels MPLC getrennt werden. Die Diastereoselektivität der Addition hängt vom Konformerenverhältnis 3′/3″ der Edukte (S)-3 ab. Der Beweis der Konfiguration an C-2′ der als Hauptprodukte anfallenden Diastereomeren (2S,2′S)-7 wird durch eine unabhängige Synthese erbracht. Die Diastereoselektivität der Addition von 6 an (S)-3 wird über eine Komplexbildung des Phenylsulfenylkations mit der Prolinestergruppe und eine sich anschließende elektrophile Reaktion zu einer Thiiranium-Zwischenstufe B mit (2S,2-R)-Konfiguration gedeutet; das (2S,2′S)-diastereomere Additionsprodukt 7 entsteht dann durch nucleophilen Angriff des Chlorids an C-2′ unter Ringöffnung.
    Zusätzliches Material: 7 Tab.
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  • 64
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 851-855 
    ISSN: 0009-2940
    Schlagwort(e): Diphosphines ; Tungsten - tungsten quadruple bond ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese und Struktur von W2Cl4{μ(iPr2PCH2CH2CH2PiPr2)}2: Eine durch sperrige, chelatisierende Diphosphane überbrückte Wolfram - Wolfram-VierfachbindungDie Reduktion von WCl4 in THF durch zwei Äquivalente Na/Hg in Gegenwart des sperrigen, chelatisierenden Diphosphinopropans iPr2PCH2CH2CH2PiPr2 (dippp) liefert den violetten, zweikernigen Komplex W2Cl4(μ-dippp)2. Der Komplex besitzt eine W-W-Vierfachbindung und β-Struktur, d.h. die chelatisierenden Diphosphinopropan-Liganden verbrücken die beiden Metall-Zentren. Die 1H-NMR-spektroskopischen Daten zeigen Tieffeldverschiebungen für die dippp-Liganden, die im Einklang mit der β-Struktur stehen. Das 31P{1H}-NMR-Spektrum besteht aus einem Singulett mit 183W-Satelliten. Die Röntgen-Stukturanalyse ergibt für die β-Struktur einen Torsionswinkel P-W-W-P von 75.9° und eine W-W-Bindungslänge von 2.297(1) Å. Aus den Molekülstruktur-Daten und den 1H-NMR-Tieffeldverschiebungen kann die diamagnetische Anisotropie χ der W-W-Vierfachbindung mit - 3000 ± 300 × 10-36 m3/Molekül abgeschätzt werden. Die für den festen Zustand beobachtete Chiralität wird auch in Lösung beibehalten.
    Notizen: The reduction of WCl4 in THF by two equivalents of Na/Hg in the presence of the bulky chelating diphosphine iPr2PCH2-CH2CH2PiPr2 (dippp) generates the purple, binuclear complex W2Cl4(μ-dippp)2. The quadruply-bonded molecule has a β structure, that is, the chelating diphosphine bridges the two metal centers. 1H-NMR spectral data show downfield shifts for the ligand protons consistent with the β structure. The 31P{1H}-NMR spectrum consists of a singlet with 183W satellites. The X-ray crystal structure has a twist angle (P-W-W-P torsion angle) of 75.9°, and the W-W bond length is 2.297(1) Å. Using the solidstate data and the observed downfield shifts in the 1H-NMR spectrum, the diamagnetic anisotropy χ has been estimated as - 3000 ± 300 × 10-36 m3/molecule. The chiral structure observed in the solid phase is retained in solution.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 65
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 861-864 
    ISSN: 0009-2940
    Schlagwort(e): Aminoiminophosphanes ; 1,3,2λ5,4-Thiazaphosphaboretidines ; 1,2,4,3,5-Trithiadiborolanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis and Characterization of 1, 3, 2λ5, 4-ThiazaphosphaboretidinesThe reaction of 1,2,4,3,5-trithiadiborolanes with silylated aminoiminophosphanes leads to the 1,3,2λ5,4-thiazaphosphaboretidines 1a-i. The formation of 1h, i is accompanied by an exchange of the substituents bonded to the N atoms. 1H-, 11B-, 13C-, 29Si-, 31P-NMR, and mass spectra are discussed.
    Notizen: Die Umsetzung von 1,2,4,3,5-Trithiadiborolanen mit silylierten Aminoiminophosphanen führt zu den 1,3,2λ5,4-Thiazaphosphaboretidinen 1a-i. Die Bildung von 1h, i wird von einem Austausch der N-ständigen Substituenten begleitet. 1H-, 11B-, 13C-, 29Si-, 31P-NMR- und Massenspektren werden diskutiert.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 66
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 857-860 
    ISSN: 0009-2940
    Schlagwort(e): Alkenylboranes ; Alkenylstannanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: A Convenient Route from Alkenylboranes to AlkenylstannanesAlkenyldialkylboranes 1 with various substituents at the C=C double bond, including organometallic groups such as the trimethylstannyl or trimethylsilyl group, react in hexane solution with (diethylamino)- or (dimethylamino)trimethylstannane (2) in the presence of a catalytic amount of lithium dimethyl- or diethylamide (3) to give aminodialkylboranes 4 and alkenyltrimethylstannanes 5 in high yields with retention of the configuration at the C—C double bond. With (diethylamino)trimethylplumbane (2c) the less stable alkenes 5Pb are obtained. A mechanism is proposed, and 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-data are reported.
    Notizen: Alkenyldialkylborane 1 mit verschiedenen Substituenten an der C=C-Doppelbindung, einschließlich organometallischer Gruppen wie dem Trimethylstannyl- oder dem Trimethylsilyl-Rest, reagieren in Hexan mit (Diethylamino)- oder (Dimethylamino)trimethylstannan (2) in Gegenwart einer katalytischen Menge von Lithium-diethylamid (3b) oder -dimethylamid (3a) in hoher Ausbeute unter Beibehaltung der Konfiguration an der C—C-Doppelbindung zu den entsprechenden Alkenylstannanen 5 und Aminoboranen 4. Durch Einsatz von (Diethylamino)trimethylplumban (2c) lassen sich die weniger stabilen Alkene 5Pb erhalten. Ein Mechanismus wird vorgeschlagen, und 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-Daten werden mitgeteilt.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 67
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1919-1924 
    ISSN: 0009-2940
    Schlagwort(e): Hydrogen transfer ; Ziegler catalysis ; Dihydroarenes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Ziegler Nickel Catalysts for Hydrogen Transfer ReactionsCatalysts prepared from Ni(acac)2 and AlEt3 show high catalytic activity in the hydrogen transfer between dihydroarenes, but hardly any isomerisation and H/D scrambling is observed. The active form of the catalyst is produced only in the presence of the starting material. Kinetic experiments, especially those concerning the introduction periods and the inhibition, are indicative of a complex reaction mechanism. The first hydrogen is preferentially abstracted from the 2-position, the second with complete cis selectivity.
    Notizen: Der aus Ni(acac)2 und AlEt3 dargestellte Katalysator zeigt eine hohe Aktivität beim H-Transfer zwischen Dihydroarenen, neben dem Isomerisierungen und H/D-Austausch kaum ablaufen. Die aktive Form entsteht erst in Gegenwart des Edukts. Kinetische Untersuchungen, vor allem zur Induktionsperiode und zur Hemmung, deuten auf einen komplexen Ablauf. Der Wasserstoff wird cis-selektiv abgespalten, primär bevorzugt aus der 2-Position.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 68
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1925-1927 
    ISSN: 0009-2940
    Schlagwort(e): Hydrogen transfer ; Olefin isomerization ; Cobalt complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Hydrogen Transfer Reactions, 13.  -  Catalysis of Disproportionation by (Dinitrogen)hydridotris(triphenylphosphine)cobalt(I)For both C—H activation and olefin isomerization, CoH(N2)(PPh3)3 (1) is a more powerful catalyst than the Wilkinson complex. In 1,2-dihydronaphthalene (2), a two-step cis abstraction of the hydrogen atoms is found with small regioselectivity in the first step.
    Notizen: Die Aktivität des Komplexes CoH(N2)(PPh3)3 (1) liegt bei der C—H-Aktivierung deutlich höher als beim Wilkinson-Katalysator. Noch effektiver wird aber eine Olefin-Isomerisierung induziert. Die zweistufige H-Abstraktion erfolgt beim 1,2-Dihydronaphthalin (2) cis-selektiv, der Primärschritt aber kaum regioselektiv.
    Materialart: Digitale Medien
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  • 69
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1935-1938 
    ISSN: 0009-2940
    Schlagwort(e): as-Triazinium salt, fused ; Ring transformation ; Solvatochromy, negative ; Zwitterion ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese und Ringtransformation von neuen kondensierten as-Triazinium-SalzenDie Reaktion des 1,2-Diaminopyridinium-Salzes 1 mit dem Furandion 2 ergab ein Pyrido-as-triazinon 3, das zum tricyclischen Furo[2,3-e]pyrido[1,2-b]-as-triazinium-Salz 5 cyclisiert wurde. Die Reaktion von 5 mit Nucleophilen führte zu unterschiedlichen Produkten: mit wäßriger Base entstand das bicyclische Triazinon 4, mit dem Methoxid-Ion und sekundären Aminen wurden die stabilen Zwitter-Ionen 7a, b erhalten, wohingegen Ammoniak und Hydrazine unter Transformation des Furanringes die neuen tricyclischen kondensierten Pyrrole 10, 11 bzw. Pyridazine 13, 14a, b ergaben.
    Notizen: The 1,2-Diaminopyridinium salt 1 was treated with furandione 2 to give pyrido-as-triazinone 3, which could be cyclized to the tricyclic furo[2,3-e]pyrido[1,2,-b]-as-triazinium salt 5. Reaction of 5 with nucleophiles resulted in different types of products. Thus, aqueous base afforded bicyclic triazinone 4, methoxide ion or secondary amine led to stable zwitterions 7a, b, whereas ammonia and hydrazines resulted in ring transformation of the furan moiety, and gave new fused tricyclic pyrroles (10, 11) and pyridazines (13, 14), respectively.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 70
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1947-1953 
    ISSN: 0009-2940
    Schlagwort(e): Enol ethers ; [n](2,4)Phloroglucinophanes ; Autoxidation ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Investigations of the Autoxidation and the Rearrangement of [n](2,4)PhloroglucinophanesIn the autoxidation of [n](2,4)phloroglucinophanes 3 hydroperoxides 7 are isolated in several cases as the first oxidation products; they react to the more stable monohydroxylated compounds 8 with different rates. Acylphloroglucinophanes 5, however, react with oxygen to give the dihydroxylated compounds 9. The autoxidation rate of the phloroglucinophanes 3, 5 is markedly larger than that of diethylphloroglucinols 6. In alkaline solution the hydroxy compounds 8 rearrange to the dihydroxycyclopentenones 12; the rate of rearrangement correlates with the decrease of ring strain.
    Notizen: Bei der Autoxidation von [n](2,4)Pholoroglucinophanen 3 können in einigen Fällen Hydroperoxide 7 als erste Oxidationsprodukte isoliert werden, die unterschiedlich rasch in die stabileren monohydroxylierten Verbindungen 8 übergehen. Aclphloroglucinophane 5 reagieren mit Luftsauerstoff dagegen zu den zweifach hydroxylierten Verbindungen 9. Die Geschwindigkeit der Autoxidation ist bei den Phloroglucinophanen 3, 5 deutlich größer als bei den 2,4-Diethylphloroglucinen 6. Im alkalischen Medium lagern sich die Hydroxyverbindungen 8 in die Dihydroxycyclopentenone 12 um, wobei für die Geschwindigkeit der Umlagerung eine Korrelation mit der Abnahme an Ringspannung gefunden wird.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 71
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1963-1967 
    ISSN: 0009-2940
    Schlagwort(e): Allenyl azides, ring closure of ; Propargyl azides, rearrangement, base-induced ; Triazafulvenes, nucleophilic addition to ; 1,2,3-Triazoles, preparation of ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Reactions of Unsaturated Azides, 7.  -  Base-catalyzed Formation of Allenyl Azides from Propargyl Azides: New Syntheses for 1,2,3-TriazolesThe propargyl azides 10, 14, 17, 20, and 28 undergo a base-catalyzed (prototropic) rearrangement to short-lived allenyl azides. These intermediates rapidly cyclize to triazafulvenes, which can be trapped by nucleophiles (methanol, sodium hydroxide, ammonia) to give 1,2,3-triazoles. Starting with the precursors 9, 13, 16, 19, and 27 one-pot syntheses lead to the heterocycles 12, 15, 18, 21, and 29. Depending on the reaction conditions, compound 10 regioselectively yields 12c (75%) by prototropic rearrangement (path B) or by migration of the azide group (path A) the isomer 11c (62%).
    Notizen: Die Propargylazide 10, 14, 17, 20 und 28 lagern sich basenkatalysiert (prototrop) zu kurzlebigen Allenylaziden um. Diese Zwischenstufen cyclisieren rasch zu Triazafulvenen, die mit Nucleophilen (Methanol, Natriumhydroxid, Ammoniak) als 1,2,3-Triazole abgefangen werden können. Ausgehend von den Vorläufern 9, 13, 16, 19 und 27 führen Eintopf-Synthesen zu den Heterocyclen 12, 15, 18, 21 und 29. In Abhängigkeit von den Reaktionsbedingungen liefert 10 über die prototrope Umlagerung (Weg B) regioselektiv 12c (75%) oder durch Azidwanderung (Weg A) die isomere Verbindung 11c (62%).
    Materialart: Digitale Medien
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  • 72
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2023-2025 
    ISSN: 0009-2940
    Schlagwort(e): Homoallylic alcohols ; [2,3] Sigmatropic rearrangement ; Stereoselective synthesis of alcohols ; [2,3] Wittig rearrangement ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reductive cleavages of allyl [(phenylthio)methyl] ethers (8, 11) and an allyl [(tolylsulfonyl)methyl] ether (14) with lithium naphthalenide in THF furnish homoallylic alcohols (9, 12). The steric course of these transformations (E/Z selectivity in the case of 9, syn/anti selectivity for 12) is very similar to that of analogous Wittig-Still rearrangements.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 73
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 74
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2049-2054 
    ISSN: 0009-2940
    Schlagwort(e): Ligating properties ; Pentaphosphaferrocenes ; Sandwich and triple-decker complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Pentaphospaferrocenes as Complex LigandsThe interaction of [Cp*Fe(P5)] (1a) with [Cr(CO)5(thf)] and [Cp(CO)2Mn(thf)], respectively, affords [Cp*Fe(P5){Cr(CO)5}2] (2) as well as [Cp*Fe(P5){Mn(CO)2Cp}n] (4a-d; n = 1-4; Cp* = η5-C5Me5). Irradiation of 1 and [CpFe(C6H6)]PF6 gives the cationic 30-VE triple-decker complexes [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5). In addition to the NMR studies 2 and 3b have been characterized by X-ray structure analyses.
    Notizen: Die Umsetzung von [Cp*Fe(P5)] (1a) mit [Cr(CO)5(THF)] bzw. [Cp(CO)2Mn(THF)] ergibt [Cp*Fe(P5){Cr(CO)5}2] (2) sowie [HCp*Fe(P5){Mn(CO)2Cp}n] (4a-d; 1-4; Cp* = η5-C5Me5). Aus 1 und [CpFe(C6H6)]PF6 lassen sich photochemisch die kationischen 30-VE-Tripeldeckerkomplexe [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5) aufbauen. Zusätzlich zu den NMR-spektroskopischen Studien wurden von 2 und 3b Kristallstrukturanalysen angefertigt.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 75
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 76
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1139-1145 
    ISSN: 0009-2940
    Schlagwort(e): C-(Alkylideneamino)ketene imines ; Isocyanides, C=C coupling with aminocarbene ligands ; (2-Azaallenyl)chromium complexes ; 2-Imidazolin-5-ones ; α-Amino acids ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Organic Syntheses via Transition Metal Complexes, 35. - (C-Amino) Ketene Imines, 2-Imidazolin-5-ones, and α-Amino Acids from Aminocarbene Chromium Complexes and IsocyanidesC-(Alkylidenamino)ketene imines 1,4-diaza-1,2,4-pentatrienes) 8 are easily accessible by C=C coupling of isocyanides R1 - NC (2, R1 = t-C4H9, c-C5H11, CH3) with the (alkylideneamino)carbene (= 2-azaallenyl-) ligand of (6). The tendency for an insertion of 2 into M=C bonds of aminocarbene complexes strongly depends on the electronic character of the aminocarbene ligand. Electron-rich aminocarbene chromium complexes like (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), show only little tendency for an insertion but mainly give cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) by substitution of CO. Electron-poor aminocarbene complexes like 6 (readily available on N-benzoylation of 1a) undergo a facile insertion of 2 into the M=C bond with smooth formation of 7. From 7 ketene imine 8 is spontaneously disengaged by a second equivalent of 2. The reaction works especially well with bulky isocyanides 2a, b. In the case of methyl isocyanide (2c) a [bis(imino)dihydropyrrol]chromium complex 15 is obtained as a minor product besides 8c. 15 results from a [4+1] cycloaddition of 2c at the ketene imine ligand of 7c. C-(Alkylideneamino)ketene imines 8 are easily accessible by our method. They prove to be very thermolabile in solution and spontaneously isomerize to give 2-imidazolin-5-ones 10 and C-amidoketene imines 11. Under the influence of wet silica gel keten imine derivatives 8 rapidly form α-amino acid amides 16 by hydrolysis with concomitant migration of a benzoyl group. Under the same conditions 11 also gives the „normal“ α-amino acid amides 17.
    Notizen: C-(Alkylideneamino)ketenimine (1,4-Diaza-1,2,4-pentatriene) 8 wurden durch C=C-Kupplung von Isocyaniden R1-NC (2, R1 = t-C4H9, c-C5H11, CH3) mit dem (Alkylideneamino)carben-(= 2-Azaallenyl-)Ligand von (6) erstmals hergestellt. Die Bereitschaft zur Insertion von 2 in M=C-Bindungen von Aminocarbenkomplexen hängt stark von den elektronischen Eigenschaften der Aminocarbenliganden ab. Elektronenreiche (Aminocarben)chromkomplexe, wie z. B. (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), zeigen eine nur geringe Neigung zur Insertion von 2 und bilden bevorzugt cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) unter Substitution von CO. Elektronenarme (Aminocarben)chromkomplexe hingegen, wie z. B. 6 (durch N-Benzoylierung von 1a leicht zugänglich), zeigen ausschließlich Insertion zu 7. Aus 7 wird spontan 8 freigesetzt durch Substitution mit einem zweiten Äquivalent 2. Sperrige Isocyanide 2a, c reagieren besonders einheitlich. Mit Methylisocyanid (2c) entsteht zusätzlich zu 8c der [Bis(imino)dihydropyrrol]-chromkomplex 15 unter [4+1]-Cycloaddition von 2c am Keteniminligand von 7c. C-(Alkylidenamino)ketenimine 8 sind nach unserem Verfahren einfach zugänglich; sie isomerisieren jedoch leicht zu 2-Imidazolin-5-onen 10 und C-Amidoketeniminen 11. An feuchtem Kieselgel entstehen aus 8 rasch α-Aminosäureamide 16 durch Hydrolyse unter Wanderung eines Benzoylrestes; aus 11 unter gleichen Bedingungen zusätzlich „normale“ α-Aminosäureamide 17.
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  • 77
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2177-2181 
    ISSN: 0009-2940
    Schlagwort(e): Benzonitriles ; Hetero Diels-Alder reactions, “inverse” ; Pyrazines, annulated ; Triazines, benzofuro- and benzothieno- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Donor-Substituted Benzoitriles as Side-Chain Dienophiles in the Intramolecular [4+2] Cycloaddition with Inverse Electron DemandExpanding the scope of the intramolecular Diels-Alder reaction of 1,2,4,5-tetrazines to include donor-substituted benzonitriles as side-chain dienophiles we describe synthetic routes to novel fused heterotricycles such as the benzofuro[3,2-e]-1,2,4-triazines 11a, b and the benzothieno[3,2-e]-1,2,4-triazines 14a, b, and 17. The doubly annulated pyrazines 22 and 23 are constructed by a subsequent second intramolecular Diels-Alder cycloaddition of the benzonitrile moiety with the fused 1,2,4-triazine system, starting from 11a and 14a.
    Notizen: Unter Einschluß donorsubstituierter Benzonitrile als Seitenkettendienophile haben wir die Anwendungsbreite der intramolekularen Diels-Alder-Reaktion von 1,2,4,5-Tetrazinen erweitert und beschreiben Synthesewege zu neuen anellierten Heterotricyclen wie den Benzofuro[3,2-e]-1,2,4-triazinen 11a, b und den Benzothieno[3,2-e]-1,2,4-triazinen 14a, b sowie 17. Die doppelt anellierten Pyrazine 22 und 23 lassen sich durch eine nachfolgende zweite intramolekulare Benzonitril/1,2,4-Triazin-Diels-Alder-Cycloaddition mit 11a bzw. 14a als Edukten herstellen.
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  • 78
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2147-2157 
    ISSN: 0009-2940
    Schlagwort(e): 1,3-Dipolar cycloadditions, intramolecular ; Nitrile oxides ; Regioselectivity ; Furanophanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Intramolecular Cycloadditions with Nitrile Oxides: Investigtions towards the Synthesis of HeterophanesThe intramolecular cycloaddition reactions of the nitrile oxides 30a-d, 35, 36, and 47, obtained in situ from the 2,5-difunctional furan hydroximoyl chlorides 12a, b, 18 and the nitro compounds 9c, d, 21, 29, are described. With 30c the expected isoxazolofuranophane of type 31 is formed in acceptable yield; the additionally formed regioisomer 32c and the dimer 34c are very minor products in this case. Whereas the highest homologue 30d gives a complex product mixture with small amounts of 31 d and the macrocycle 34d as the only identified compounds, the derivatives bearing a shorter side chain (30a, b; n = 1, 2) give rise to the exclusive reaction of the dipole with a double bond of the furan system (to give 33a, b). The same behavior is observed in the case of the electronically and sterically modified dipole systems 35/36 and 47, resp.; in spite of the much more favorable conditions for the formation of cyclophanes the cycloadditions result in the exclusive formation of the heterotricycles 41, 42 and 49. Possible preparative applications of the isomeric cycloaddition compounds are discussed.
    Notizen: Die intramolekularen Cycloadditionsreaktionen der aus 2,5-difunktionellen Furan-Hydroximsäurechloriden (12a, b und 18) bzw. den Nitroverbindungen 9c, d, 21 und 29 in situ hergestellten Nitriloxide 30a-d, 35, 36 und 47 werden beschrieben. Eine Reaktion zu den angestrebten Isoxazolo-furanophanen des Typs 31 verläuft für 30c in brauchbarer Ausbeute; das Regioisomere 32c sowie das Dimere 34c treten hierbei nur in geringem Maße auf. Während das höchste Homologe 30d neben 31d und dem Makrocyclus 34d hauptsächlich Zersetzungsprodukte bildet, reagieren die Derivate mit kürzerer Seitenkette (30a, b; n = 1, 2) ausschließlich unter dipolarer Addition an eine Furandoppelbindung zu 33a, b. Für n = 1 entsprechen diesem Verhalten auch die elektronisch bzw. sterisch modifizierten Dipolsysteme 35/36 und 47, die trotz günstigerer Voraussetzungen für die Cyclophanbildung nur zu den Tricyclen 41, 42 bzw. 49 reagieren. Die präparativen Anwendungsmöglichkeiten der isomeren Cycloadditionsverbindungen als Synthesezwischenprodukte werden diskutiert.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 79
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2183-2185 
    ISSN: 0009-2940
    Schlagwort(e): [4 + 2] Cycloaddition ; 3,5-Dihydroxytropone ; Singlet oxygen ; Y aromaticity ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese von 3,5-DihydroxytroponWir beschreiben eine vierstufige Synthese des bisher unbekannten 3,5-Dihydroxytropons (6), die von Tropon ausgeht und eine [4 + 2]-Cycloaddition mit Singulett-Sauerstoff einschließt.
    Notizen: Starting from tropone, the hitherto unknown 3,5-dihydroxytropone (6) is prepared in a four-step synthesis including a [4 + 2] cycloaddition reaction of singlet oxygen.
    Materialart: Digitale Medien
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  • 80
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2207-2208 
    ISSN: 0009-2940
    Schlagwort(e): Allenes ; Hetero Diels-Alder reactions ; Catalysis, heterogeneous ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Some examples of cycloadditions of 1-ethoxy-1,2-propadiene with 1-oxa-1,3-dienes, catalyzed by acid-free silica gel, are reported.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 81
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 82
    ISSN: 0009-2940
    Schlagwort(e): Bisporphyrinates, cerium(IV) ; Lanthanoid porphyrins ; Metalloporphyrins ; Tetrapyrrole complexes, sandwich-like ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Metallkomplexe mit Tetrapyrrol-Liganden, LIV.  -  Synthese, Spektren, Struktur und Redox-Chemie von Cer(VI)-Bisporphyrinaten mit gleichen und verschiedenen Porphyrin-Ringen im Sandwich-SystemWeitere symmetrische Cer(IV)-Bisporphyrinate werden aus Cer-(III)-acetylacetonat und Tetraphenylporphyrin, Tetra-p-chlorphenylporphyrin, und Hexadecahydrotetrabenzporphyrin hergestellt. Aus dem letzteren Porphyrin entsteht auch ein Biscer(III)-Tripeldecker; ein solcher bildet sich als einziges Produkt aus Octamethylporphyrin. Aus einem Gemisch zweier verschiedener Porphyrine, nämlich Octaethylporphyrin [H2(OEP)], und Tetraphenyl-porphyrin [H2(TPP)] oder Tetra-p-chlorphenylporphyrin [H2-(TClP)] erhält man neben den symmetrischen Spezies Ce(OEP)2 und Ce(TPP)2 die unsymmetrischen („gemischten“) Doppeldecker Ce(OEP)(TPP) oder Ce(OEP)(TClP), die verschiedene Porphyrin-Ringe im Sandwich-System haben und sich trennen lassen. Die Kristallstrukturanalyse von Ce(OEP)(TPP) zeigt CeIV in quadratisch-antiprismatischer Umgebung der Pyrrol-N-Atome der Porphyrin-Ringe. Während die IR- und NMR-Spektren der unsymmetrischen Doppeldecker-Überlagerungen der Spektren, die einzelnen Ringe darstellen, zeigen ihre UV/VIS-Spektren und die cyclischen Voltammogramme, daß die zwei unterschiedlichen Porphyrin-Ringe sich wie ein gemeinsames π-Elektronensystem verhalten. Die Darstellung der π-Kation-Radikal-Salze [Ce(OEP)2]-ClO4 und [Ce(OEP)(TPP)]SbCl6 wird ebenfalls beschrieben. In letzterem scheint sich das Defektelektron bevorzugt im OEP-Ring aufzuhalten.
    Notizen: Further symmetrical cerium(IV) bisporphyrinates are prepared from cerium(III) acetylacetonate and tetraphenylporphyrin, tetra-p-chlorophenylporphyrin, and hexadecahydrotetrabenzporphyrin. In the latter case, a biscerium(III) triple-decker is also found which is the only product in the case of octamethylporphyrin. From a mixture of two different porphyrins, namely octaethylporphyrin [H2(OEP)] and either tetraphenylporphyrin [H2(TPP)] or tetra-p-chlorophenylporphyrin [H2(TClP)], besides the symmetrical species Ce(OEP)2 and Ce(TPP)2, the unsymmetrical (“mixed”) double-deckers Ce(OEP)(TPP) or Ce(OEP)(TClP) are obtained which have different porphyrin rings in the sandwich system and can be separated by chromatography. The crystal structure analysis of Ce(OEP)(TPP) shows CeIV in a square-antiprismatic geometry of the pyrrole N atoms of the porphyrin rings. While the IR and NMR spectra of the unsymmetrical double-deckers are superpositions of the spectra of the individual rings, their UV/VIS spectra and cyclic voltammograms indicate that the two porphyrin rings behave as a common π-electron system. The preparation of the π-cation radical salts [Ce(OEP)2]ClO4 and [Ce(OEP)(TPP)]SbCl6 is also described. In the latter, the defect electron seems to reside preferentially in the OEP ring.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 83
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2261-2264 
    ISSN: 0009-2940
    Schlagwort(e): Iron, thiocarbonyl complex ; Iron-tin bond ; NMR, 13C-, 17O-, and 119Sn ; Dynamic molecules ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Formation of Fe-Sn Bonds by the Reaction of Tris(trimethylstannyl)amine with Fe(CO)5 and Fe(CO)4CS; 13C-, 17O-, and 119Sn-NMR-Spectroscopic StudiesThe reaction between N(SnMe3)3 and Fe(CO)5 gives the known complex cis-Fe(CO)4(SnMe3)2 (1) in high yield. In the analogous reaction of Fe(CO)4CS the complex fac-Fe(CO)3(CS)(SnMe3)2 (2) is obtained together with small amounts of 1. In addition to the 13C-NMR data, the 17O- and 119Sn-NMR measurements proved particularly useful for studying the dynamic behaviour of 1 and 2.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 84
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2273-2274 
    ISSN: 0009-2940
    Schlagwort(e): Fluorine, application in organometallic chemistry ; Rhenocene(V)-trichloride ; Rhenocene(VII)-dichloride trication ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Dichlorobis(η5-cyclopentadienyl)rhenium(VII) Tris(hexafluoroantimonate): Synthesis of the First Rhenocene(VII) Dichloride CationRhenocene trichloride ([Cp2ReCl2]⊕ Cl⊖, 1) reacts with one equivalent of AgSbF6 and three equivalents of SbF5 to provide [Cp2ReCl2]3⊕[SbF6]⊖3 (2) in high yield. 2 contains the first rhenocene(VII) dichloride cation and is the first member of a 16-electron group-7 species of the type [Cp2MCl2]n⊕ [EF6]n⊖ (M = Ti, Zr, Hf: n = 0; M = V, Nb: n = 1; M = Mo, W: n = 2; M = Re: n = 3; E = As, Sb).
    Materialart: Digitale Medien
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  • 85
    ISSN: 0009-2940
    Schlagwort(e): Manganese complexes ; Thiophosphinito complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Metal-Containing Heterocycles: Preparation, Properties, Reactions, LXVII.  -  Stereochemical Impacts on the Transition of Monomeric Thiophosphinito Manganese Compounds to the Dimeric Complexes The η2-thiophosphinito manganese complexes (3d, e) and the dimeric complexes (4a-c, f) are obtained from BrMn(CO)5 (1) and the secondary phosphane sulfides R2P(S)H (2a-f) [R = Me (a), Et (b), n-Pr (c), i-Pr (d), Cy (e), Ph (f)] in the presence of the auxiliary base Et(i-Pr)2N with elimination of CO. For the kinetic stabilization of 3d, e sterically demanding substituents R at the phosphorus are suitable. The Mn—S bond in 3e is easily cleaved under CO pressure (100 bar) resulting in the formation of (5e). The reaction 3e ⇆ 5e is reversible.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 86
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2283-2287 
    ISSN: 0009-2940
    Schlagwort(e): Indium, trialkyl derivatives ; Dialkylchloroindium ; Alkyldichloroindium ; Alkylindium dialkylamides ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and Properties of iPr2InCl, iPrInCl2, and (iPr2InHRtBu)2The reactions of triisopropylindium (1) with half an equivalent or two equivalents of indium (III) chloride leads to iPr2InCl (2) and iPrInCl2 (3), respectively. (iPr2InNHtBu)2 (4) can be synthesized from 2 and LiNHtBu. According to NMR, IR, and RE studies, 2-4 from dimers in solution and solid state. The X-ray analysis of 4 is reported.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 87
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2311-2317 
    ISSN: 0009-2940
    Schlagwort(e): Allenes, 1,3-diamino- and 1-amino-3-thio- ; Propene iminium salts ; Propyne iminium salts ; MO calculations ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Propyne Iminium Salts: Ambifunctional reactivity reactivity towards Sulfur and Nitrogen NucleophilesPropyne iminium ions 2a-d have been studied by both ab initio (3-21G//3-21G for 2a) and MNDO calculations (2a-d). It is found that the amino group stabilizes the propargyl cation structure at the expense of the allenyl cation structure. Furthermore, the highest positive charge density is located at the amino-substituted carbon atom.  -  Reactions of 2-propyne iminium triflates 6a, b with thiols, thiolates, morpholine, lithium morpholide, and phenylhydrazine have been investigated. C-1 attack at 6, expected under kinetically controlled conditions, is observed in a few cases only. In all other cases, products resulting from C-3 attack takes place leading either to 1,3-donorsubstituted allenes (8, 10, 12) in the absence of proton sources or to their C-2-protonated forms (9, 11, 13-15) otherwise.
    Notizen: Für die Propiniminium-Ionen 2a-d werden ab-initio- (3-21G//3-21G für 2a) und MNDO-Rechnungen (2a-d) durchgeführt. Danach stabilisiert die Aminogruppe die Propargylkation- eindeutig gegenüber der Allenylkation-Struktur. Die höchste positive Ladungsdichte befindet sich am aminosubstituierten Kohlenstoffatom.  -  Umsetzungen der 2-Propiniminium-triflate 6a, b mit Thiolen, Thiolaten, Morpholin, Lithium-morpholid und Phenylhydrazin zeigen, daß nur in einigen Fällen unter kinetisch kontrollierten Bedingungen der erwartete C-1-Angriff erfolgt, ansonsten wird C-3-Angriff gefunden. Letzterer führt in Abwesenheit von Protonquellen zu 1,3-donorsubstituierten Allenen (8, 10, 12), andernfalls entstehen deren C-2-protonierte Formen (9, 11, 13-15).
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 88
    ISSN: 0009-2940
    Schlagwort(e): Diels-Alder reactions, intramolecular ; Allenecarboxyamides, N-(hetarylmethyl)- ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Cycloadditons, 17.  -  Influence of Methyl and Phenyl Groups in the Allenic ω-Position on the Thermally Induced Isomerizations of N-[2-Furanyl-(Thienyl-, Pyrrolyl-)methyl] allenecaboxamindesThe N-(2-hetarylmethyl)-1,2-alkadienecarboxamides 9a-q were synthesized by the ylide route, and their readiness to participate in the intramolecular Diels-Alder reaction was studied. Whereas the pyrrole derivatives 9p and 9q and the thiophene derivative 9o without directly bonded phenyl nuclei only decompose, the thiophene allenes 9m and 9n form the “normal” tricycles 12a and 12b by reaction of their amide phenyl nucleus (R1 = Ph). In all N-furfurylallenecarboxamides 9a-1 the furan nucleus is involved in the intramolecular Diels-Alder reaction, irrespective of the amine substituent R1. The furan nucleus reacts in all cases with the terminal allenic double bond to form the oxatricycles 10a-1 containing a six-membered lactam moiety. Reaction with the first allenic double bond (formation of 11c, d, and g) only takes place, when the reaction with the other double bond is slowed down by one or two methyl groups in the ω-position and the formation of 11 is not prevented by a methyl group in the furan 5-position.
    Notizen: Die N-(2-Heteroarylmethyl)-1,2-alkadiencarboxamide 9a-q werden auf dem Ylid-Weg synthetisiert und auf ihre Bereitschaft zur intramolekularen Diels-Alder-Reaktion untersucht. Die Pyrrolderivate 9p und 9q und das Thiophen-Derivat 9o ohne direkt gebundenen Phenylkern zeigen lediglich Zersetzung, während die Thiophen-Allene 9m und 9n durch Reaktion ihrer Amid-Phenylkerne (R1 = Ph) die „normalen“ Tricyclen 12a und 12b bilden. In allen Furfuryl-allencarboxamiden (9a-1) geht der Furankern die intramolekulare Diels-Alder-Reaktion ein, unabhängig von der Art des Aminsubstituenten R1. Der Furankern reagiert in allen Fällen mit der endständigen Doppelbindung zu den Oxatricyclen 10a-1 mit sechsgliedrigem Lactamteil. Reaktion mit der ersten allenischen Doppelbindung (s. Bildung von 11c,d und g) wird daneben nur beobachtet, wenn durch Einbau von Methyl-gruppen in die ω-Position die Reaktion mit der endständigen Doppelbindung stark verlangsamt und die Bildung von 11 nicht durch eine Methylgruppe in der Furan-5-Position verhindert wird.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 89
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2377-2389 
    ISSN: 0009-2940
    Schlagwort(e): EPC syntheses ; Δ4-1,3-Oxazoline, derivatives ; Simmons-Smith reaction ; Sakurai reaction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Cycloadditions to the Double Bond of Methyl (R)-2-tert-Butyl-Δs4-1,3-oxazoline-3-carboxylates1The title compounds (with or without an additional substituent, such as methyl or vinyl, in the 5-position) are allowed to react with peracids (→ dihydroxy derivatives 3), with cyclopropanation reagents (such as ICH2ZnEt, N2CHCOOEt, HCBr3, or HCCl3/NaOH → products 5-9), with tetracyanoethylene and OsO4 (see four- and five-membered rings in 19, 20), with dienophiles (maleic anhydride, see 23). The double bond of the oxazolines reacts in a highly diastereoselective manner, with the attack preferred from the face of the five-membered ring remote from the tert-butyl group. Some of the products obtained undergo or are subjected to further reactions (4, 12-18, 23, 29-33). Stereochemical and synthetic aspects of the reactions are discussed.
    Notizen: Die Titelverbindungen (mit und ohne zusätzliche Substituenten wie z. B. Methyl oder Vinyl in der 5-Stellung) werden mit Persäuren (→ Dihydroxyderivate 3), mit Cyclopropanierungsreagentien (wie z.B. ICH2ZnEt, N2CHCOOEt, HCBr3 oder HCCl3/NaOH → Produkte 5-9), mit Tetracyanethylen und OsO4 (→ Produkte 19-20) und mit Dienophilen (Maleinsäureanhydrid, siehe 23) umgesetzt. Die Doppelbindung der Oxazoline reagiert hoch diastereoselektiv, wobei der bevorzugte Angriff von der der tert-Butylgruppe abgewandten Seite erfolgt. Einige der erhaltenen Produkte werden weiter umgesetzt (siehe 4, 12-18, 23, 29-33). Stereochemische und synthetische Aspekte der Reaktionen werden diskutiert.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 90
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2397-2398 
    ISSN: 0009-2940
    Schlagwort(e): Nucleophilic ring opening ; Regioselectivity ; Ambident nucleophiles ; Aziridines ; Tryptamine ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions with Aziridines, 52.  -  branched-Chain Tryptamine Compounds from Indolyllithium and Activated AziridinesReaction of indolyllithium 1 with activated aziridines 2 in toluene provides the tryptamines 3 or 4 in good yields.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 91
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2407-2409 
    ISSN: 0009-2940
    Schlagwort(e): Organoantimony halides ; Aziridines, cycloaddition of, α-cleavage of ; Heterocumulenes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the presence of catalytic amounts of organoantimony(V) halides such as Ph4SbI, Ph4SbBr, Ph3SbBr2, and Ph3SbCl2, the cycloaddition of aziridines 1a-g with heterocumulenes (phenyl isothiocyanate, carbon disulfide, and carbon dioxide) selectively gave ring-expanded cycloadducts 3a-d, f, g, and 6e by α-cleavage of the aziridine rings.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 92
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1263-1275 
    ISSN: 0009-2940
    Schlagwort(e): Rotational barriers ; Olefins, strained ; Heat of hydrogenation ; Force-field calculation ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Rotational Barriers of Strained OlefinesFor the olefins 1-8 heats of formation have been derived from heats of hydrogenation and force-field calculations, respectively. From the kinetics of their geometrical isomerisation the corresponding values for the transition states were obtained. The rotational barriers, which vary by nearly 30 kcal/mol, can be described by a unique torsional potential (65.9 ± 0.9 kcal/mol), which is independent of the degree of substitution, if a correction is made for the steric energy contribution in the ground- and transition-states.
    Notizen: Für die Olefine 1-8 wurde durch Hydrierwärme-Messung bzw. Kraftfeld-Rechnung die Bildungsenthalpie der Grundzustände und durch kinetische Analyse der geometrischen Isomerisierung die der Übergangszustände ermittelt. Die um fast 30 kcal/mol variierenden Rotationsenthalpien lassen sich mit einer einheitlichen, vom Substitutionsgrad unabhängigen Torsionsbarriere (65.9 ± 0.9 kcal/mol) beschreiben, wenn um die sterischen Energiebeiträge der Grund- und Übergangszustand korrigiert wird.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 93
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1285-1290 
    ISSN: 0009-2940
    Schlagwort(e): 2-Cyclopropylidene-1,3-diones ; Hetero Diels-Alder reaction ; Cyclopropane derivatives ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: [4+2] Cycloaddition reactions of 2-Cyclopropylidene-1,3-diones with Electron-Rich AlkynesCyclopropylidenedimedone 3, an unstable and highly reactive intermediate, is trapped in a Hetero Diels-Alder reaction by the addition of ynamines 7a-c, f, ynether 7d, or phenylacetylene (7e). Hydrolysis of the resulting cycloadducts 8a-d, f leads to carboxylic acid derivatives 9a-d, f. The latter may be regarded as the result of a twofold nucleophilic substitution at a cyclopropane system according to their synthesis by the sequence 17 → 5 → 8 → 9. An opening of the cyclopropane ring takes place during hydrolysis of cycloadduct 8e producing 11. Analogously, 2-cyclopropylidene-1,3-diones 13A-13C can be generated by aminocyclopropylation of CH acids 18A-18C and subsequent deamination induced by an acylation reaction. Trapping of 13A-13C by ethoxyacetylene (7d) or ethyl vinyl ether (4) provides the analogous cycloadducts 14A, B and 15C.
    Notizen: Cyclopropylidendimedon 3, eine unbeständige und hochreaktive Zwischenstufe, kann durch Inamine 7a-c, f, Inether 7d oder Phenylacetylen (7e) in einer Hetero-Diels-Alder-Reaktion abgefangen werden. Die resultierenden Cycloaddukte 8a-d, f sind zu Carbonsäurederivaten 9a-d, f hydrolysierbar, die entsprechend ihrer Herstellung über die Reaktionssequenz 17 → 5 → 8 → 9 als Produkte einer zweifachen nucleophilen Substitution am Cyclopropan anzusehen sind. Das Cycloaddukt 8e läßt sich dagegen nur unter Öffnung des Dreirings zu 11 hydrolysieren. Analog können die 2-Cyclopropyliden-1,3-dione 13A-13C durch Aminocyclopropylierung von CH-Säuren 18A-18C und anschließende Desaminierung erzeugt und unter Zusatz von Ethoxyacetylen (7d) oder Ethylvinylether (4) zu den Cycloaddukten 14A, 14B und 15C abgefangen werden.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 94
    ISSN: 0009-2940
    Schlagwort(e): Diels-Alder reaction ; Cyclopropanes ; Dienophile reactivity ; MNDO calculations ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Diels-Alder Reactions with Diacceptor-Substituted Methylene-cyclopropanes - A New Aspect for the Twofold Nucleophilic Substitution at Cyclopropanes(Diacylmethylene)cyclopropanes 3, generated from aminocyclopropanes 1 or 2 and acetyl chloride as highly reactive intermediates, are trapped by dienes 9a-c yielding the Diels-Alder products 10. Regioisomers 10Ab and 10Ac were isolated exclusively from the interaction of 1A with pentadiene 9b and isoprene (9c), respectively. Cycloadditions with bicyclic methylenecyclopropanes 3A and 3B stereospecifically generated the 1α,6α,7β-isomers 10A and 10B. Starting from 10 the products 16, 19, and 20 are obtained by a degradation reaction of the Meldrum's acid moiety or by an oxidative ring cleavage of the cyclohexene unit. An X-ray structural analysis is reported for 10Ac. Using MNDO calculations the reactivity of various (diacylmethylene)cyclopropanes 3 as dienophiles has been studied.
    Notizen: (Diacylmethylen)cyclopropane 3, die als hochreaktive Zwischenstufen aus den Aminocyclopropanderivaten 1 bzw. 2 in Gegenwart von Acetylchlorid erzeugt werden, reagieren mit Dienen 9a-c zu Diels-Alder-Produkten 10. Aus der Umsetzung von 1A mit Pentadien 9b bzw. Isopren (9c) werden ausschließlich die Regioisomeren 10Ab und 10Ac isoliert. Die Cycloadditionen an die bicyclischen Methylencyclopropane 3A und 3B verlaufen stereospezifisch zu 1α,6α,7β-Isomeren 10A und 10B. Aus 10 lassen sich durch Abbau der Meldrumsäure bzw. durch oxidative Ringöffnung des Cyclohexens die Folgeprodukte 16,19 und 20 herstellen. Von 10Ac wurde eine Kristallstrukturanalyse angefertigt. Die Dienophil-Reaktivität von verschiedenen (Diacylmethylen)cyclopropanen 3 wird mit MNDO-Rechnungen untersucht.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 95
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1323-1328 
    ISSN: 0009-2940
    Schlagwort(e): Nitriles ; Spiro compounds ; Propellanes ; Indan derivatives ; Cycloaddition ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthese with Nitriles, LXXXII1). - On spiro [indan-pyrans] and Indene-propellanes - Adducts of 2-(Diccyanomethylene)-1,3-indandione with 1,3-Dicarbonyl CompoundsThe reactivity of 2-(dicyanomethylene)-1,3-indandione (1) towards 1,3-dicarbonyl compounds depends strongly on the nature of the CH acidic component. While the reaction with dimedone yields a spiro[chromene-4,2′indan] (2), indene-propellanes (3) are formed with acetoacetic esters. Adducts of acetylacetone and benzoylacetic acid ethyl ester to 1 have been identified as spiro[indan-2,2′-pyrans] (4). The propellane structure 3 is proven by X-ray analysis. Adducts 6 of CH acidic components with 3-(dicyanomethylene)-2-indolones 5 are used for reference measurements.
    Notizen: 2-(Dicyanmethylen)-1,3-indandion (1) zeigt gegenüber 1,3-Dicarbonylverbindungen ein überraschend differenziertes Reaktionsverhalten, das von der CH-aciden Komponente abhängt. Während mit Dimedon ein Spiro[chromen-4,2′-indan] (2) entsteht, führt die Reaktion mit Acetessigsäure-ethyl- bzw. -tert-butylester zur Bildung der Inden-propellane 3. Die Addukte von Acetylacaton und Benzoylessigsäure-ethylester an 1 erweisen sich als Spiro[indan-2,2′-pyrane] (4). Die Propellanstruktur 3 wird durch eine Röntgenkristallstrukturanalyse abgesichert. Addukte 6 CH-acider Komponenten an 3-(Dicyanmethylen)-2-indolone 5 werden für Vergleichsmessungen verwendet.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 96
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1623-1627 
    ISSN: 0009-2940
    Schlagwort(e): Binuclear complexes ; Molybdenum complexes ; Rhodium complexes ; Sulfur dioxide bridges ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Sulfur(IV) Compounds as Ligands, IX.  -  Binuclear Molybdenum-Rhodium Complexes with Sulfur Dioxide as a Bridging LigandThe hetero-binuclear complexes [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) and [MoRh(CN)(CO)3(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) are the first compounds which contain sulfur dioxide as a bridging ligand connected to two metal atoms from different groups of the periodic table. The synthesis starts from Mo(CO)3(NCMe)3 (7), which reacts with the chelating ligands Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm), and Ph2AsCH2AsPh2 (daam) to give the mononuclear precursors Mo(CO)3-(η2-Ph2E1CH2E3 Ph2)(η1-Ph2E2CH2E4 Ph2) (9-12). With [Rh2Cl2(CO)4] these are converted to the binuclear complexes [MoRhCl(CO)4(μ-Ph2E1CH2E3 Ph2)(μ-Ph2E2CH2E4Ph 2)] (15-18). Reversible CO/SO2 exchange finally gives 1-4 and the analogous bromide 5, the cyanide complex 6 is obtained from 1 and NaCN in liquid ammonia.
    Notizen: Die heteronuklearen Zweikernkomplexe [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) und [MoRh(CN)(CO)3-(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) sind die ersten Verbindungen, in denen Schwefeldioxid als Brückenligand an zwei Metallatome aus verschiedenen Gruppen des Periodensystems gebunden ist. Die Synthese geht von Mo(CO)3(NCMe)3 (7) aus, das mit den Chelatliganden Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm) und Ph2AsCH2AsPh2 (daam) zu den einkernigen Vorstufen Mo(CO)3(η2-Ph2E1CH2E3 Ph2) (η1-Ph2E2CH2E4 Ph2) (9-12) umgesetzt wird. Daraus entstehen mit [Rh2Cl2(CC)4] die Zweikernkomplexe [MoRhCl(CO)4(μ-Ph2E1CH2E3Ph 2)(μ-Ph2E2CH2E4Ph2)] (15-18). Reversibler CO/SO2-Austausch ergibt schließlich 1-4 und das analoge Bromid 5, der Cyanokomplexe 6 wird aus 1 und NaCN in flüssigem Ammoniak erhalten.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 97
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1825-1850 
    ISSN: 0009-2940
    Schlagwort(e): Organoboranes, unsaturated ; Organosilanes, unsaturated ; Aminotriorganoborates ; Cyclization ; 2,5-Dihydro-organo-1,2,5-azasilaboroles ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Organosubstituted 2,5-Dihydro-1,2,5-azasilaboroles - Methods of Preparation and Spectroscopic CharacterisationThe compounds (E)-R22R2′ElIVC(R3) = C(R4)BR25 [(E)-1a to -g] are prepared from Na[R34,5BC ≡ CR3] with ClElIVR22R2′ [ElIV = Si, Ge, Sn] or from R22R2′SiC ≡ CR3 with BR34,5 (R4,5 = CH3, C6H5). The substituted silol 1z is obtained from (CH3)2Si(C ≡ CCH3)2 and B(C2H5)3, the mixture of (Z/E)-1t from (CH3)3SiC ≡ CH and B(C2H5)3. - ClSi(CH3)2C(CH3)2C(CH3)=C(C2H5)B(C2H5)Cl (C) reacts with LiN(CH3)2 to form (CH3)2NSi(CH3) 2C(CH3)2 C(CH3)=C(C2H5) B(C2H5)N(CH3)2 (E)-1n. - (E)-1a to (E)-1g or (E)-1a or (E)-1aGe and (E)-1aSn add MNH2 (M = Na, K) to yield the compounds MNH2-1, which react to the solid alkaline metal heterocycles M-2 after liberating R2H. From. (E)-1a or (E)-1b with LiNH2 the compounds (E)-C2H5CH=CR4Si(CH3)3 (A, B) are obtained. - On heating M-2a to M-2g eliminate R5H (C2H6) and smoothly from the solid compounds M-3, from which the heterocycles (4a-f) are prepared with CH3I. The 1-phenyl derivatives 5a, b are obtained from 4a,b with aniline. M-2c,d react with HCl to give the compounds 6c,d from which 7c,d are formed after C2H6 elimination. The 5-chloro compound 4i is used for the preparation of the heterocycles 4 with R5 = H, C(CH3)3, and N(CH3)2. - All compounds 1-7 are characterized by multinuclear NMR spectroscopy, the volatile compounds 1 and 4-7 also by their mass spectra.
    Notizen: Die Verbindungen (E)-R22R2′ElIVC(R3) = C(R4)BR25 [(E)-1a bis -g] stellt man aus Na[34,5BC ≡ CR3] mit ClElIVR22R2′ [ElIV = Si, Ge, Sn] oder aus R22R2′SiC ≡ CR3 mit B34,5 (R4,5 = CH3, C6H5) her. Aus (CH3)2Si(C ≡ CCH3)2 und B(C2H5)3 sind das substituierte Silol 1z, aus (CH3)3)SiC ≡ CH und B(C2H5)3 im Autoklaven u. a. (Z/E)-1t zugänglich. - ClSi(CH3)2C(CH3) = C(C2H5)B(C2H5)Cl (C) und LiN(CH3)2 bilden (E)-1n. - (E)-1a bis (E)-1g bzw. (E)-1aGe und (E)-1aSn reagieren mit MNH2 (M = Na, K) zu den Additionsverbindungen MNH2-1, aus denen unter R2H-Abspaltung die festen Alkalimetall-Heterocyclen M-2 gebildet werden. (E)-1a und (E)-1b liefern mit LiNH2 (E)-C2H5CH=CR4Si(CH3)3 (A, B). - Aus M-2a bis M-2g erhält man beim Erhitzen unter R5H(C2H6)-Abspaltung glatt M-3, die mit CH3I zu den Heterocyclen (4a-f) reagieren. Die 1-Phenyl-Derivate 5a,b gewinnt man aus 4a,b mit Anilin. Aus M-2c,d sind mit HCl die Verbindungen 6c, d zugänglich, die unter C2H6-Abspaltung 7c,d liefern. Aus der 5-Chlor-Verbindung 4i stellt man die Heterocyclen 4 mit R5 = H, C(CH3)3 und N(CH3)2 her. - Sämtliche Verbindungen werden mit Multikern-NMR-Spektroskopie, die flüchtigen Verbindungen 1 und 4-7 auch massenspektrometrisch charakterisiert.
    Zusätzliches Material: 18 Tab.
    Materialart: Digitale Medien
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  • 98
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1857-1861 
    ISSN: 0009-2940
    Schlagwort(e): Tris(diphenylphosphino)ethene derivatives ; 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadiene derivatives ; Molybdenum complex ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Contributions to the Chemistry and Structures of Tris(diphenylphosphino)enthen and 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadieneReaction of tris(diphenylphosphino)ethene (1), obtained by basecatalyzed hydrophosphorylation of Ph2PC≡CPPh2 with Ph2PH, with 2 equivalents of H3B · OC4H8 affords 1,1-bis(boranatodi-phenylphosphonio)-2-(diphenylphosphino)ethene (2). Methylation of 1 with MeI gives the monoquaternary salt 3, the molecular structure of which was determined by X-ray crystallography. A trisulfide 4 is available by treatment of 1 with elemental sulfur. - 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadiene (5) was isolated as a byproduct in the synthesis of 1. 1,1,4,4-substitution was established by X-ray analysis of the tetrasulfide 6, obtained by treatment of 5 with elemental sulfur. Reaction of 5 with 2 equivalents of Mo(CO)6 yields the symmetrical, dinuclear complex 7.
    Notizen: Das durch basenkatalysierte Addition von Ph2PH an Ph2PC≡CPPh2 erhaltene Tris(diphenylphosphino)ethen (1) reagiert mit 2 Äquivalenten H3B · OC4H8 zu 1,1-Bis(boranatodiphenylphosphonio)-2-(diphenylphosphino)ethen (2). Die Behandlung von 1 mit Iodmethan liefert neben nicht näher untersuchten Spaltprodukten das Monoquartärsalz 3, in dem die Oniumfunktion am mittleren der drei Phosphoratome auftritt. Die Kristallstruktur wurde röntgenographisch bestimmt. Bei Behandlung von 1 mit Schwefel entsteht das Trisulfid 4.  -  Bei der Darstellung von 1 wird als Nebenprodukt 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadien (5) gebildet. Die Substitution in den 1,1,4,4-Positionen wurde ebenfalls durch Röntgenstrukturanalyse des Tetrasulfids 6 bestätigt, das durch Reaktion von 5 mit elementarem Schwefel darstellbar ist. 5, dessen Bildungsmechanismus noch nicht geklärt ist, reagiert mit 2 Äquivalenten Mo(CO)6 zum zweikernigen Molybdänkomplex 7.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 99
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1897-1900 
    ISSN: 0009-2940
    Schlagwort(e): Cyclooctatetraenyl complexes ; Cyclopentadienyl complexes ; Lanthanide amides ; Organolanthanides ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Organometallic Compounds of the Lanthanides, 50.  -  N,N,N′ - Trimethylethylenediamine Derivatives of Yttrium, Holmium, and LutetiumThe reactions of LiN(CH3)CH2CH2N(CH3)2 with YCl3, HoCl3, LuCl3, as well as with (C5H5)2YCl and (C4H9C8H7)LuCl result in the formation of the amides Li[Ln{N(CH3)CH2CH2N(CH3)2}4] [Ln = Y (1), Ho (2), Lu (3)], Li[(C5H5)2Y{N(CH3)CH2CH2N-(CH3)2}2] (4), and Li[(C4H9C8H7)Lu{N(CH3)CH2CH2N(CH3)2}2] (5), respectively. The 1H- and 13C-NMR spectra of the new compounds as well as the X-ray crystal structure of 2 are reported and discussed.
    Notizen: LiN(CH3)CH2CH2N(CH3)2 reagiert mit YCl3, HoCl3 und LuCl3, sowie mit (C5H5)2LuCl und (C4H9C8H7)LuCl unter Bildung der homoleptischen Amide Li[Ln{N(CH3)CH2CH2N(CH3)2}4] [Ln = Y (1), Ho (2), Lu (3)], sowie von Li[(C5H5)2Y{N(CH3)CH2-CH2N(CH3)2}2] (4) und Li[(C4H9C8H7)Lu{N(CH3)CH2CH2N-(CH3)2}2] (5). Die 1H- und 13C-NMR-Spektren der neuen Verbindungen und die Einkristall-Röntgenstrukturanalyse von 2 werden beschrieben und diskutiert.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 100
    ISSN: 0009-2940
    Schlagwort(e): Heterobimetallic complexes, alkyne-bridged ; Carbonyl complexes ; Molybdenum ; Tungsten ; Rhenium ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Hydrocarbon-Bridged Metal Complexes, XII.  -  Nucleophilic Addition of Carbonylmetallates to Cationic Alkyne Molybdenum Complexes: A Rational Way to Heterobimetallic Tetrahedranes MM′C2 (M = Mo, W; M′ = Re, Mn, Mo)The reactions of cationic alkyne complexes [Cp(L1)(L2)M(RC≡CR)]+ (L1 = CO, PR3, P(OMe)3; L2 = C2Me2, CO, P(OMe)3; M = Mo, W) with [Re(CO)5]- or [Mn(CO)5]- give heterobimetallic tetrahedranes Cp(OC)2M(μ2-η2:η2-RC≡CR)M′(CO)3L1 (M = Mo, W; M′ = Re, Mn) and Cp(OC)2Mo(μ2-η2:η2-MeC≡CMe)Re(CO)2[P(OMe)3]2. Similarly, the reaction of [Cp(OC)Mo(RC≡CR)2]+ or [Cp(Ph3P)(OC)Mo(RC≡CR)]+ with [CpW(CO)3]- provides a rational synthesis of Cp(OC)2Mo(μ2-η2:η2-RC≡CR)W(CO)2Cp. The dimetallatetrahedranes contain a semibridging CO group. The structures of Cp(OC)2Mo(μ2-η2:η2-H3CC≡CCH3)Re(CO)4 and Cp(OC)2Mo(μ2-η2:η2-H3CC≡CCH3)Re(CO)2[P(OMe)3]2 have been determined by X-ray crystallography.
    Notizen: Die Umsetzung der kationischen Alkin-Komplexe [Cp-(L1)(L2)M(RC≡CR)]+ (L1 = CO, PR3, P(OMe)3; L2 = C2Me2, CO, P(OMe)3, M = Mo, W) mit [Re(CO)5]- oder [Mn(CO)5]- liefert die heterodimetallischen Tetrahedrane Cp(OC)2M(μ2-η2:η2-RC≡CR)M′(CO)3L1 (M = Mo, W;M′ = Re, Mn) und Cp(OC)2-(μ2-η2:η2-MeC≡CMe)Re(CO)2[P(OMe)3]2. Ebenso lassen sich in gezielter Weise aus [Cp(OC)Mo(RC≡CR)2]+ oder [Cp(Ph3P)-(OC)Mo(RC≡CR)]+ und [CpW(CO)3]- die Alkin-verbrückten Komplexe Cp(OC)2Mo(μ2-η2:η2-RC≡CR)W(CO)2Cp aufbauen. Die Dimetallatetrahedrane enthalten stets eine semiverbrückende CO-Gruppe. Die Strukturen von Cp(OC)2Mo(μ2-η2:η2-H3C-C≡CCH3)Re(CO)4 und Cp(OC)2Mo(μ2-η2:η2-H3CC≡CCH3)-Re(CO)2[P(OMe)3]2 wurden röntgenographisch bestimmt.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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