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  • 1980-1984  (7,847)
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  • Inorganic Chemistry  (12,695)
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  • Cat
  • Insulin
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  • 1
    Electronic Resource
    Electronic Resource
    Studies on acute glucose-induced aldosterone suppression: Role of renin-angiotensin system (1984)
    Springer
    Journal of molecular medicine 62 (1984), S. 213-217 
    Details
    ISSN: 1432-1440
    Keywords: Aldosterone ; Glucose ; Insulin ; Potassium ; Renin-angiotensin system ; Cortisol ; Captopril
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Glucose loading is known to cause acute suppression of plasma aldosterone and stimulation of plasma renin activity. The relative contribution of variations in circulating angiotensin II to the regulation of aldosterone secretion following glucose loading was assessed in ten normal subjects. The effects of a standard oral glucose loading test (100 g) on plasma concentrations of glucose, insulin, potassium, aldosterone, renin activity and cortisol were studied (a) under basal conditions, and (b) after inhibition of angiotensin II with the converting enzyme inhibitor captopril (50 mg t.i.d. during 3 days). Under basal conditions the acute increase in plasma glucose and insulin after glucose loading was accompanied by a significant decrease (P〈0.01) in plasma cortisol and aldosterone and by a significant increase in plasma renin activity (P〈0.01); plasma potassium was decreased slightly but not significantly. Following captopril treatment preloading plasma renin activity was increased significantly, most probably reflecting an effective reduction of angiotensin II. Glucose loading caused a similar suppression of plasma aldosterone, as observed under basal conditions. This observation suggests that renin activation does not substantially contribute to the acute regulation of plasma aldosterone after an oral glucose load.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01721046
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  • 2
    Electronic Resource
    Electronic Resource
    Neurotensin — Was ist gesichert über seine Rolle als Hormon im Magen-Darmtrakt? (1984)
    Springer
    Journal of molecular medicine 62 (1984), S. 523-530 
    Details
    ISSN: 1432-1440
    Keywords: Neurotensin ; Gastrointestinal hormones ; Gastric secretion ; Pancreatic secretion ; Motility ; Insulin ; Glucagon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neurotensin is a tridecapeptide originally isolated and characterized from bovine hypothalamus and later, in identical form, from bovine and human intestine. In the rat about 85% of immunoreactive neurotensin is found in the gut and about 10% in the brain. When an antibody specific for the amino terminal region of neurotensin was used the highest concentrations were found in the mucosa of the ileum, while an antibody specific for the biologically active region, the carboxyl terminus, also detected large amounts in the mucosa of the upper gastrointestinal tract. After a meal neurotensin — as measured by carboxyl terminal antibodies — rises after 5 min, a time in which the chymus has not yet reached the ileum, the main source of whole neurotensin. It is therefore possible that the carboxyl terminal molecules of neurotensin, found in the upper gastrointestinal tract, play an important physiological role. In plasma, neurotensin is rapidly degraded into smaller amino terminal and therefore biologically inactive molecules. Increases of carboxyl terminal neurotensin have been found in plasma in only a very few studies. The nature of this immunoreactive material has not yet been established. Therefore, the physiological role of neurotensin as a circulating hormone is unknown. Potential actions of neurotensin include thermoregulation, regulation of hormone release from brain (pituitary hormones) and gut (glucagon, insulin, somatostatin, pancreatic polypeptide), increase of vascular permeability, vasodilatation, inhibition of gastric acid secretion, stimulation of pancreatic secretion and changes of gut motility from the fasting to the fed type.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01727746
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  • 3
    Electronic Resource
    Electronic Resource
    Effect of continuous and oscillatory portal vein insulin infusion upon glucose-induced insulin release in rats (1984)
    Springer
    Research in experimental medicine 184 (1984), S. 67-71 
    Details
    ISSN: 1433-8580
    Keywords: Oscillations ; Insulin ; Glucose
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The present study was designed to determine the effect of low dose continuous and oscillatory intraportal insulin infusions upon subsequent glucose-induced insulin release. In overnight-fasted and anesthetized rats with indwelling catheters in the jugular vein, carotic artery, and mesenteric vein insulin was infused intraportally for 3 h via the mesenteric vein catheter at a continuous rate of 45 µU/kg·min, or the same amount of insulin was administered at alternating high (72 µU/kg·min) and low infusion rates (18 µU/kg·min), respectively, in 2-, 4-, 8-, and 16-min cycles (oscillatory infusions). Another group received a continuous infusion of saline. Glucose (0.4 g/kg) was given i.v. 30 min after the end of the insulin or saline infusion. During the 3-h infusion of insulin or saline the peripheral glucose level remained unchanged in all groups. In response to the i.v. glucose load peripheral arterial plasma insulin levels were significantly elevated after preceding oscillatory infusions compared to the continuous insulin infusion. As compared to the group receiving saline the glucose-induced insulin response after continuous insulin infusion was significantly reduced. The plasma glucose responses were not different except for inexplicably elevated glucose levels in the 4-min cycle group. No difference was observed for plasma glucagon levels in all groups. The present data demonstrate an augmented responsiveness of theβ-cell to glucose after a preceding oscillatory infusion of insulin and an impaired responsiveness to glucose after continuous insulin infusion. This indicates that an oscillatory insulin release might be of importance for an adequate regulation ofβ-cell function.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01852224
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  • 4
    Electronic Resource
    Electronic Resource
    The blood vessels of the cat girdle placenta. Observations on corosion casts, scanning electron microscopical and histological studies (1984)
    Springer
    Anatomy and embryology 170 (1984), S. 209-216 
    Details
    ISSN: 1432-0568
    Keywords: Placenta ; Fetal microvasculature ; Corrosion casts ; Scanning electron microscopy ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The fetal microvascular architecture of the feline near-term placenta was investigated using scanning electron micrographs of partially fractured corrosion casts from plastic-filled vessels. The findings were compared with those on corresponding semithin histological sections. The branches of both umbilical arteries and veins roughly follow a course parallel to the zonary girdle on the allantochorionic side of the feline placenta in an acute-angled pattern of ramifications. They join the double-layered capilary networks in the chorionic lamellae of the labyrinth, which generally exhibit a chorio-uterine orientation and are partially twirled. On the allantochorionic side of the labyrinth, these fetal capillary networks are “suspended” on the maternal stem-artery-system of the placenta; on the uterine side, they have peduncular or tuft-like endings of capillary loops and are flattened by the uterine septa, which at this level converge into the maternal veins. The chorionic capillary lamellae have a variable breadth and length and therefore need shorter or longer arterioles and venules from the allantochorionic side to become irrigated at any level of the labyrinth. As a result, the feline placenta is characterized by a generally one-way crosscurrent type of materno-fetal blood flow.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00319006
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  • 5
    Electronic Resource
    Electronic Resource
    An anatomical study of the projections from the dorsal column nuclei to the midbrain in cat (1984)
    Springer
    Anatomy and embryology 170 (1984), S. 29-43 
    Details
    ISSN: 1432-0568
    Keywords: Anatomy ; Anterograde tracing ; Dorsal column nuclei ; Midbrain ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The termination of the fibers from the dorsal column nuclei (DCN) to the midbrain has been investigated in the cat with the degeneration method, the anterograde horseradish peroxidase (HRP) method and autoradiography after 3H-leucine injections. The results show that the DCN project to several midbrain regions. The external nucleus of the inferior colliculus (IX) receives the heaviest projection from both the gracile and cuneate nuclei. The DCN fibers form three joint terminal zones in IX. Each terminal zone contains clusters with dense aggregations of DCN fibers. Fairly dense terminal networks are found in the posterior pretectal nucleus (PP) and the compact part of the anterior pretectal nucleus (PAc) as well. More scattered DCN fibers are present in the cuneiform nucleus (CF), the lateral part of the periaqueductal gray (PAG1), the red nucleus (NR), the nucleus of the brachium of the inferior colliculus (B), the mesencephalic reticular formation (MRF) and the intermediate and deep layers of the superior colliculus (SI, SP). The projections to all regions are mainly contralateral. Most of the few ipsilateral fibers terminate in IX. A somatotopic organization was seen in IX and NR. The gracile fibers terminate preferentially in the caudal and lateral part of IX and the cuneate ones preferentially in its rostral and medial part. In the red nucleus the gracile fibers terminate ventral to the cuneate ones. In the pretectal region there was a predominance for gracile fibers. There also appeared to be quantitative differences in the projections from various levels of the gracile nucleus, with more midbrain projecting fibers originating in the rostral than in the middle and caudal parts of the nucleus.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00319455
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  • 6
    Electronic Resource
    Electronic Resource
    Anatomy of the cecum of the cat (1984)
    Springer
    Anatomy and embryology 170 (1984), S. 177-186 
    Details
    ISSN: 1432-0568
    Keywords: Cecum ; Cat ; Macroscopic anatomy ; Light, scanning and transmission electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In a series of comparative anatomical studies on the ceca of various mammals the cat was chosen as representative of a “typical” carnivore. In the domestic cat, the cecum is conspicuously small and macroscopically relatively undifferentiated in comparison to most herbivores. Microscopically (light, scanning and transmission electron microscopy), however, it is characterized by an abundance of goblet cells and enterocytes rich in organelles, suggestive of functional activity. In addition to the morphological description, which also includes arterial supply and mesenteries of the cecum, the discussion is focussed on 1) the possible functional significance of the numerous goblet cells 2) a general categorization of the different types of ileal-caeco-colical junctions and 3) speculations concerning the justification for considering the carnivore cecum as being rudimentary.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00319003
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  • 7
    Electronic Resource
    Electronic Resource
    The termination of spinomesencephalic fibers in cat (1984)
    Springer
    Anatomy and embryology 170 (1984), S. 265-277 
    Details
    ISSN: 1432-0568
    Keywords: Midbrain ; Spinal cord ; Cat ; Degeneration-HRP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The projections to the midbrain from the spinal cord have been investigated in the cat with the degeneration technique and by using horseradish peroxidase (HRP) as an anterograde tracer. Two types of spinal cord lesions were performed: 1) Cordotomies at cervical or thoracic levels transecting the ventral and lateral funiculi. 2) Transections of the ventral, ventrolateral, dorsolateral or dorsal funiculus, respectively, at cervical levels. In the anterograde tracing experiments HRP was injected into the spinal cord at cervical, lumbar or sacral levels. The results show large projections to the lateral and ventrolateral parts of the periaqueductal gray (PAG1), the posterior pretectal nucleus (PP) and the nucleus of Darkschewitsch (D). More moderate projections go to the medial division of the periaqueductal gray (PAGm), the cuneiform nucleus (CF), the mesencephalic reticular formation (MRF), lateral part of the deep layer of the superio colliculus (SP) and magnocellular medial geniculate nucleus (GMmc), while scattered spinal fibers are present in the dorsal part of the periaqueductal gray (PAGd), the external inferior collicular nucleus (IX), the intermediate layer of the superior colliculus (SI), the lateral part of the red nucleus (NR) and in the Edinger-Westphal portion of the oculomotor nucleus (3). In addition a few fibers are present in the interstitial nucleus of Cajal (CA) and anterior pretectal nucleus (PAc). The results indicate that at midcervical levels most of the spinomesencephalic fibers ascend in the ventral funiculus, with only a moderate fraction ascending in the ventral half of the lateral funiculus. Almost no fibers ascend in the dorso-lateral funiculus and none appear to pass in the dorsal funiculus. No distinct somatotopic pattern was found in the spinomesencephalic projections, but more fibers from cervicobrachial segments terminate in the rostral than in the caudal parts of the terminal fields in PAG, CF, SP and IX, while the lumbar fibers were more numberous in the caudal parts. PP seems to receive spinal fibers mainly from the caudal half of the cord.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00318730
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  • 8
    Electronic Resource
    Electronic Resource
    Effect of contact material on vibration-induced insulin aggregation (1984)
    Springer
    Diabetologia 27 (1984), S. 373-378 
    Details
    ISSN: 1432-0428
    Keywords: Insulin ; administration and dosage ; therapeutic use ; insulin infusion devices
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The tendency of insulin to form insoluble aggregates is a major obstacle to the development of implantable insulin infusion systems for treatment of insulin-deficient diabetic patients. A test system was developed to examine the kinetics of insulin aggregation under controlled conditions of temperature, vibration and contact material in an effort to provide design criteria for minimising aggregation. The contact materials tested were all potentially suitable for pump reservoirs on engineering criteria and included metals (stainless steel, titanium and a titanium alloy) and various plastics (polypropylene, polytetrafluoroethylene, Polyvinylchloride, polyamide, cellulose butyrate and silicone elastomer). The rate of insulin aggregation was markedly affected by the nature of the contact material. Hydrophilic materials, particularly polyamide and cellulose butyrate (2% of total insulin aggregated after 96 h vibration), appeared more compatible with insulin stability than did hydrophobic ones, such as polypropylene (16% aggregation) and Polyvinylchloride (37% aggregation). A specially formulated ‘pump’ insulin preparation, stabilised by addition of polyethylenepolypropyleneglycol, was significantly superior (three to five times more stable) to a regular neutral insulin formulation under most, but not all, conditions. Standard clinical syringes (polypropylene) performed poorly with both insulin formulations but especially with the neutral regular insulin (100% aggregation after 96 h vibration). In addition to physical aggregates, significant amounts (5%–30%) of the insulin remaining in solution were no longer detectable by immuno- or receptorassay in all materials tested. Appropriate combinations of insulin formulations and materials can minimise insulin aggregation and denaturation, but since the mechanisms involved are as yet poorly understood, realistic testing of proposed reservoir components and insulin formulations must be a prerequisite in insulin infusion pump planning and design. These testing procedures should be designed to test for denaturation in solution as well as for precipitation of insulin.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00304853
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  • 9
    Electronic Resource
    Electronic Resource
    Factors governing the human immune response to injected insulin (1984)
    Springer
    Diabetologia 26 (1984), S. 266-271 
    Details
    ISSN: 1432-0428
    Keywords: Insulin ; insulin antibody ; immunogenicity ; immune response genes ; haemocyanin ; HLA ; DR7 ; C2 ; C4 ; factor B ; Gm ; C-peptide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Seventy-nine patients were observed prospectively during their initial period of treatment with conventional bovine insulins. Insulin antibody levels 6 months after starting insulin therapy did not correlate with age, gender or β cell function at onset of treatment. Patients who required soluble insulin in addition to isophane insulin developed higher levels of insulin antibody. Patients bearing the HLA-B8, DR3 and C4AQO alleles had lower levels of insulin antibody, whereas those bearing DR7 produced significantly higher levels. Other alleles at the C4A, C4B, C2, factor B or Gm loci did not appear to have a significant effect on insulin antibody production. The hyporesponsiveness of B8/DR3/C4AQO-positive individuals probably reflects a non-specific abnormality of immunity whereas the enhanced responsiveness of those positive for DR7 suggests the presence of a specific immune response gene for insulin
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00283648
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  • 10
    Electronic Resource
    Electronic Resource
    Effect of co-ingestion of fat on the metabolic responses to slowly and rapidly absorbed carbohydrates (1984)
    Springer
    Diabetologia 26 (1984), S. 50-54 
    Details
    ISSN: 1432-0428
    Keywords: Insulin ; gastric inhibitory polypeptide ; insulin sensitivity ; glucose tolerance ; diabetes ; diet ; fat ; rate of carbohydrate digestion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The present study examined the acute effects of coingestion of fat (37.5 g) on the post-prandial metabolic responses to 75 g of carbohydrate which was either slowly absorbed (lentils) or rapidly absorbed (potatoes). Co-ingestion of fat resulted in a significant flattening of the post-prandial glucose curves, the effect being more pronounced for the rapidly absorbed potatoes. This was probably due to delayed gastric emptying. However, the post-prandial insulin responses to either carbohydrate were not significantly reduced by fat, suggesting that the insulin response to a given glucose concentration was potentiated in the presence of fat. The gastric inhibitory polypeptide (GIP) responses to both carbohydrates were greatly increased in the presence of fat. To investigate further the possible roles of GIP in the entero-insular axis, a 5-g bolus of glucose was injected intravenously 1 h after lentils ± fat. This was sufficient to raise the glucose levels above the threshold reported for GIP to potentiate insulin secretion. However, despite the large differences in circulating GIP levels, the insulin response to glucose was not affected by the presence of fat. These results suggest that (1) the rate of absorption of carbohydrate is a major determinant of post-prandial metabolic responses even in the presence of fat, (2) fat-stimulated GIP secretion does not potentiate glucose-induced insulin secretion, and (3) the potentiation of the insulin response to glucose when carbohydrate is co-ingested with fat is consistent with the well-documented insulin resistance associated with high fat diets.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00252263
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  • 11
    Electronic Resource
    Electronic Resource
    Evidence for post-transcriptional regulation by insulin of 3-hydroxy-3-methylglutaryl coenzyme A reductase and sterol synthesis in human mononuclear leucocytes (1984)
    Springer
    Diabetologia 26 (1984), S. 366-369 
    Details
    ISSN: 1432-0428
    Keywords: Insulin ; 3-hydroxy-3-methylglutaryl coenzyme A ; sterol synthesis ; human mononuclear leucocytes ; post-transcriptional regulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Incubation of freshly isolated human mononuclear leucocytes in lipid-depleted serum for 4 h resulted in a two-fold increase in 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) reductase activity. Insulin, when added to the incubation medium at concentrations of 10 and 100 nmol/l at zero time, caused additional increases in the enzyme activity of 30% and 37%, respectively. The hormone action was not immediate because no effect was observed when insulin was added at 4 h and activity examined thereafter. Under these conditions sterol synthesis from 14C-acetate and tritiated water was strictly proportional to the activity of HMG-CoA reductase. Cycloheximide (20 μg/ml), a translational inhibitor of protein synthesis, prevented the insulin-mediated increase in the enzyme activity and the incorporation of 14C-acetate into sterols. Cordycepin (50 μg/ml) inhibited messenger RNA synthesis by 〉 50%, but had no inhibitory effect on the induction of HMG-CoA reductase and sterol synthesis. Low density lipoprotein (80 μg protein/ml) and complete serum blocked the induction of the enzyme and sterol synthesis from 14C-acetate caused by lipid-depleted serum. The insulin-effect, however, remained unchanged. The results suggest that insulin may regulate the de novo synthesis of HMG-CoA reductase and accordingly sterol synthesis at a post-transcriptional level.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00266038
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  • 12
    Electronic Resource
    Electronic Resource
    An autoradiographic study of topographical relationships between pallidal and cerebellar projections to the cat thalamus (1984)
    Springer
    Experimental brain research 54 (1984), S. 95-106 
    Details
    ISSN: 1432-1106
    Keywords: Cerebellothalamic projections ; Pallidothalamic projections ; Ventral nuclei of thalamus ; Autoradiography ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Injections of 3H-leucine were made in the entopeduncular nucleus or dentate nucleus of the cerebellum in eight cats. The terminal projection zones of both pathways in the thalamus were studied using the sagittal plane and their relationships to one another as well as to cytoarchitectural boundaries of thalamic nuclei were compared. The data indicate that the territories controlled by the two projection systems are almost entirely segregated. The segregation is mainly along the antero-posterior axis as the main pallidal projection zone occupies the medio-ventral VA while the main dentate projection zone lies posterior to it in the VL. Furthermore, the dorsolateral part of the VA not occupied by pallidal projections receives dentate projections. In the VM, both afferent systems terminate in the lateral part of the nucleus with pallidal territory located anteriorly and dentate territory located posteriorly, again without overlap. As the delineations of nuclear subdivisions in the ventral thalamus of the cat have been a subject of some controversy, it is suggested that the boundaries of the VA, VL and VM in the cat thalamus be defined on the basis of basal ganglia and cerebellar projection zones.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235822
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  • 13
    Electronic Resource
    Electronic Resource
    Distribution of corticospinal neurons with collaterals to lower brain stem reticular formation in cat (1984)
    Springer
    Experimental brain research 54 (1984), S. 107-120 
    Details
    ISSN: 1432-1106
    Keywords: Corticospinal collaterals ; Sensorimotor cortex ; Corticobulbar pathways ; Fluorescent tracers ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The fluorescent retrograde double-labeling technique has been used to determine whether corticospinal neurons in the cat sensorimotor cortex distribute collaterals to the lower brain stem reticular formation. In this study the fluorescent tracers Nuclear Yellow and Diamidino Yellow 2HCl were used in combination with Fast Blue. One tracer was injected unilaterally in the spinal cord and the other was injected ipsilaterally in the bulbar medial reticular formation. The distribution of the retrogradely labeled neurons was studied in the contralateral hemisphere. In the sensorimotor cortex a large population of neurons was found which were labeled from the spinal cord and were double-labeled from the brain stem. These branching neurons were concentrated in the rostromedial part of area 4 and the adjoining lateral part of area 6. In this region the percentages of corticospinal neurons which were double-labeled from the brain stem ranged from 5% laterally to 30% medially. In two cats it was demonstrated by means of the anterograde transport of HRP that the corticobulbar fibers from this region which must include the corticospinal collaterals are distributed to the reticular formation of the lower brain stem. In view of the fact that the double-labeled neurons are concentrated in the anterior part of the motor cortex, those branching neurons are in all likelihood involved in the control of neck, back and shoulder movements. This control is probably exerted by way of two routes i.e. by way of the direct corticospinal connections to spinal interneurons, and by way of the indirect cortico-reticulospinal connections established by the cortical fibers to the bulbar reticular formation. The present findings suggest that this dual control may be exerted by one and the same cell.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235823
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  • 14
    Electronic Resource
    Electronic Resource
    Specialized subregions in the cat motor cortex: Anatomical demonstration of differential projections to rostral and caudal sectors (1984)
    Springer
    Experimental brain research 53 (1984), S. 259-276 
    Details
    ISSN: 1432-1106
    Keywords: Motor cortex ; Thalamocortical ; Corticocortical ; HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary (1) Ipsilateral cortico-cortical and thalamo-cortical projections to the cat motor cortex were determined from the locations of retrogradely labeled neurons following single small intracortical injections of HRP in area 4γ. These projections were also examined by studying the distribution of anterogradely transported axonal label following multiple injections of HRP or of tritiated amino acids in areas 1–2 of SI and in area 2pri (SII). (2) The number of retrogradely labeled cells in areas 1–2 and in area 2pri differed markedly between HRP injection sites located in the precruciate (anterior sigmoid gyrus) and postcruciate (posterior sigmoid gyrus) subregions of area 4γ. These associational projections from primary and secondary somatosensory cortices were dense to postcruciate subrogions but weak to the precruciate subregions. (3) The associational projections from areas 1–2 and from area 2pri to the postcruciate subregion of area 4γ were topographically organized, but no clear topographic organization could be demonstrated for the precruciate projection. (4) Anterograde terminal labeling following injection of either HRP or tritiated amino acids into areas 1–2 and area 2pri confirmed the preferential projection of somatosensory cortex to the postcruciate subregion of motor cortex. The projection from somatosensory areas 1–2 was uniform over its terminal field, but that from area 2pri was more patchy and complex. (5) HRP injections in area 4γ gave rise to lamellae of labeled neurons in the ventrolateral nucleus of thalamus (VL). A topographic relationship was found between the site of injection and the location of the lamella of labeled neurons. (6) The percentage of retrogradely labeled neurons in the shell zone surrounding the border of the ventrolateral nucleus and the ventrobasal complex (VB) was greater following postcruciate than precruciate injections, whereas fewer retrogradely labeled neurons were found in central lateral nucleus (CL) after postcruciate injections than after precruciate injections. (7) These observations support the hypothesis that differential cortical and thalamic projections to different subregions of area 4γ may give rise to the different physiological properties of neurons observed in these subregions (Vicario et al. 1983; Martin et al. 1981).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00238155
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  • 15
    Electronic Resource
    Electronic Resource
    Pyramidal control of skin potential responses in the cat (1984)
    Springer
    Experimental brain research 54 (1984), S. 283-288 
    Details
    ISSN: 1432-1106
    Keywords: Skin potential response ; Cat ; Pyramidal tract ; Reticulospinal tracts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Pyramidal command of Skin Potential Response (SPR) was investigated in 20 cats paralyzed by gallamine and under a halothane anaesthetic. For each animal, a transection of the medulla sparing only the pyramidal tract was carried out. The pyramidal tract and Mesencephalic Reticular Formation (MRF) were stimulated before and after the transection. Results taken before transection show that the SPR can be elicited from stimulation of the pyramidal tract and the MRF. After transection, stereotaxic stimulations of the pyramidal tract still evoked the SPR even after aspiration of the medullary tissue posterior to the section and overlying the pyramids. Control reticular stimulations with higher stimulus intensities failed to evoke the SPR. These results show that stimulation of the pyramidal tract can elicit the SPR independently of reticulospinal neurons. It is hypothesized that a group of corticospinal fibers could transmit volleys having autonomic activity on preganglionic autonomic neurons of the intermediate zone of the grey matter.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00236228
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  • 16
    Electronic Resource
    Electronic Resource
    Afferents to the cortical pupillo-constrictor areas of the cat, traced with HRP (1984)
    Springer
    Experimental brain research 54 (1984), S. 377-381 
    Details
    ISSN: 1432-1106
    Keywords: Pupillo-constrictor areas ; Afferents ; HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Afferents of the cortical pupillo-constrictor areas (PCAs) of the cat were studied using the horseradish peroxidase method. PCAs receive heavy cortical inputs from areas 7, 19, 21, the lateral suprasylvian area, the splenial visual area, and subcortically from the claustrum, the intralaminar nuclei, the pulvinar-lateral posterior nuclear complex.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00236240
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  • 17
    Electronic Resource
    Electronic Resource
    The control of rapid limb movement in the cat (1984)
    Springer
    Experimental brain research 55 (1984), S. 134-144 
    Details
    ISSN: 1432-1106
    Keywords: Cat ; Tracking ; Isometric ; Updating ; Delayed feedback
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. In cats trained to track a moving display by making rapid, isometric force adjustments, responses are characterized by extremely short reaction times (60–70 ms) and a stereotyped temporal configuration. The animal uses early derivatives of display movement to scale force responses to target stimuli of different sizes according to a learned relationship between initial display motion and required force (Ghez and Vicario 1978a, 1978b). In the present study we altered that relationship by using double stimulation and delayed feedback to assess the animals' ability to update their responses. 2. In experiments where a second target stimulus followed the first after a controlled interval (15–120 ms) on random trials, the animal modified its response in the appropriate direction with little or no increase in reaction time. When the second stimulus called for a return to baseline, the animal aborted the ongoing response. When the second stimulus called for a doubling of force, the animal increased its phasic force output; however, this increase was not sufficient to reach the new target level and late responses were emitted. 3. The control response which followed each experimental double stimulation trial showed consistent differences from other controls in the amplitude of both peak force and peak dF/dt. Control responses following trials calling for a return were reduced in size; those following stimuli requiring response doubling were increased. We concluded that the experimental trials not only elicited modification of ongoing responses but also caused the animal to alter its internalized gain function relating initial display derivatives to required force. 4. In experiments where feedback was delayed after giving a first target stimulus such that the compensatory display failed to reflect the animal's initial response, the animal emitted a new updated response 70–80 ms after the first. The display trajectory which caused the cat to update its response on delayed feedback trial was identical to that of control trials with long reaction times. In this case, however, the information eliciting response updating had to be derived as a difference between the actual display trajectory and that expected by the animal, based on its experience with the tracking task. This suggests that the animal develops an internal model of display properties which is used to determine when a new response is required.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00240507
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    The transformation of cross-reinnervated slow-twitch muscle after deafferentation in the cat (1984)
    Springer
    Experimental brain research 55 (1984), S. 152-157 
    Details
    ISSN: 1432-1106
    Keywords: Deafferentation ; Cross reinnervation ; Contractile properties ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Cross-reinnervations were effected between the extensor digitorum longus and soleus muscles in the cat hind limb. At the same time dorsal root section or ganglionectomy was performed over segments L6-S1. Completeness of the deafferentation was subsequently confirmed either by dissection or by dorsal root recording. The isometric and forcevelocity properties of the muscles were measured. In animals with a unilateral cross plus deafferentation the conversion of the contractile properties of the normally slow-twitch soleus to those resembling a fast-twitch muscle was typical of that seen with an intact afferent supply. In cats with a bilateral cross-reinnervation and unilateral deafferentation there was no significant difference in the degree of transformation between the two sides. It is concluded that at least for the conversion of a slow-twitch to a fast-twitch muscle afferent feedback does not play a major role.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00240509
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  • 19
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    Electronic Resource
    Contralateral corticofugal projections to cat visual thalamus (1984)
    Springer
    Experimental brain research 53 (1984), S. 462-466 
    Details
    ISSN: 1432-1106
    Keywords: Visual cortex ; Contralateral connections ; Thalamus ; Cat ; Sub-cortical commissures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Contralateral corticofugal projections from visual cortical areas to thalamic nuclei were demonstrated in the cat using anterograde transport of tritiated proline. Thalamic nuclei receiving projections from contralateral visual cortex include both subdivisions of the lateral-posterior nucleus, the posterior nucleus of Rioch, and the posterior nuclear complex.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00238176
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  • 20
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    An HRP study of the cat's spinal respiratory motoneurones during postnatal development (1984)
    Springer
    Experimental brain research 56 (1984), S. 458-467 
    Details
    ISSN: 1432-1106
    Keywords: Cat ; Postnatal development ; Phrenic motoneurones ; Intercostal motoneurones ; Horseradish peroxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The localization and morphology of spinal respiratory motoneurones (phrenic and intercostal) were studied in the cat by retrograde labelling using Horseradish Peroxidase (HRP), at different stages of postnatal development. At birth, the distribution of the phrenic and intercostal motoneurones in the cervical and thoracic ventral horn, respectively, is similar to that observed in adult animals. At birth, the phrenic and intercartilaginous motoneurone somata have respectively 60% and 40% of their adult volume, appearing much more developed than the motoneurones involved in the motor control of limbs. During postnatal development, the phrenic and intercartilaginous motoneurones undergo a characteristic sagittal elongation without evident modification along their transverse axes. From birth, the ratio of the somatic volume to that of its corresponding motor column markedly decreases inside of the phrenic column compared to the data obtained in the limb's muscle motor columns by other authors. Similar determinations in intercostal motor columns give intermediate values between those obtained from the phrenic column and from the motor system. These results indicate that the motoneurones innervating the respiratory muscles have some specific features of development.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237986
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  • 21
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    Electronic Resource
    Brainstem afferents to the lateral geniculate nucleus of the cat (1984)
    Springer
    Experimental brain research 54 (1984), S. 253-258 
    Details
    ISSN: 1432-1106
    Keywords: Lateral geniculate nucleus ; Pretectal nuclei ; Superior colliculus ; Parabigeminal nucleus ; Reticular formation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The ascending connections from the brainstem to the dorsal division of the lateral geniculate nucleus were examined using retrograde transport of horseradish peroxidase. Labelled cells were identified in a variety of structures, including the nucleus of the optic tract (NOT), the posterior pretectal nucleus (NPP), the superior colliculus (SC), the parabigeminal nucleus (PBN), the midbrain reticular formation (MRF), locus coeruleus and nucleus sub-coeruleus, the substantia nigra (SN), and parts of the raphe complex. The projections from NOT, NPP, MRF, LC and PBN were all bilateral in origin. The most intense labelling was observed in the nucleus of the optic tract and the superior colliculus. Colliculo-geniculate cells were located primarily in the superficial gray lamina II1 and II2 of Kaneseki and Sprague (1974), but sparse labelling was also observed in lamina II3 and in statum opticum (lamina III). Consistent with the report of Harrell et al. (1982), these cells represent a morphologically diverse population, which includes stellate cells, granule cells, and both vertical and horizontal fusiform cells. A similarly diverse population of cell types contributes to the geniculate projection arising from NOT. These results confirm and extend earlier descriptions of the brainstem projections to the cat LGNd, and serve to emphasize the diversity of brainstem influences over the geniculate.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00236224
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    Neck muscle afferent input to spinocerebellar tract cells of the central cervical nucleus in the cat (1984)
    Springer
    Experimental brain research 55 (1984), S. 286-300 
    Details
    ISSN: 1432-1106
    Keywords: Central cervical nucleus ; Spinocerebellar tract ; Neck muscle afferents ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Extracellular and intracellular recordings were made from spinocerebellar tract neurones of the central cervical nucleus (CCN) in C1–C3 segments of the anaesthetized cat. These neurones were identified by antidromic activation from the cerebellar peduncle. Stimulation of the ipsilateral dorsal root elicited extracellular spikes or EPSPs with a monosynaptic latency in almost all CCN neurones in the same segment (segmental input). Late excitatory effects were also observed in about one third of CCN neurones. The monosynaptic EPSP was occasionally followed by an IPSP. The excitatory input from the dorsal root to CCN neurones was extended over several segments for some CCN neurons (extrasegmental input). Monosynaptic excitation was evoked in CCN neurones after stimulation of dorsal neck muscle nerves as well; i.e. splenius (SPL), biventer cervicis and complexus (BCC), rectus capitus dorsalis, and obliquus capitus caudalis. Thresholds for this excitation were near the threshold of the nerve, suggesting that it originated from group I fibres. The component of excitation added after strong stimulation of neck muscle nerves would be attributed to group II fibres. When a CCN neurone received excitatory input from the nerve of one muscle, it was generally not affected by stimulation of other nerves in the same segment. Such muscle specificity of segmental input was the principal pattern of connexion of neck muscle afferents with CCN neurones. In some cases, however, excitatory convergence from SPL and BCC nerves onto single CCN neurones or excitation from the SPL nerve and inhibition from the BCC nerve were also observed. Nearly half of the CCN neurones received input from one muscle nerve of the same segment and not from the afferent of the same muscle of different segments, indicating a segment specificity of input. In the remaining CCN neurones, weaker excitatory effects were induced from afferents of different segments as well. In such extrasegmental effects, inputs to CCN neurones from caudal segments predominated in frequency over those from rostral segments. The origin of extrasegmental input was generally confined to the same muscle. Low threshold muscle afferents from the SPL and BCC were intraaxonally stained with HRP. The collaterals of the stained fibre distributed branchlets and terminals to the CCN, laminae VII, VIII, and motor nuclei. Two fibres responding to local muscle prodding or stretch showed a similar morphology. The findings indicated that muscle spindle afferents from primary endings projected to the CCN.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237279
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    A physiological study of identification, axonal course and cerebellar projection of spinocerebellar tract cells in the central cervical nucleus of the cat (1984)
    Springer
    Experimental brain research 55 (1984), S. 272-285 
    Details
    ISSN: 1432-1106
    Keywords: Central cervical nucleus ; Spinocerebellar tract ; Cerebellum ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Spinocerebellar tract (SCT) neurones in and around the central cervical nucleus (CCN) were physiologically identified by antidromic activation of these cells on stimulation of the cerebellum. Among the Spinocerebellar tract cells thus identified, those ascending the contralateral spinal funiculi were found in the CCN and ventralwards, whereas those ascending the ipsilateral funiculi existed mostly dorsal to the CCN partly overlapping with crossed cells in the nucleus. Mapping sites from which CCN cells were antidromically activated showed that axons of the CCN-SCT cross at the same segment, ascend the ventral funiculus initially, the lateral funiculus at rostral C1 and the lateral border of the medulla to reach the cerebellar peduncle, enter the cerebellum mainly via the restiform body but possibly also via the superior peduncle. Systematic mapping of stimulation within the cerebellum indicated that the CCNSCT projects to the medial part of the anterior lobe and the posterior lobe bilaterally. Projection to lobules I–II was found in almost all CCN-SCT cells examined. Three fourths of CCN-SCT cells projected to the posterior lobe, as revealed by less extensive mapping. Mapping of axonal regions of the same single CCN-SCT cells showed that they project multifocally in the cerebellum, where projection to lobules I–II was common and that to other areas varied with individual cells. Conduction velocites decreased within the cerebellum probably as the result of repeated branching. Mossy fibre responses evoked on stimulation of the C2 dorsal root in cats with the transected dorsal funiculi were shown to be mediated mostly via the CCN-SCT. Mapping the field potential showed that the response was by far the largest in lobules I–II. This suggested that the terminals provided by the CCN-SCT are the densest in these lobules.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237278
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    Electronic Resource
    Endogenous peroxidase-like activity in the feline dorsal column nuclei and spinal cord (1984)
    Springer
    Experimental brain research 55 (1984), S. 325-332 
    Details
    ISSN: 1432-1106
    Keywords: Endogenous peroxidase ; Light and electron microscopy ; Spinal cord ; Dorsal column nuclei ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Endogenous peroxidase-like activity was investigated with a combined light and electron microscopical technique in 15 cats. The lateral cervical nucleus, the dorsal column nuclei, and segments C6 and L5 of the spinal cord were incubated with diaminobenzidine-tetrahydrochloride (DAB) or tetramethylbenzidine (TMB). After histochemical reaction with DAB a considerable amount of activity was found in nerve cells, astrocytes and pericytes. The neuronal labelling was mainly located in mitochondria of axon terminals and in dendrites whereas the astrocytic and pericytic activity was found in cytoplasmic dense bodies. The quantity of stained structures differed considerably between the animals. In TMB reacted tissue endogenous peroxidase-like activity was only sparsely seen. It was found mainly in frozen sections, in which the neuropil and perivascular structures sometimes contained granules and irregular filaments. The significance of the findings is discussed in relation to observations in tracer studies using horseradish peroxidase.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237283
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    Electronic Resource
    Effects of accessory optic system lesions on vestibulo-ocular and optokinetic reflexes in the cat (1984)
    Springer
    Experimental brain research 55 (1984), S. 49-59 
    Details
    ISSN: 1432-1106
    Keywords: Accessory optic system ; Vestibulo ocular reflex ; Optokinetic nystagmus ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Horizontal vestibulo-ocular reflex (VOR) and optokinetic nystagmus (OKN) were studied before and after lesions within the accessory optic system (AOS) in the cat. Post-lesion retinal input to the AOS was evaluated using the autoradiographic technique. Unilateral lesion of the lateral terminal nucleus of the AOS (LTN) and the resulting retinal deafferentation of the medial terminal nucleus of the AOS (MTN) induced a spontaneous nystagmus in the dark whose slow phase was directed ipsilaterally to the lesion. VOR gain was reduced for both directions with a maximal decrease for stimulation directed ipsilaterally to the lesion. OKN gain obtained for both directions of binocular stimulation was decreased, mainly when the stimulus was directed contralaterally to the lesion. After two postoperative weeks, spontaneous nystagmus disappeared and the VOR symmetry recovered simultaneously. A symmetrical OKN was only observed after one month. In spite of the known visual selectivity for vertical direction in LTN-MTN cells, the results of this study support a functional involvement of these nuclei in horizontal VOR and OKN.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00240497
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    Differences between cats in response properties of horizontal semicircular canal primary afferents (1984)
    Springer
    Experimental brain research 56 (1984), S. 162-166 
    Details
    ISSN: 1432-1106
    Keywords: Vestibular nerve afferents ; Semicircular canal biophysics ; Semicircular canal time constants ; Vestibular neurophysiology ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The response properties of cat horizontal canal afferents (N = 81) were characterized by three parameters: their long time constants (τ), low frequency gain constants (G1), and middle frequency gain constants (Gm). An average value of each of these parameters was calculated for each of eight animals and comparisons were made across animals. There were significant differences between individual animals in their average values of τ and Gm. There was also a significant negative correlation between τ's and Gm's. An animal with a larger average τ tended to have a smaller average Gm. We also used anatomic data on membranous canal duct diameter from the literature to independently estimate the potential effect of interanimal anatomic variability on the predicted range of τ and Gm values in a population. We then compared the data from our 81 afferents with the predictions from the anatomic data.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237453
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    Electronic Resource
    Inspiratory on-switch evoked by stimulation of the mesencephalon: Activity of phrenic and laryngeal motoneurones (1984)
    Springer
    Experimental brain research 55 (1984), S. 197-204 
    Details
    ISSN: 1432-1106
    Keywords: Phrenic and laryngeal motoneurones ; Inspiratory on-switch ; Stimulation ; Mesencephalic structures ; Patterned response ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In anaesthetized cats (chloralose-urethan) the effects of brief tetanic electrical stimulation (50 to 100 ms) of the mesencephalic central gray matter and reticular formation on the inspiratory on-switch were studied during the expiratory (E) phase on the gross and unitary activities of phrenic, laryngeal inspiratory and laryngeal expiratory nerves. On the inspiratory laryngeal and phrenic nerves, stimulation elicited a short latency gross response concomitant with the train: the inspiratory Primary Response (Prim.R.) which is followed by an inspiratory Patterned Response (Patt.R.) of longer duration which corresponded to the inspiratory on-switch. The Patt.R. generally appeared from the Prim.R. within a latent period (Silent Phase: Sil.P.) as long as 100 ms. On the expiratory laryngeal nerve, stimulation elicited a brief activation (expiratory Prim.R.) concomitant with the beginning of the inspiratory laryngeal Prim.R. and which rapidly stopped as the latter continued during the stimulus train. The inspiratory Prim.R. corresponded to a simultaneous activation of both early and late (so defined during their spontaneous discharge) inspiratory motoneurones. The laryngeal motoneurones were more strongly activated than the phrenic ones. During the inspiratory Patt.R. all the phrenic motoneurones presented a recruitment delay earlier, compared with the spontaneous one, whereas the recruitment drastically changed from an inspiratory laryngeal motoneurone to another. Thus, the two pools of motoneurones presented different properties of activation. During the inspiratory Sil.P. no concomitant expiratory laryngeal activation was observed when most of the inspiratory motoneurones were inactive. As some inspiratory laryngeal motoneurones did not stop firing, the existence of some central respiratory neurones exhibiting a similar persistent activity and subserving the inspiratory on-switch mechanisms may be hypothesized.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237270
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    Electronic Resource
    Ascending projections from the nucleus of the brachium of the inferior colliculus in the cat (1984)
    Springer
    Experimental brain research 54 (1984), S. 203-211 
    Details
    ISSN: 1432-1106
    Keywords: Ascending auditory pathway ; Inferior colliculus ; Medial geniculate body ; Cat ; Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ascending projections from the nucleus of the brachium of the inferior colliculus (NBIC) in the cat were studied by the autoradiographic tracing method. Many fibers from the NBIC ascend ipsilaterally in the lateral tegmentum along the medial border of the brachium of the inferior colliculus. At midbrain levels, fibers from the NBIC end in the superior colliculus, the pretectum, the central gray and the peripeduncular tegmental region bilaterally with ipsilateral predominance. NBIC fibers to the superior colliculus are distributed densely to laminae VI an III throughout the whole rostrocaudal extent of the colliculus. In the pretectum, NBIC fibers terminate in the anterior and medial nuclei and the nucleus of the posterior commissure. NBIC fibers to the dorsal thalamus are distributed largely ipsilaterally. Many NBIC fibers end in the dorsal and medial divisions of the medial geniculate body, but few in the ventral division. The NBIC also sends fibers to the suprageniculate, limitans and lateralis posterior nuclei and the lateral portion of the posterior nuclear complex; these regions of termination of NBIC fibers constitute, as a whole, a single NBIC recipient sector. Additionally, the NBIC sends fibers to the centralis lateralis, medialis dorsalis, paraventricular and subparafascicular nuclei of the thalamus.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00236219
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    Electronic Resource
    Locomotion in adult cats with early vestibular deprivation: Visual cue substitution (1984)
    Springer
    Experimental brain research 54 (1984), S. 395-405 
    Details
    ISSN: 1432-1106
    Keywords: Neonatal ; Bilabyrinthectomy ; Recovery ; Locomotion ; Vision ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Four cats labyrinthectomized shortly after birth (DELAB) exhibited the classical vestibular syndrome and recovery, while their motor development was otherwise unimpaired. As adults, they were tested for visual vestibular substitution in a locomotor task with either orientation requirements (tilted platforms) or balance requirements (narrow platforms). Visual motion cues or static visual cues were controlled using normal or stroboscopic lighting, or darkness. Measurements of the average speed of locomotion showed that: Although all cats increase their speed when more visual cues become available, a marked deficit occurs in darkness only in the DELAB cats. With either vestibular cues alone or static visual cues alone, cats are able to reach the same level of performance in the tilted platform test, which suggests a total visual-vestibular interchangeability in orientation. DELAB cats perform very poorly in the narrow rail test. When continuous vision is allowed in the narrow rail test the DELABs' performance rises but does not match that of the control group. A specific deficit in balance for the DELAB group is thus reduced by normal continuous vision as compared to stroboscopic vision, suggesting a significant, though imperfect, substitution of motion visual cues for the missing dynamic vestibular cues. Dynamic visual cues play only a minor role in most situations, when locomotory speed is high. This results support the view that both the vestibular and the visual system can subserve two distinct functions: dynamic information may stabilize the stance in narrow unstable situations, during slow locomotion. and static orientation cues may mainly control the direction for displacement. Possible interactions between head positioning and body orientation in the DELAB cats are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235464
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    Shortage of binocular cells in area 17 of visual cortex in cats with congenital strabismus (1984)
    Springer
    Experimental brain research 55 (1984), S. 470-482 
    Details
    ISSN: 1432-1106
    Keywords: Congenital microstrabismus ; Cat ; Visual cortex ; Binocularity ; Visual axis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Twenty-nine pigmented offspring of an innately esotropic female cat exhibited varying deficits in the number of binocular cells recorded in area 17 of the visual cortex as compared to 12 normal cats. Misalignment of the two eyes in these cats was found in the awake as well as in the paralysed state. Pupillography combined with measurements of visual disparity yielded abnormal esotropia of up to 8.4° under paralysis, which corresponds to an abnormal convergence of the freely moving eyes of up to 14° (average 7.4°). In the majority of animals cortical binocularity was found reduced by the two eyes controlling independent sets of separate units (U-shaped ocular dominance distribution) whereas in 7 cats the reduction was due to a partial loss of one eye's influence. The proportion of monocular units correlated with the degree of crossover of the visual axes (r = 0.73). Anatomical investigation of the retinofugal projections revealed normal appearance in three previously recorded cats in which more than 50% of cortical units had been monocularly driven. The small angles of esotropia and the “normal” appearance of eye position judged by the pupillary positions in the orbit of these cats, might suggest that we found an animal model for microstrabismus.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235278
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    Electroretinographic responses and retrograde changes of retinal morphology after intracranial optic nerve section. A quantitative analysis in the cat (1984)
    Springer
    Experimental brain research 55 (1984), S. 483-493 
    Details
    ISSN: 1432-1106
    Keywords: Optic nerve section ; Cat ; Pattern ERG ; Retinal morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Previous experiments have shown that the ERG response to alternating gratings vanishes gradually within 4 months after transection of the optic nerve, changes begin after 2–3 weeks. The response to gratings of low spatial frequencies deteriorates earlier than the response to gratings of high spatial frequencies (Maffei and Fiorentini 1981). Quantitative analysis of ganglion cell sizes in retinal wholemounts shows that ganglion cell shrinkage and ganglion cell loss begin at three weeks in the periphery of the retina, particularly in the temporal retina. The same morphological alteration subsequently becomes apparent also in the area centralis and the nasal retina, respectively. The main and early cell loss occurs among medium sized ganglion cells, supposedly the beta-cells. Among the alpha-cells only shrinkage is observed up to two months postoperatively. Light- and electron microscopic examination of cross sections through the retina show that pathological changes are restricted to the innermost layers.
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    URL: http://dx.doi.org/10.1007/BF00235279
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    Evidence for glutamate as a neurotransmitter in the cat vestibular nerve: radioautographic and biochemical studies (1984)
    Springer
    Experimental brain research 56 (1984), S. 523-531 
    Details
    ISSN: 1432-1106
    Keywords: Glutamatergic synapses ; Vestibular nerve lesion ; Vestibular nuclei ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Evidence that glutamate acts as a neuro-transmitter in vestibular nerve fibers was sought (1) by electron microscope radioautographic identification of the uptake sites of [3H]-glutamic acid after incubation of slices of cat vestibular nuclei, and (2) by measuring changes in sodium-dependent high affinity glutamate uptake in nerve endings containing homogenates from normal and deafferented vestibular nuclei 8 to 11 days after unilateral vestibular nerve lesion. Electron microscopic radioautography revealed that glutamate had been taken up by numerous nerve endings projecting over the whole vestibular nuclear complex. The biochemical approach indicated that after section of the vestibular nerve, a significant decrease in high affinity glutamate uptake occurred in the vestibular nuclei, which lost their exclusively ipsilateral projection. This decrease varied from one area of the deafferented vestibular nuclei to another, reaching −58% in the lateral area of the central part corresponding to the ventral lateral vestibular nucleus and the rostral part of the descending vestibular nucleus. It is concluded that glutamate (or aspartate) is used by the vestibular nerve fibers as a neurotransmitter in the vestibular nuclei.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00237993
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    Origin of signals conveyed by the ventral spino-cerebellar tract and spino-reticulo-cerebellar pathway (1984)
    Springer
    Experimental brain research 54 (1984), S. 426-431 
    Details
    ISSN: 1432-1106
    Keywords: Spinal cord ; Scratch reflex ; Ventral spino-cerebellar tract ; Spino-reticulo-cerebellar pathway ; Cerebellum ; Cooling the nervous tissue ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary (1) The “fictitious” scratch reflex was evoked in decerebrate curarized cats by pinna stimulation. Activity of neurons of the ventral spinocerebellar tract (VSCT) from the L4 and L5 segments of the spinal cord as well as of neurons of the spinoreticulo-cerebellar pathway (SRCP) from the lateral reticular nucleus of the medulla oblongata was recorded. Cooling and destruction of different parts of the lumbo-sacral enlargement of the spinal cord were performed. (2) Cooling of the L5 or L6 segment abolished the rhythmic activity in the greater part of the spinal hindlimb centre but did not affect the generation of rhythmic oscillations in the remaining (rostral) segments of the lumbo-sacral enlargement. Under these conditions, neither the rhythmic activity of VSCT neurons located rostral to the thermode nor that of SRCP neurons changed. (3) A normal rhythmic activity of SRCP neurons also persisted after destruction of grey matter in the L3 and L4 segments. It can be concluded that activity of these neurons is independent of whichever part of the enlargement generates rhythmic oscillations. (4) From these observations a hypothesis is advanced that the main content of signals conveyed by the VSCT and SRCP to the cerebellum is the information regarding activity of the generator of rhythmic oscillations that is located in the L3-L5 spinal segments.
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    URL: http://dx.doi.org/10.1007/BF00235467
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    Electronic Resource
    Corticocortical connections to the motor cortex from the posterior parietal lobe (areas 5a, 5b, 7) in the cat demonstrated by the retrograde axonal transport of horseradish peroxidase (1984)
    Springer
    Experimental brain research 54 (1984), S. 476-484 
    Details
    ISSN: 1432-1106
    Keywords: Corticocortical connections ; Motor cortex ; Areas 4, 5a, 5b, 7 ; Posterior parietal lobe ; Retrograde transport of HRP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neurons in the parietal region of the cerebral cortex, projecting to the ipsilateral distal forelimb area of the motor cortex (area 4γ) were identified in the cat brain using the horseradish peroxidase (HRP) retrograde tracing method. After making microinjections of HRP into the distal forelimb area of the motor cortex, clusters of HRP-labeled cell bodies were observed in different regions of the ipsilateral parietal cortex. In particular these clusters of labeled cells were found in areas 5a, 5b and 7. The area 5a cluster is formed from closely packed irregularly-shaped cells, the area 5b cluster is made up of dispersed medium-sized pyramidal cells, while area 7 contains a cluster of widely dispersed small pyramidal cells. Typically, labeled cell bodies were found in lamina III of cortex. Labeled cell bodies were neither observed in the contralateral cortex nor in the visual cortex (areas 17, 18 and 19). Since parietal cortex receives projections from primary somatosensory and visual cortex, the projections from parietal to motor cortex may well form the neural substrate for the processing of convergent sensory information used in voluntary movements.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235473
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  • 35
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    The use of retrograde transport of horseradish peroxidase for studying the dendritic trees and axonal courses of particular groups of tract cells in the spinal cord (1984)
    Springer
    Experimental brain research 54 (1984), S. 529-537 
    Details
    ISSN: 1432-1106
    Keywords: Cat ; Rat ; Spinal tract neurons ; Retrograde HRP transport ; Procedure and evaluation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Modifications have been made in Mesulam's method for labelling neurons by retrograde transport of horseradish peroxidase, with tetramethylbenzidine as chromogen, with the object of increasing the extent of labelling of dendrites and axons. A procedure was devised specifically for studying spinomedullary and medullospinal tract systems, involving implanting easily-made HRP-agar pellets into areas of controlled damage in particular spinal fascicles, and sealing the site of implant with cyanoacrylate glue. Lesions of other fascicles were often made to limit transport to the implanted fascicle. Fourth-order dendrites were regularly labelled over long (30 cm or more) transport distances: axons were also labelled over this whole distance, often allowing exact study of the initial course of particular axons. Controls in both cat and rat showed that the uptake of HRP under these circumstances occurred almost wholly from the region of axonal damage at the site of implant which can be characterized histologically.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00235478
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  • 36
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    Electronic Resource
    Inotropic effect of prenalterol in amitriptyline poisoning (1984)
    Springer
    Intensive care medicine 10 (1984), S. 209-211 
    Details
    ISSN: 1432-1238
    Keywords: Amitriptyline ; Hydrocortisone ; Insulin ; Prenalterol ; Cardiac failure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A case of severe amitriptyline poisoning with grade IV coma, seizures, bradycardia and hypotension who did not respond to dopamine was successfully treated with prenalterol, a new cardioselective β-agonist. The case is discussed with respect to plasma concentrations of dopamine, prenalterol and amitriptyline. Prenalterol, hydrocortisone and insulin may be useful as inotropic agents in tricyclic poisoning where dopamine fails to provide an adequate response.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00259441
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  • 37
    Electronic Resource
    Electronic Resource
    Vanadate stimulates the pumped movements of Na in skeletal muscle (1984)
    Springer
    Pflügers Archiv 400 (1984), S. 413-417 
    Details
    ISSN: 1432-2013
    Keywords: Sodium pump ; Na-K ATPase ; Na fluxes ; Vanadate ; Insulin ; Skeletal muscle ; Ouabain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We have measured the effects of concentrations of vanadate ranging between 0.01 and 10 mM on the22Na efflux of frog sartorius muscles. The addition of vanadate had no effects when concentrations lower than 0.5 mM were used; higher concentrations increased Na efflux. The increase was abolished by the addition of ouabain (10−5M). In muscles pretreated with ouabain vanadate did not modify Na efflux. The stimulatory effects of vanadate on Na efflux were also observed in Na-free solutions indicating that the effux of vanadate was not caused mainly either by an increase in the exchange of Na for Na or by an increase in Na entry into the muscle. We also examined the effects of vanadate on muscles immersed in solutions containing 20 mM K+; both vanadate and increased K+ produced stimulations of Na efflux that were additive. Similarly when the effects of vanadate and insulin were measured on the Na efflux of the same muscle, additive effects were found. As the ouabain-sensitive Na efflux in frog muscle is generally agreed to be due to the activity of the Na-K ATPase, our findings suggest that the net effect of vanadate in intact muscle cells is an increase in the activity of the Na pump. Since vanadate affects many enzymes it is quite possible that the stimulatory action is not due to a direct effect on the Na-K ATPase but may be mediated through an intermediary step. Regardless of the specific mechanism, it is evident that, our results as well as other findings in the literature, strongly indicate that Na pumping by intact cells can be increased by vanadate administration. Hence it is not justified to attribute the physiological modifications caused by vanadate administration to blockade of the Na-K ATPase unless the attribution is justified by specific experimental evidence.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00587542
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  • 38
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    Electronic Resource
    Energetics of active sodium-potassium transport following stimulation with insulin, adrenaline or salbutamol in rat soleus muscle (1984)
    Springer
    Pflügers Archiv 401 (1984), S. 160-166 
    Details
    ISSN: 1432-2013
    Keywords: Biological transport ; Insulin ; Energy metabolism ; Epinephrine ; Endocrinology ; Albuterol (salbutamol) ; Active sodium-potassium transport ; Muscle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The total metabolic energy expenditure associated with active Na−K-transport over the first 20 min of stimulation with insulin, adrenaline or salbutamol (ΔHmNa−K) was determined from direct calorimetric and tracer ion flux measurements in isolated muscles at rest. The reversible work performed by the Na−K-pump during the same interval of time (WrevNa−K) was calculated as the product of the ouabain-suppressible Na−K transfers and the mean free energy increase imparted to the two ions as they are transported against their electrochemical gradients across the plasma membrane. Comparison of membrane potential and intracellular Na and K concentrations before and after the stimulations indicated that part of WrevNa−K had contributed to increase the ion electrochemical gradients in the preparation (i.e. had not been lost as heat) during the 20 min period. Accordingly, the maximum value of ΔHmNa−K was taken as the sum of the ouabain-suppressible heat production and WrevNa−K. Following stimulation with insulin, adrenaline or salbutamol this maximum corresponded to 10, 10 and 12% respectively, of basal metabolism. Under the same three conditions, the minimum “energetic efficiency” of the active Na−K-transport process, defined as the ratio between WrevNa−K and maximum ΔHmNa−K, was 35, 41 and 38%, respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00583876
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  • 39
    Electronic Resource
    Electronic Resource
    Long-term follow-up of children with craniopharyngioma (1984)
    Springer
    European journal of pediatrics 142 (1984), S. 179-185 
    Details
    ISSN: 1432-1076
    Keywords: Craniopharyngioma ; Growth ; Insulin ; Neurosurgery ; Radiotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Management of craniopharyngiomas is still controversial. 28 children with this tumor were studied. GH deficiency was present in 22 patients following surgery, 10 of these GH-lacking patients had normal or accelerated growth (usually associated with rapid weight gain) postoperatively. Somatomedin levels were normal in three of six normally growing patients. After craniotomy their basal and TRH-stimulated prolactin levels were in the normal range, but their insulin secretion was markedly increased. Postoperatively there was a significant correlation between peak insulin levels following arginine infusion and growth velocity in all patients. Complete tumor removal could be performed in 28% of our patients. Altogether 36% of all patients had at least one tumor recurrence. Recent literature with the addition of our series showed tumor recurrence in 22% of patients with “total” tumor excision and in 72% of patients with partial tumor removal. Radiotherapy seems to be capable of destroying craniopharyngioma tissue. The recurrence rate was only 26% in patients with subtotal excision plus radiotherapy. Unless radical tumor removal can be attempted with safety, subtotal tumor removal plus radiotherapy appears to be the treatment of choice for craniopharyngioma.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00442445
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  • 40
    Electronic Resource
    Electronic Resource
    Peripheral nerve phospholipids in acrylamide neuropathy (1984)
    Springer
    Archives of toxicology 55 (1984), S. 178-181 
    Details
    ISSN: 1432-0738
    Keywords: Cat ; Phospholipids ; Acrylamide ; Neuropathy ; Lipids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Treatment of cats with acrylamide, either 7.5 or 15 mg/kg IM, once a day for 10 days, resulted in increases of 31 and 47% in the phospholipid content of sciatic nerve, respectively, from a control level of 41.1±2.7 mg/kg wet weight. Determination of the distribution of individual phospholipids indicated no significant differences between control cats and those receiving a cumulative dose of 150 mg/kg acrylamide. In a separate experiment, cats were treated with the 150 mg/kg dose of acrylamide and the sciatic nerve was divided into proximal and distal portions at the level of the triceps surae nerve. Significant increases in phospholipid content were observed in both the proximal and distal portions of peripheral nerve of the acrylamide-intoxicated cats. This effect was present even when the phospholipid content was expressed in terms of total protein, dry weight or total lipid. Total weight of nerve segments, however, was significantly decreased in the neuropathic animals. The data are consistent with a focal degeneration of axons with relative sparing of phospholipids.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00316124
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  • 41
    Electronic Resource
    Electronic Resource
    The representation of contrast and other stimulus parameters by single neurons in area 17 of the cat (1984)
    Springer
    Pflügers Archiv 401 (1984), S. 304-314 
    Details
    ISSN: 1432-2013
    Keywords: Visual cortex ; Contrast/response function ; Orientation and direction sensitivity ; Ocularity ; Binocular responses ; Feature specific responses ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The responses of neurons in area 17 were tested as a function of various stimulus parameters. The thresholds of individual cortical neurons were at contrasts between 0.01 and 0.1 (increment of 0.5×10−1 cd/m−2 on a background of 3 cd/m−2), the dynamic ranges were 1.0–2.0 log units of increment, and all cells showed a response decrease at increments above a certain maximum (supersaturation response). The averaged contrast/response curve for all neurons was S-shaped in the logarithmic plot, had a dynamic range of 2.5 log units, reached its maximum at a contrast of 0.75 and supersaturated above this level. The contrast/ sensitivity curves changed their slope under different stimulus conditions. They became flatter when the non-dominant eye was stimuated as compared to dominant eye stimulation or when the stimulation was done at a non-optimal orientation or direction, and they became steeper when both eyes were stimulated. But the maximum was reached at the same contrast and supersaturation was seen above maximum contrast no matter whether a cell was stronlgy (e.g. binocular stimulation at optimal orientation) or weakly excited (non-dominant or non-optimal orientation stimulation). After normalization, the averaged population contrast/response curves were virtually identical at all stimulus conditions. It was concluded, that range as well as maximum and supersaturation of cortical contrast/response curves are determined before the input reaches the cortex, and that the cortical cells summate, essentially, linearly. The findings furthermore demonstrate that the supersaturation of the cortical input must be due to subtractive inhibition, and that the same is true for the orientation sensitive inhibition in the cortex itself. Both, the peripheral contrast and the cortical orientation dependant inhibition cannot be explained by multiplicative inhibition. The fact, that the responses of neurons depend on many variables relativates their significance for feature representation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00582601
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  • 42
    Electronic Resource
    Electronic Resource
    Angioarchitecture of the pancreas of the cat (1984)
    Springer
    Cell & tissue research 235 (1984), S. 675-682 
    Details
    ISSN: 1432-0878
    Keywords: Endocrine pancreas ; Angioarchitecture ; Cat ; Scanning and transmission electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary By the use of scanningand transmission electron microscopy, the possible sources of errors in interpretation of the microcirculation of the pancreas can be reduced in comparison to the classical India-ink injection method. Sphincter-like structures in the capillary wall of the cat pancreas are established by pericytes. These sphincters encircle the junctional zones between the endocrine and exocrine capillaries. They are assumed to be regulatory structures of blood flow and to regulate indirectly hormone secretion according to demand.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00226968
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  • 43
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    Electronic Resource
    Scanning electron-microscopic study of Reissner's fiber in the caudal spinal cord of the cat and rabbit (1984)
    Springer
    Cell & tissue research 237 (1984), S. 181-183 
    Details
    ISSN: 1432-0878
    Keywords: Reissner's fiber ; Scanning electron microscopy ; Spinal cord ; Cat ; Rabbit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The caudal portion of Reissner's fiber was examined by scanning electron microscopy (SEM) in the spinal cord of the cat and rabbit. In some preparations of both species the fiber displayed in the sinus terminalis of the central canal either stump-like terminations or structural modifications such as knot-like swellings and convolutions. In the same area homogeneous material could also be found, which obviously originated from the disintegrating fiber.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00229214
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  • 44
    Electronic Resource
    Electronic Resource
    Effects of prolonged maternal fast on the pancreas of 18–21-day-old foetal rats (1984)
    Springer
    Cell & tissue research 237 (1984), S. 169-179 
    Details
    ISSN: 1432-0878
    Keywords: Foetal pancreas ; β Cells ; Insulin ; Fasting mothers ; Morphometry ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary After maternal fasting for 72 h the pancreatic β cells of 18-day-old foetal rats show a conspicuous enrichment in secretory material, with an increase of pancreatic insulin concentration and a marked development of the rough endoplasmic reticulum and the Golgi apparatus. The morphometric analysis shows that the intracytoplasmic migration of the secretory granules is inhibited, principally inside the cell web. Consequently the number of secretory granules fused with plasma membrane decreases and this is associated with a decreased foetal plasma insulin. The difference in the ultrastructural aspect of the β cells of foetuses from fasting mothers and of foetuses from fed mothers is less conspicuous at 19 days of gestation and progressively disappears at 20 and 21 days. The modifications in ultrastructural aspect and in functional state are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00229213
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  • 45
    Electronic Resource
    Electronic Resource
    Ultrastructure of dynamic and static skeletofusimotor endings in a cat muscle spindle (1984)
    Springer
    Cell & tissue research 238 (1984), S. 151-158 
    Details
    ISSN: 1432-0878
    Keywords: Skeletofusimotor innervation ; Muscle spindles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Endings of four β skeletofusimotor axons in a spindle of the cat tenuissimus muscle were examined in semithin (1-μm thick) and ultrathin transverse serial sections. Two (dynamic) β axons terminated on the nuclear bag1 intrafusal muscle fiber and on extrafusal fibers of the dark type. Two (static) β axons terminated on the nuclear chain intrafusal fibers and extrafusal fibers of the intermediate type. The degree of indentation of axon terminals into the muscle surface, thickness of the sole plate and extent of folding of subjunctional membranes differed among intrafusal and extrafusal terminations of the same axon. Endings of β axons on the bag1 and chain fibers were also morphologically dissimilar. Motor axons may not determine ending morphology. Rather the form and structure of a β bag1 or chain ending may be determined by the type of intrafusal fiber on which the ending lies and the ending's distance from the primary sensory axon.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00215156
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  • 46
    Electronic Resource
    Electronic Resource
    Effects of a rapid change in muscle glycogen availability on metabolic and hormonal responses during exercise (1984)
    Springer
    European journal of applied physiology 53 (1984), S. 57-62 
    Details
    ISSN: 1439-6327
    Keywords: Muscle glycogen ; Time sequence ; Free fatty acids ; Insulin ; Exercise in humans
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary To evaluate the metabolic and hormonal adaptations following a rapid change in muscle glycogen availability, 14 subjects had their muscle glycogen content increased in one leg (IG) and decreased in the other (DG). In group A (n=7), subjects exercised on a bicycle ergometer at 70% maximal oxygen uptake for 20 min using the DG leg. Without resting these same subjects exercised another 20 min using the IG leg. Subjects in group B (n=7) followed the same single-leg exercise protocol but in the reverse order. In order to get some information on the time sequence of these possible adaptations, blood samples were collected at rest and at the beginning and the end of each exercise period (min 5, 20, 25, and 40). Results indicated that 5 min after the switch from the DG leg to the IG leg. transient increases in plasma free fatty acids (1.20 to 1.39 meq·l−1) and serum insulin (10.1 to 12 mU·l−1) concentrations occured. Between minute 25 and 40 of exercise, the DG to IG switch was accompanied by a decrease in free fatty acids and glycerol concentrations as well as an increase in lactate levels. An opposite response was observed in the IG to DG condition during the same time span. Plasma norepinephrine, epinephrine, glucagon, and serum cortisol concentrations were not significantly affected by the leg change. These results suggest a rapid preferential use of muscle glycogen when available and a time lag in the response of the extramuscular substrate mobilization factors.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00964691
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  • 47
    Electronic Resource
    Electronic Resource
    Metabolic and hormonal responses to prolonged physical exercise in dogs after a single fat-enriched meal (1984)
    Springer
    European journal of applied physiology 53 (1984), S. 267-273 
    Details
    ISSN: 1439-6327
    Keywords: Exercise ; Triglycerides ; Free fatty acids ; Glycerol ; Insulin ; Catecholamines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Metabolic and hormonal responses to prolonged treadmill exercise in dogs fed a fat-enriched meal 4 h prior to the exercise were compared to those measured 4 h after a mixed meal or in the postabsorptive state. Ingestion of the fat-enriched meal caused significant elevations in the resting values of plasma triglyceride (TG), free fatty acid (FFA), and glycerol concentrations. A reduction of the plasma TG concentration (from 1.6±0.2 to 1.1±0.10 mmol·l−1,P〈0.005) occurred only in dogs exercising after the fat-enriched meal. No significant changes in this variable were noted in dogs fed a mixed meal, whilst in the postabsorptive state exercise caused an increase in the plasma TG level (from 0.42±0.03 to 0.99±0.11 mmol·l−1,P〈0.01). The exercise-induced elevations in plasma FFA and glycerol concentrations were the highest in the dogs given the fat-enriched meal. Plasma glycerol during exercise correlated with the initial values of circulating TG (r=0.73). The plasma FFA-glycerol ratio, at the end of exercise was lowest in the dogs taking the fat-enriched meal (1.39±0.19), suggesting an increased utilization of FFA in comparison with that in the postabsorptive state (3.27±0.37) or after a mixed meal (2.88±0.55). Basal serum insulin (IRI) concentrations were similarly enhanced in dogs fed fat-enriched and mixed meals, and they were reduced to control values within 60 min of exercise. Plasma adrenaline and noradrenaline concentrations correlated with time of exercise (r=0.84 andr=0.96, respectively) and were unaffected by the nutritional modifications. It is concluded that ingestion of a single fat-enriched meal considerably modifies the exercise-induced changes in lipid metabolism. The pattern of changes in plasma TG, FFA, and glycerol concentrations indicates an enhanced hydrolysis of plasma chylomicron-TG, suggesting that this lipid source may contribute markedly to exercise metabolism.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00776601
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  • 48
    Electronic Resource
    Electronic Resource
    Further increase in high density lipoprotein in trained males after enhanced training (1984)
    Springer
    European journal of applied physiology 52 (1984), S. 426-430 
    Details
    ISSN: 1439-6327
    Keywords: Apoproteins ; Lipoproteins ; Insulin ; Blood lactate ; Physical training
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Eight well-trained males were studied before, during and after 6 months of a progressively increased amount of endurance training in order to elucidate the effects on the apoproteins and apo-lipoproteins. Initially high HDL-cholesterol levels were revealed (1.62±0.15 mmol×l−1, mean ± SE.). After a transient but not significant, slight decline at the onset of the increased training program (1.57±0.06 mmol×l−1) HDL-cholesterol increased gradually to the end of the training period (1.92±0.12 mmol×l−1). There was an increased aerobic capacity as judged by maximal oxygen uptake and by lactate concentration during standardized submaximal work. However, at the end of the training period, a levelling off in maximal oxygen uptake was revealed, while HDL-cholesterol was still increasing. The present data demonstrate that HDL can be influenced by training at all levels of aerobic capacity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00943374
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  • 49
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    Electronic Resource
    Charge-Transfer-Komplexe von Tetrathiafulvalen (TTF) mit 1,2,5-Thiadiazolchinonen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1940-1953 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Charge-Transfer Complexes of Tetrathiafulvalene (TTF) with 1,2,5-Thiadiazolequinones1)The syntheses and the X-ray structure analyses of the charge-transfer complexes of tetrathiafulvalene (TTF) with naphtho[2,3-c][1,2,5]thiadiazole-4,9-dione (1 : 2) (2) and benzol[1,2-c: 4,5-c′]-bis[1,2,5]thiadiazole-4,8-dione (1 : 1) (4) are reported. In their crystal structures both compounds are built up by mixed columnar stacks of donors and acceptors, forming a characteristic packing motive for organic D-A complexes with properties of an electrical insulator.
    Notes: Es wird über die Synthese und die Einkristallröntgenstrukturanalysen der Charge-Transfer-Komplexe von Tetrathiafulvalen mit Naphtho[2,3-c][1,2,5]thiadiazol-4,9-dion (1 : 2) (2) und Benzo-[1,2-c: 4,5-c′]bis[1,2,5]thiadiazol-4,8-dion (1 : 1) (4) berichtet. Beide Verbindungen weisen in ihrer Kristallstruktur aus Donoren und Acceptoren gemischte kolumnare Stapel auf, ein charakteristisches Packungsmotiv organischer D-A-Komplexe mit elektrischen Isolatoreigenschaften.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170523
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  • 50
    Electronic Resource
    Electronic Resource
    Notizen. Die Erzeugung von Nitrosylsalzen in wasserfreien organischen Medien (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1973-1976 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Generation of Nitrosyl Salts in Dry Organic MediaTrimethylsilyl halides (CH3)3SiX (2a - c, X = Cl, Br, I) are sufficiently electrophilic to cleave, in an equilibrium reaction, alkyl nitrites O = NOR (1a, b, R = i-C5H11, C2H5) with formation of O = NX (3a - c) and (CH3)3SiOR (4a, b). This reaction serves as a convenient in-situ-method to generate nitrosyl compounds NOX in chlorinated hydrocarbons as inert organic media.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170526
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  • 51
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    Iminoborane beim thermischen Zerfall der Dialkylazidoborane (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1954-1964 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Iminoboranes from the Thermal Decomposition of DialkylazidoboranesIminoboranes RB = NR (1a - f) are formed by the thermal decomposition of azidoboranes R2BN3 (5a - f) in the gas phase or in solution. At low temperature, the iminoboranes 1b, d, e (R = iPr, iBu, sBu) can be trapped from the gas phase. They are characterized and brought to reaction as isolated species. Without other reactands, the iminoboranes dimerize or trimerize to form the cyclic products 2 or 3, respectively, or polymerize to the wax-like solids 4. Produced in solution below 100 °C, the iminoboranes are azidoborated by the educts 5 to give the (azidoboryl)amines 6 which are transformed into the borazines 3 at 160 - 180 °C. Iminoboranes undergo an ethyloboration with BEt3, a cycloaddition with PhN3, and in the absence of the strongly reactive R2BN3 a concurring cycloaddition and azidosilation with Me3SiN3 with formation of 7 - 10, respectively.
    Notes: Iminoborane RB = NR (1a - f) entstehen beim thermischen Zerfall von Azidoboranen R2BN3 (5a - f) in der Gasphase oder in Lösung. Die aus der Gasphase abgeschiedenen Produkte 1b, d, e (R = iPr, iBu, sBu) lassen sich bei tiefer Temperatur isolieren, charakterisieren und isoliert umsetzen. Mit sich selbst reagieren die in der Gasphase ergzeugten Iminoborane 1a - f unter Cyclodi-oder -trimerisierung oder unter Polymerisierung zu Produkten von Typ 2, 3 bzw. 4. In Lösung unterhalb 100 °C erzeugt, werden die Iminoborane von den Edukten 5 zu Produkten 6 azidoboriert; diese lassen sich bei 160 - 180 °C in Borazine 3 überführen. Iminoborane erfahren durch BEt3 eine Ethyloborierung zu 7, mit PhN3 eine Cycloaddition zu 8 und mit Me3SiN3 nebeneinander eine Cycloaddition zu 9 und eine Azidosilierung zu 10, sofern nicht das Edukt R2BN3 zugegen ist, das dem Azid Me3SiN3 in der Reaktivität gegenüber 1 überlegen ist.
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170524
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    Azodesilylierung  -  eine neue aprotische Diazotierungstechnik (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1965-1972 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azodesilylation - a Novel Aprotic Diazotization TechniqueNitrosyl compounds NOA (4a - e, A = Cl, Br, BF4, CF3SO3, I) - generated partially in situ from O = N - OR/(CH3)3SiA (7a, b, R = i-C5H11, C2H5/8a, b, e, A = Cl, Br, I) - react in aprotic organic media with N,N-bissilylated organylamines RN[Si(CH3)3]2 (3b, R = C6H5; 15, R = CH3) under generation of diazonium systems R - N2+ A- and formation of non-nucleophilic hexamethyldisiloxane (6b). This method represents the first nucleophile excluding diazotization technique on the basis of three-coordinated nitrogen and is termed „azodesilylation“.
    Notes: Nitrosylverbindungen NOA (4a - e, A = Cl, Br, BF4, CF3SO3, I) - teilweise in situ hergestellt aus O = N - OR/(CH3)3SiA (7a, b, R = i-C5H11, C2H5/8a, b, e, A = Cl, Br, I) - reagieren mit N,N-bissilylierten Organylaminen RN[Si(CH3)3]2 (3b, R = C6H5; 15, R = CH3) in aprotischen organischen Medien unter Bildung von Diazonium-Systemen R - N2+ A- und nicht-nucleophilem Hexamethyldisiloxan (6b). Diese Methode repräsentiert die erste, Nucleophile ausschließende Diazotierungstechnik auf der Basis von 3fach koordiniertem Stickstoff und wird als „Azodesilylierung“ bezeichnet.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170525
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    Acid-catalyzed Cyclization of the Ene-Product Derived from α-Pinene and PTAD (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1977-1979 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Säurekatalysierte Cyclisierung des En-Produkts aus α-Pinen und PTADAluminiumchlorid-katalysierte Reaktion des En-Produkts 2 aus 4-Phenyl-4H-1,2,4-triazol-3,5-dion (PTAD) und α-Pinen (1), des 1-(6,6-Dimelthyl-2-methylenbicyclo[3.1.1]hept-3-yl)-4-phenyl-1,2,4-triazolidin-3,5-dions, ergab 3,8,8-Trimelthyl-N-phenyl-4,5-diazatricyclo[4.2.1.03,7]nonan-4,5-dicarboxamid (6) in 78% Ausbeute. Auch Bortrifluorid-etherat, trockener Chlorwasserstoff und p-Toluolsulfonsäure katalysieren die Cyclisierung von 2 zu 6, aber nicht in diesem Maße. Der Mechanismus der Cyclisierung wird über eine Gerüstumlagerung der Carbenium-Ionen-Zwischenstufen gedeutet.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170527
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    Kettenverlängerung bei Tetrafluor-1,2-ethandisulfenyldichlorid durch Reaktion mit Wasserstoffperoxid (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1980-1981 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chain Lengthening of Tetrafluoro-1,2-ethanedisulfenyl Dichloride by the Reaction with Hydrogen PeroxideThe reaction of the little compound ClSCF2CF2SCl (1) with aqueous H2O2 results in the formation of ClS2CF2CF2SSCF2CF2SO2Cl(2), which is characterized on the basis of 19F NMR, mass, IR, and Raman spectroscopy.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170528
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    Fluorierungen von Adamantanderivaten mit Sauerstoffdifluorid (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1982-1986 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorination of Adamantane Derivatives with Oxygen DifluorideFluorination of adamantane and adamantane derivatives 1 with OF2 in the absence of an HF-trap gives fluoroadamantanes 2 and adamantanols 3 in varying amounts. Increasing yields of 2 are obtained in the presence of Na2CO3 as an HF-trap. In addition, the fluorooxahomoadamantanes 4b and e are formed in this reaction. The fluorination of adamantanone (5) with OF2 leads to analogous products.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170529
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    Photoelectron Spectra of Some Reduction Products of [2.2]Paracyclophane (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1987-1990 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photoelektronenspektren einiger Reduktionsprodukte von [2.2]ParacyclophanAnhand des He(I)-Photoelektronen(PE)-Spektrums von 2,3′,5,6′-Tetrahydro[2.2]paracyclophan (2) wird gezeigt, daß die Through-Bond-Wechselwirkung zwischen den Sechsringen klein, innerhalb der Cyclohexadienringe aber groß ist. Über die PE-Spektren der weiteren Hydrierungsprodukte 3 und 4 wird berichtet.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170530
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    Synthesen mit Cyclobutadienen, 5. 5,5,6,6-Tetracyan-5,6-dihydrodewarbenzol/3,3,4,4-Tetracyan-3,4-dihydrobenzavalen - ein neues äquilibrierendes System (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1991-1993 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses with Cyclobutadienes, 51). 5,5,6,6-Tetracyano-5,6-dihydro-Dewar benzene/3,3,4,4-Tetracyano-3,4-dihydrobenzvalene - a Novel Equilibrating SystemThe cyclobutadiene 3 reacts with tetracyanoethylene to give a 1 : 1-mixture of the dihydro-Dewar benzene 5 and the dihydrobenzvalene 6, which can be separated by crystallisation. In deuteriochloroform solution 5 and 6 are in a 1 : 1 equilibrium.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170531
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    Masthead (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170601
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    Elektronenreiche Heterocyclen als Donorgruppen in Fluoreszenzfarbstoffen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2275-2286 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electron Rich Heterocycles as Donor Groups in Fluorescent DyesThe synthesis of N-methylphthalimides substituted with the donor groups pyrazole, triazole, benzotriazole, and naphthotriazole in position 4 is described (17, 18, 14, 12). The substituent constants of these groups are obtained by alkaline hydrolysis of the corresponding phthalimide dyes. Their solvatochromism in absorption and fluorescence gives information about charge distribution in ground- and excited state.
    Notes: Die Darstellung von N-Methylphtalimiden wird beschrieben, die in 4-Stellung die Donorgruppen Pyrazol, Triazol, Benzotriazol und Naphthotriazol tragen (17, 18, 14, 12). über die alkalische Hydrolyse des Imids werden die Substituentenkonstanten der Reste bestimmt. Die Solvatochromie in Absorption und Fluoreszenz gibt Information über die Ladungsverteilung in Grund- und angeregtem Zustand.
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    URL: http://dx.doi.org/10.1002/cber.19841170619
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    Aromaten(phosphan)metall-Komplexe, IV. Darstellung von (6-Phosphonio-η5-cyclohexadienyl)-ruthenium(II)-Verbindungen und ihre Umwandlung in dikationische (Benzol)ruthenium(II)-Komplexe [C6H6Ru(PR3′)PR3″]2+ (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 142-151 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Arene(phosphane)metal Complexes, IV1). Synthesis of (6-Phosphonio-η5-cyclohexadienyl)ruthenium(II) Compounds and their Conversion into Dicationic (Benzene)ruthenium(II) Complexes[C6H6Ru(PR3)(PR3′)PR3″]2+The complexes [C6H6RuCl(PR3)PR3′]PF6 (1 - 4) and [C6H6RuCl2(PR3)] (9, 10) react with phosphanes PR3″ in the presence of NH4PF6 to give the (6-phosphonio-η5-cyclohexadienyl)ruthenium(II) compounds [(6-R3″P-η5-C6H6)Ru(PR3)(PR3′)PR3″](PF6)2 (5 - 8 11). Similarly, from [C6H6Ru(CH3CN)3](PF6)2 (12) and PMe3 the complex [(6-Me3P-η5-C6H6)Ru(PMe3)2CH3CN](PF6)2 (13) is formed. The IR and NMR spectra of 5 - 8, 11, and 13 indicate that the phosphonio group is in the exo-position at the sp3 carbon atom of the cyclohexadienyl ligand. Below - 30°C, rotation around the metal-ring bond is so hindered that rigid conformers are detected. Compounds 5 - 8 react with trifluoroacetic acid with elimination of the phosphonio group to yield the PF6 salts of the half-sandwich type complexes [C6H6Ru(PR3)(PR3′)PR3″]2+ (14 - 17).
    Notes: Die Komplexe [C6H6RuCl(PR3)PR3)]PF6 (1 - 4) und [C6H6RuCl2(PR3)] (9, 10) reagieren mit Phosphanen PR3″ in Gegenwart von NH4PF4 zu den (6-Phosphonio-η5-cyclohexadienyl)-ruthenium(II)-Verbindungen [(6-R3″P-η5-C6H6)Ru(PR3)(PR3″](PF6)2 (5 - 8, 11). Aus [C6H6Ru(CH3CN)3](PF6)2 (12) und PMe3 erhält man analog den Komplex (6-Me3P-η5-C6H6)Ru(PMe3)2CH3CN](PF6)2 (13). Die IR- und NMR-Spektren von 5 - 8, 11 und 13 weisen darauf hin, daß sich die Phosphoniogruppierung in der exo-Position am sp3-C-Atom des Cyclohexadienylliganden befindet. Unterhalb - 30°C ist die Rotation um die Metall-Ring-Bindung so stark behindert, daß starre Konformere nachweisbar sind. Die Verbindungen 5 - 8 reagieren mit Trifluoressigsäure unter Abspaltung der Phosphoniogruppe zu den PF6-Salzen der Halbsandwich-Komplexe [C6H6Ru(PR3)(PR3′)PR3″]2+ (14 - 17).
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170111
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    Aromaten(phosphan)metall-Komplexe, VI. Synthese von [(RC6H5)OsI(PMe3)2PF6 aus (exo-6-RC6H6)OsI(PMe3)2: Ein Beitrag zum Mechanismus der Aromatisierung substituierter Cyclohexadienylliganden durch „endo-H-Abstraktion“ (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 161-171 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Arene(phosphane)metal Complexes, VI1). Synthesis of [(RC6H5)OsI(PMe3)2]PF6 from (exo-6-RC6H6)OsI(PMe3)2: A contribution to the Mechanism of Aromatization of Substituted Cyclohexadienyl Ligands by „endo-H Abstraction“The compounds (exo-6-RC6H6)OsI(PMe3)2 (2 - 5, 7) react smoothly with [CPh3]PF6 in acetone to give the (arene)osmium(II) complexes [(RC6H5)OsI(PMe3)2]PF6 (8 - 12) in quantitative yield. The hydride elimination proceeds via two (cyclohexadienyl)hydridoosmium(IV) intermediates (13 and 14, 15, respectively) which can be prepared from 2, 5, 6 (R = CH3, n-C4H9, t-C4H9) and CF3CO2H/NH4PF6. The (cyclohexadienyl)hydrido complexes [(RC6H6)Os(H)I(PMe3)2]+ undergo an intramolecular isomerization which leads to a cation possessing a CH2 group in the six-membered ring. This cationic complex or (more probably) the neutral compound (2- or 3-RC6H6)OsI(PMe3)2 formed on deprotonation reacts with [CPh3]+ by abstraction of an exo-hydrogen atom.
    Notes: Die Verbindungen (exo-6-RC6H6)OsI(PMe3)2 (2 - 5, 7) reagieren mit [CPh3]PF6 in Aceton rasch und quantitativ zu den (Aromaten)osmium(II)-Komplexen [(RC6H5)OsI(PMe3)2]PF6 (8 - 12). Die Hydrid-Eliminierung verläuft über zwei (Cyclohexadienyl)hydridoosmium(IV)-Zwischenstufen (13 bzw. 14, 15), die aus 2, 5, 6 (R = CH3, n-C4H9, t-C4H9) und CF3CO2H/NH4PF6 synthetisiert werden können. Die (Cyclohexadienyl)hydrido-Komplexe [(RC6H6)Os(H)I(PMe3)2]+ gehen eine intramolekulare Isomerisierung ein, wobei ein Kation mit einer CH2-Gruppe im Sechsring entsteht. Dieses Komplexkation oder (wahrscheinlicher) die nach Deprotonierung erhaltene Neutralverbindung (2- bzw. 3-RC6H6)OsI(PMe3)2 reagiert mit [CPh3]+ unter Abstraktion eines exo-H-Atoms.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170113
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    Aromaten(phosphan)metall-Komplexe, V. Zur Addition von Carbanionen an (Benzol)ruthenium(II)- und -osmium(II)-Komplexe. Kristall- und Molekülstruktur von (exo-6-n-C4H9-η5-C6H6)OsI(PMe3)2 (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 152-160 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Arene(phosphane)metal Complexes, V1). On the Addition of Carbanions to (Benzene)ruthenium(II) and -osmium(II) Complexes. The Crystal and Molecular Structure of (exo-6-n-C4H9-η5-C6H6)OsI(PMe3)2The complex [C6H6RuCl(PMe3)2]PF6 (1) reacts with methyllithium to give a mixture of products that contains (η5-C6H6CH3)RuCH3(PMe3)2 (2) as the main component. From 1 and LiC6H5/LiBr the bromide 3 is primarily formed but the final product is (η5-C6H6C6)H5RuC6H5(PMe3)2 (4). Reaction of [C6H6OsI(PMe3)2]PF6 (5) with organyllithium compounds LiR (R = CH3, C2H5, n-C3H7, n-C4H9, t-C4H9, C6H5) yields the complexes (η5-C6H6R)OsI(PMe3)2 (6 - 11). 31P NMR spectra of 6 - 11 indicate restricted rotation at low temperatures around the metal-ring axis. According to X-ray structure analysis of 9 (R = n-C4H9) the cyclohexadienyl ring possesses an envelope conformation. The n-butyl group occupies the exo-position at the sp3-C atom.
    Notes: Der Komplex [C6H6RuCl(PMe3)2]PF6 (1) reagiert mit Methyllithium zu einem Produktgemisch, welches (η5-C6H6CH3)RuCH3(PMe3)2 (2) als Hauptkomponente enthält. Aus 1 und LiC6H5/LiBr entsteht über 3 bei längeren Reaktionszeiten (η5-C6H6C6H5)RuC6H5(PMe3)2 (4). Die Umsetzung von [C6H6OsI(PMe3)2]PF6 (5) mit Organyllithium-Verbindungen LiR (R = CH3, C2H5, n-C3H7, n-C4H9, t-C4H9, C6H5 ergibt die Komplexe (η5-C6H6R)OsI(PMe3)2 (6 - 11), in denen nach den 31P-NMR-Spektren die Rotation um die Metall-Ring-Bindung bei tiefen Temperaturen stark eingeschränkt ist. Die Röntgenstrukturanalyse von 9 (R = n-C4H9) beweist die „Envelope“-Konformation des Cyclohexadienylrings. Die n-Butylgruppe befindet sich in der exo-Position am sp3-C-Atom.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170112
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    Radikalionen, 55. Die Einelektronen-Oxidation von Tetrahedran zum Cyclobutadien-Radikalkation (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 172-186 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Radical Ions, 55. The One-Electron Oxidation of Tetrahedrane to Cyclobutadiene Radical CationTetra-tert-butyltetrahedrane, on one-electron oxidation using AlCl3 in CH2Cl2, opens to form tetra-tert-butylcyclobutadiene radical cation, which can also be generated under identical reaction conditions from tetra-tert-butylcyclobutadiene itself. The assignments of the ESR and ENDOR spectra are supported by deutero substitution of one tert-butyl group and by MNDO hypersurfaces for the thermal and for the oxidative structural changes of both C4 skeletons. The feasible formation of a valence isomeric tert-butyl(tri-tert-butylcyclopropenyl)carbene radical cation is discussed.
    Notes: Tetra-tert-butyltetrahedran öffnet sich bei Einelektronen-Oxidation mit AlCl3 in CH2Cl2 zum Tetra-tert-butylcyclobutadien-Radikalkation, das unter gleichen Reaktionsbedingungen auch aus Tetra-tert-butylcyclobutadien erzeugt werden kann. Die Zuordnungen der ESR- und ENDOR-Spektren werden durch Deutero-Substitution einer tert-Butyl-Gruppe sowie durch MNDO-Hyperflächen für die thermischen und oxidativen Strukturänderungen der beiden C4-Gerüste gestützt. Die mögliche Bildung eines valenzisomeren tert-Butyl(tri-tert-butylcyclopropenyl)carben-Radikalkations wird diskutiert.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170114
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    Saure Komplexone mit Donor-verstärkter Pyridin-Ankergruppe (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 948-954 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Acidic Complexones Bearing Donor-enhancing Pyridine Anchour GroupsThe synthesis, complex stability and -selectivity for alkaline earth metal ions of 2,6-pyridinebis-(methylamine)-N, N, N′, N′-tetraacetic acid (3a) and of their donor-enforced analogues 3b, c are described. The acid dissociation constants and the stability constants of the metal complexes have been measured potentiometrically at 25°C in water of constants ionic strength (μ = 0.1). The stability order is Ca 〉 Mg 〉 Sr 〉 Ba which is analogues to the selectivity of EDTA and comparable aliphatic complexones. The magnitudes of the stability constants of 3a are comparable to those of EDTA, while the donor-enforced analogues 3b, c form less stable complexes with alkaline earth metal ions.
    Notes: Synthese, Komplexstabilität und -selektivität gegenüber Erdalkalimetall-Ionen von 2,6-Pyridinbis(methylamin)-N, N, N′, N′-tetraessigsäure (3a) und ihren Donor-verstäkten Analoga 3b, c werden beschrieben. Die Bestimmung der Dissoziations- und Komplexbildungskonstanten erfolgt potentionmetrisch bei 25°C in Wasser konstanter ionaler Stärke (μ = 0.1). Die Bildungskonstanten der Metallkomplexe nehmen in der Reihenfolge Ca 〉 Mg 〉 Sr 〉 Ba ab und folgen damit der bei EDTA und vergleichbaren aliphatischen Komplexonen vorgefundenen Selektivität. 3a weist mit EDTA vergleichbare hohe Komplexbildungskonstanten auf, während die Donor-verstärkten Analoga 3b, c schwächere Erdalkalimetallkomplexe bilden.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170308
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    Darstellung und Röntgenstrukturanalyse des Diels-Alder-Addukts von 4-Phenyl-4H-1,2,4-triazol-3,5-dion an Octavalen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 959-965 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and X-Ray Structure Analysis of the Diels-Alder Adduct of 4-Phenyl-4H-1,2,4-triazole-3,5-dione with OctavaleneIn the reaction of 4-phenyl-4H-1,2,4-triazole-3,5-dione with octavalene (1) the Diels-Alder adduct 2 is formed. From its X-ray structure analysis the dihedral angle for the bicyclo[1.1.0]butane group, the 2- and 4-positions of which are spanned by four atoms, has been determined to be 122.7°. The bridging bond C1 - C3 has a length of 1.487 Å.
    Notes: Aus Octavalen (1) und 4-Phenyl-4H-1,2,4-triazol-3,5-dion bildet sich das Diels-Alder-Addukt 2. Seine Röntgenstrukturanalyse ergab für das Bicyclo[1.1.0]butan-Gerüst, dessen 2- und 4-Stellung durch vier Atome überbrückt sind, einen Interplanarwinkel von 122.7°. Die Brückenbindung C1 - C3 hat eine Länge von 1.487 Å.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170310
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    Kondensierte Ringsysteme, XV. Über die Reaktion von α-Chlorsulfoxiden mit Kalium-tert-butylat am Beispiel der Synthese von Oxapropellenen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 966-981 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensed Ring Systems, XV. About the Reaction of α-Chloro Sulfoxides with Potassium tert-Butoxide by the Example of the Synthesis of OxapropellenesThe synthesis of dithia- 1a - 3a and oxathiapropellenes 1b - 3b is described. From 1b - 3b the α-chloro sulfoxides 4 - 6 and α-chloro sulfones 4a - 6a are prepared, or which in most cases several stereoisomeric racemates are obtained. The constitution, configuration, and conformation of the α-chloro sulfoxide 4, the main product obtained from 1b, was elucidated by X-ray structure analysis. Only in that way it was possible to deduce the constitutions and configurations of the other stereoisomeric α-chloro sulfoxides 4 - 6 and α-chloro sulfones 4a - 6a, respectively, using 13C NMR spectroscopy. By the reaction of the α-chloro sulfones 4a - 6a with potassium tert-butoxide (Ramberg-Bäcklund reaction) the corresponding oxapropellenes 7 - 9 are obtained only in low yields (〈 10%). Contrary, the α-chloro sulfoxides 4 - 6, und analogous conditions give yields of 80 - 90% (from 4, 6) and 25% (from 5).
    Notes: Es wird die Synthese der Dithia- 1a - 3a und Oxathiapropellene 1b - 3b beschrieben. Aus 1b - 3b werden die α-Chlorsulfoxide 4 - 6 und α-Chlorsulfone 4a - 6a hergestellt, von denen meist mehrere stereoisomere Racemate erhalten werden. Konstitution, Konfiguration und Konformation des Hauptprodukts der aus 1b erhaltenen α-Chlorsulfoxide 4 wurden durch Röntgenstrukturanalyse ermittelt. Erst dadurch wurde es möglich, mit Hilfe der 13C-NMR-Spektroskopie die Konstitutionen und Konfigurationen der anderen stereoisomeren α-Chlorsulfoxide 4 - 6 und α-Chlorsulfone 4a - 6a aufzuklären. Bei der Reaktion der α-Chlorsulfone 4a - 6a mit Kalium-tert-butylat (Ramberg-Bäcklund-Reaktion) erhält man die entsprechenden Oxapropellene 7 - 9 nur in geringer Ausbeute (〈 10%), während die α-Chlorsulfoxide 4 - 6 unter analogen Bedingungen Ausbeuten von 80 - 90% (aus 4, 6) und 25% (aus 5) ergeben.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170311
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    Über die Selektivität bei der Umsetzung von Carbokationen mit Nucleophilen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 982-989 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Selectivity of the Reaction of Carbocations with NucleophilesThe problem of the selectivity of the nucleophilic attack on carbocations according to the HSAB-principle is discussed in relation to the solvolysis in ether of 7,7-bis(trifluoromethylsulfonyloxy)-norbornane (2) and 7,7-bis(trifluoromethylsulfonyloxy)-2-norbornene (4) in presence of dimethyl-magnesium, magnesium iodide and methylmagnesium iodide. The nucleophiles and carbocations are arranged according to the hard-soft-scale, so our results can be explained.
    Notes: Das Problem der Selektivität beim nucleophilen Angriff an Carbokationen wird im Rahmen des HSAB-Prinzips am Beispiel der Solvolysen in Ether von 7,7-Bis(trifluormethylsulfonyloxy)norbornan (2) und 7,7-Bis(trifluormethylsulfonyloxy)-2-norbornen (4) in Anwesenheit von Dimethylmagnesium, Magnesiumiodid und Methylmagnesiumiodid erörtert. Die Nucleophile und die als Zwischenstufen auftretenden Carbokationen werden auf der Hart-weich-Skala eingeordnet, wobei die Ergebnisse erklärt werden können.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170312
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    Dichloropalladium(II)-Komplexe mit α-Aminosäuren, α-Aminosäureestern, Dipeptiden und Dipeptidestern (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1003-1012 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dichloropalladium(II) Complexes with α-Amino Acids, α-Amino Acid Esters, Dipeptides, and Dipeptide EstersA series of trans-dichloropalladium(II) complexes Cl2PdL2 (L = α-amino acid, α-amino acid ester, dipeptide, dipeptide esters) and cis-Cl2Pd(histidine) has been prepared and spectroscopically characterized. The X-ray structure of trans-Cl2Pd(GlyOEt)2 (3b) has been determined.
    Notes: Eine Reihe von trans-Dichloropalladium(II)-Komplexen Cl2PdL2 mit (L = α-Aminosäure, α-Aminosäureester, Dipeptid, Dipeptidester) sowie cis-Cl2Pd(Histidin) wurde dargestellt und spektroskopisch charakterisiert. Die Röntgenstruktur von trans-Cl2Pd(GlyOEt)2 (3b) wurde bestimmt.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170314
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    Der Nachweis eines Radikalketten-Mechanismus für die Knabe-Reaktion von 1,2-Dihydro-2-methylpapaverin (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1436-1454 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Evidence for a Radical Chain Mechanism for the Knabe Reaction of 1,2-Dihydro-2-methylpapaverineA free radical chain mechanism is proposed for the Knabe reaction and the accompanying elimination reaction on account of their nonintegral reaction order and of successful inhibition experiments. 3,4-Dimethoxybenzyl radicals are the chain carrying species. Battersby's synthesis of N-methylpavine (19) from 1,2-dihydro-2-methylpapaverine (9) is dependent on the presence of formic acid as radical chain inhibitor. In the presence of inhibitors 1-benzyl-1,4-dihydro-2-methyl-isoquinolinium ions like 10 are persistent species whose chemistry can now be investigated.
    Notes: Die Knabe-Reaktion von 1,2-Dihydro-2-methylpapaverin (9) und die begleitende Eliminierungsreaktion wurden durch ihre gebrochene Reaktionsordnung und durch die Möglichkeit der Inhibition als Radikalkettenreaktionen erkannt, deren kettentragendes Radikal das 3,4-Dimethoxybenzylradikal ist. Die Synthese von N-Methylpavin (19) aus 1,2-Dihydro-2-methylpapaverin (9) ist an die Anwesenheit von Ameisensäure als Inhibitor der Radikalketten gebunden. Durch Zusatz von Inhibitoren können nun Immoniumionen 10 und analoge Verbindungen stabilisiert und ihre Chemie untersucht werden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170414
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    Azobrücken aus Azinen, III. Unerwartete Bildung einer Verbindung mit parallelen C=C- und N=N-Bindungen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1455-1464 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azo Bridges from Azines, III. Unexpected Formation of a Compounds with Parallel C=C and N=N Bonds2)Dialdehyde 5 reacts with hydrazine at pH 〉 7 to form the trimeric azine 6Tr, at pH 〈 4, however, to yield unexpectedly 8, which contains parallel C=C and N=N bonds in close proximity. The complex reaction is clarified. 8 is characterized by structure proving reactions and its spectroscopic data.
    Notes: Der Dialdehyd 5 reagiert mit Hydrazin bei pH 〉 7 zu dem trimeren Azin 6Tr, bei pH 〈 4 unerwartet zu 8, das parallel benachbarte C=C- und N=N-Bindungen besitzt. Der komplexe Reaktionsverlauf wird aufgeklärt. 8 wird durch struktursichernde Reaktionen und spektroskopische Daten charakterisiert.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170415
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    Azobrücken aus Azinen, IV. Intramolekulare [2 + 2]-Photocycloaddition zwischen parallelen C=C- und N=N-Bindungen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1465-1475 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azo Bridges from Azines, IV1). Intramolecular [2 + 2] Photocycloaddition of Parallel C=C and N=N BondsThe parallel C=C and N=N bonds in the rigid molecules 1 - 10 photocyclize nearly quantitatively, forming 1,2-diazetidines 11 - 20. Their structure is confirmed by spectroscopic methods and for 13 by X-ray analysis. Radiation induced denitrogenation, the normal reaction for similar compounds without neighbouring C=C bonds, is suppressed even with the sensitive derivatives of 2,3-diazabicyclo[2.2.1]heptene. Photocyclization of 6, carrying two neighbouring C=C bonds, includes only the norbornene bond.
    Notes: In den starren Molekülen 1 - 10 reagieren die benachbarten parallelen C=C- und N=N-Bindungen nahezu quantitativ unter Photocyclisierung zu den 1,2-Diazetidinen 11 - 20, deren Struktur spektroskopisch und für 13 durch Kristallstrukturanalyse bewiesen wird. Die in Abwesenheit der C=C-Bindung beobachtete Photo-Denitrogenierung unterbleibt selbst bei den empfindlichen Derivaten des 2,3-Diazabicyclo[2.2.1]heptens. Photocyclisierung von 6 mit zwei zur N=N-Bindung benachbarten C=C-Bindungen tritt nur mit der Norbornendoppelbindung ein.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170416
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    Aminosäuren, 2. N-Acetyl-α,β-didehydro-α-aminosäureester durch Stickstoffabspaltung aus α-Azidocarbonsäureestern mit Rhenium-Katalysatoren (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1497-1512 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Amino Acids, 21,2). N-Acetyl α,β-Didehydro α-Amino Acid Esters from α-Azidocarboxylic Acid Esters and Acetic Anhydride by Nitrogen Elimination with Rhenium Catalystsα-Azidocarboxylic acid esters 2 react with acetic anhydride in presence of catalytic amounts of rhenium heptasulfide and - if necessary - by addition of hydrochloric acid to give N-acetyl 3 or/and N,N-diacetyl-α,β-didehydro-α-amino acids esters 4 in very good yields. Exclusively monoacetylated products 3 are formed if water ist added before work up.
    Notes: Beim Erwärmen von α-Azidocarbonsäureestern 2 in Acetanhydrid/Essigsäure in Gegenwart katalytischer Mengen Rheniumheptasulfid und gegebenenfalls unter Zugabe von Chlorwasserstoff entstehen in sehr guten Ausbeuten N-Acetyl- 3 und/oder N,N-Diacetyl-α-β-didehydro-α-amino-säureester 4. Durch Zugabe von Wasser vor der Aufarbeitung erfolgt partielle Deacetylierung unter ausschließlicher Bildung der N-Monoacetylverbindungen 3.
    Additional Material: 7 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170419
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    Aminosäuren, 3. N-Acetylierte α-β-Didehydro-α-aminosäure-Derivate durch Stickstoffabspaltung aus α-Azidocarbonsäureamiden und α-Azido-ω-aminocarbonsäurelactamen mit Rhenium-Katalysatoren (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1513-1522 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Amino Acids, 31). N-Acetylated α-β-Didehydro α-Amino Acid Derivatives by Nitrogen Elimination from α-Azido-carboxylic Acid Amides and α-Azido-ω-aminocarboxylic Acid Lactams with Rhenium Catalystsα-Azidocarboxylic acid amides 2 and α-azido-ω-aminocarboxylic acid lactams 6, respectively, react with acetic anhydride in the presence of rhenium catalysts by nitrogen eliminations to give N-acetyl- 7 and N,N-diacetyl-α,β-didehydro-α-amino acid amides 8, α-acetylamino- 11 and α-diacetylamino-α,β-didehydro-ω-aminocarboxylic acid lactams 12, respectively. Reactions of the educts 6c, d - with a ring size 7 or 8 - additionally lead to the oxazoloazepine 14c and the oxazoloazocine 14d, respectively.
    Notes: Bei der Umsetzung von α-Azidocarbonsäureamiden 2 mit Acetanhydrid in Gegenwart von Rheniumkatalysatoren entstehen unter Stickstoffabspaltung N-Acetyl- 7 und N,N-Diacetyl-α,β-didehydro-α-aminosäureamide 8, bei der von α-Azido-ω-aminocarbonsäurelactamen 6 α-Acetyl-amino- 11 und α-Diacetylamino-α,β-didehydro-ω-aminocarbonsäurelactamen 12, wobei sich aus den Verbindungen 6c, d, mit der Ringgliederzahl 7 bzw. 8 außerdem noch das Oxazoloazepin 14c bzw. das Oxazoloazocin 14d bilden.
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    URL: http://dx.doi.org/10.1002/cber.19841170420
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    Beiträge zur Chemie des Phosphors, 1311,2). Synthese und Eigenschaften der Methylendiphosphirane (t-BuP)2C = CR2 (R = H, Me, 4-ClC6H4) (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1542-1550 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Phosphorus, 131. Synthesis and Properties of the Methylenediphosphiranes (t-BuP)2)C = CR2 (R = H, Me, 4-ClC6H4)The first methylenediphosphiranes (diphosphamethylenecyclopropanes) (t-BuP)2C = CH2 (1), (t-BuP)2C = CMe2 (2), and (t-BuP)2C = C(4-ClC6H4)2 (3) were synthesized by [2 + 1] cyclocondensation of K(t-Bu)P - P(t-Bu)K with the corresponding 1,1-dichloroolefins. The homocyclophosphanes (t-BuP)n (n = 4,3) and in the case of 1 mainly H(t-Bu)P - P(t-Bu)H are formed as by-products. The three-membered heterocycles 2 and 3 could be purely isolated as surprisingly stable compounds. According to an X-ray single-crystal analysis 3 possesses approximately C2 symmetry and exhibits one of the smallest bonding angles ψ (P - P - C) = 52.4° on a phosphorus atom experimentally proved so far. Along [100] there are canals filled with disordered n-pentane molecules.
    Notes: Die ersten Methylendiphosphirane (Diphosphamethylencyclopropane) (t-BuP)2C = CH2 (1), (t-BuP)2C = CMe2 (2) und (t-BuP)2C = C(4-ClC6H4)2 (3) wurden durch [2 + 1]-Cyclokondensation von K(t-Bu)P - P(t-Bu)K mit den entsprechenden 1,1-Dichlorolefinen synthetisiert. Als Nebenprodukte entstehen die Homocyclophosphane (t-BuP)n (n = 4,3) und im Fall von 1 vor allem H(t-Bu)P - P(t-Bu)H. Die Dreiringheterocyclen 2 und 3 konnten als thermisch überraschend beständige Verbindungen in reiner Form isoliert werden. 3 besitzt nach der Röntgenstrukturanalyse annähernd die Symmetrie C2 und enthält mit ψ (P - P - C) = 52.4° einen der kleinsten experimentell gesicherten Bindungswinkel am Phosphor. Längs [100] liegen fehlgeordnet mit n-Pentan gefüllte Kanäle vor.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170422
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    Amination, III. Trimethylsilanol as Leaving Group, V. Silylation - Amination of Hydroxy N-Heterocycles (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1523-1541 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminierung, III. Trimethylsilanol als austretende Gruppe, V. Silylierung-Aminierung von Hydroxy-N-heterocyclenDurch Silylierung-Aminierung lassen sich Hydroxy-N-heterocyclen (z. B. 18, 21, 26 u. a.) bequem in einer Einstufen-Eintopfreaktion aminieren (→ 20, 23 - 25 etc.). Aromatische Hydroxy-N-heterocyclen werden durch Silylierung in aktivierte und lipophile Zwischenprodukte vom Typ 3, 8 umgewandelt, die sich in situ mit Ammoniak, primären oder sekundären Aminen zu den entsprechenden mono-, bis- und tris-aminierten Produkten (5, 10) umsetzen. Die Additions-Eliminierungsreaktion von Aminen an O-silylierte Heterocyclen ist Lewissäure-katalysiert und verläuft gewöhnlich in hohen Ausbeuten, falls die austretende Gruppe Trimethylsilanol in situ durch überschüssiges Silylierungsmittel in Hexamethyldisiloxan umgewandelt wird. Anwendungsbreite und Grenzen dieser einfachen Methode werden diskutiert.
    Notes: Hydroxy N-heterocycles such as 18, 21, 26, and others are efficiently aminated in a one-step/one-pot procedure by silylation-amination to give 20, 23 - 25 etc. Silylation converts aromatic hydroxy N-heterocycles into activated and lipophilic intermediates of type 3, 8 which react in situ with ammonia, primary or secondary amines to form the corresponding mono-, bis- or tris-aminated products (5, 10). This addition-elimination of amines to O-silylated heterocycles in Lewis acid-catalyzed and proceeds usually in high yields if the leaving group trimethylsilanol is converted in situ by excess silylated agent into hexamethyldisiloxane. Scope and limitations of this simple procedure are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170421
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    Benzonitril als 6-Elektronen-Donor-Ligand: Die Cluster Fe3(CO)9(μ3(η2)-NCC6H5) und Fe4(CO)12(μ4(η2)-NCC6H5) (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1572-1582 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Benzonitrile as a 6-Electron Donor Ligand: The Clusters Fe3(CO)9(μ3(η2)-NCC6H5) and Fe4(CO)12(μ4(η2)-NCC6H5)The reaction of Fe3(CO)12 with benzonitrile in the presence of hydrogen leads to the benzonitrile complexes Fe3(CO)9(μ3(η2)-NCC6H5) (1a) and Fe4(CO)12(μ4(η2)-NCC6H5) (2). Their structures were determined crystallographically. The benzonitrile ligand is coordinated to the iron atoms formally via on „s̰-bond“ and two „π-bonds“ in 1a, and via three s̰-bonds and one π-bond in 2.
    Notes: Die Reaktion von Fe3(CO)12 mit Benzonitril in Anwesenheit von Wasserstoff führt zu den beiden Benzonitril-Komplexen Fe3(CO)9(μ3(μ2)-NCC6H5) (1a) und Fe4(CO)12(μ4(η2)-NCC6H5) (2). Ihre Strukturen wurden kristallographisch aufgeklärt. Der Benzonitril-Ligand ist in 1a formal über eine „s̰-Bindung“ und zwei „π-Bindungen“, in 2 über drei s̰-Bindungen und eine π-Bindung an die Eisenatome koordiniert.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170425
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    Kernspin-Kopplungskonstanten mit Platin-195 als Kriterien für die Konfigurations-Bestimmung platin-organischer Verbindungen des zweiwertigen Platins (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1606-1619 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Spin-Spin Coupling Constants by Platinium-195 as Criteria for a Configuration Determination in Platinum Organic CompoundsThe platinum organic compounds [Pt(η4-1,5-cyclooctadiene)(XC6H4)2] and cis-[Pt(P(n-Bu)3)2-(XC6H4)2] (X = H, 4-CH3, 4-(CH3)3C, 4-(CH3)2N, 3-F, 4-F, 4-CH3O, 4-CF3; 3a - 4, cis-4a - h) as well as trans-[Pt(P(n-Bu)3)2(4-CH3OC6H4)2] (trans-4g) and trans-[Pt(P(n-Bu)3)2(4-CF3C6H4)2] (trans-4h) have been studied by 31P-, 13C-, and 1H NMR spectroscopy. The coupling constants 1J[195Pt, 31P], nJ[195Pt, 13C], nJ[195Pt, H], and 2J[31P, 13C] show a clear correlation to the ligand configuration at the dsp2-hybridized platinum and can therefore be used as basis for configuration determination.
    Notes: Die platin-organischen Verbindungen [Pt(η4-1,5-cyclooctadien)(XC6H4)2] und cis-[Pt(P(n-Bu)3)2-(XC6H4)] (X = H, 4-CH3, 4-(CH3)3C, 4-(CH3)2N, 3-F, 4-F, 4-CH3O, 4-CF3; 3a - h, cis-4a - h) sowie trans-[Pt(P(n-Bu)3)2(4-CH3OC6H4)2] (trans-4g) und trans-[Pt(P(n-Bu)3)2(4-CF3C6H4)2] (trans-4h) wurden 31P-, 13C- und 1-NMR-spektroskopisch untersucht. Die Kopplungskonstanten 1J[195Pt, 31P], nJ[195Pt, 13C], nJ[195Pt, H] und 2J[31P, 13C] zeigen eine eindeutige Abhängigkeit von der Konfiguration der Liganden am dsp2-hybridisierten Platin; sie können daher zur sicheren Konfigurations-Bestimmung verwendet werden.
    Additional Material: 8 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170429
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    Zur Struktur von N-Methylencarbonsäureamiden: Röntgenstrukturergebnisse, spektroskopische Untersuchung und quantenmechanische Berechnungen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1597-1605 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Structure of N-Methylenecarboxamides: X-Ray Data, Spectroscopy, and Quantum Mechanical CalculationsN-(Diphenylmethylene)acetamide (1) has been studied by X-ray crystallography as an example for the polyfunctional, highly reactive N-methyleneamides. The dihedral angle (C = N - C = O = 73°) and the bond lengths indicate that there is only little interaction between the C = O and the C = N groups. Extensive ab initio 3-21G calculations for the parent molecule H2C = N - CH = O (2) predict a C - N rotational barrier of ca. 4 kcal/mol with a cisoid form (C = N - C = O = 23°) as the most stable structure. MNDO data as well as spectroscopic properties (IR, 13C NMR) suggest high molecular flexibility due to the many electronic interactions possible for the nitrogen atom.
    Notes: Als Beispiel für die polyfunktionellen N-Methylencarbonsäureamide wurde N-(Diphenylmethylen)acetamid (1) röntgenographisch untersucht. C = N - C = O-Torsionswinkel (73°) und Bindungslängen deuten auf nur geringe Wechselwirkungen zwischen C = O- und C = N-Molekülteil. Ausführliche ab initio-3-21G-Berechnungen am Grundsystem H2C = N - CH = O (2) sagen eine C - N-Rotationsbarriere von ca. 4 kcal/mol voraus, wobei als stabilste Struktur eine cisoide Form (C = N - C = O-Winkel = 23°) gefunden wurde. MNDO-Daten und spektroskopische Untersuchungen (IR, 13C-NMR) deuten ebenfalls auf hohe molekulare Beweglichkeit, die vor allem durch die vielfältigen elektronischen Wechselwirkungsmöglichkeiten des Stickstoffatoms verursacht wird.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170428
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    Reduktion von β-Lactamen, I. Reduktion von 3,3,3′,3′-Tetramethyl[1,1′-biazetidin]-2,2′-dion mit komplexen Hydriden (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1659-1670 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reduction of β-Lactams, I. Reduction of 3,3,3′,3′-Tetramethyl[1,1′-biazetidine]-2,2′-dione with Complex HydridesReduction of the title compound 7 with lithium aluminium hydride leads to four products 8 to 11 in yields depending on the reaction conditions. Compounds 8 to 10 are also obtained from the bicyclic hydrazide 12, isomeric with 7. Therefore, the reduction of 7 and 12 is likely to proceed in part via common intermediates. A reaction scheme is proposed to account for the generation of the products. With other hydride reagents complex reaction mixtures are obtained from 7. The reduction of 7 to 3,3,3′,3′-tetramethyl-1,1′-biazetidine (13) failed.
    Notes: Die Reduktion der Titelverbindung 7 mit Lithiumaluminiumhydrid liefert die vier Produkte 8 - 11 in von den Reaktionsbedingungen abhängigen Mengenverhältnissen. Da die Verbindungen 8 - 10 auch aus dem mit 7 isomeren bicyclischen Hydrazid 12 erhalten werden, muß die Reduktion von 7 und 12 z. T. einheitlich ablaufen. Hierfür wird ein Reaktionsschema vorgeschlagen. Mit anderen Hydridübertragungsreagenizen entstehen aus 7 komplexe Produktgemische. Die Reduktion von 7 zu 3,3,3′,3′-Tetramethyl-1,1′-biazetidin (13) gelang nicht.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19841170503
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  • 80
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    Synthese von (Trimethylstannyl)adamantan-Derivaten (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 565-574 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of (Trimethylstannyl)adamantane DerivativesReaction of brominated adamantane compounds with (trimethylstannyl)lithium afforded a series of (trimethylstannyl)adamantane derivatives. Additionally, we found products from fragmentation and reduction reactions which allowed conclusions concerning the mechanisms. Surprisingly high stereoselectivities were observed in most instances. By Wurtz synthesis we obtained 2-adamantyltriphenylstannane.
    Notes: Die Umsetzung bromierter Adamantanverbindungen mit (Trimethylstannyl)lithium lieferte eine Reihe von (Trimethylstannyl)adamantan-Derivaten. Wir fanden zusätzlich Fragmentierungs- und Reduktionsprodukte, die Rückschlüsse auf den Mechanismus zuließen. Überraschend ist die hohe Stereoselektivität der meisten Reaktionen. Durch Wurtz-Synthese wurde auch 2-Adamantyltriphenylstannan erhalten.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170212
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  • 81
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    Substituenteneinflüsse auf das Valenzgleichgewicht 4,8-substituierter Homotropilidene (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 575-584 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Influence of Substituents on the Valence-tautomeric Equilibrium of 4,8-Substituted HomotropilidenesThe valence-tautomeric equilibrium of 4,8-substituted homotropilidenes 2 - 4 is governed by electronic (preference of a substituent for attachment to a cyclopropyl or an aliphatic carbon atom) and steric factors. The conformational change chair → boat, which precedes the Cope rearrangement of a homotropilidene, cannot take place when both endo-8- and cis-4-substituents are present.
    Notes: Das Valenzgleichgewicht 4,8-substituierter Homotropilidene 2 - 4 wird durch elektronische (Präferenz eines Substituenten für Cyclopropyl- oder aliphatische Verknüpfung) und sterische Faktoren bestimmt. Die der Cope-Umlagerung vorgeschaltete Konformationsänderung Sessel → Boot wird verhindert, wenn das Homotropiliden sowohl in endo-8- wie in cis-4-Stellung substituiert ist.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841170213
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  • 82
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    Heterocyclische β-Enaminoester, 311). Neue 6:7-, 6:8- und 5:6:7-Kombinationen heterokondensierter Pyrimidine aus den Iminophosphoranen heterocyclischer β-Enaminoester. - Stabile heterocyclische Ylide (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 585-621 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic β-Enamino Esters, 311). Novel 6:7-, 6:8, and 5:6:7-Combinations of Heterocondensed Pyrimidines from Iminophosphoranes of Heterocyclic β-Enamino Esters. - Stable Heterocyclic YlidesWith acetylenic esters the (5-azolylimino)triphenylphosphoranes 10a - d do not show any cyclo-addition tendency, while the (2-thienylimino)triphenylphosphoranes 8a, b yield the stable ylids 13a, b. By treatment with phenyl isocyanate the iminophosphoranes 16a - m, 17, and 18a, b afford the carbodiimides 19a - m, 20, and 21a, b; however, 10b - d give the O-ethylisoureas 24b - d. 19a, b, e, f, h are transformed in aqueous ethanol into 6:7-bicycles, namely into oxepino[2,3-d]pyrimidines 25a, b, e, f, h. With isopropylamine the 2-isopropylamino-6:7-bicycles 31a - c, e - h are formed analogously, while in the case of thiocin 21a the 6:8-bicycle 34 is obtained. The salts 33f, g are formed by treating 19f, g or 25f with aqueous diethylamine. Accordingly, 2-aminoethanol, 3-aminopropanol, and ethylenediamine react with 19a, b, f, l to afford the 2-hydroxy- and 2-aminoalkyl-6:7-bicycles 36a - f; by treatment with hydrazine the 2-hydrazinooxepino- and -thiepino[2,3-d]pyrimidines 38a - h and 39 are obtained, which are converted with functional C1-units into 5:6:7-tricycles 43a - d, 45'a, b.
    Notes: Die (5-Azolylimino)triphenylphosphorane 10a - d zeigen mit Acetylendicarbonsäureestern keine Tendenz zur Cycloaddition, während die (2-Thienylimino)triphenylphosphorane 8a, b, zu den stabilen Yliden 13a, b reagieren. Mit Phenylisocyanat ergeben die Iminophosphorane 16a - m, 17 und 18a, b die Carbodiimide 19a - m, 20 und 21a, b; 10b - d liefern statt dessen die O-Ethylisoharnstoffe 24b - d. In wäßrigem Ethanol werden 19a, b, e, f, h in 6:7-Bicyclen, nämlich in die Oxepino[2,3-d]pyrimidine 25a, b, e, f, h umgewandelt. Mit Isopropylamin bilden sich die 2-Isopropylamino-6:7-Bicyclen 31a - c, e - h und im Fall des Thiocins 21a der 6:8-Bicyclus 34. Die Salze 33f, g entstehen durch Einwirkung von wäßrigem Diethylamin auf 19f, g bzw. auf 25f. 2-Aminoethanol, 3-Aminopropanol und Ethylendiamin ergeben mit 19a, b, f. l analog die 2-Hydroxy- und 2-Aminoalkyl-6:7-Bicyclen 36a - f; mit Hydrazin werden die 2-Hydrazinooxepino- und -thiepino[2,3-d]pyrimidine 38a - h und 39 erhalten, die mit funktionellen C1-Bausteinen zu den 5:6:7-Tricyclen 43a - d, 45'a, b führen.
    Additional Material: 24 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170214
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    Addition von Aldehyden an aktivierte Doppelbindungen, XXXIV1). Addition von Aldehyden an cyclische α-Methylenketone (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 682-693 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Addition of Aldehydes to Activated Double Bonds, XXXIV1). Addition of Aldehydes to Cyclic α-Methylene KetonesThe thiazolium salt-catalyzed addition of aldehydes to the cyclic α-methylene ketones 3, 4, 7, 8, 48, and 49 leads to γ-diketones 9 - 22, 50 - 53; some of them were converted into unsaturated ketones 23 - 28, pyrroles 29 - 34, 37 - 43, and furans 35, 36, 44 - 46. The α-methylene ketones were synthesized by retro Diels-Alder reaction of the corresponding norbornene compounds 1, 2, 5, 6, 47.
    Notes: Die Thiazoliumsalz-katalysierte Addition von Aldehyden an die cyclischen α-Methylenketone 3, 4, 7, 8, 48 und 49 führt zu γ-Diketonen 9 - 22, 50 - 53, aus denen einige ungesättigte Ketone 23 - 28, Pyrrol- 29 - 34, 37 - 43 und Furanderivate 35, 36, 44 - 46 synthetisiert wurden. Die Darstellung der α-Methylenketone erfolgte durch Retrospaltung entsprechender Norbornenderivate 1, 2, 5, 6 und 47.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170221
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    Diazadienes as Controlling Ligands in Catalysis, 51). Synthesis of Chiral Diazadienes R* - N = CR' - CR' = N - R* (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 694-701 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diazadiene als Steuerliganden in der Katalyse, 51). Synthese chiraler Diazadiene R* - N = CR' - CR' = N - R*Die im Prinzip einfache Kondensationsreaktion von Glyoxal (als Hydrat) und 2,3-Butandion mit primären Aminen führt leider bei aliphatischen Aminen mit tertiärem bzw. sekundärem α-Kohlenstoff oftmals zu unerwünschten Additionsprodukten. Unter speziellen Synthesebedingungen können mit (R)-1-Phenylethylamin (1) und (1S,2S,3S,5R)-3-(Aminomethyl)pinan die gewünschten Diimine (Diazadiene (dad): R* - N = CR' - CR' = N - R*, R' = H, CH3) 4, 6 - 8 erhalten werden. Aus (S)-2-Amino-1-butanol (3) werden je nach Dion-Komponente ein Morpholinomorpholin 9 bzw. ein Bioxazolidin 10 gebildet, die von elektronenreichen Metallen in ihrer isomeren Form als Diazadiene gebunden werden ((dad)Mo(CO)4 11 und 12). Die offenkettige dad-Form ist durch O-Silylierung (14, 15) stabilisierbar. Die (dad)Eisen(0)-katalysierte Dimerisierung von Butadien zu 4-Vinyl-1-cyclohexen mit diesen dad-Liganden ergibt Enantiomerenüberschüsse e.e. bis zu 16%.
    Notes: The condensation of glyoxal (as hydrate) or 2,3-butanedione with primary amines is, in principle, a simple reaction. Unfortunately, aliphatic amines with secondary or tertiary α-carbons often give unwanted addition products. Under special reaction conditions the desired diimines (diazadienes (dad): R* - N = CR' - CR' = N - R*, R' = H, CH3) 4, and 6 - 8 are obtained from (R-1-phenyl-ethylamine (1) and (1S,2S,3S,5R)-3-(aminomethyl)pinane (2). Depending on the dione, a morpholinomorpholine 9 and a bioxazolidine 10 are formed from (S)-2-amino-1-butanol (3), which are bound by electron-rich metals in their isomeric dad form ((dad)Mo(CO)4 11 and 12). The acyclic dad structure is stabilized by O-silylation (14, 15). The (dad)iron(0) catalyzed dimerization of butadiene with these controlling ligands to 4-vinyl-1-cyclohexene occurs with an enantiomeric excess up to 16%.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170222
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    Anwendung der hochaufgelösten Festkörper-NMR-Spektroskopie zur Bestimmung der Ring-Ketten-Tautomerie (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 702-709 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Application of High-Resolution Solid State NMR Spectroscopy for the Determination of the Ring-Chain TautomerismThe structure of the benzaldehyde derivatives 1 and 2 showing ring-chain tautomerism was investigated by NMR spectroscopy in the solid state and in solution. Difficulties in preparing single crystals, low solubility, and the presence of solvent in the crystal prevent an X-ray analysis and other spectroscopic methods. The structural problem was solved by C-13 CP-MAS NMR spectroscopy. 2-[2-(Methylamino)ethyl]-3-nitrobenzaldoxime (1) exists in the chain form in the crystal but is in equilibrium with the cyclic isomer in solution. Two different types of crystals were obtained from the aminoethenylbenzaldehyde derivative 2, one of them containing the chain the other the cyclic form of 2. Signal assignments in the solid state result from comparison with the spectra in solution, which have been partially assigned by 2D 1H 13C NMR shift correlation.
    Notes: Die Struktur der Benzaldehyd-Derivate 1 und 2, die Ring-Ketten-Tautomerie zeigen, wird durch NMR-Spektroskopie im festen und gelösten Zustand untersucht. Schwierigkeiten beim Züchten von Einkristallen sowie die Schwerlöslichkeit bzw. die Anwesenheit von Kristallösungsmittel verhinderten die Anwendung der Röntgenstrukturanalyse und anderer spektroskopischer Methoden. Mit Hilfe von C-13-CP-MAS-NMR-Spektren wird das Strukturproblem lösbar. In 2-[2-(Methyl-amino)ethyl]-3-nitrobenzaldoxim (1) liegt im Kristall die offene Form vor, die in Lösung mit dem cyclischen Tautomeren 1b im Gleichgewicht steht. Vom Aminoethenylbenzaldehyd-Derivat 2 lassen sich zwei verschiedene Kristalle gewinnen, in denen alternativ die offene und die cyclische Struktur vorliegt. Zur Signalzuordnung werden die Festkörper-NMR-Spektren mit den z. T. durch 2D-1H-13C-NMR-Verschiebungskorrelation zugeordneten C-13-Spektren verglichen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170223
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    Asymmetrische Katalysen, 121). Neue optisch aktive P, N-Liganden und ihr Einsatz in der Rh-katalysierten asymmetrischen Hydrierung und Hydrosilylierung (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 710-724 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Asymmetric Catalyses, 121). New Optically Active P,N Ligands and Their Use in Rh-Catalyzed Asymmetric Hydrogenation and HydrosilylationNew P,N-ligands 2, 4 and 5 were prepared by Schiff base condensation of (2-formylphenyl)diphenyl- and tris(2-formylphenyl)phosphane with (R)-(+)-1-phenylethylamine and ethylenediamine. (R)-(+)-aminphos (6) was obtained by hydrogenation of the C = N bond in (R)-(+)-iminphos (2). The new imine ligands form stable chelate complexes. The pseudotetrahedral CpFe(CO)[R)-(+)-iminphos]PF6 was separated into the diastereoisomes with respect to the Fe configuration. The square planar Rh[(R)-(+)-iminphos]2X is obtained as a cis/trans mixture. The isolated Rh complexes and the combinations [Rh(COD)Cl]2/2, 4, and 6, respectively, were used as catalysts for the homogeneous hydrogenation of (Z)-α-(acetylamino)cinnamic acid and for the hydrosilylation of acetophenone with diphenysilane. The optical yield of 1-phenyl-ethanol, the product of hydrolysis of the hydrosilylation, increases with increasing ligand excess, decreasing catalyst concentration, and decreasing temperature.
    Notes: Neue P,N-Liganden 2, 4 und 5 wurden durch Schiffbasenkondensation von (2-Formylphenyl)diphenyl- und Tris(2-formylphenyl)phosphan mit (R)-(+)-1-Phenylethylamin und Ethylendiamin dargestellt. (R)-(+)-aminphos (6) wurde durch Hydrierung der C = N-Bindung in (R)-(+)-iminphos (2) erhalten. Die neuen Imin-Liganden bilden stabile Chelatkomplexe. Das pseudotetraedrische CpFe(CO)[(R)-(+)-iminphos]PF6 wurde in die Diastereomeren bezüglich der Fe-Konfiguration getrennt. Das quadratisch-planare Rh[(R)-(+)-iminphos]2X fällt als cis/trans-Gemisch an. Die isolierten Rh-Komplexe und die Kombinationen [Rh(COD)Cl]2/ 2, 4 bzw. 6 wurden als Katalysatoren für die homogene Hydrierung von (Z)-α-(Acetylamino)zimtsäure und für die Hydrosilylierung von Acetophenon mit Diphenylsilan eingesetzt. Die optische Ausbeute an 1-Phenylethanol, dem Hydrolyseprodukt der Hydrosilylierung, steigt mit zunehmendem Ligandenüberschuß, mit abnehmender Katalysatorkonzentration und mit abnehmender Temperatur.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170224
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    Synthese und Solvolyse von (Z)/(E)-1-Methyl-2-[2-(1-propin-1-yl)phenyl]vinyl-triflat und 1-Methylen-2-[2-(1-propin-1-yl)-phenyl]ethyl-triflat (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3021-3033 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Solvolysis of (Z)/(E)-1-Methyl-2-[2-(1-propyn-1-yl)phenyl]vinyl Triflate and 1-Methylene-2-[2-(1-propyn-1-yl)phenyl]ethyl TriflateThe synthesis and solvolysis of the triflates (Z)/(E)-8 and 20 in various solvents are described. The (E)-triflate 8 reacts in trifluoroethanol by rearrangement via the intermediate naphthyl cation 9 to give the naphthyl ether 22 and the naphthyl triflate 24. The identification of 1-bromo-2,3-dimethylnaphthalene (26) after addition of bromide ions to the solvolysis confirms 9 as a reactive intermediate. The (Z)-triflate 8 solvolyses preferably to the elimination product 28, the formation of [(3-methyl-2-naphthyl)methyl] (trifluoroethyl) ether (23), however, can not be explained via the cation 9 as an intermediate. The solvolysis of the triflate 20 leads also to the rearranged products 22 and 23.
    Notes: Die Synthese und Solvolyse der Triflate (Z)/(E)-8 und 20 in verschiedenen Lösungsmitteln wird beschrieben. Das (E)-Triflat 8 reagiert in Trifluorethanol bevorzugt unter Umlagerung über das intermediäre Naphthylkation 9 zum Naphthylether 22 und zum Naphthyltriflat 24. Der Nachweis von 1-Brom-2,3-dimethylnaphthalin (26) nach Bromidionenzusatz zur Solvolyse bestätigt 9 als reaktive Zwischenstufe. Das (Z)-Triflat 8 solvolysiert bevorzugt zum Eliminierungsprodukt 28, die Bildung des [(3-Methyl-2-naphthyl)methyl]-(trifluorethyl)-ethers (23) kann jedoch nicht über das Kation 9 als Zwischenstufe erklärt werden. Die Solvolyse des Triflates 20 führt ebenfalls zu den Umlagerungsprodukten 22 und 23.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19841171004
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    Notizen.Bestimmung absoluter Geschwindigkeitskonstanten bei der radikalischen Addition an Alkene nach der “Quecksilbermethode” (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3160-3164 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurement of Absolute Rates of Radical Additions to Alkenes by the “Mercury Method”Using the 5-hexenyl radical (2) as “radical clock” the rates of radical additions to methyl acrylate (5a) and acrylonitrile (5b) are measured by the “mercury method” (Table 1). Alkyl radicals are trapped by the alkylmercury hydride 1 with rate constants of at least 107 1 · mol-1 · s-1.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841171015
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  • 89
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    Electronic Resource
    Masthead (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841171101
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  • 90
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    Radikalkettenreaktionen mit Maleinsäureanhydriden  -  Zur kontrathermodynamischen Stereoselektivität (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3175-3182 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Radical Chain Reactions with Maleic Anhydrides  -  Contrathermodynamic StereoselectivityThe reactions of cyclohexylmercuric chloride with NaBH4 and alkenes 1a-g yield 60-84% of products 3, 4 and 6 in a radical chain process (table 1). Caused by steric effects of substituents Z at least 97% of the radical attack occurs at the unsubstituted carbon atom of maleic anhydrides 1c-g. Only fluoromaleic anhydride 1b is attacked by cyclohexyl radicals predominantly at the substituted carbon atom, because fluorine is a tiny, electron releasing substituent. Radicals 2 are trapped predominantly from the anti-direction by the H-donor (figure 1), yielding cis-compounds 3 as main products. This „contrathermodynamic“ stereoselectivity ranges between 2.3 and 19 (table 1).
    Notes: Die Reaktion von Cyclohexylquecksilberchlorid mit NaBH4 und den Alkenen 1a-g liefert in einer Radikalkettenreaktion die Produkte 3, 4 und 6 in 60- bis 84proz. Ausbeuten (s. Tab. 1). Wegen der sterischen Effekte der Substituenten Z erfolgt der Angriff der Radikale zu mindestens 97% am unsubstituierten C-Atom der Maleinsäureanhydride 1c-g. Allein das Fluormaleinsäureanhydrid 1b wird bevorzugt am substituierten C-Atom durch Cyclohexyl-Radikale angegriffen. Die Ursache für diese umgekehrte Regioselektivität liegt in der geringen Raumerfüllung und dem elektronenspendenden Effekt des Fluoratoms. Die H-Übertragung auf die Radikale 2 erfolgt überwiegend von der anti-Seite (s. Abb. 1), so daß die thermodynamisch instabileren cis-Verbindungen 3 als Hauptprodukte entstehen. Diese „kontrathermodynamische“ Stereoselektivität liegt zwischen 2.3 und 19 (s. Tab. 1).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841171103
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  • 91
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    Reaktive Platin-Komplexe mit α-Aminosäurederivaten und ihre P- und N-Kernresonanzspektren (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1241-1245 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactive Platinum Complexes with α-Amino Acid Derivatives and their 31P- and 15N Nuclear Magnetic Resonance SpectraThe α-amino acidate chelate complexes (n-Bu3P)(Cl)⊓PtNH2CH(R)COO (1a - c) (R = H, CH3, CHMe2) react with thionyl chloride, phosphorus pentachloride, or acetyl chloride by cleavage of the chelate ring to give complexes with α-amino acyl chloride or acetic glycine anhydride as ligands: (n-Bu3P)Cl2Pt(NH2CH2COCl) (2), (n-Bu3P)Cl4Pt(NH2CH(CHMe2)COCl) (6), (n-Bu3P)-Cl2Pt(NH2CH2CO(O)OCCH3) (4). Using 15N enriched amino acids, the IR, 15N and 31P NMR spectra indicate cis orientation of phosphane and amino groups in all these complexes.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170336
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  • 92
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    Synthesen mit Alkendiazoniumsalzen, III. ω,ω′-Di-1H-1,2,3-triazolylalkane aus Ethendiazonium- hexachloroantimonaten und ω,ω′-Diaminoalkanen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1246-1249 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses with Alkenediazonium Salts, III. ω,ω′-Di-1H-1,2,3-triazolylalkanes from Ethenediazonium Hexachloroantimonates and ω,ω′-DiaminoalkanesReaction of the ethenediazonium hexachloroantimonates 2 with ω,ω′-diaminoalkanes 3 leads to ω,ω′-di-1H-1,2,3-triazolylalkanes 5.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170337
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  • 93
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    Beiträge zur Chemie des Bors, 135. Additionsverbindungen von 1,3,2-Diazaborolidinen mit Aluminium- und Galliumhalogeniden (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1222-1234 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 1351). Addition Compounds of 1,3,2-Diazaborolidines with Aluminium and Gallium Halides1,3-Dimethyl-1,3,2-diazaborolidines 3 - 6 add aluminium and gallium halides, respectively, in a 1 : 1 molar ratio. The ligand is monodentate in these coordination compounds (3a - e, 4a, 5a, b, 6a). Addition occurs at one of the ring nitrogen atoms irrespective of the B-substituent. A consequence of this coordination is a long BN bond to the chiral tetracoordinated nitrogen atom as well as a considerable shortening of the BN bond involving the tricoordinate ring nitrogen. In addition, the almost planar five-membered ring adopts the envelope conformation as shown by an X-ray structure analysis of 5a. In contrast, the 2-(dimethylamino)diazaborolidine 7 yields unstable 1 : 1 besides stable 1 : 2 adducts 8. In these the Lewis acid is also coordinated to the ring nitrogen atoms only.
    Notes: Die 1,3-Dimethyl-1,3,2-diazaborolidine 3 - 6 addieren Aluminium- oder Galliumhalogenide im Molverhältnis 1 : 1 zu Koordinationsverbindungen 3a - e, 4a, 5a, b, 6a, in denen der Ligand einzähnig ist. Die Anlagerung erfolgt unabhängig vom B-Substituenten an einem Ringstickstoff-Atom. Folge dieser Koordination ist die Ausbildung einer langen BN-Bindung zum chiralen tetra-koordinierten Ring-Stickstoff, eine erhebliche Verkürzung der BN-Bindung zum dreifach koordinierten endocyclischen Stickstoffatom und der Übergang des nahezu planaren Fünfrings in die „envelope“-Konformation, wie die Röntgenstrukturanalyse von 5a belegt. Im Gegensatz dazu liefert das 2-(Dimethylamino)diazaborolidin 7 mit AlX3 und GaX3 instabile 1 : 1- und stabile 1 : 2-Addukte 8. In diesen ist die Lewis-Säure nur an den Ringstickstoff-Atomen koordiniert.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170334
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  • 94
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    Eine einfache Synthese primärer Amine über ihre N,N-Bis(trimethylsilyl)-Derivate (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1250-1254 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Simple Synthesis of Primary Amines via their N,N-Bis(trimethylsilyl) DerivativesPrimary halogen compounds 1 or the corresponding tosylates react with sodium bis(trimethylsilyl)amide (2) in hexamethyldisilazine to form N,N-bis(trimethylsilyl)amines 3, which are converted into the amine hydrochlorides 5 by treatment with aqueous HCl.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170338
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  • 95
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    Dibenz[a,j]anthracene via Photo-cyclodehydrogenation of 9,10-Dihydro-2-styrylphenanthrene (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1255-1258 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dibenz[a,j]anthracen durch Photocyclodehydrierung von 9,10-Dihydro-2-styrylphenanthrenWährend aus 2-Styrylphenanthren (1) durch Photocyclodehydrierung Benzo[c]chrysen (2) entsteht, läßt sich unter Ausnutzung der „ΣF*-Regel“5) aus 9,10-Dihydro-2-styrylphenanthren (4) durch Photocyclodehydrierung zu 6 und anschließende Dehydrierung Dibenz[a,j]anthracen (3) erhalten.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170339
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  • 96
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    Eine einfache Synthese der 5-Cyan-2-pyridincarbonsäure und ihres Amids (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1259-1261 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Simple Synthesis of 5-Cyano-2-pyridinecarboxylic Acid and its AmideThe title compounds 3 and 2 (X = CN) are prepared in good yields by regioselective carbamoylation of 3-cyanopyridine in a Minisci reaction and by consecutive amide hydrolysis with amyl nitrite in HCl-saturated acetic acid. The observed regioselectivity apparently remains confined to carbamoyl and possibly acyl radicals and to - M-effect substituents in 3-position.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170340
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  • 97
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    Masthead (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170401
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  • 98
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    Electronic Resource
    Masthead (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170101
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  • 99
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    Zur Umsetzung von 2-Pyrrolcarbaldehyd mit heterosubstituierten Ethenen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1424-1435 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Reaction of 2-Pyrrolecarbaldehyde with Hetero-substituted Ethenes3H-Pyrrolizines 1 have been obtained from reactions of 2-pyrrolecarbaldehyde with ethenylphosphonates 2 and the phosphane oxide 5, respectively, the ratio of products depending on the structure of the educts. On varying the reaction conditions a controlled synthesis of both isomers 1e/f was achieved. Pyrrolizines, formed in a reaction of 2 pyrrolecarbaldehyde with ethenyl phenyl sulfone (3), could not be isolated since the reaction proceeded to give more complex pyrrolizine derivatives and the cyclazine 11. A mechanism is proposed for this multistep reaction. N-Alkylation of 2-pyrrolecarbaldehyde with dihaloalkanes has been carried out using phase transfer catalysis.
    Notes: Umsetzungen des 2-Pyrrolcarbaldehyds mit Ethenylphosphonaten 2 und dem Phosphanoxid 5 führten zu 3H-Pyrrolizinen 1, wobei das Mengenverhältnis der gebildeten Isomeren von der Struktur der Edukte abhängt. In einem Falle (1e/1f) gelang die gezielte Synthese beider Isomeren durch Variation der Reaktionsbedingungen. Die aus 2-Pyrrolcarbaldehyd und Ethenylphenylsulfon (3) entstandenen Pyrrolizine 1e/f reagieren weiter unter Bildung komplexer Pyrrolizinderivate und des Cyclazins 11. Für diese Mehrstufenreaktion wird ein Mechanismus vorgeschlagen. Unter Phasentransfer-Bedingungen gelingen Alkylierungen des 2-Pyrrolcarbaldehyds mit Dihalogenalkanen.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170413
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  • 100
    Electronic Resource
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    Anodische Oxidation von Organoborverbindungen (1984)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1400-1423 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Anodic Oxidation of OrganoboranesOrganoboranes are converted into more easily oxidizable borates by reaction with nucleophiles and the alkyl groups are dimerized by anodic oxidation. The oxidation potentials (Ep) of the borates depend strongly on the nature of the complexing nucleophile, for instance Ep = +0.37V (vs. SCE) with OH- or +1.65V with tetrahydrofuran. The dimer yields are optimized with trioctylborane (5) by variation of the electrode material and the electrolyte. At the platinum anode in sodium hydroxide-methanol/tetrahydrofuran yields of 80% are obtained for acyclic alkyl groups, and lower ones for cycloalkyl groups. They exceed those obtained by the Kolbe electrolysis or the oxidation with neutral hydrogen peroxide and they are comparable to those of the AgNO3 oxidation. - The selective preparation of unsymmetrical products from borates with different alkyl groups is not possible, the dimerization proceeds likely via free radicals that couple statistically. Good yields of unsymmetrical coupling products are achieved, when one olefin is used in excess. With chloro-, ethoxy-, acetoxy-, and aryl-substituted alkyl groups the dimers are obtained in 21 - 66% yield, with bromide the yield are lower and with nitriles the dimerization fails.
    Notes: Organoborane werden durch Nucleophile in leichter oxidierbare Borate übergeführt und die Alkylreste durch anodische Oxidation dimerisiert. Die Oxidationspotentiale (Ep) der Borate werden stark vom komplexierenden Nucleophil beeinflußt, z. B. Ep = +0.37V (gKE) mit OH- oder + 1.65 V mit Tetrahydrofuran. Mit Trioctylboran (5) werden die Dimerenausbeuten (10) durch Variation von Elektrodenmaterial und Elektrolyt optimiert. An der Platinanode in KOH-Methanol/Tetrahydrofuran liegen die Ausbeuten für acyclische Alkylreste um 80%, die für Cycloalkane niedriger. Sie übertreffen die der Kolbe-Elektrolyse oder der Oxidation mit neutralem Wasserstoffperoxid und sind denen bei der Oxidation mit Silbernitrat vergleichbar. - Die selektive Darstellung unsymmetrischer Produkte aus Boraten mit unterschiedlichen Alkylresten gelingt nicht; die Dimerisierung verläuft wahrscheinlich über freie Radikale, die statistisch kuppeln. Gute Ausbeuten an unsymmetrischen Kupplungsprodukten werden jedoch erzielt, wenn ein Olefin im Überschuß eingesetzt wird. Mit chlor-, ether-, ester- und arylsubstituierten Alkylresten erhält man Dimere mit 21 - 66% Ausbeute. Mit Bromiden gelingt die Kupplung schlecht, mit Nitrilen überhaupt nicht.
    Additional Material: 12 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19841170412
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