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  • 1970-1974  (4,021)
  • 1965-1969  (4,232)
  • 1920-1924  (3,032)
  • 1850-1859
  • Inorganic Chemistry  (11,094)
  • Bone
Material
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 309-315 
    ISSN: 1432-0827
    Keywords: Osteoblast ; Matrix ; Bone ; Scanning electron microscope
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les territoires sécrétoires des ostéoblastes d'os pariétal de rats sont déterminées en utilisant la microscopie électronique à balayage. Le territoire moyen de 4.620 cellules, dans 19 territoires, est de 154 μm2 par ostéoblaste. Les valeurs extrêmes par champ varient de 136 à 177 μm2 par ostéoblaste. Quatre cent cellules sont mesurées individuellement; la valeur moyenne par ostéoblaste est de 143 μm3 avec une déviation standard de 33. Le taux d'apposition journalier, mesuré par la tétracycline pendant 8 jours, est de 3.12 μm (déviation standard 0.22). Ce qui correspond à une production matricielle journalière d'environ 470 μm3 par ostéoblaste.
    Abstract: Zusammenfassung Die Ausscheidungsbereiche von Ratten-Osteoblasten des Scheitelbeines wurden mit dem Raster-Elektronenmikroskop direkt gemessen. Der durchschnittliche Bereich von 4620 Zellen in 19 Gesichtsfeldern war 154 μm2 per osteoblast. Der Streubereich lag in den verschiedenen Gesichtsfeldern zwischen 136 und 177 μm2 per Osteoblast. 400 Zellen wurden einzeln gemessen. Bei diesen war der Durchschnittswert per Osteoblast 143 μm2, mit einer Standard-Abweichung von 33. Die tägliche Anlagerungsrate während einer Periode von 8 Tagen war 3,12 μm (Standard-Abweichung 0,22); sie wurde mittels Tetracyclinmarkierung der Mineralisierungsfront gemessen. Dies ergab eine tägliche Produktionsrate der Matrix von etwa 470 μm3 per Osteoblast.
    Notes: Abstract The secretory territories of rat osteoblasts on the parietal bone were measured directly using scanning electron microscopy. The mean territory of 4620 cells in 19 fields was 154 μm2 per osteoblast. The range for the fields was 136 to 177 μm2 per osteoblast. Four hundred cells were measured individually—for these the mean value per osteoblast was 143 μm2 with a standard deviation of 33. The daily rate of apposition over an 8 day period was 3.12 μm (standard deviation 0.22) measured by tetracycline marking of the mineral front. This gave a daily matrix production rate of approximately 470 μm3 per osteoblast.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 327-331 
    ISSN: 1432-0827
    Keywords: Bone ; Piezoelectricity ; Collagen ; Aging
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The piezoelectric constant of mature and immature bone (defined herein) has been measured in an effort to determine whether it varies with age. It was found that the average value of the piezoelectric constantd 14 of femur from three week old calves was 58% of the value of femur from three year old bulls. The results were interpreted to indicate qualitative differences in the corresponding collagen matrices. Mature human tibia from males ranging in age from 21 to 53 years of age showed a small but significant increase ind 14 with age. Some data concerning diseased human bone, and well-preserved human bone excavated in Peru are also presented.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 333-337 
    ISSN: 1432-0827
    Keywords: Bone ; Materials ; Histology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des métaux poreux et des céramiques sont implantés dans l'osin vivo et sont prélevés, après différents intervalles, pour étudier histologiquement la colonisation tissulaire. Les implants prélevés sont fixés avec les tissus environnants et inclus dans des epoxy-résines, de faible viscosité. Les échantillons sont coupés à l'aide d'une scie diamantée et fixés sur des lames pétrographiques, pour être ensuite amincis à environ 75 μm. Ils sont légèrement colorés au bleu de méthylène et à l'alizarine rouge S, qui donne un bon contraste entre tissus durs et mous et démontrent la présence d'os calcifié dans les implants poreux métalliques et céramiques.
    Abstract: Zusammenfassung Poröse Metall- und Keramikstücke wurden in vivo in Knochen implantiert und nach verschiedenen Intervallen entnommen, um histologisch zu untersuchen, wie weit sie ins Gewebe eingewachsen waren. Die entnommenen Implantate mit dem sie umgebenden Gewebe wurden fixiert, dehydriert und in ein niedrigvisköses Epoxy-Harz eingebettet. Die Proben wurden mit einer Diamantsäge in dicke Schnitte zerteilt, auf Steinscheiben zementiert und von Hand auf etwa 75 μm geschliffen. Sie wurden mit Methylenblau und Alizarin-Rot S schwach gefärbt; dies ergibt einen großen Kontrast zwischen Knochen und Weichgewebe und zeigt die Bildung von verkalktem Knochen innerhalb poröser Metall- und Keramik-Implantate deutlich.
    Notes: Abstract Porous metals and ceramics were implanted in bonein vivo and retrieved at intervals for histological evaluation of tissue ingrowth. Recovered implants with surrounding tissues were fixed, dehydrated and embedded in a low-viscosity epoxy resin embedding medium. The embedded samples were cut into thick sections with a diamond saw, cemented to petrographic slides, and hand-ground to approximately 75 μm. They were lightly stained with methylene blue and Alizarin Red S, which provided great contrast between the bone and soft tissues, and clearly demonstrated the formation of calcified bone within porous metal and ceramic implants.
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  • 4
    ISSN: 1432-0827
    Keywords: Osteogenesis ; Osteoinduction ; Bone ; Matrix ; Cell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Bone matrix demineralized in 0.6 N HCl at 2° for 24 h and implanted in muscle in allogeneic rats possesses consistently reproducible bone morphogenetic activity. Experiments on implants of matrix, obtained from donors injected with3H-tyrosine or3H-tryptophan, or Na35SO4, suggest that bone morphogenetic property is a protein or apart of a protein that is (1) insoluble in buffer solutions, pH 3.6 and 5.0; (2) degraded in buffer solutions at pH 7.4 by an endogenous sulfhydryl-group neutral proteinase; (3) digested by trypsin at 15° within 8 h without solubilization of the helical regions, possibly even without degradation of the nonhelical ends of the bone collagen molecule, and without any loss of the periodic ultrastructure of the collagen fibrils; (4) degraded or removed by 0.1 N NaOH at 2° within 24 h without solubilization of collagen; (5) biologically active even after nitration of tyrosyl groups with tetranitromethane. The release of only one-third of the radioactivity with loss of nearly all yield of new bone by limited tryptic digestion of3H-borohydride-reduced matrix indicates that the bone morphogenetic response is the function of a non-collagenous component. Autoradiographs of implants of matrix with non-collagenous proteins labelled with3H-tryptophan,3H-tyrosine, or both3H-tyrosine and3H-phenyl-alanine demonstrate random dissemination of the radioactive constituents and no evidence of local transfer of labelled proteins or soluble protein derivatives. Hypothetically, the bone morphogenetic response is controlled by an insoluble acidic bone morphogenetic protein or polypeptide (BMP) and a soluble neutral proteinase (BMP-ase) resembling trypsin in activity except functionally more specific for BMP. Firmly bound but separable from bone collagen, BMP is one of many short-lived morphogenetic substances appearing and disappearing throughout embryonic development and persisting in postfetal life. Where the BMP receptor resides and how it activates cell mechanisms of differential repression and derepression of such genes as code for osteogenesis is unknown.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 15 (1974), S. 333-339 
    ISSN: 1432-0827
    Keywords: Vitamin D ; Bone ; Resorption ; Calcium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A series of analogues of vitamin D have been tested for their ability to stimulate bone resorption in two test systems used previously to investigate the metabolites of vitamine D. These analogues were tested (a) by directly comparing their action on bone explants of mouse half-calvariain vitro, and (b) by injecting them into young mice and measuring the degree of resorptionin vitro when explants were prepared 18 hours after the injection. It is concluded that the key functional groups concerned with enhancing the activity of vitamin D3 are the 1α- and the 25-hydroxyl,both together; the cis ring structure for ring A appears necessary. 1α-Hydroxycholecalciferol (1α-OHD3) is about as active as 25-OHD3 in the direct test, but its potency is much nearer to that of 1,25-(OH)2D3 when tested by the second (indirect) method; it seems likely that 1α-OHD3 is converted into 1,25-(OH)2D3 in vivo. The results are discussed in relation to the designing of analogues for clinical and experimental use.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 145-152 
    ISSN: 1432-0827
    Keywords: EHDP ; Bone ; Chemistry ; Serum ; Rabbits
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The effects of disodium ethane-1-hydroxy-1,1-diphosphonate (EHDP) on bone and serum chemistry were investigated in adult rabbits. EHDP was administered by subcutaneous injection at doses of 0.25, 2.5 and 10 mg/kg body weight/day for of 28 days. Blood samples were obtained weekly from each rabbit and serum levels of total calcium, ionized calcium, inorganic phosphate and alkaline phosphatase were determined. At the end of the treatment period all rabbits were sacrificed and the tibiae removed for chemical analysis and histological evaluation. The effect of EHDP administration on serum chemistry was both dose- and time-related. The highest of the three doses, 10 mg/kg/day, resulted in a time-related decrease in total serum calcium. This dose also caused a rapid but transient reduction in serum ionized calcium. The effect of EHDP on serum inorganic phosphate was biphasic. Administration of 2.5 mg/kg/day resulted in a time-related elevation in this parameter, whereas the 10 mg/kg/day dose resulted in a time-related hypophosphatemic response. There were no significant drug-related changes in tibial fat-free dry weight, ash weight, total calcium or total phosphorus values. However, administration of 2.5 and 10 mg/kg/day EHDP resulted in increased osteoid tissue as measured histologically. These results are compared with data from other EHDP studies, and discussed in relation to the maturity and growth-state of the experimental animals.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 261-275 
    ISSN: 1432-0827
    Keywords: Dentine ; Bone ; Mineralization ; Density gradient fractionation ; Proteoglycans
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract In order to obtain enough material to analyse the organic matrix of mineralizing tissue a technique for preparative separation according to the degree of mineralization was developed. The method employs ultracentrifugation of powdered material in density gradients made from acetone and bromoform. The density range of the fractions is checked by refractive index measurements of the gradient medium. The amount of the material in the fractions is checked by weighing and their degree of mineralization is estimated by determining the Ca/N and P/N ratios. The homogeneity of the fractions is determined by soft X-ray microscopy. Isolated dissected microscopic bone structure (osteones and lamellar bone fragments) with different degrees of mineralization were fractionated in this way. Chromatography on Sepharose 2B of proteoglycans from costal cartilage exposed to an acetone-bromoform gradient revealed no effect of the gradient medium on the molecular size of the proteoglycans.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 153-160 
    ISSN: 1432-0827
    Keywords: Lysosomes ; Bone ; Resorption ; Osteoclast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des techniques histochimiques de microscope photonique et électronique montrent que les ostéoclastes métaphysaires chez des rats “sans incisive” présentent des quantités plus importantes de phosphatase acide, d'acryl sulfatase et de trimétaphosphatase acide lysosomiales. L'activité en phosphatase lysosomiale à pH neutre est aussi plus élevée dans les ostéoclastes métaphysaires, sauf dans les cellules situées sous la métaphyse, où l'enzyme est absente. L'absence de résorption de la matrice organique semble en rapport avec l'absence de bordures en brosse et une absence d'enzyme lysosomiale extracellulaire. Malgré cette absence, une dissolution de cristaux inorganiques a été mise en évidence au microscope électronique, suggérant que la dissolution minérale est un processus distinct de la désintégration enzymatique de la matrice organique.
    Abstract: Zusammenfassung Histochemische Techniken für Licht- und Elektronenmikroskopie zeigten, daß metaphysäre Osteoklasten “Schneidezahl-loser” (SL) Ratten erhöhte Mengen von lysosomaler saurer Phosphatase, von Arylsulfatase und von saurer Trimetaphosphatase enthielten. Die Aktivität der lysosomalen Phosphatase bei neutralem pH war in den metaphysären Osteoklasten ebenfalls erhöht, außer in den Zellen direkt unterhalb der Wachstumsplatte, wo dieses Enzym nicht vorkam. Es konnte überhaupt keine Resorption der organischen Matrix festgestellt werden, was übereinzustimmen schien mit der Abwesenheit eines gekräuselten Saumes und einer gleichzeitigen Abwesenheit des extrazellulären lysosomalen Enzyms. Trotzdem wurde im Elektronenmikroskop das Verschwinden anorganischer Kristalle festgestellt, was darauf schließen läßt, daß die Auflösung des Minerals nicht derselbe Vorgang ist wie die enzymatische Auflösung der organischen Matrix.
    Notes: Abstract Histochemical techniques for light and electron microscopy showed that metaphyseal osteoclasts in “incisors absent” rats contained greater than normal amounts of lysosomal acid phosphatase, aryl sulfatase and acid trimetaphosphatase. Lysosomal phosphatase activity at neutral pH was also elevated in the metaphyseal osteoclasts except in those cells immediately beneath the growth plate, where this enzyme was absent. The failure of any discernable resorption of organic matrix appeared to correlate with the absence of a ruffled border and a concomittant absence of extracellular lysosomal enzyme. Despite this failure, electron microscopic evidence of inorganic crystal removal was noted, suggesting that mineral dissolution represents a separate process from the enzymatic breakdown of organic matrix.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 13-36 
    ISSN: 1432-0827
    Keywords: Osteoclast ; Bone ; Resorption ; Crystals ; Organic-inorganic relationships
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The organic-inorganic relationships in bone matrix undergoing osteoclastic resorption have been studied in rat tibial diaphyses using electron microscope techniques in an attempt to identify the steps of the resorption process. Results suggest that bone resorption occurs in two phases: the first, an extracellular phase, leads to bone matrix fragmentation and partial dissolution, and the second, an intracellular phase, to complete digestion of the breakdown products of the bone matrix. The first component of the bone matrix to be attacked by the osteoclast is the ground substance. This induces the release of the crystals lying between, and on, the collagen fibrils; any crystals lying within fibrils are released later, when the fibrils break up. As this stage proceeds, the collagen fibrils retain their normal intrinsic texture, but gradually loose their lateral aggregation, appearing as individual fibrils (some of them uncovered by crystals), mixed with fragments of fibrils and many free crystals. The loosened but otherwise structurally normal collagen fibrils, and their fragments, are strongly argyrophilic. Complete dissolution of the disaggregated fibrils occurs outside the cell, both in the resorption zone and in the initial portion of the channels of the ruffled border. The free crystals present in the resorption zone and those phagocytosed in cytoplasmic vacuoles are organic-inorganic structures, whose organic component (the crystal ghost) is, at least in part, of proteoglycan nature. Dissolution of inorganic material occurs within the cytoplasmic vacuoles of the osteoclasts. Results are viewed in relation to the process of bone resorption and, as far as crystal ghosts are concerned, to that of bone calcification. A tentative summary of the various steps involved in the mechanism of bone resorption is given.
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  • 10
    ISSN: 1432-0827
    Keywords: Bone ; Parathyroid ; 25-Hydroxycholecalciferol ; Adenosine 3′, 5′ cyclic monophosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Phenytoin, at a concentration which is known to inhibit parathyroid extract-induced bone resorptionin vitro, has been shown to have no significant effect on either the cyclic AMP content of four-day-old mouse calvaria which had been in tissue culture for 48 h or on the increase in cyclic AMP content occurring after the addition of parathyroid extract to the medium. Phenytoin has also been shown to be an effective inhibitor of bone resorptionin vitro induced by 25-hydroxycholecalciferol. These observations suggest that the inhibitory effect of phenytoin on parathyroid extract and hormone-induced bone resorption takes place beyond the cyclic AMP stage.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 219-226 
    ISSN: 1432-0827
    Keywords: Bone ; Phosphate ; ATP ; Calcium ; Mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract An active constituent of the leaves ofSolanum malacoxylon (SM) is shown to promote calcium resorption and citrate production in embryonic chick frontal bone culturedin vitro. When injected into rats, SM reduces the ATP content of liver and kidneys. This phenomenon may be related to the ability of SM to stimulate mitochondrial ATPase activity at pH 9.4. SM significantly reduces the concentration of phosphate necessary to alter the uptake of calcium and respiration of siolated mitochondria. The data suggest that SM influences calcium and phosphate metabolism by affecting ion movements into and out of mitochondria.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 143 (1974), S. 159-183 
    ISSN: 1432-0568
    Keywords: Bone ; Femur ; Development ; Gravity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The significance of similitude principles for the postnatal development of the cross-sectional area at midlength of the human and rat femur has been subjected to an investigation based both on theory and on observation. Cross sections were taken from 69 femora of female Sprague-Dawley rats 34, 72, 102, and 840 days old and from the right human femora of 94 males and 58 females ranging from 1 day to 89 years of age. The regression of the square-root of the cross-sectional area divided by π on femur length is linear in the rats. The empirical regression line estimated by the method of least squares from the measurements and the theoretical curve calculated on the assumption of adaptive allometric growth and centrically applied loads are more or less alike in slope and elevation. The corresponding empirical relationship in the human femora turned out statistically nonlinear in the males and linear in the females. Comparing the empirical regression functions with five theoretical curves, it has been revealed that the observations are best approximated by two curves calculated on the assumption of centrically or eccentrically applied loads and adaptive allometric growth of the cross-sectional diameter. It was further uncovered that the cross-sectional diameters at midlength of the femur are not changed isometrically with femur length both in rats and in man. Considering a simple model of the human body in the stance phase of slow walking gait on the scale of a neonate and an adult male, the hypothesis was advanced that the stresses at midlength of the femur are not altered much while the femur grows from neonate to adult size, because the outer and inner radii of the femur actually change during growth in such a way that the effects due to scale are appropriately compensated.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 251-255 
    ISSN: 1432-0827
    Keywords: Cartilage ; Bone ; Vitamin A ; Phosphatases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Au cours d'une étude du cartilage épiphysaire de poulets normaux et déficients en vitamine A, la composition organique et l'activité phosphatasique du cartilage au repos, du cartilage en voie d'ossification et de l'os nouvellement formé ont été mesurées. Le cartilage en voie d'ossification et l'os nouvellement formé ont un contenu plus élevé en matériel inorganique, phosphate et collagène que le cartilage au repos. Une déficience en vitamine A provoque une augmentation du contenu en phospholipide de tous les trois tissus. Le cartilage au repos, en cas de déficience en vitamine A, présente, après homogénéisation et centrifugation, un surnageant dont l'activité en phosphatase alcaline et en glycérophosphatase est plus élevée que celle des témoins. Il semble que les effets enzymatiques de l'avitaminose A soient liés à des altérations de la membrane lysosomiale avec décharge de phosphatases. La minéralisation normale semble aussi faire intervenir une activité phosphatasique.
    Abstract: Zusammenfassung Diese Arbeit beschreibt Untersuchungen des Epiphysenknorpels bei normalen Küken und solchen mit Vitamin-A-Mangel. Die organische Zusammensetzung und die Phosphatase-Aktivität in ruhendem Knorpel, ossifizierendem Knorpel und neugebildetem Knochen wurden gemessen. Der ossifizierende Knorpel und der neugebildete Knochen hatten einen höheren Gehalt an anorganischem Material, an Phosphat und Kollagen als der ruhende Knorpel. Vitamin-A-Mangel führte zu einem erhöhten Phospholipidgehalt in allen drei Geweben. Nach Homogenisierung und Zentrifugierung fand sich im Überstand des ruhenden Knorpels von Vitamin-A-Mangelgewebe eine höhere alkalische Phosphatase- und Glycero-phosphatase-Aktivität als bei den Kontrollen. Es wird angenommen, daß die Wirkung des Vitamin A-Mangels auf die Enzyme im Zusammenhang steht mit der Schädigung der lysosomalen Membran, wobei Phosphatasen freigesetzt werden, und daß die normale Mineralisierung die Phosphatasen-Aktivität ebenfalls anregt.
    Notes: Abstract This paper reports studies of the epiphyseal cartilage in normal and vitamin A deficient chicks. The organic composition and the phosphatase activity in the resting cartilage, ossifying cartilage and new bone were measured. The ossifying cartilage and new bone had a higher content of inorganic material, phosphate and collagen than the resting cartilage. Vitamin A deficiency caused increase in the phospholipid content of all three tissues. The resting cartilage from vitamin A deficient tissue had, after homogenisation and centrifugation, a supernatant with an activity of alkaline phosphatase and glycerophosphatase higher than that in control samples. It is considered that effects of vitamin A deficiency on enzymes are related to defects of the lysosomal membrane with release of phosphatases, and that normal mineralisation also involves phosphatases activity.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 283-289 
    ISSN: 1432-0827
    Keywords: Sodium fluoride ; Osteoporosis ; Bone ; Strength ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'utilisation thérapeutique de fluorure de sodium a été recommandée dans le traitement de diverses maladies osseuses ostéopéniques. Cet emploi est basé principalement sur les effects ostéosclérotiques bien connus du fluorure de sodium, mais on connait mal son effet sur la force de résistance osseuse. L'influence de diverses concentrations de fluorure de sodium sur la force de résistance osseuse de jeunes rats soumis à des régimes riches et pauvres en calcium a été étudiée. L'administration de fluorure de sodium augmente le diamètre osseux, indiquant une stimulation de la formation de l'os périosté, mais la force de résistance osseuse est réduite ou non modifiée par l'ingestion de fluor.
    Abstract: Zusammenfassung Die therapeutische Verwendung von Natriumfluorid ist für eine Anzahl von Knochenmangel-Krankheiten empfohlen worden. Die Empfehlungen basieren hauptsächlich auf den bekannten osteosklerotischen Wirkungen von Natriumfluorid; über dessen Effekt auf die Knochenstärke ist wenig bekannt. In dieser Arbeit wurde der Einfluß verschiedener Konzentrationen von Natriumfluorid auf die Knochenstärken von wachsenden Ratten mit hoher und niederer Calciumeinnahme untersucht. Die Verabreichung von Natriumfluorid erhöhte den Knochendurchmesser, was auf eine Stimulierung der Periostbildung hinwies, die Knochenstärke wurde jedoch durch Fluorideinnahme herabgesetzt oder nicht beeinflußt.
    Notes: Abstract The therapeutic use of sodium fluoride has been recommended in a variety of osteopenic bone diseases. The recommendations are based mainly on the known osteosclerotic effects of sodium fluoride and little information is available as to its effect on bone strength. The influence of various concentrations of sodium fluoride on bone strength in growing rats on high and low calcium diets was studied. The administration of sodium fluoride increased bone diameter, indicating stimulation of periosteal bone formation, but bone strength was reduced or not affected by fluoride ingestion.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 291-299 
    ISSN: 1432-0827
    Keywords: Bone ; Collagenase ; Lysozyme
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Du lysozyme de blanc d'œuf, ainsi que des protéines basiques, telles que de l'histone et une base dépourvue de protamine, semblent inhiber la collagénase osseuse de souris. L'inhibition de collagénase osseuse de souris par le lysozyme est mise en évidence lorsque l'activité de la collagénase est étudiée en utilisant du collagène comme substrat à l'état solide, mais non lorsque le collagène est utilisé en solution. D'autre part, l'inhibition de l'activité en collagénase par l'histone et une base dépourvue de protamine est observée dans les deux systèmes. L'inhibition de collagénase ossuese de souris par des molécules polyanioniques est intéressante, étant donné que des travaux antérieurs ont montré que plusieurs molécules polyanioniques telles que l'héparine, le sulfate de dextrane et l'acide polyethylenesulfonique augmentent l'activité de collagénase osseuse de souris dans les mêmes conditions expérimentales. Comme le lysozyme est largement présent dans les tissus conjonctifs et que sa concentration carie avec l'ampleur du remaniement tissulaire, l'inhibition de la collagénase osseuse de souris suggère un role éventuel dans la régulation de la dégradation du collagène, pendant le remaniement des tissus collagéniquesin vivo au cours d'états normaux et pathologiques.
    Abstract: Zusammenfassung Lysozyme aus Hühnereiweiß sowie Basis-Proteine, wie z. B. Histon und Protamin-freie Basen, erwiesen sich als Hemmer der Mäuseknochen-Kollagenase. Diese Hemmung durch Lysozym wurde festgestellt, wenn für die Messung der Kollagenase-Aktivität Kollagen in Substanz als Substrat verwendet wurde, nicht aber, wenn das Substrat aus gelöstem Kollagen bestand. Andererseits wurde die Hemmung der Kollagenase-Aktivität durch Histon und Protamin-freie Basen in beiden Versuchssystemen festgestellt. Die Hemmung von Mäuseknochen-Kollagenase durch polykationische Moleküle ist interessant, vor allem im Hinblick auf frühere Feststellungen, daß mehrere polyanionische Moleküle, wie Heparin, Dextransulfat und Polyaethylensulfonsäure, die Aktivität der Mäuseknochen-Kollagenase unter denselben experimentellen Bedingungen erhöhen. Da Lysozym in Bindegeweben überall verteilt ist und da dessen Konzentration mit der Neubildungsrate des Gewebes variiert, läßt die Hemmung der Mäuseknochen-Kollagenase durch Lysozym dessen mögliche Rolle in der Regulierung des Kollagenabbaues vermuten, und zwar während der Neubildung von Kollagengeweben in vivo in normalen und pathologischen Zuständen.
    Notes: Abstract Egg white lysozyme, as well as basic proteins such as histone and protamine-free base, were found to inhibit mouse bone collagenase. The inhibition of mouse bone collagenase by lysozyme was detected when the activity of the collagenase was assayed using collagen as the substrate in the solid state, but not when the collagenase activity was assayed using collagen in solution as the substrate. On the other hand, the inhibition of collagenase activity by histone and protamine-free base was observed in both assay systems. The inhibition of mouse bone collagenase by polycationic molecules is interesting in light of previous findings that several polyanionic molecules, such as heparin, dextran sulfate and polyethylenesulphonic acid, enhance the activity of mouse bone collagenase under the same experimental conditions. Since lysozyme is widely distributed in connective tissues and its concentration varies with the rate of tissue remodeling, the inhibition of mouse bone collagenase by lysozyme suggests its possible role in the regulation of collagen degradation during the remodeling of collagenous tissuesin vivo during normal and pathological states.
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  • 16
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    Calcified tissue international 15 (1974), S. 11-20 
    ISSN: 1432-0827
    Keywords: Bone ; Growth ; Resorption ; Caudal ; Vertebra ; Fluorescence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode de mesure de l'apposition et de la résorption osseuse est mise au point au niveau de la septième vertèbre caudale de jeunes rats, pesant 25–90 g, pendant la période de croissance. Cette pièce osseuse a des avantages certains par rapport à d'autres localisations, car elle est symétrique en coupe transversale et non affectée par des forces corticales. En utilisant trois marqueurs d'os différents, fluorescents en lumière ultra-violette, administrés à des intervalles de 3, 5 ou 7 jours, les modifications de croissance sont observées sur des coupes transversales centrales, non décalcifiées, de la septième vertèbre caudale. Une formation osseuse linéaire se développe à une vitesse moyenne de 10.0 μ/jour et une résorption linéaire de 6.1μ/jour est notée. Pendant la période de croissance observée, la formation osseuse s'observe exclusivement à la surface du périoste et la résorption se fait le long de la surface de l'endoste. A ce niveau l'os est totalement résorbé, chez des animaux de 25 g en 22–26 jours. Il semble que chez des animaux plus âgés, une formation osseuse endostée se développe rendant alors impossible toute étude prolongée dans cette région.
    Abstract: Zusammenfassung Es wird eine Methode zur Messung der Knochenbildungs- und Resorptionsgeschwindigkeiten im siebten Caudalwirbel junger Ratten während ihrer Wachstumsperiode von 25–90 g beschrieben. Dieser Knochen hat gegenüber jenen, die vorgängig untersucht wurden, den großen Vorteil, in transversalen Schnitten symmetrisch und unbeeinflußt von kortikalen Unregelmäßigkeiten zu sein. Die Art der Wachstumsveränderungen wurden an nichtentkalkten zentralen Transversalschnitten der siebten Caudalwirbeln bestimmt; dazu wurden drei verschiedene, farbige, im UVbereich fluoreszierende Knochenmarkierungssubstanzen verabreicht und zwar in 3-, 5- oder 7tägigen Intervallen. Die lineare Knochenbildung fand mit einer mittleren Geschwindigkeit von 10,0 μ pro Tag statt, die lineare Knochenresorption mit einer solchen von 6,1 μ pro Tag. Während der untersuchten Wachstumsperiode fand die Knochenbildung ausschließlich an der Periostoberfläche und die Knochenresportion an der endostalen Oberfläche statt. Der Knochen, der beim 25 g schweren Tier an diesem Ort vorlag, verschwand durch die endostale Resorption innerhalb von 22–26 Tagen
    Notes: Abstract A method for measuring bone formation and resorption rates in the seventh caudal vertebra of young rats during the growth period from 25–90 g is reported. This bone site has unique advantages over those previously studied, being symmetrical in transverse section and uncomplicated by cortical drift. Utilising three different coloured ultraviolet fluorescent bone labelling substances administered at either 3, 5 or 7 day intervals, the nature of growth changes was determined from undecalcified central transverse sections of the seventh caudal vertebrae. Linear bone formation occurred at a mean rate of 10.0 μ/day and linear bone resorption at 6.1 μ/day. During the growth period studied, bone formation occurred exclusively on the periosteal surface and bone resorption on the endosteal surface. Bone existing in this site in 25 g animals was completely removed by endosteal resorption within 22–26 days. Evidence exists that in older rats endosteal bone formation occurs and renders the site unsuitable for long term studies.
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  • 17
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    Calcified tissue international 15 (1974), S. 315-324 
    ISSN: 1432-0827
    Keywords: Bone ; Mineral ; Osteogenesis ; Interference microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A method based on tetracycline labeling was developed for selecting, in frozen sections of fetal mouse femur, bone foci approximately 6, 24, 48 and 72 h of age. Microinterferometric measurements of these foci permitted a calculation of the effective thickness (t) and refractive index (n) of each focus. After demineralizing the sections by a method which left the organic portion of the bone intact, the foci were re-measured andt andn of the organic compartment of each focus were determined;t andn of the mineral compartment were calculated by difference. A sharp decrease and subsequent rise in then of whole bone occurred between 6 and 48 h. These changes derived from the mineral compartment, and were thought to have resulted from the formation of amorphous calcium phosphate and hydroxyapatite, respectively. The mineral present in 6 h foci, however, was believed to be some precursor of amorphous calcium phosphate.
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  • 18
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    Calcified tissue international 15 (1974), S. 329-332 
    ISSN: 1432-0827
    Keywords: Microradiography ; Bone ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A low cost, self-contained, commercially available, X-ray apparatus which possesses the essential qualifications necessary to produce high resolution microradiographs of undecalcified bone is described. The widespread current use of this machine in pathology laboratories may make purchase of such a unit optional.
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  • 19
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    Calcified tissue international 16 (1974), S. 73-88 
    ISSN: 1432-0827
    Keywords: Dentine ; Bone ; Histocytochemistry ; Physiological Calcification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Histochemical methods were used to detect differences in amino acid reactive groups between bone and osteoid, dentine and predentine. Three major differences were found: Predentine and osteoid contained more reactive sulphydryls than their mineralized counterparts. The greatest reaction for this reactive group was obtained at the mineralizing front. Dentine and bone contained a complex between amino and carboxylic acid groups; predentine and osteoid did not have this complex and carboxylic acid residues were less in these tissues. Dentine and bone contained much greater amounts of histidine or a histidine-like component than did predentine and osteoid. It is proposed that these differences are involved in initiation of mineralization.
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  • 20
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    Calcified tissue international 16 (1974), S. 169-182 
    ISSN: 1432-0827
    Keywords: Histochemistry ; Alkaline phosphatases ; Calcification ; Bone ; Teeth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Activity of alkaline phosphatases in unfixed cold microtome setions from the lower first molar area of newborn mice was recorded by histochemical methods. A substrate specificity test included the following phosphate compounds: ATP, CTP, GTP, UTP, ADP, AMP, GP, PPi, MDP and naphthol AS-TR phosphate. Intense staining was obtained in osteoblasts, stratum intermedium of the enamel organ and odontoblasts with all the substrates, except PPi and MDP. Staining of skeletal muscle fibres was obtained only with triphosphates as substrates. Addition of-SH groups decreased the hydrolysis of triphosphate compounds in cells involved in mineralization while the hydrolysis of monophosphate was inhibited. In contrast triphosphatase activity in striated muscle was enhanced when-SH compounds were added. Demineralization with EDTA diminished the cytoplasmic staining but induced a nuclear staining in hard tissue forming cells when triphosphates were used as substrates. No cytoplasmic and only slight nuclear staining was seen with GP or AMP as substrates. The triphosphate hydrolyzing capacity of tongue muscle fibres was, however, increased after the decalcification treatment. Addition of Mg2+ ions to the incubation media distinctly lowered the hydrolysis of triphosphates in the investigated tissues whereas the hydrolysis of ADP, AMP, GP and naphthol AS-TR phosphate remained unchanged. In view of the findings the triphosphatase activities at alkaline pH of muscle fibres and of cells related to hard tissue formation are considered to be due to activity of separate enzymes. The orthophosphate liberating enzyme activities at alkaline pH in osteoblasts, stratum intermedium and odontoblasts may be expressions of the catalytic functions of one common enzyme. Furthermore, the results indicate that CaATP might be the substrate used by the alkaline ATPase in mineralizing areas.
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  • 21
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    Calcified tissue international 16 (1974), S. 239-250 
    ISSN: 1432-0827
    Keywords: EHDP ; Bone ; Collagen ; Histology ; Bone chemical analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The purpose of this study was to determine the short-term effects of various systemic doses of disodium ethane-1-hydroxy-1,1-diphosphonate (EHDP) on bone organic matrix and to relate these effects to the corresponding dose-related changes in bone mineral. EHDP was administered daily by subcutaneous injection at doses of 0.25, 2.5 and 40 mg/kg body weight for periods of one and two weeks. At both time intervals, rat tibiae were quantitatively analyzed for mineral content (ash, calcium and phosphorus) and for organic matrix content (matrix weight, nitrogen and certain amino acids). The latter data were correlated with semiquantitative histological analyses of the tibiae. Results of this study demonstrate that the short term effects of EHDP on bone chemistry and histology are variable and depend on the systemic dose and the duration of treatment. Systemic doses of 0.25 and 2.5 mg/kg EHDP following daily administration for one week resulted in transitory decreases in bone mineral content compared to controls. Following two weeks of treatment, both of these dose levels resulted in increased bone mineral content and, in addition, the 2.5 mg/kg dose resulted in tibiae which contained more organic matrix compared to control bones. In contrast to the low dose effects, a high systemic dose of EHDP—e.g. 40 mg/kg administered daily for 1 or 2 weeks—appears to act solely by inhibiting mineralization of newly-formed matrix.
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  • 22
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    Calcified tissue international 14 (1974), S. 31-48 
    ISSN: 1432-0827
    Keywords: Bone ; Cartilage ; Calcification ; Collagen ; Phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode pour l'étude de la croissance des os longs de foetus de rat, en culture d'organe, dans un milieu chimiquement défini, a été mise au point. Les extrémités cartilagineuses et les parties centrales de l'os sont analysées séparément pour leur croissance et minéralisation en étudiant leur contenu en collagène, calcium et phosphate, poids sec, et incorporation de proline marquée en hydroxyproline. La croissance et la minéralisation des parties centrales osseuses sont plus lentes dans un milieu chimiquement défini qu'in vivo. La croissance peut être accélérée en ajoutant au milieu des acides aminés non essentiels, de l'albumine ou du sérum. Les extrémités cartilagineuses présentent une augmentation plus importante en poids et contenu en collagène que les parties centrales et l'adjonction de diverses substances a moins d'effet sur la croissance. La croissance et la minéralisation des parties centrales sont augmentées en élevant la concentration du milieu en phosphate de 1.5 à 4.5 mM, avec ou sans adjonction de sérum ou d'albumine. A une concentration faible de calcium (0.5 mM), la croissance et la minéralisation des parties centrales sont arrêtées. A une concentration faible en magnésium (0.5 mM), la minéralisation est augmentée, mais la croissance est arrêtée.
    Abstract: Zusammenfassung Es wird eine Methode beschrieben, mit welcher das Wachstum der Röhrenknochen von Rattenembryos in einem chemisch bestimmten Medium in Organkultur untersucht werden kann. Die Knorpelenden und Knochenschäfte wurden gesondert auf Wachstum und Mineralisation geprüft, indem Collagen-, Calcium- und Phosphatgehalt, das Trockengewicht und der Einbau von markiertem Prolin in Hydroxyprolin gemessen wurden. Wachstum und Mineralisation des Knochenschaftes waren langsamer in einem chemisch bestimmten Medium als in vivo. Das Wachstum konnte beschleunigt werden, indem dem Medium nicht-essentielle Aminosäuren, Albumin oder Serum beigegeben wurden. Die Knorpelenden zeigten eine viel stärkere Zunahme an Gewicht und Collagengehalt als die Schäfte, und Anreicherung des Mediums hatte weniger Wirkung auf ihr Wachstum. Das Wachstum und die Mineralisation der Knochenschäfte nahmen zu, wenn die Phosphatkonzentration im Medium zwischen 1,5 und 4,5 mM erhöht wurde, und zwar unabhängig davon, ob dem Medium Serum oder Albumin beigegeben wurde oder nicht. Bei niederer Calciumkonzentration (0,5 mM) im Medium wurden Wachstum und Mineralisation der Knochenschäfte beeinträchtigt. Bei niedriger Magnesiumkonzentration (0,5 mM) wurden die Mineralisation erhöht, das Wachstum hingegen gehemmt.
    Notes: Abstract A method for studying the growth of fetal rat long bones in a chemically defined medium in organ culture is described. Cartilage ends and bone shafts were analyzed separately for growth and mineralization by measuring the collagen, calcium, and phosphate content, dry weight, and incorporation of labeled proline into hydroxyproline. Growth and mineralization of the bone shaft were slower in a chemically defined medium thanin vivo. Growth could be enhanced by supplementation of the medium with non-essential amino acids, albumin or serum. Cartilage ends showed a greater increase in weight and collagen content than the shafts, and medium supplements had less effect on their growth. Bone shaft growth and mineralization were enhanced by increasing medium phosphate concentration over a range of 1.5 to 4.5 mM whether or not the medium was supplemented with serum or albumin. At a low medium calcium concentration (0.5 mM) bone shaft growth and mineralization were impaired. At a low magnesium concentration (0.5 mM) mineralization was enhanced, but growth was impaired.
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  • 23
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    Calcified tissue international 14 (1974), S. 83-86 
    ISSN: 1432-0827
    Keywords: Bone ; Reproductive cycle ; Pigeons ; Amorphous ; Crystalline
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une étude de diffraction aux rayons X, au cours du cycle de ponte d'oeufs de pigeon, a été entreprise pour évaluer les modifications de la proportion entre les phases de phosphate de calcium amorphe et apatitique. La partie médullaire du fémur de pigeon est totalement résorbée au cours du cycle de reproduction. Au cours de ce processus, l'os contenant plus de phosphate de calcium amorphe est résorbé avant celui qui est riche en cristaux. Ainsi l'os à contenu amorphe plus élevé est métaboliquement plus actif que l'os riche en cristaux. L'os médullaire qui peut être induit chez le pigeon mâle par traitement aux oestrogènes, ressemble, au point de vue diffraction aux rayons X, à l'os médullaire des femelles au début du cycle de reproduction.
    Abstract: Zusammenfassung Mittels Röntgen-Diffraktion wurden die Veränderungen in den prozentualen Mengen der amorphen und der kristallinen Calciumphosphat-Phasen im Femur der Taube während des Eierlegens untersucht. Der medulläre Teil des Taubenfemur wird während des Fortpflanzungscyclus vollständig resorbiert. Dabei wird der Teil des Knochens, der mehr amorphes Calciumphosphat enthält, vor dem kristallreichen Teil resorbiert. Daraus folgt, daß der Stoffwechsel des Knochens mit höherem amorphem Gehalt aktiver ist als derjenige des Knochens mit höherem kristallinem Gehalt. Weiter konnte mittels Röntgendiffraktion festgestellt werden, daß der medulläre Knochen, welcher in männlichen Tauben durch Oestrogenbehandlung erzeugt werden kann, dem weiblichen medullären Knochen am Anfang des Fortpflanzungscyclus gleicht.
    Notes: Abstract This is an X-ray diffraction study of the changes in the proportional amounts of the amorphous and apatitic calcium phosphate phases in pigeon femur during the egg-laying cycle. The medullary portion of pigeon femur is completely resorbed in the reproductive cycle. In this process the portion of bone which is higher in amorphous calcium phosphate is resorbed before the crystal-rich portion. Thus, bone with a higher amorphous content is more metabolically active than more crystalline bone. Finally, medullary bone which can be produced in male pigeons by estrogen treatment was found by X-ray diffraction to resemble female medullary bone at the beginning of the reproductive cycle.
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  • 24
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    Calcified tissue international 14 (1974), S. 49-58 
    ISSN: 1432-0827
    Keywords: Glycosaminoglycans ; Intracellular ; Chondrocytes ; Cartilage ; Embryonal ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les glycosaminoglycanes acides de chondrocytes isolés, en suspension, sont étudiés. La matrice extracellulaire est isolée par traitement successif à la trypsine et à la collagénase d'os d'embryons de poulet, âges de 15 à 17 jours. Après digestion à la papaïne et élimination des acides nucléïques par traitement à la DNAse et à la RNAse, les glycosaminoglycanes sont précipités par le CPC et isolés sous la forme de leur sel sodique. Les analyses des propriétés de solubilité du CP glycosaminoglycane par le microfractionnement d'Antonopoulos et coll. (1964) révèlent la présence de glycosaminoglycanes intracellulaires de poids moléculaire et/ou de densité de charge nettement plus faibles que ceux de la matrice extracellulaire. Sur des électrophorèses de microzones, une petite partie des glycosaminoglycanes intracellulaires isolées présente une mobilité similaire à celle des solutions témoins de sulfate de chondroitine, alors que la portion la plus importante ne se déplace qu'à mi-distance de l'acide hyaluronique et montre une large trainée, indiquant une faible charge négative. Ce fait semble dû à une perte de l'influence de régulation des composants matriciels éliminées, sur la synthèse des glycosaminoglycanes et au rejet dans le milieu de glycosaminoglycanes initialement synthétisé. Pour la première fois, une faible quantité d'acide hyaluronique intracellulaire est mise en évidence par une mobilité électrophorétique typique.
    Abstract: Zusammenfassung Saure Glykosaminoglycane von isolierten Chondrocyten in Suspension wurden untersucht, und die extracelluläre Matrix von 15–17 Tage alten Knochen von Kükenembryos wurde durch die aneinanderfolgende Behandlung mit Trypsin und Collagenase erhalten. Nach der Papain-Verdauung und Beseitigung der Nucleinsäuren mittels DNS- und RNSase-Behandlung wurden die Glykosaminoglycane mit CPC gefällt und als Natriumsalz isoliert. Untersuchungen der Löslichkeit der CP-Glykosaminoglycane mittels des Mikrofraktionierungsverfahrens von Antonopouloset al. (1964) zeigten intracelluläre Glykosaminoglycane mit meist niedrigerem Molekulargewicht und/oder niedrigerer Ladungsdichte als diejenigen der extracellulären Matrix. In der Mikro-Zonen-Elektrophorese zeigte nur ein kleiner Teil der isolierten intracellulären Glykosaminoglycane eine Mobilität, die dem Standard des Chondroitinsulfats entsprach. Der größte Teil legte nur die halbe Distanz der Hyaluronsäure zurück und zeigte breites “Tailing”, was auf eine niedrigere negative Ladung hindeutet. Die Ursache dafür wurde interpretiert als Verlust eines regulierenden Einflusses der entfernten Matrixkomponenten auf die Glykosaminoglycan-Synthese und als Abgabe ursprünglich synthetisierter Glykosaminoglycane in das Medium. Es wurde erstmals, anhand der typischen elektrophoretischen Beweglichkeit, eine kleine Menge von intracellulärer Hyaluronsäure nachgewiesen.
    Notes: Abstract Acid glycosaminoglycans were studied from isolated chondrocytes in suspension and the extracellular matrix obtained by sequential trypsin and collagenase treatment of 15- to 17-day-old embryonic chick bone. After papain digestion and removal of the nucleic acids by treatment with DNAse and RNAse, the glycosaminoglycans were precipitated by CPC and isolated as their sodium salt. Analyses of the CP-glycosaminoglycan solubility properties with the microfractionation procedure of Antonopouloset al. (1964) showed intracellular glycosaminoglycans of predominantly lower molecular weight and/or charge density than those of extracellular matrix. On micro-zone electrophoresis, only a minor part of the isolated intracellular glycosaminoglycans showed a mobility similar to that of the chondroitin sulphate standards while the major part moved only half the distance of hyaluronic acid and showed broad tailing, indicating a low negative charge. This was considered to be due to loss of a regulatory influence of the removed matrix components upon glycosaminoglycan synthesis and to release of originally synthesized glycosaminoglycans into the medium. For the first time, a small amount of intracellular hyaluronic acid was shown by typical electrophoretic mobility.
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  • 25
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    Calcified tissue international 14 (1974), S. 161-168 
    ISSN: 1432-0827
    Keywords: Diphosphonates ; Osteoid Synthesis ; Hydroxyproline ; Bone ; Formation-Resorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Deux diphosphonates, à savoir l'éthane-1-hydroxy-1,1-diphosphonate (EHDP) et le dichlorométhane diphosphonate (Cl2MDP), inhibentin vitro la résorption osseuse qui est stimulée soit par la parathormone ou par voie intrinsèque dans un système de culture d'os en remaniement. Alors que le Cl2MDP est plus efficace que l'EHDP dans l'inhibition de la résorption, ce fait semble en rapport avec une diminution de le formation de tissu ostéoide. Il s'en suit une diminution biochimique et morphologique marquée du remaniement osseux avec le Cl2MDP à une concentration équivalent à 10 μg de phosphore/ml de milieu de culture. La différence d'activité entre l'EHDP et le Cl2MDP peu être liée à leur affinité relative pour les surfaces du minéral osseux et, par suite, à leur concentration effective dans la fluide extracellulaire osseux. Les diphosphonates pourraient aussi affecter l'os indirectement si l'on admet que le degré de minéralisation de la matrice est important pour l'induction et la régulation de l'activité ostéoblastique dans l'os en voie de remaniement.
    Abstract: Zusammenfassung Zwei Diphosphonate, Aethan-1-hydroxy-1,1-diphosphonat (EHDP) und Dichloromethylen-Diphosphonat (Cl2MDP) hemmen in vitro die Knochenresorption. Diese wird verfolgt entweder mittels Stimulierung durch PH oder in einem Kultursystem, in welchem normale Knochenneubildung stattfindet. Während Cl2MDP die Resorption wirksamer hemmt als EHDP, scheint es ebenfalls eine Verminderung der Osteoidbildung zu verursachen. Dies bewirkt eine deutliche biochemische und morphologische Herabsetzung der Knochenneubildung, bei einer Cl2MDP-Konzentration von 10 μg Phosphor/ml Kulturmedium. Die unterschiedliche Wirksamkeit von EHDP und Cl2MDP läßt sich wahrscheinlich auf ihre verschiedenen Affinitäten zu der Oberfläche des Knochenminerals und somit auf ihre tatsächliche freie Konzentration in der extracellulären Flüssigkeit des Knochens zurückführen. Ausgehend von der Annahme, daß die Anregung und Regulierung der Osteoblasten-Aktivität bei der Knochenneubildung vom Ausmaß der Matrix-Mineralisation bestimmt wird, läßt sich die Vermutung aufstellen, daß die Diphosphonate die Knochenbildung auch indirekt beeinflussen können.
    Notes: Abstract Two Diphosphonates, ethane-1-hydroxy-1,1-diphosphonate (EHDP) and dichloromethylene diphosphonate (Cl2MDP) inhibitin vitro bone resorption, which is either stimulated by parathyroid hormone or intrinsic in a bone remodeling culture system. While Cl2MDP is more effective than EHDP in inhibiting resorption, it also appears to result in a related diminution in osteoid formation. This effect causes a marked biochemical and morphological depression of bone remodelling with Cl2MDP at a concentration equivalent to 10-μg-phosphorus/ml of culture medium. The difference in activity between EHDP and Cl2MDP may be related to their relative affinities for the bone mineral surfaces and hence their effective free concentration in the bone extracellular fluid. It is hypothesized that diphosphonates may also affect bone formation indirectly if one assumes that the degree of mineralization of the matrix is important in the induction and regulation of osteoblastic activity in remodelling bone.
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  • 26
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    Calcified tissue international 14 (1974), S. 195-210 
    ISSN: 1432-0827
    Keywords: Bone ; Fossil bone ; Bone resorption ; Boring channels ; Fungi
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'action ostéoclasique exercée par un champignon appartenant au genreMucor sur des os inhumés a été étudiée au point de vue morphologique. L'érosion ossuse donne lieu à des cavités et à des canalicules de percement, dont les parois apparaissent régulièrement calcifiées jusqu'a l'interface avec le champignon, ce qui veut dire que la réabsorption intéresse en même temps la matrice organique et les cristallites. Au contraire des ostéoclastes, la membrane du champignon ne montre jamais un bord en brosse au niveau des points où elle se met en contact avec le tissu osseux. De même l'examen au microscope électronique ne décele apparemment aucun passage de matériel dans l'épaisseur de la membrane ainsi que dans le protoplasme du champignon, ce qui porte à admettre qu'un processus de solubilisation a lieu au préalable. Seulement dans le cas où le champignon présente des phénomènes de vieillissement, des données font prévoir la libération d'une substance capable de décalcifier la matrice organique. Tous les résultats ci-dessu sont discutés de façon analytique et comparés à ceux fournis par les canalicules de percement des os fossiles.
    Abstract: Zusammenfassung Die osteoklastische Aktivität eines der Mucor-Gattung angehörenden Pilzes auf begrabene Knochen wurde morphologisch untersucht. Die Wirkung dieses Pilzes in der Knochenerosion führt zu Resorptionshöhlen und Bohrkanälen, deren Wände scharf und bis zur Oberfläche gut verkalkt sind; das bedeutet, daß die Knochenresorption gleichzeitig die Kristalliten und die organische Matrix in Mitleidenschaft zieht. Im Gegensatz zu den normalen Osteoklasten zeigt die Membran des Pilzes an den Berührungsstellen mit dem Knochengewebe keinen Bürstensaum. Ebenfalls läßt eine elektronenmikroskopische Untersuchung keinen Durchgang von Substanzen durch die Membran und das Protoplasma des Pilzes erkennen, so daß man annehmen muß, daß vorher ein Auflösungsprozeß stattgefunden hat. Die Vermutung liegt nahe, daß eine Substanz, welche den anorganischen Knochenanteil aufzulösen vermag, sich
    Notes: Abstract A morphological investigation has been carried out on the osteoclastic activity revealed by a fungus of theMucor genus on buried bone. The hallmark of its activity in eroding bone is the finding of resorption pits and boring channels whose walls are sharp and well calcified up to the free edge, suggesting that bone resorption affects crystallites and the organic matrix simultaneously. Unlike normal osteoclastic cells, the fungal membrane in contact with the bone shows no brush border. As the electron microscope reveals no migration of material to the fungal membrane and its protoplasm, the view is expressed that the material which reaches the fungus has been previously solubilized. There is good reason for supposing that a substance capable of solubilizing the inorganic bone fraction spreads freely through bone tissue, decalcifying the matrix, where, but only where, hyphae show the effects of ageing. All the findings are thoroughly discussed and compared with those furnished by the boring channels in fossil bone.
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  • 27
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    Calcified tissue international 14 (1974), S. 245-249 
    ISSN: 1432-0827
    Keywords: Bone ; Repair ; Histology ; Implant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Um modèle expérimental, destiné à l'étude de la cicatrisation osseuse, est mis au point. Il permet d'obtenir du tissu osseux pour des études qualitatives et quantitatives. Des tubes de nylon sont implantés dans l'alvéole d'incisives extraites de cobayes. Une étude histologique de coupes longitudinales montrent que les implants de nylon ne retardent pas la cicatrisation des lésions osseuses et contiennent suffisamment de tissus pour des études biochimiques.
    Abstract: Zusammenfassung Es wurde ein Modellsystem zum Studium der Knochenwiederherstellung entwickelt, mit Hilfe dessen man von dem sich wiederbildenden Knochengewebe Proben für die qualitative und quantitative Bestimmung entnehmen kann. Dazu wurden in die Alveolen extrahierter Schneidezähne von Meerschweinchen Nylonschläuchlein eingelegt. Die histologische Untersuchung von Längsschnitten zeigte, daß die Nylonimplantate den Wiederherstellungsprozeß des Knochendefektes nicht verzögerten, daß sie herauspräpariert werden konnten und genügend Gewebe enthielten, um für biochemische Untersuchungen verwendet zu werden.
    Notes: Abstract A model system for the study of bone repair has been developed which allows the recovery of repairing osseous tissue for qualitative and quantitative evaluation. Nylon tubes were implanted in the alveoli of extracted incisors in guinea pigs. A histological study of longitudinal sections showed that the nylon implants did not delay the reparative processes of the bony defect, could be dissected out and contained sufficient tissue to be used in biochemical studies.
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  • 28
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    Calcified tissue international 15 (1974), S. 45-54 
    ISSN: 1432-0827
    Keywords: Bone ; Fluoride ; Microhardness ; Mineralization ; Strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Microhardness was measured in sampling sites in the tibial diaphysis of control rats that received less than 1 ppm fluoride in the drinking water, and experimental rats that received 30, 90 and 120 ppm fluoride in the drinking water for 17 days. The latter dose was toxic, as evidenced by a decreased final body weight in this group. By means of tetracycline labelling, it was possible to measure bone hardness in four zones of increasing bone age: I) 3 days, II) 8 days, III) 13 days and IV) 22 days. Zones I through III represented bone formed during fluoride treatment, and Zone IV bone formed before fluoride treatment. In the control group, microhardness increased from Zone I to II, probably because mineral concentration was relatively low in Zone I, and remained constant thereafter. In the 90 and 120 ppm fluoride-treated groups, maximum microhardness was not achieved until Zone III. This delay was probably due to the fact that fluoride in large doses inhibits the rate of mineralization. In the 30 ppm fluoride-treated group, there was no delay in achievement of maximum microhardness; microhardness values in Zones I and III were greater than those in control animals, and microhardness in Zone III was higher than that in Zone IV. These results show that: 1) bone microhardness is increased in bone formed during fluoride treatment in rats given 30 ppm fluoride in the drinking water, 2) toxic doses of fluoride delay, but do not prevent achievement of normal maximum microhardness, and 3) changes in microhardness are seen only in bone formed during fluoride treatment.
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  • 29
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    Calcified tissue international 15 (1974), S. 71-76 
    ISSN: 1432-0827
    Keywords: Bone ; Calcium ; Deficiency ; Osteoporosis ; Species
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract 21-day-old rats and mice were fed a low-calcium diet (0.02% Ca) or a normal diet (0.5% Ca) for two weeks. Administration of the low-calcium diet resulted in greater decreases in femur ash content and serum calcium in rats than in mice. Microscopic examination revealed that metatarsal bones from a majority of the rats fed a low-calcium diet displayed moderate or severe osteoporotic changes whereas bones from mice were either normal or displayed only slight osteoporotic changes under the same experimental conditions. These results indicate that mice are better able to adapt to a low-calcium diet than are rats of the same age.
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  • 30
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    Calcified tissue international 15 (1974), S. 111-123 
    ISSN: 1432-0827
    Keywords: Fluoride ; Calcium ; Phosphorus ; Bone ; Periosteum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode d'estimation de la surface périostée de l'os en voie de minéralisation est mise au point et appliquée à des porcs recevant 2 mg de fluorure par Kg de poids et par jour pendant 10 mois. L'adjonction de fluor intervient significativement dans le cas d'une déficience en calcium et phosphore. La surface en voie de minéralisation est nettement réduite. Lorsque le calcium et phosphore sont normaux, l'addition de fluorure augmente nettement la surface en voie de minéralisation. Le microscope électronique à balayage permet de mettre en évidence au niveau de l'os une perte de l'orientation longitudinale des fibers et des surfaces poreuses irrégulières chez les animaux soumis au floor.
    Abstract: Zusammenfassung Zur Bestimmung der verkalkenden Oberfläche des Periosts wurde eine Methode entwickelt und bei Schweinen angewandt, welche während etwa 10 Monaten 2 mg Fluorid per kg Körpergewicht und per Tag erhalten hatten. Dieses zusätzliche Fluorid hatte eine signifikante Wirkung bei Calcium- und Phosphormangel. Die verkalkende Oberfläuche ging stark zurück, während jedoch, wenn kein Calcium- und Phosphormangel bestand, das zusätzliche Fluorid die verkalkende Oberfläche vergrößerte. Beobachtungen mit dem Raster-Elektronenmikroskop am Knochen zeigten, daß die Längsorientierung der Fasern fehlte und daß Knochen von mit Fluorid gefütterten Tieren unregelmäßige, poröse Oberflächen aufwiesen.
    Notes: Abstract A method for estimating periosteal bone-mineralizing surface was developed and applied to swine fed 2 mg of fluoride/kg of body weight/day for about 10 months. Added fluoride interacted significantly with calcium and phosphorus deficiency. Mineralizing surface was greatly reduced, whereas when calcium and phosphorus were adequate, added fluoride greatly increased mineralizing surface. Scanning electron microscope observations of bone disclosed loss of longitudinal orientation of fibers and irregular porous surfaces in bone from fluoride-fed animals.
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  • 31
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    Calcified tissue international 15 (1974), S. 125-132 
    ISSN: 1432-0827
    Keywords: Bone ; Collagen ; Formic Acid ; Crosslinkages ; Cyanogen Bromide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Bovine and chicken bone collagens have been solubilized and presumably denatured (gelatin) by treatment of demineralized, powdered tissue with 70% formic acid. Short periods of extraction such as four hours at 30°, conditions commonly used during cyanogen bromide cleavage of collagen, solubilized 50% and 15% of the chicken and bovine bone collagens respectively. Treatment of the tissues with sodium borohydride partially inhibited the extraction of collagen from chicken bone, but had little effect on the extraction of calf bone collagen. The heterogeneity of the bone gelatin from both species on disc electrophoretic analysis suggested that peptide bonds had been cleaved in some of the collagen chains during exposure to formic acid, thus facilitating the solubilization of the bone collagen as the gelatin. Analysis of the collagen extracted from chicken bone for reducible crosslinks indicated that a large proportion of these bonds had remained intact, in contrast to a previous finding that most of these crosslinks were destroyed in bone gelatin extracted by 4 M CaCl2, at pH 7.0. The stability of the major reducible crosslinks in bone collagen to severe acid conditions may explain in part some of its unique properties, such as its failure to swell or be solubilized in dilute acid, which distinguish it from soft tissue collagens.
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  • 32
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    Calcified tissue international 15 (1974), S. 173-179 
    ISSN: 1432-0827
    Keywords: Bone ; Strength ; Tension ; Compression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A simple method is described for visualising regions of bone that have yielded in tension. The appearance of such regions is quite different from that of regions that have yielded in compression. The significance of these findings is discussed.
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  • 33
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    Calcified tissue international 15 (1974), S. 189-199 
    ISSN: 1432-0827
    Keywords: Bone ; Densitometry ; X-ray ; Radiation ; Specific gravity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract X-ray and γ-radiation techniques for evaluating bone density under field conditions in cattle and sheep were investigated. The best results were obtained from measurements of the density of radiographs of tibial tarsal bones of sheep and from the absorption of γ-radiation of the tibial tarsal bones of sheep and the fibular tarsal bones of cattle. The γ-radiation techniques may be carried out rapidly under field conditions (up to 30 animals an hour) and bone density can be estimated with a standard error of 0.042–0.046 SG units.
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  • 34
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    Calcified tissue international 15 (1974), S. 181-188 
    ISSN: 1432-0827
    Keywords: Biopsy ; Bone ; Calcium ; Phosphorus ; Specific gravity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The specific gravities (SG) of bone samples taken from various parts of the skeleton of cattle and sheep were determined gravimetrically in an effort to establish which sites give the most reproducible and uniform results, so that between animals, or sequential within animals, comparisons may be made with maximum sensitivity. Samples obtained from the mandible of sheep and the rib of cattle and sheep were found to be too variable to be useful for most purposes. Best results were obtained using whole bones which are easily prepared, such as the tibial tarsal bones of cattle and sheep and the fibular tarsal bone of cattle. These bones gave within animal deviations of 0.012–0.024 SG units, when comparing left bone with right bone. Slightly higher values were obtained for coccygeal vertebrae from cattle and distal metacarpal condyles from sheep. SG was related to ash, calcium and phosphorus contents of coccygeal vertebrae of cattle and it is considered that, for survey work on the mineral status of the bones of cattle and sheep, the correlations are sufficiently high to make their determination unnecessary. This will enable radiation determined SG techniques to be applied to this type of work.
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  • 35
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    Calcified tissue international 16 (1974), S. 335-338 
    ISSN: 1432-0827
    Keywords: Fluoride ; Plasma ; Bone ; Age
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Fluoride analyses were carried out on blood samples from fasting subjects and on iliac crest biopsies obtained at autopsy, using an ion-selective electrode. Correlation coefficients of 0.53 and 0.67 respectively were determined between plasma fluoride and age, and bone fluoride and age. The proportionate rates of increase of fluoride levels in plasma and bone with age and the similarity of the correlation coefficients suggest that the fasting plasma fluoride concentration is in equilibrium with bone fluoride.
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  • 36
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    Calcified tissue international 16 (1974), S. 305-313 
    ISSN: 1432-0827
    Keywords: Osteosarcoma ; Lyophilization ; Induction ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Bone formation was induced by iso- and home-implantation of lyophilized mouse osteosarcoma, in which an osteogenic activity is observed. The inducing factor is present exclusively in osteosarcoma, such as BF and Gardner, while not in non-osteogenic tumors, such as Ehrlich ascites tumor (2N & 4N) or mouse mammary carcinoma. The production of bone was rapid and extensive. It usually occurred within 21 days, and the time required for osteogenesis was almost the same as that reported in previous studies.
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  • 37
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    Cell & tissue research 148 (1974), S. 11-26 
    ISSN: 1432-0878
    Keywords: Dentine ; Bone ; Collagen structure ; Collagen mineralization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary It has been previously shown that the distances between the nuclei within the collagen bundles of mineralizing tissues were in good agreement with the repeat distances of the cross-banding pattern of collagen, which supports the assumption that the distances between the mineral deposits reflect to a good approximation the distances between nucleation centres on the collagen macromolecule. However, the lateral separation of the nuclei were significantly higher than the distances between close-packed triple helices. Recently a new model of collagen aggregation has been proposed in which the smallest morphological units are subfibrils (Ø approx. 39 Å) packed in tetragonal array. This led us to measure once again the lateral separation between a) close-packed calcium phosphate needles lying in bundles at (1) the mineralizing front of mantle dentine and (2) at the mineralizing front of rat tail bone, and b) between the uranyl-lead nuclei produced in the staining of rat tail tendon. The mean lateral distances separating these nuclei fell within the range of 39–47 Å, which is a little higher than the distances of 39 Å which separate the microholes between the subfibrils in the tetragonal packing model, which are regarded as the likely sites of nucleation. If, however, it is assumed that the forces generated during mineralization can cause the collagen fibres to swell, then the lateral separation of the nuclei and the distances between the microholes would correspond very closely.
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  • 38
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 68-77 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoelectron Spectra and Molecular Properties, XXVI. The Delocalisation of Sulfur Electron Pairs in Sulfides and DisulfidesThe photoelectron (PE) spectra of sulfides R—S—R (R=H, CH3, C2H5, n- und i-C3H7, n- and tert-C4H9) and disulfides R—S—S—R (R=H, CH3, C2H5, n- and i-C3H7, tert-C4H9, —[CH2]4—) are comparatively discussed. For sulfides the first ionization energy, which decreases as expected with increasing degree of alkylation, can also be obtained from the charge transfer excitation energies of their σ-complexes with tetracyanoethylene (TCNE). Disulfides show a splitting of the first PE-band in a clear dependence on the dihedral angle of the sulfur electron pairs. All observations can be rationalised within MO models as interactions of the sulfur electron pairs with the σ-skeleton and/or with each other.
    Notes: Die Photoelektronen(PE)-Spektren von Sulfiden R—S—R (R=H, CH3, C2H5, n- und i-C3H7, n- und tert-C4H9) und Disulfiden R—S—S—R (R=H, CH3, C2H5, n- und i-C3H7, tert-C4H9, —[CH2]4—) werden vergleichend diskutiert. Bei den Sulfiden R—S—R kann die mit steigendem Alkylierungsgrad erwartungsgemäß abnehmende erste Ionisierungsenergie auch aus den Charge-transfer-Anregungsenergien ihrer σ-Komplexe mit Tetracyanäthylen (TCNE) abgelesen werden. Bei Disulfiden R—S—S—S—R wird eine Aufspaltung der ersten PE-Bande in deutlicher Abhängigkeit vom Diederwinkel zwischen den Schwefel-Elektronen-paaren beobachtet. Die Befunde lassen sich mit MO-Modellen als Wechselwirkungen der Schwefel-Elektronenpaare mit dem σ-Gerüst und/oder untereinander verstehen.
    Additional Material: 6 Ill.
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  • 39
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 93-101 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nickelalkyl Ylid ComplexesFrom reactions of [(CH3)3P]3 Ni(CH3)2 and [(CH3)3P]2Ni(CH3)Cl with the ylid (CH3)3PCH2, molecular (1) an ionic complexes (2) are obtained, containing three covalent Ni—C-σ-bonds of square planar nickel atoms. These bonds are strongly stabilized by the proximity of the ylid onium center. Excess ylid converts 2 into a binuclear complex 3, where the metal atoms are bridged by dimethylphosphonium-bismethylid units, with formation of [(CH3)4P]Cl as a byproduct. An isoelectronic dimethylphosphinate complex, 4, containing a similar eight-membered ring structure, has also been prepared.
    Notes: Durch die Reaktion von Dimethyltris(trimethylphosphin)nickel und Methylbis(trimethyl-phosphin)nickel-chlorid mit Trimethylmethylenphosphoran werden molekulare (1) bzw. ionische (2) Ylid-Komplexe erhalten, in denen das quadratisch-planar konfigurierte Nickel-atom jeweils drei kovalente Ni—C-σ-Bindungen ausbildet. Diese Bindungen werden durch das Onium-Zentrum der Ylide erheblich stabilisiert. 2 liefert mit überschüssigem Ylid unter Abspaltung von [(CH3)4P]Cl einen zweikernigen Komplex 3, dessen Metallatome durch Dimethylphosphonium-bis-methylid-Brücken verbunden sind. Hierzu existiert ein isoelektronischer Dimethylphosphinat-Komplex 4, der ebenfalls Achtringstruktur besitzt.
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  • 40
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 123-127 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of carbonyl-stabilized Sulfonium-ylides of 1,3-Dithiolane with Acylating Reagents and Activated AcetylenesIn aqueous sodium hydroxide monophenacyl-1,3-dithiolanium bromides 3 form carbonylstabilized 1,3-dithiolanium-1-phenacylides 4. These yield with acylation reagents and activated acetylenes new resonance-stabilized sulfonium-ylides 6, 8, 10.
    Notes: Monophenacyl-1,3-dithiolanium-bromide 3 bilden in wäßriger Natronaluge carbonyl-stabilisierte 1,3-Dithiolanium-1-phenacylide 4. Diese reagieren mit Acylierungsmitteln und aktivierten Acetylenen zu neuen mesomeriestabilisierten Sulfonium-yliden 6, 8, 10.
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  • 41
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 145-151 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Amino Acids and Peptides, IX. On Pyruvoyl Amino AcidsAmino acid derivatives were tranformed to Pyruvoyl amino acid derivatives by use of pyruvoyl chlorid, p-nitrophenyl pyruvate, hydroxymaleic anhydride and the DCC-procedure. The application range of the different acylations is discussed. A convenient method for the preparation of pyruvoyl chloride is given.
    Notes: Aminosäurederivate werden mit Brenztraubensäurechlorid, Brenztraubensäure-p-nitrophenylester, Hydroxymaleinsäureanhydrid und mit Hilfe des DCC-Verfahrens zu Pyruvoylaminosäurederivaten umgesetzt. Die Anwendungsbreite der verschiedenen Acylierungen wird verglichen. Ein Weg zur praktischen Herstellung von Brenztraubensäurechlorid wird ausgearbeitet.
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  • 42
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 253-262 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of Hexakis(phenylthio)ethaneThe structure of hexakis(phenylthio)ethane has been determined by single crystal X-ray diffraction. The phase determination was carried out by means of the Symbolic Addition Method. The structure has been refined with 1780 observed reflections to an R-value of 10.9%. The pseudo bodycentered unit cell contains two molecules, which are situated at the center at 0, 0, 0 and 1/2, 1/2, 1/2, respectively. The bodycentering is almost perfect for the six sulfur atoms, but does not involve the central ethane bonding, which implies that the sulfur atoms, that are connected by the centering, are bonded to different carbon atoms. The six sulfur atoms are staggered around the ethane C—C bond. The S—C—S angles of 113° are larger than the ideal tetrahedrane angles by the same amount by which the S—C—C angles of 105° are smaller. The ethane C—C distances are 1.59 and 1.56 Å respectively.
    Notes: Die Struktur des Hexakis(phenylthio)äthans wurde mit Röntgenmethoden bestimmt. Die Phasenbestimmung wurde mit der symbolischen Additionsmethode durchgeführt. Die Struktur wurde unter Benutzung von 1780 beobachteten Reflexen bis auf einen R-Wert von 10.9% verfeinert. Die pseudoinnenzentrierte Elementarzelle enthält zwei Moleküle, die um die Symmetriezentren in 0, 0, 0 bzw. 1/2, 1/2, 1/2 gelagert sind. Die Innenzentrierung ist nahezu genau für die sechs Schwefelatome, aber gilt nicht für die zentrale Äthanbindung, was zur Folge hat, daß die durch Zentrierung verbundenen Schwefelatome an verschiedene Kohlenstoffatome gebunden sind. Die sechs Schwefelatome sind gestaffelt um die Äthan-C—C-Bindung angeordnet. Die S—C—S-Winkel sind mit 113° etwas größer, die S—C—C-Winkel mit 105° um denselben Betrag kleiner als der Tetraederwinkel. Die Äthan-C—C-Abstände betragen 1.59 bzw. 1.56 Å.
    Additional Material: 5 Ill.
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  • 43
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 305-316 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Benzothiazole N-Oxides, II. New Synthesis of Substituted 2-BenzothiazolonesIn the presence of phosphoryl chloride, 2-carbamoylbenzothiazole N-oxides undergo a new intramolecular redox reaction to give 2-benzothiazolones. In two cases investigated, also 2-ethoxycarbonylbenzothiazole N-oxides undergo this rearrangement. The spectroscopic data are discussed.
    Notes: 2-Carbamoylbenzothiazol-N-oxide gehen in Gegenwart von Phosphoroxychlorid eine neuartige intramolekulare Redoxreaktion unter Bildung von 2-Benzothiazolonen ein. In zwei untersuchten Fällen unterliegen unterliegen auch 2-Äthoxycarbonylbenzothiazol-N-oxide dieser Umlagerung. Spektroskopische Daten werden diskutiert.
    Additional Material: 7 Tab.
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  • 44
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aromatic Sulfenyl Chlorides, IX. Preparation, Oxidation, and Spectroscopic Investigation of 1-Substituted 5-Tetrazolyl Aryl Disulfides1-Substituted 5-tetrazolyl mesityl disulfides were synthesized which on oxidation with hydrogen peroxide gave disulfide S2, S2-dioxides (thiolsulfonates). The structure of these as well as that of the 1-substituted 5-tetrazolyl p-tolyl disulfide S2, S2-dioxides synthesized earlier was elucidated by means of their i. r. and n. m. r. spectra. The supposed structures have been established by synthesis.
    Notes: Es wurden 1-substituierte (5-Tetrazolyl)mesityldisulfide hergestellt, welche zu Disulfid-S2, S2-dioxiden (Thiosulfonate) oxidiert wurden. Deren Struktur und die der früher hergestellten 1-substituierten (5-Tetrazolyl)p-tolyldisulfid-S2, S2-dioxide wurde anhand ihrer IR- und NMR-Spektren wahrscheinlich gemacht. Die angenommenen Strukturen wurden durch Synthese bewiesen.
    Additional Material: 2 Tab.
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  • 45
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 367-379 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Lithio-1,3,5-trithianes Generation in Solution, Reactions with Electrophiles, and Use in Nucleophilic Acylation1,3,5-Trithiane and 2-mono- as well as 2,4,6-trisubstituted trithianes are shown to be metallated by n-butyllithium in THF. Reaction of the lithio derivatives thus obtained with electrophiles leads to more highly substituted trithianes which in some cases can be isolated in a pure form. The n.m.r. spectra of the products at room temperature are described. Mercury(II)-assisted solvolysis of alkyltrithianes „liberates“ the most highly substituted carbon with formation of carbonyl compounds or their O-acetals. This completes a sequence of reactions which suggests use of lithiotrithianes as reagents for nucleophilic acylation. Advantages and disadvantages of this procedure compared to the dithiane method are discussed.
    Notes: 1,3,5-Trithian selbst sowie 2-mono- und 2,4,6- trisubstituierte Trithiane lassen sich mit n-Butyllithium in Tetrahydrofuran metallieren. Umsetzung der Lithiumderivate mit Elektrophilen führt zu höher substituierten Trithianen, die teilweise in reiner Form isoliert werden können. Die NMR-Spektren der erhaltenen Produkte bei Raumtemperatur werden beschrieben. Quecksilber(II)-assistierte Solvolyse von alkylierten Trithianen führt zu Carbonyl-verbindungen oder deren O-Acetalen unter „Herauslösung“ des höchstsubstituierten C-Atoms, was die Verwendung von Lithiotrithianen als nucleophile Acylierungsmittel ermöglicht. Vor- und Nachteile gegenüber der Dithian-Methode werden diskutiert.
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  • 46
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Dependence of the Bond-length in some N,O-Dibenzoylhydroxylamines on the Torsion of the Carboxylic and Hydroxamic Groups against the Benzene Nuclei. The Crystal Structures of N,O-Dibenzoyl-(C14H11NO3), N,O-Bis(2-chlorobenzoyl)-(C14H9Cl2NO3), N-BenzoylO-p-toluoyl- (C15H13NO3), and N-Benzoyl-O-o-toluoylhydroxylamines (C15H13NO3)The crystal structures of four N,O- dibenzoylhydroxylamines - 1: N,O-dibenzoylhydroxylamine (C14H11NO3), 2: N,O- bis(2-chlorobenzoyl)hydroxylamine (C14H9Cl2NO3), 3: N-Benzoyl-O-p toluoylhydroxylamine (C15H13NO3), 4: N-benzoyl-O-o- toluoylhydroxylamine (C15H13NO3) - have been determined by X-ray techniques, using direct methods for phase determination. The torsion angles ϕ of the C—C- bonds between the phenyl groups and the hydroxamic acid groups or the carboxylic groups, respectively, have been calculated. The values of the intramolecular distances of these bonds, plotted versus cos2 ϕ, can be approximated by a straight line. Extrapolating to ϕ = 90°, the pure sp2-sp2-C—C-single-bond is found to be 1.513 Å.
    Notes: Die Kristallstrukturen von vier N,O- Dibenzoylhydroxylaminen - 1: N,O-Dibenzoylhydroxylamin (C14H11NO3), 2: N,O -Bis(2-chlorbenzoyl)hyroxylamin (C14H9Cl2NO3), 3: N-Benzoyl-O-p-toluoylhydroxylamin (C15H13NO3), 4: N- Benzoyl-O-o-toluoylhydroxylamin (C15H13NO3) - wurden röntgenographisch unter Anwendung direkter Methoden zur Lösung des Phasenproblems bestimmt. Die C—C- Bindungslängen zwischen den Phenylgruppen einerseits und den Hydroxamsäure- bzw. Carboxylatgruppen andererseits lassen sich als Funktion der Verdrillungswinkel ϕ dieser Bindung durch eine Gerade darstellen, wenn man die Bindungslängen gegen cos2 ϕ aufträgt. Der reine sp2-sp2-C—C- Einfachbindungsabstand (ϕ = 90°) ist danach 1.513 Å.
    Additional Material: 10 Ill.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 680-685 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Synthesis of Tetracyclo[3.3.0.02.8.04.6]octan-3-ones by Intramolecular Thermal [2π + 2σ]-CycloadditionThe synthesis of the tetracyclooctanone 19 by thermolysis of the tricyclic acetal 15 and subsequent removal of the acetal group is described. Thus, a third synthetic access to this system is now available. The reaction involves the cycloaddition of a thermally ring-opened cyclopropane to a double bond.
    Notes: Die Synthese des Tetracyclooctanons 19 durch Thermolyse des tricyclischen Acetals 15 und anschließende Entacetalisierung wird beschrieben. Damit bietet sich ein dritter synthetischer Zugang zu diesem System an. Die Reaktion beinhaltet die Cycloaddition eines thermisch ringgeöffneten Cyclopropans an eine Doppelbindung.
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  • 48
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 717-720 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 49
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 731-734 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 785-795 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pteridines, LX. Synthesis and Autoxidation of 7, 8-DihydroxanthopterinsThe synthesis of 7,8-dihydroxanthopterin (18) and of various N- and C-methyl derivatives (19-27, 30) is described. Their pKa values and u.v. spectra have been determined and the behaviour during autoxidation has been investigated. The monoanions are subject to autoxidation which is catalysed strongly by ammonia and primary amines. A mechanism for the autoxidation is discussed in which the existence of various intermediates is based on the oxidative behaviour of differently blocked N- und C-methyl derivatives.
    Notes: Die Synthese des 7,8-Dihydroxanthopterins (18) und verschiedener N- und C-Methyl-Derivate (19-27, 30) wird beschrieben. Ihre pKa-Werte und UV-Spektren werden bestimmt und ihr Autoxidationsverhalten untersucht. Die Monoanionen unterliegen der Autoxidation, welche durch Ammoniak und primäre Amine stark katalysiert wird. Ein Mechanismus wird diskutiert und verschiedene Zwischenprodukte anhand von blockierten N- und C-Methyl-Derivaten wahrscheinlich gemacht.
    Additional Material: 4 Ill.
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  • 51
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 832-837 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of 6,6-Bis(dimethylamino)fulvene6,6-Bis(dimethylamino)fulvene crystallizes in the space group Pn21a, the lattice constants being ao = 13.344 Å, bo = 7.844 Å and co = 9.438 Å. The structure has been solved by superposition and by direct methods in the space group Pnma. The structure was refined by block-diagonal-least-squares to R = 0.037.
    Notes: Das 6,6-Bis(dimethylamino)fulven kristallisiert in der Raumgruppe Pn21a mit den Gitter-konstanten ao = 13.344 Å, bo = 7.844 Å und co = 9.438 Å. Die Struktur wurde durch Superposition und anschließende Resymmetrisierung der Patterson-Funktion und mit direkten Methoden in der zentrosymmetrischen Obergruppe Pnma gelöst.
    Additional Material: 2 Ill.
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  • 52
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 847-853 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bromine/Lithium Exchange in Vinyl and Aryl Bromides with tert-Butyl Lithium. On the Ring Enlargement via Dibromocarbene AdductsTwofold molar excess of tert-butyl lithium replaces vinylic and arylic bromine by lithium. The tert-butyl bromide formed is dehydrohalogenated rapidly to isobutene by tert-butyl lithium even at very low temperatures. Transformation of 1-bromo-1-cyclooctene and - cyclononene via the lithium derivatives to vinyl thioethers 1d, e, and i in high yields opens up a simple alternative route from olefin dibromocarbene adducts to ring enlarged ketones. The bromobenzenes 2a and 3a reveal that the Br/Li-exchange described here is not accompanied by arine formation; it is feasible even in the presence of sensitive benzylic CH2-groups as present in 3.
    Notes: Vinylisch und an Aromaten gebundenes Brom läßt sich quantitativ mit zweifachem molarem Überschuß an tert-Butyllithium gegen Lithium austauschen. Das entstehende tert-Butylbromid wird selbst bei tiefen Temperaturen von tert-Butyllithium rasch zu Isobuten dehydrohalogeniert. Die Überführung von 1-Brom-1-cycloocten und -1-cycloneone in Vinylthioäther 1d, e und i über die Lithiumderivate ist in hoher Ausbeute möglich und eröffnet einen einfachen Weg von Dibromcarbenaddukten an Olefine zu ringerweiterten Ketonen. Am Beispiel der Brombenzole 2a und 3a wird gezeigt, daß der hier beschriebene Br/Li-Austausch nicht von Arin-Bildung begleitet und auch in Gegenwart der empfindlichen benzylischen CH2-Gruppe von 3 durchführbar ist.
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  • 53
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 892-897 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N-VinylimidazolecarboxylatesN-Vinylation of imidazolecarboxylates with vinyl acetate leads to the formation of the N-vinylimidazoles 3a, 3b, 6, 8a, 8b und 9a. The structures are determined by mass and n.m.r. spectra. 3a, 6, 8a are polymerizable.
    Notes: Durch N-Vinylierung von Imidazolcarbonsäureestern mit Vinylacetat werden die N-Vinylimidazole 3a, 3b, 6, 8a, 8b und 9a, erhalten. Die Strukturen werden mit Hilfe von NMR-und Massen-Spektren gesichert. 3a, 6, 8a und 8bsing polymerisationsfähig.
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  • 54
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 929-936 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclizations, XIII. New Polycyclic Pyrimidines with Bridge-Head NitrogenThe base-catalized condensation of 2,3,3-trimethyl-3H-benz[f]indole (9) with dielectrophilic iso(thio)cyanates to polycyclic pyrimidines with bridge-head nitrogen (11, 15, 16) in most cases involves preliminary formation of 1: 2 adducts followed by elimination of diacylamides. Contrary to this the less nucleophilic 2,3,3-trimethyl-3H-pyrrolo [2,3-b]pyridine (20) affords the analogue pyrimidines by intermediacy of 1:1 adducts and elimination of water or ethanol solely.
    Notes: Die basenkatalysierte Kondensation von 2,3,3-Trimethyl-3H-benz[f] indol (9) mit dielektrophilen Iso(thio)cyanaten zu polycyclischen Pyrimidinen mit Brückenkopf-Stickstoff (11, 15, 16) verläft meist über die Bildung von 1:2-Addukten als Zwischenstufe und Eliminierung von Diacylamiden. Dagegen liefert das weniger nucleophile 2,3,3-Trimethyl-3 H-pyrrolo[2.3-b]-pyridin (20) analoge Systeme (22, 23) ausschließlich über 1: 1-Addukte und Eliminierung von Wasser bzw. Äthanol.
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  • 55
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 686-697 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkaloids from Rhamnaceae, XVIII. Amphibine-F, -G and -H, further Peptide Alkaloids from Ziziphus amphibia A. Cheval.From the complex mixture of crude alkaloids from Ziziphus amphibia A. Cheval., in addition to the already described Amphibines-A, -B, -C, -D and -E, three further peptide alkaloids Amphibine-F, -G and -H have been isolated and their structures elucidated (1-3). Amphibine-F and -G (1, 2) belong to the class of cyclic peptide alkaloides having a fourteen-membered ring system made up from trans-3-hydroxyproline, p-hydroxystyrylamine and an α-aminoacid. Amphibine-H (3) has a thirteen-membered ring system formed from 5-hydroxy-2-methoxystyrylamine and the aminoacids trans-3-hydroxyproline and phenylalanine.
    Notes: Aus dem komplexen Rohbasengemisch von Ziziphus amphibia A. Cheval. wurden neben den bereits beschriebenen Amphibinen-A, -B, -C, -D und -E drei weitere Peptidalkaloide Amphibin-F, -G und -H isoliert und in der Struktur geklärt (1-3). Die Amphibine-F und -G (1, 2) zählen zu den Cyclopeptidalkaloiden mit 14 gliedrigem Ringsystem aus trans-3-Hydroxyprolin, p-Hydroxystyrylamin und einer α-Aminosäure. Das Amphibin-H (3) weist ein 13 gliedriges Ringsystem auf, das aus den Aminosäuren trans-3-Hydroxyprolin und Phenylatanin sowie aus 5-Hydroxy-2-methoxystyrylamin gebildet wird5).
    Additional Material: 3 Ill.
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  • 56
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 698-705 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Preparation of New ChloroformamidinesAction of phosphine/carbon tetrachloride or dichlorotriphenylphosphorane on N,N,N′-trisubstituted ureas leads to the formation of even such chloroformamidines which are not or only difficultly obtainable by the conventional methods. The spectroscopic and analytic data of the new compounds are given.
    Notes: Durch Einwirkung von Phosphin/Tetrachlorkohlenstoff oder von Dichlortriphenylphos-phoran auf N,N,N′-trisubstituierte Harnstoffe können auch solche Chlorformamidine dargestellt werden, die nach den bisherigen Methoden nicht oder nur schwer zugänglich sind. Die spektroskopischen und analytischen Daten der neuen Verbindungen sind angegeben.
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  • 57
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 721-724 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 725-726 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 59
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 739-744 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Fulvenes, VIII. Indeno[2,1-c]-1,2-dithioles, a Group of New PseudoazulenesAcylation of 2-pyrrolidinoindene (4) with carboxylic acid chlorides and subsequent hydrolysis leads to the 1-acyl-2-indanones 6, which have been condensed with diacetyl disulfide in aequous perchloric acid/acetic acid to afford the 8H-indeno[2,1-c]-1,2-dithiolium-perchlorates 7. These are deprotonated with N-ethyldiisopropylamine to yield the indeno[2,1-c]-1,2-dithioles 10, a group of new pseudoazulenes.
    Notes: Acylierung von 2-Pyrrolidinoinden (4) mit Carbonsäurechloriden und nachfolgende Verseifung liefert die 1-Acyl-2-indanone 6, die mit Diacetyldisulfid in wäßriger Perchlorsäure, Eisessig zu den 8H-Indeno[2,1-c]-1,2-dithiolium-perchloraten 7 kondensieren. Letztere lassen sich durch N-Äthyldiisopropylamin zu den Indeno[2,1-c]-1,2-dithiolen 10, einer Gruppe neuer Pseudoazulene, deprotonieren.
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  • 60
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 759-770 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereochemistry and Reactivity of Tetrahalogenated 2,3-Diazabicyclo[3.2.0]hept-2-enes and Bicyclo [2.1.0] pentanesThe addition of diazoalkanes to tetrahalogenated cyclobutenes 1-3 leads to 6,6,7,7-tetrahalo-2,3-diazabicyclo[3.2.0]hept-2-enes 4-8, the structure and stereochemistry of which are determined by means of n. m. r. spectroscopy. Thermal decomposition of 4, 5, and 8 in boiling toluene affords the tetrahalobicyclo[2.1.0]pentanes 9, 10, and 12 in good yields. Under the same conditions 7 decomposes in a stereospecific manner to form 11 and small amounts of 13. Sodium methoxide converts 9-11 into the cyclobutenes 14 and 15. Under the influence of sulfuric acid 10 forms the cyclobutenedione 16 or a mixture of cyclopentenones 18, 19 depending on the reaction conditions.
    Notes: Addition von Diazoalkanen an die tetrahalogenierten Cyclobutene 1-3, führt zu 6,6,7,7-Tetrahalogeno-2,3-diazabicyclo[3.2.0]hept-2-enen 4-8, deren Konstitution und Stereochemie auf NMR-spektroskopischem Weg ermittelt wurde. Durch thermische Zersetzung der Bicyclen 4,5 und 8 in siedendem Toluol erhält man in guten Ausbeuten Tetrahalogenobicyclo-[2.1.0]pentane 9,10 und 12. Unter gleichen Bedingungen entstehen aus 7 in stereospezifischer Reaktion 11 sowie geringe Mengen des Cyclobutens 13. Mittels Natriummethylat werden die Bicyclen 9-11 zu den Cyclobutenen 14, 15 abgebaut; unter dem Einfluß von konz. Schwefelsäure entsteht aus 10 je nach Reaktionsbedingungen das Cyclobutendion 16 bzw. ein Gemisch der Cyclopentenone 18 und 19.
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1221-1227 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conversion of Aldehydes into Nitriles without Isolation of IntermediatesAldehydes are converted into nitriles without isolation of the intermediates by treating their oximes with carbodiimides in the presence of copper(II)ions and triethylamine. The entire process requires 3 hours at room temperature; it is unsuccessful if the oxime does not form or is consumed by competition reactions.
    Notes: Aldehyde können ohne Isolierung von Zwischenprodukten in Nitrile übergeführt werden, indem ihre Oxime in Gegenwart von Kupfer(II)-Ionen und Triäthylamin mit Hilfe von Carbodiimiden dehydratisiert werden. Der gesamte Prozeß erfordert bei Raumtemperatur durchweg 3 Stunden. Das Verfahren versagt, wenn die Oximbildung gestört ist oder das Oxim Konkurrenzreaktionen eingeht.
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  • 62
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Reactivity of Silicon Transition Metal Complexes, V. The Modified Alkali Salt Elimination Method  -  a General Procedure for the Synthesis of Silicon Transition Metal CompoundsThe heterogeneous reaction of the sodium carbonylmetallates Na[Fe(CO)2π-C5H5], Na[M(CO)3π-C5H5] (M=Mo, W), and Na[Mn(CO)5] with various halo- and organohalosilanes leads to the formation of the corresponding silyl complexes. The new compounds are characterized by spectroscopy and the chemical properties are described. The results of a decomposition study of the trimethylsilyl-VIB transition metal complexes are discussed in connection with former synthetic experiments. Exchange reactions of these species with heterosiloxanes can be used for a qualitative estimation of relative metal-metalloid bond reactivity.
    Notes: Die Umsetzung der komplexen Metallate Na[Fe(CO)2π-C5H5], Na[M(CO)3π-C5H5] (M=Mo, W) und Na[Mn(CO)5] mit verschiedenen Halogen- und Organohalogensilanen führt in heterogener Reaktion zu den Silylkomplexen dieser Metalle. Die neuen Verbindungen werden spektroskopisch charakterisiert und ihre chemischen Eigenschaften beschrieben. Die Ergebnisse einer Zerfallsstudie der Trimethylsilyl-VIB-Übergangsmetallkomplexe werden im Zusammenhang mit früheren Syntheseversuchen diskutiert. Der Verlauf von Austauschreaktionen der gleichen Verbindungen mit Heterosiloxanen (Ge, Sn) ermöglicht eine qualitative Abschätzung der Reaktivität der Metall- Metalloideinheit.
    Additional Material: 7 Tab.
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  • 63
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1057-1065 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on 4-Pyrones, 51. Aminoalkylation of ChromonesThe aminoalkylation of 2-methylchromones (1b, e and 2b, c) leads to the formation of benzopyrano[3.2-c]pyridinium chlorides (9a-d and 11a-e).
    Notes: Die Aminoalkylierung von 2-Methylchromonen (1b, e sowie 2b, c) führt zu Benzopyrano-[3.2-c]pyridinium-chloriden (9a-d sowie 11a-e).
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  • 64
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1069-1069 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mass Spectrometric Investigation of Amides, VII. Intramolecular Interactions of Bifunctional Groups in the electron Impact Induced Fragmentation of Piperidides and PiperideidesThe activation energy ∊ for the electron impact induced splitting of the N-carbonyl bond in bifunctional amides is estimated. A clear correlation is shown of ∊ with the ring size of the transition state and the nucleofuge or nucleophilic properties of the nitrogen groups. Furtheron by means of [D]-labelled model compounds selective hydrogen migrations have been established.
    Notes: Die Aktivierungsenergie ∊ für die elektronenstoßinduzierte Spaltung der N-Carbonylbindung bifunktioneller Amide wird bestimmt. Es ergibt sich ein klarer Zusammenhang von ∊ mit der Ringgröße des Übergangszustandes und den nucleofugen bzw. nucleophilen Eigenschaften der Stickstoffgruppen. Ferner werden mit Hilfe [D]-markierter Modellverbindungen selektive Wasserstoffübertragungen nachgewiesen.
    Additional Material: 3 Tab.
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1126-1135 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Nature of Benzonorbornen-2-yl Cations, II. Solvolysis of Isopropylidene-substituted benzonorbornen-2yl EstersThe 2-epimeric at C-7 and C-3 substituted benzonorbornenols 4a, 6a, 7a and 8a are synthesized. The rate of solvolysis of the tosylates 4b and 6b is measured in acetic acid, that of the 3,5-dinitrobenzoates 7b and 8b in 90% dioxane. The solvolysis products are determined in 80% acetone puffered with 2,6-lutidine. The epimeric 7-isopropylidene derivatives 4b and 6b solvolyse by a different mechanism; the exo derivative 4b reacts exclusively with assistance of the benzene ring, the endo compound by participation of the homoallylic double bond. The epimeric 3-isopropylidene derivatives 7b and 8b solvolyse to a common intermediate allylic ion 10. The kexo/kendo ratio is reduced to 9 due to the presence of this neighbouring group, which is a measure of the steric factor in the secondary benzonorbornen-2-yl system.
    Notes: Die epimeren Benzonorborneole 4a und 6a sowie 7a und 8a werden synthetisiert. Die Solvolysegeschwindigkeit der Tosylate 4b und 6b wird in Eisessig, die der 3,5-Dinitrobenzoate 7b und 8b in 90 proz. Dioxan gemessen. Die Reaktionsprodukte werden in 80 proz., mit 2,6-Lutidin gepuffertem Aceton bestimmt. Die epimeren 7-Isopropyliden-Verbindungen 4b und 6b solvolysieren nach einem unterschiedlichen Mechanismus; die exo-Verbindung 4b reagiert ausschließlich mit Beteiligung des Aromaten, die endo-Verbindung 6b mit der der Isopropyliden-Doppelbindung. Die epimeren 3-Isopropyliden-Verbindungen 7b und 8b solvolysieren zu einem gemeinsamen Allyl-Ion 10 als produktbestimmende Zwischenstufe. Das Verhältnis kexo/kendo wird durch diese Nachbargruppe auf 9 herabgesetzt, welches ein Maß für den sterischen Anteil des sekundären Benzonorbornen-2-yl-Systems ist.
    Additional Material: 1 Ill.
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  • 67
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXXII. Cleavage of the Double Bond of 1-vinyl-2-pyrrolidone and β-Substituted 1-Vinylpyrrolidones by Reaction with Pentacarbonyl(methoxyphenylcarbene)chromium(0)Pentacarbonyl(methoxyphenylcarbene)chromium(0) reacts with 1-vinyl-2-pyrrolidone to form α-methoxystyrene by transfer of a methylene group to the carbene moiety. The origin of the transfered methylene group is proved by using methylsubstituted 1-vinylpyrrolidones. The reaction products are identified by their i.r., 1H n.m.r., and mass spectra. As reaction mechanism a cyclic transition state is proposed, which explains the breaking and following formation of a double bond analogously to the heterolytic fragmentation according to Grob.
    Notes: Bei der Umsetzung von Pentacarbonyl(methoxyphenylcarben)chrom(0) mit 1-Vinyl-2-pyrrolidon entsteht durch Übertragung einer Methylengruppe auf den Carben-Rest α-Meth-oxystyrol. Durch Einsetzen methylsubstituierter 1-Vinylpyrrolidone wird die Herkunft der übertragenen Methylengruppe bewiesen. Die Produkte werden anhand ihrer IR-, 1H-NMR- und Massenspektren identifiziert. Als Reaktionsmechanismus wird ein cyclischer Übergangszustand vorgeschlagen, der - in Analogie zur heterolytischen Fragmentierung nach Grob - die Spaltung und Neuknüpfung einer Doppelbindung erklärt.
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1207-1212 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemical Reactions, XXIII. The Photocyclisation of 9-Benzylidenexanthenes and 9-BenzylidenethioxanthenesDehydrocyclisations of the 9-benzylidenexanthenes in u.v. or sunlight (6a-6d→7a-7d) were realized. 6 may be considered as derived from stilbene, and 7 as derived from phenanthrene. Therefore the photoprocess 6→7 is analogue to the photoprocess cis-stilbene → phenanthrene.
    Notes: Dehydrocyclisierungen der Benzylidenxanthene im UV-oder Sonnenlicht (6a-6b→7a-7d) wurden durchgeführt. Da 6 als substituierte cis-Stilbene und 7 als substituierte Phenanthrene aufgefaßt werden können, liegen Analogiereaktionen zu dem Photoprozeß cis-Stilben → Phenanthren vor.
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  • 69
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1228-1234 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Dynamic Behaviour of Mono-cyclopentadienylarsinesMono-cyclopentadienylarsines (3a-e) are synthesized by the reaction of cyclopentadienyl-trimethylsilane (1) or cyclopentadienyllithium (5) with the halogenoarsines 2a-e. They are very sensitive against air and moisture and thermally unstable. The cp-ligands are σ-bonded; the molecules have a fluxional structure. The rapidity of the degenerate metallotropic rearrangements is influenced by the other ligands on the arsenic atom.
    Notes: Mono-cyclopentadienylarsine (3a-e) werden durch Umsetzung von Cyclopentadienyl-trimethylsilan (1) oder Cyclopentadienyllithium (5) mit den Halogenarsinen 2a-e dargestellt. Sie sind äußerst luft- und feuchtigkeitsempfindlich und thermisch instabil. Es liegen σ-gebundene Cp-Liganden und Moleküle mit fluktuierender Struktur vor. Die Geschwindigkeit der entarteten metallotropen Umlagerungen wird durch die anderen Liganden am Arsenatom beeinflußt.
    Additional Material: 3 Tab.
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  • 70
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1318-1328 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enehydrazines, 9. 1-Alkyl-3-hydroxypyrazoles from Hydrazones or HydrazinesReaction of dimethyl acetylendicarboxylate with hydrazinen oder Alkyl hydrazonen gives the methyl 1-alkyl-3-hydroxy-5-pyrazolecarboxylats 9 and 13a-e, subsequent saponification and decarboxylation gives the 1-alkyl-3-hydroxypyrazoles 11 and 15a-e. The cyclization of 13f to lactone 19a is a structure proff. Starting from benzaldehyde hydrazones, 2-pyrazoline-4,5-dicarboxylic esters are the main products.
    Notes: Durch Umsetzung von Acetylendicarbonsäure- dimethylester mit Hydrazinen oder Alkyl-hydrazonen erhält man die 1-Alkyl-3-hydroxy-5-pyrazolcarbonsäure-methylester 9 und 13a-e, durch Verseifung und Decarboxylierung hieraus die 1-Alkyl-3-hydroxypyrazole 11 und 15a-e. Die Cyclisierung von 13f zum Lacton 19a ist strukturbeweisend. Bei Verwendung von Benzaldehyd-hydrazonen entstehen hauptsächlich 2-Pyrazolin-4,5- dicarbonsäureester.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1334-1343 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrophilic Addition of Disulfur Dichloride to Alkynes, 3. Reaction of Asymmetric of Asymmetric Substituted Alkynes with Disulfur DichlorideDisulfur dichloride adds to the triple bond of asymmetric substituted alkynes to afford vinyl sulfides, which are constitution isomers. Substituents R with a negative I-effect yield „Markownikof“ products whereas a positive I-effect leads to the formation of „anti-Markownikoff“ products. The addition is always trans. The obtained sulfides are oxidized with H2O2 in glacial acetic acid to yield the corresponding sulfones.
    Notes: Die bei der elektrophilen Addition von Dischwefeldichlorid an asymmetrische Alkine gebildeten Vinylsulfide sind Konstitutions -Isomere. Substituenten R mit negativem Induktionseffekt führen zu „Markownikoff“-Produkten, während ein positiver I-Effekt „anti-Markownikoff“-Orientierungen liefert. In allen Fällen erfolgt eine trans-Addition. Die erhaltenen Sulfide werden nach der Oxidation mit Wasserstoffperoxid/Eisessig als Sulfone isoliert.
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  • 72
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1371-1379 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Oxidative Addition Reactions of Nitroalkanes to Tetrakis(triphenylphoshine)platinum(0)The oxidative addition of nitromethane to Pt(PPh3)4 in polar protic solution provides a convenient and safe method for the preparation of trans-(Ph3P) 2Pt(CNO)2 Pt(CNO2)(3). From Pt(PPh3)4 and nitromethane or 2-nitropropane cis-(Ph3P) 2Pt(NO2)2 (2) is obtained. The reactions of Pd(PPh3)4 or Rh(PPh3)2CO)Cl with CH3NO2 or some of its derivatives afford isocyanato compounds. Formaidoxime hydrochloride reacts with Pt(PPh3)4 to give trans-(Ph3P)2Pt-(CN)Cl (4).
    Notes: Die oxidative Addition von Nitromethan an Pt(PPH3)4 in polarem, protischem Medium liefert gefahrlos und in guter Ausbeute trans-(Ph 3P)2Pt(CNO)2 (3). Aus Pt(PPh3)4 und Nitromethan bzw. 2-Nitropropan wird cis-(Ph3P)2Pt(NO2)2 (2) erhalten. Die Umsetzungen von Pd(PPh 3)4 oder Rh(PPh3)2(CO)Cl mit Nitromethan oder Methylnitrolsäure führen zu Isocyanatoverbindungen. Formaldoxim-hydrochlorid reagiert mit Pt(PPh 3)4 zu trans-(Ph3P)2Pt(CN)Cl (4).
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  • 73
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1720-1730 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Botrydial, a Sesquiterpene Antibiotic from the Culture Solution of the Fungus Botrytis cinereaThe antibiotic botrydial (3) and its dihydro derivative (1) were isolated from the culture solution of the fungus Botrytis cinerea. Their structural formulas were elucidated by means of a series of chemical transformations together with the application of spectroscopic methods, especially a detailed analysis of the n.m.r. spectra. The basic skeleton of botrydial is a bicyclic, non-isoprenoid sesquiterpene system.
    Notes: Aus der Nährlösung des Pilzes Botrytis cinerea wurden das antibiotisch wirksame Botrydial (3) und sein Dihydroderivat (1) isoliert. Durch eine Folge chemischer Umwandlungen, verbunden mit der Anwendung spektroskopischer Methoden, insbesondere einer detaillierten Analyse der NMR-Spektren, wurden ihre Konstitutionsformeln abgeleitet. Botrydial liegt ein bicyclisch nicht-isoprenoides Sesquiterpenskelett zugrunde.
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  • 74
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1767-1768 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1773-1776 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occuring Terpene Derivatives, XXXVI. Synthesis of 8-Hydroxybrickellol and Dehydronerol isovalerateThe sesquiterpene 7 named 8-hydroxybrickellol as well as the isovalerate of dehydronerol (14) have been synthesized.
    Notes: Das 8-Hydroxybrickellol benannte Sesquiterpen 7 sowie der Isovaleriansäureester des Dehydronerols (14) werden synthetisch dargestellt.
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  • 76
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1420-1427 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reactions of Phosphorus Ylids with Excess Alkohol and AlkanethiolThe alkoxytetraalkylphosphoranes of the formula R4POR′, obtained from equimolar amounts of ylid and alkohol, which contain pentacoordinate phosphorus atoms, are converted into ionic products (1 - 7) by addition of excess alkohol. In these compounds phosphonium cations R4P⊕ are accompanied by hydrogen-bonded hydrogenalkoholate anions of the types [R′O…H…OR′]⊖, [H2(OR′)3]⊖, and [H3(OR′)4]⊖. This structure is proposed on the basis of n.m.r., i.r., and Raman-spectroscopic data. With ylids and alkanethiols only salt-like products R4P⊕RS⊖ are formed.
    Notes: Die aus äquimolaren Mengen von Yliden und Alkoholen zugänglichen, kovalent gebauten Alkoxytetraalkylphosphorane R4POR′ mit pentakoordinierten Phosphoratomen werden durch Addition von überschüssigem Alkohol in die Produkte 1 - 7 verwandelt, in welchen Phosphonium-Kationen R4P⊕ den wasserstoffbrückenverknüpften Hydrogenalkoholat-Anionen vom Typ [R′O…H…OR′]⊖, [H2(OR′)3]⊖ und [H3(OR′)4]⊖ gegenüberstehen. Der Strukturvorschlag stützt sich auf NMR-, IR- und Raman-spektroskopische Untersuchungen. Aus Yliden und Alkanthiolen entstehen nur die salzartigen Phosphonium-alkanthiolate R4 P⊕RS⊖.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1472-1482 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangements of 3-Substituted Norbornanediazonium Ions3-Oxonorbornane-2-endo-diazonium ions (1), generated by acid-catalyzed decomposition of 3-diazonorcamphor (5) in alcoholic solutions, produce derivatives of endo-bicyclo[2.2.1]heptane 3 and bicyclo [3.1.1]heptane derivatives 4, varying with the nucleophilicity of the solvent. This suggests the 7-bridged ion 2 as intermediate, which plays also an important part in the deamination of 3,3-dimethoxynorcamphor tosylhydrazone (16) in alkaline solutions as shown by the formation of 3 and 4. In the alkaline deamination of 3,3- dimethoxy-5-norbornen-2-on tosylhydrazone (32) in methanol the homoallylic ion 34 is dominating.
    Notes: 3-Oxonorbornan-2-endo-diazonium-Ionen (1), erzeugt durch sauer katalysierte Zersetzung von 3-Diazonorcampher (5) in alkoholischen Lösungen, ergaben endo-Bicyclo[2.2.1]heptan-3 und Bicyclo[3.1.1]heptan-Derivate 4, deren Menge von der Nucleophilie des eingesetzten Lösungsmittels abhängig ist. Dies läßt das 7-verbrückte Ion 2 als Zwischenstufe vermuten, welches auch bei der Desaminierung des 3,3-Dimethoxynorcampher-tosylhydrazons (16) in alkalischen Lösungen eine entscheidende Rolle spielt, wie die Bildung der Produkte 3 und 4 beweist. Bei der alkalischen Desaminierung des 3,3-Dimethoxy-5-norbornen-2-on-tosylhydrazons (32) in Methanol ist jedoch die Homoallylumlagerung zum Kation 34 produkt-bestimmend.
    Additional Material: 4 Tab.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1536-1544 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Derivatives of Guanidines Containing Phosphorus and SulfurN-Chloroguanidines 1 react with tervalent phosphorous compounds or with sulfides to yield N-guanylphosphine imidium (3) or sulfimidium salts (9). Dehydrohalogenation gives the respective N-guanyl phosphine imides and sulfimides. The structure and reactions of these compounds are discussed.
    Notes: Die Umsetzung von N-Chlorguanidinen 1 mit tervalenten Phosphorverbindungen sowie Sulfiden führt zu N-Guanylphosphinimidium- (3) bzw. -sulfimidium-Salzen (9). Durch Dehydrohalogenierung werden die entsprechenden Phosphinimide und Sulfimide erhalten. Die Eigenschaften dieser Verbindungen - insbesondere die Struktur-und Bindungsverhältnisse-sowie ihre Reaktionen werden untersucht.
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1568-1578 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conformational Analysis, III. exo-Anomeric Effect and Circular Dichroism of Glycopyranosyl AzidesTetra-O-acetyl-aldopentopyranoses and penta-O-acetyl-aldohexopyranoses react readily with trimethylsilyl azide in the presence of BF3 or SnCl4 to afford the corresponding glycosyl azides 1a - 11 (table 1). Only the anomeric glycosyl azide having the azido group „trans“ to the 2-acetoxy group is obtained in each case. The polarization of the Cl—Nx and Nx—Nz bonds in glycosyl azides is such that in both cases the dipole is directed toward Nx. It can be deduced that glycosyl azides, like methyl glycopyranosides, should exhibit an exo-anomeric effect which strongly favors the conformers 9 and 12. The application of the azide-octant rule predicts a negative Cotton effect for the α-D-glycosyl azide 12 and a positive effect for the β-D-glycosyl azide 9. Circular dichroism measurements are in good agreement with these predictions, indicating the operation of an exo-anomeric effect in the glycosyl azides.
    Notes: Tetra-O-acetyl-pentopyranosen und Penta-O-acetyl-hexopyranosen setzen sich mit Trimethylsilylazid bei Gegenwart von BF3 oder SnCl4 leicht zu den entsprechenden Glycosylaziden 1a bis 11 um (Tab. 1). Es entsteht stets nur das anomere Glycosylazid, in dem die Azidogruppe und 2-OAc „trans“ zueinander angeordnet sind. In Glycosylaziden sind die Bindungen Cl—Nx und Nx—Nz in der Weise polarisiert, daß der Dipol in beiden Fällen zum Nx weist. Hieraus wird abgeleitet, daß bei Glycosylaziden wie bei Methylglycosiden ein exo-anomerer Effekt wirksam sein sollte, der die Konformeren 9 und 12 stark bevorzugt. Die Anwendung der Azid-Oktantenregel sagt für das α-D-Glycosylazid 12 einen negativen, für das β-D-Glycosylazid 9 einen positiven Cotton-Effekt voraus. Messungen des Circular-dichroismus stimmen mit diesen Voraussagen gut überein, was für einen exo-anomeren Effekt bei Glycosylaziden spricht.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1645-1648 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermally Induced Reactions of Imidazole Derivatives, IV. Kinetics of the Thermal Rearrangement of 2,4,4-Triaryl-5-methylthio-4H-imidazolesThe thermal rearrangements of the title compounds 1a - d into the 2,4,5-triarylimidazoles 2 in different solvents and at different temperatures are first order reactions. No linear relation exists between the effect of the p-substituents of the migrating aryl groups on the reaction rates and their Hammett-Brown σ+ values. The solvent has practically no effect on the rearrangement rate of 1c. The activation parameters of the rearrangement 1c → 2c are given.
    Notes: Die thermische Umlagerung der Titelsubstanzen 1a - d in die 2,4,5-Triarylimidazole 2 in verschiedenen Lösungsmitteln und bei verschiedenen Temperaturen folgt einem Geschwindigkeitsgesetz 1. Ordnung. Der Einfluß des p-Substituenten der wandernden Arylgruppe ändert sich nicht linear mit den Hammett-Brownschen σ+-Werten. Das Lösungsmittel hat praktisch keinen Einfluß auf die Umlagerungsgeschwindigkeit von 1c. Die Aktivierungsparameter der Umlagerung 1c → 2c werden angegeben.
    Additional Material: 1 Ill.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1676-1683 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vinyl Cations, 15. Preparation and Solvolysis of the Stereoisomeric 1-Bromomethylene-2-methylcyclopropanesThe stereoisomeric 1-bromomethylene-2-methylcyclopropanes (6Z and 6E) are synthesized and their solvolysis rates and products in ethanol/Water mixtures are determined. 6Z and 6E solvolyse at approximately the same rates. Both isomers yield only the rearranged products 12, 14, 16 and 18, which are formed from both isomers in the same ratio. The products as well as the kinetic data are explained by assuming the formation of the stabilized cyclopropylidenemethyl cation 7.
    Notes: Die stereoisomeren 1-Brommethylen-2-methylcyclopropane (6Z und 6E) wurden dargestellt und die Solvolysegeschwindigkeiten sowie die Produkte in Äthanol/Wasser-Gemischen bestimmt. 6Z und 6E solvolysieren dabei etwa mit gleicher Geschwindigkeit. Aus beiden Isomeren entstehen ausschließlich die umgelagerten Produkte 12, 14, 16 und 18 im gleichen Mengenverhältnis. Produktanalyse und Kinetik werden mit der Bildung des stabilisierten Cyclopropylidenmethylkations 7 erklärt.
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    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1684-1701 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dispiro[2.0.2.4]deca-7,9-diene and Related Model Compounds: Synthesis, U.V, N.M.R, and Photoelectron-Spectroscopic InvestigationsDispiro[2.0.2.4]deca-7,9-diene (4) and spiro[2.5]octa-4,6-diene (5 can be obtained from the corresponding monoolefins 6 and 10, respectively, by bromine addition and subsequent dehydrobromination. The u. v. spectra of 5 and 4 with λmax = 269 nm (log ε = 3.4) and 284 nm (3.7), respectively, show bathochromic shifts of their longest wavelength bands as compared to 1,3-cyclohexadiene. An analysis of the 1H n. m. r. chemical shifts and H, H-coupling constants for the olefinic protons in 4 indicates that there is no cyclic electron delocalization in this ring system. The six-membered ring in 4 is only slightly flatter than the one in 1,3- cyclohexadiene. The photoelectron spectroscopic data of 4, 5, spiro[2.5]octane (13), spiro[2.5]oct-4-ene (15), dispiro[2.0.2.4]decane (14), and dispiro[2.0.2.4]dec-7-ene (16) demonstrate the effect of the interaction between π-orbitals and cyclopropyl Walsh-orbitals; an assignment for the first bands in the p. e. spectra of these compounds is proposed.
    Notes: Dispiro[2.0.2.4] deca-7,9-dien (4) und Spiro[2.5]octa-4,6-dien (5) lassen sich aus den entsprechenden Monoolefinen 6 bzw. 10 durch Bromierung und anschließende Dehydrobromierung gewinnen. Die UV-Absorptionen von 5 und 4 mit λmax = 269 nm (log ε = 3.4) bzw. 284 nm (3.7) sind bathochrom verschoben gegenüber denjenigen des 1,3-Cyclohexadiens. Aus einer Analyse der Chemischen Verschiebungen und H,H-Kopplungskonstanten der olefinischen Protonen im 1H-NMR-Spektrum von 4 ist zu schließen, daß 4 kein cyclisch delokalisiertes Elektronensystem enthält. Der Sechsring in 4 ist nur wenig stärker eingeebnet als derjenige im 1,3-Cyclohexadien. Anhand der Photoelektronen-Spektren von 4, 5 sowie Spiro[2.5]octan (13), Spiro[2.5]oct-4-en (15), Dispiro[2.0.2.4]decan (14) und Dispiro[2.0.2.4]dec-7-en (16) wird der Effekt der Wechselwirkung zwischen π-Orbitalen und Cyclopropyl-Walsh-Orbitalen aufgezeigt; für die jeweils ersten Banden in den PE-Spektren dieser Verbindungen wird eine Zuordnung vorgeschlagen.
    Additional Material: 4 Ill.
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  • 83
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1748-1763 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Asymmetric Hydrogenation with 1,4-Bis(dimethylamino)-(2S,3S)- and -(2R,3R)-butane-2,3-dio(DBD)/Lithium Aluminium HydrideThe diaminodiol 6 (DBD) mentioned inthe in the title is readily available in two steps from commercial diethyl tartrate. It reacts with lithium aluminium hydride (LAH) or deuteride to give chirally modified 1:1-complexes which reduce aldehydes, ketones, and ozonides to optically active carbinols in optical yields of up to 75%. Since both enantiomers of DBD are to accessible, both dextro- and levo-rotatory products may be prepared at will. DBD is easily separated from products and recovered without loss of activity. The (-)- DBD-LAH-complex reduces both dialkyl and aryl alkyl ketones to give samples enantiomerically enriched with carbinols of (S)- configuration, while the (+)-DBD-complex acts the other way around. This result is independent of the mode of preparation of the complex, of the ratio of reducing reagent over substrate, of addition of alcohols or water, of reaction temperature, or solvent. The effects of some of these influences upon the optical yields are large. Optimum conditions are given; the efficiency of the DBD-LAH-complex is compared with similar chirally modified LAH derivatives already known. A mechanism explaining the stereochemical results is proposed.
    Notes: Das aus Weinsäureester in zwei Stufen leicht zugängliche, im Titel genannte Diaminodiol 6 (DBD) setzt sich mit Lithiumaluminiumhydrid (LAH) und -deuterid zu chiral modifizierten 1: 1-Komplexen um. Diese reduzieren Aldehyde, Ketone und Ozonide zu opt. aktiven Carbinolen in optischen Ausbeuten bis zu 75%. Da beide Enantiomeren von DBD zugänglich sind, lassen sich gezielt (+)- oder (-)-drehende Produkte darstellen. DBD ist von den Produkten bequem abtrennbar und ohne opt. Verluste zurückgewinnbar. Mit (-)-DBD-LAH- Komplex entstehen Dialkyl- und Alkyl-aryl- carbinole mit (S)-, aus dem enantiomeren Komplex mit (R)-Konfiguration des Überschußenantiomeren. Dies ist völlig unabhängig von Darstellungsmodus des Komplexes, molarem Verhältnis von Reduktionsmittel und Substrat, Zusätzen von Alkoholen oder Wasser, Reaktionstemperatur oder -lösungsmittel. Die Einflüsse dieser Faktoren auf die opt. Ausbeuten, für die optimale Bedingungen angegeben werden, sind indessen zum Teil groß. Vergleiche mit bekannten Komplexen aus LAH und anderen chiralen Liganden werden gezogen. Es wird ein Vorschlag zur Erklärung der stereochemischen Befunde gemacht.
    Additional Material: 1 Tab.
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  • 84
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1777-1779 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occurring Terpene Derivatives, XXXVII. Synthesis of the Sesquiterpene from Elvira biflora DCThe aromatic sesquiterpene 11 isolated from Elvira biflora DC has been synthesized starting with the p-cresol 2-butenyl ether (1).
    Notes: Das aus Elvira biflora DC isolierte aromatische Sesquiterpen 11 wird ausgehend vom p-Cresol-2-butenyläther (1) synthetisiert.
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  • 85
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1823-1834 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactivity of Nitrile Ylides of Different OriginThermolysis and photolysis of 2,3-dihydro- 1,4,2λ5-oxazaphospholes 2, photolysis of 1- azetines 3 as well as 1,3-elimination of hydrogen chloride from imidoyl chlorides 4 proceeds via the nitrile ylide intermediate 1. This is deduced from the same product ratio of the isomeric cycloadducts 5:6 on trapping with acrylic acid esters.
    Notes: Die Thermolyse und Photolyse von 2,3-Dihydro-1,4,2λ5-oxazaphospholen 2, die Photolyse von 1-azetine 3 wie auch die 1,3-Eliminierung von Chlorwasserstoff aus Imidoylchloriden 4 verläuft über die Nitril-ylid-Zwischenstufe 1. Dies wird aus dem jeweils gleichen Produkt-verhältnis der isomeren Cycloaddukte 5:6 bei der Abfangreaktion mit Acrylsäureestern abgeleitet.
    Additional Material: 9 Tab.
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  • 86
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1903-1914 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,8-Di-tert-butyl-[9-13C]-9-fluorenyl, Bis(2-tert-butylphenyl)[α-13C]methyl and their DimersThe preparation of the title compounds is reported. The 1H n. m. r. spectra of the dimers of 1 and [9-13C]-1, respectively, yield the cyclohexadiene structure 12 for the dimer. The 1H n. m. r. spectrum of [α-13C]-2 dimer confirms structure 1411). The e. s. r. results of 1 and 2 are discussed.
    Notes: Die Darstellung der Titelverbindungen wird beschrieben. Die 1H-NMR-Spektren der Dimeren von 1 bzw. [9-13C]- 1 ergeben die Cyclohexadien-Struktur 12 für das Dimere. das 1H-NMR-Spektrum des [α-13C]- 2-Dimeren bestätigt die Struktur 14 11). Die ESR-Ergebnisse (a(H) und a(13C)) von 1 und 2 werden diskutiert.
    Additional Material: 3 Ill.
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  • 87
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemistry of Small Rings, 30. Photochemistry of β,γ-Unsaturated Aldehydes.  -  Mechanism of the Photofragmentation of Phenyl-substituted CyclopentenecarbaldehydesA new synthesis of β,γ-unsaturated cyclopentenecarbaldehydes 1 by thermolysis of bicyclo-[3.1.0]hexenols 13 is described. Photolysis of the aldehydes 1 in benzene solution affords the cis-configurated cyclopentenes 2 in good yields. Cyclopentaphenanthrenes 16 are isolated as byproducts. 2 undergoes an electrocyclic reaction to form 17, which is then dehydrogenated to 16. The quantum yields of the photofragmentation and -cyclization are Φ2 = 0.23 and Φ16 = 0.07, respectively. From the emission spectra of 1a the energy of the singlet and triplet state is calculated to ES1 = 84.1 and ET1 = 62.2 kcal/mole. The kinetics of photoreactions 1 → 2 → 16 are studied using ED- and EDQ-diagrams. Sensitization studies demonstrate that the photoreaction 1 → 2 can also occur via a triplet state, but with reduced effectivity. Since quenching with piperylene is ineffective the reaction 1 → 2 very probably involves predominantly an n-π-singlet state. The mechanism proposed for the stereospecific, intramolecular reaction 1 → 2 involves the formation of a formyl allyl radical as a main intermediate.
    Notes: Eine neue Synthese von β,γ-ungesättigten Cyclopentencarbaldehyden 1 durch Thermolyse von Bicyclo [3.1.0]hexenolen 13 wird beschrieben. Die Photolyse der Aldehyde 1 in Benzol ergibt in guten ausbeuten die cis-konfigurierten Cyclopentene 2 und als Nebenprodukte die Cyclopentaphenanthrene 16.2 geht durch elektrocyclischen Ringschluß in 17 über, das unter Dehydrierung in 16 umgewandelt wird. Die Quantenausbeuten der photofragmentierung bzw. -cyclisierung betragen Φ2 = 0.23 bzw. Φ16 = 0.07. aus den Emissionsspektren von 1a wird die Energie von singulett- und Triplett-Zustand zu ES1 = 84.1 bzw. ET1 = 62.2 kcal/mol errechnet. Die Kinetik der Photoreaktionen 1 → 2 → 16 wird mit Hilfe von Ed- und EDQ-Diagrammen näher studiert. Wie Sensibilisierungsstudien zeigen, kann die Photoreaktion 1 → 2, wenn auch mit geringerer Effektivität, über einen Triplett-Zustand verlaufen. Sie läßt sich mit Piperylen nicht löschen, weshalb die Reaktion 1 → 2 weitgehend über einen angeregten n-π-S1-Zustand formuliert wird. Für den Mechanismus der stereospezifischen, intramolekularen (D-Markierung) Reaktion 1 → 2 wird ein Formyl-Allyl-Radikalpaar als Wesentliche Zwischenstufe vorgeschlagen.
    Additional Material: 7 Ill.
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  • 88
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1882-1890 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoelectron Spectra and Molecular Properties, XXXIV. CyanamideThe PE spectrum of cyanamide is easily assigned by comparison with that of the isoelectronic acetonitrile. The orbital sequence obtained is supported by vibrational fine structures, by the PE spectrum of dimethylcyanamide, and by CNDO calculations. Furthermore, the calculated charge densities render possible an appreciation of properties of cyanamide and its alkyl derivatives.
    Notes: Das PE-Spektrum von Cyanamid läßt sich durch Vergleich mit dem des isoelektronischen Acetonitrils zwanglos zuordnen. Die so abgeleitete Orbitalreihenfolge wird durch Schwingungsfeinstrukturen, das PE-Spektrum von Dimethylcyanamid sowie durch CNDO-Rechnungen gestützt. Die berechneten Ladungsdichten erlauben darüber hinaus. Eigenschaften von Cyanamid und seinen Alkylderivaten zu verstehen.
    Additional Material: 2 Ill.
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  • 89
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1915-1924 
    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, VI. Synthesis of [4.2.2]Propella-7,9-diene, a Dewar Benzene Bridged in 1,4-PositionThe reaction of 8,11-dithia [4.3.3] propellane (1, n = 4) with N-chlorosuccinimide and monoperphthalic acid yields a mixture of four isomeric dichlorinated disulfones (2, n = 4). The major isomer 7 is formed in 40% yield. Upon treatment of 2 (n = 4) with potassium tert-butoxide at low temperatures [4.2.2] propella-7,9-diene2) (3, n = 4) is obtained. The constitution of 3 (n = 4) is deduced by 1H and 13C n. m. r as well as mass spectrometry.
    Notes: Die Umsetzung des 8,11-Dithia [4.3.3] propellans (1, n = 4) mit N-Chlorsuccinimid und Monoperphthalsäure führt zu einem Gemisch von vier isomeren dichlorierten Disulfonen (2, n = 4), von denen das Hauptprodukt 7 in 40proz. Ausbeute entsteht. 2 (n = 4) läßt sich mit Kalium-tert-butylat bei tiefen Temperaturen in das [4.2.2]Propella-7,9-dien2)(3, n = 4) überführen, dessen Konstitution durch die 1H-, 13C-NMR- und Massenspektren bewiesen wird.
    Additional Material: 6 Ill.
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  • 90
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1988-1997 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photoisomerisation Reactions in Bicyclo[3.2.2]nona-6,8-diene DerivativesFrom the photochemical behavior of suitably substituted derivatives (dicarboxylic ester 3a, dicarboxylic acid 3b, bis(trifluoromethyl)-derivative 3c) it is concluded, that in the bicyclo-[3.2.2]nona-6,8-diene skeleton 1 (n = 3) the [2π + 2π]-Cycloaddition to 2 (n = 3) neither by direct nor by sensitized excitation takes place. Instead 1,3-alkyl shift (3a → 6a) and di-π-methane-rearrangement 3a → 7a, 3c → 8c) are observed. Arguments for this behavior differing from the lower homologues 1 (n = 0, 1, 2) are discussed.
    Notes: Aus dem photochemischen Verhalten geeignet substituierter Derivate (Diester 3a, Dicarbonsäure 3b, Bis-trifluormethyl-Derivat 3c) wird geschlossen, daß im Bicyclo[3.2.2]nona-6,8-dien-Gerüst 1 (n = 3) die [2π + 2π]-Cycloaddition zu 2 (n = 3) weder bei direkter noch bei sensibilisierter Lichtanregung stattfindet. Als Ersatzreaktionen werden 1,3-Alkylverschiebung (3a → 6a) und Di-π-Methanumlagerung (3a → 7a, 3c → 8c) beobachtet. Gründe für dieses von den niedrigeren Homologen 1 (n = 0, 1, 2) abweichende Verhalten werden diskutiert.
    Additional Material: 1 Ill.
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  • 91
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: PFT-13C-N.M.R. and Mass Spectra of Heterocycles.  -  1,2-Diazaspiro[4.4]nonatetraenesl Azaindolizines, and 3aH-Indazoles13C n.m.r. spectra obtained by the pulse Fourier transform method of 1,2-diazaspiro[4.4]-nonatetraenes 1, azaindolizines 2, and 3aH-indazoles 3 are described. A combination of highest and lowest field resonances allows an unambigous distinction between 1 and 2. A similiar approach is suggested for 3. Estimated increments from model compounds agree well with the c.m.r. spectra. „Strickspektren“ demonstrate the effect of the substituents on the chemical shift of 1 - 3. The mass spectra of 1 - 3 are discussed briefly.
    Notes: Die mit der Puls-Fourier-Transform-Methode erhaltenen 13C-NMR-Spektren von 1,2- Diazaspiro[4.4]nonatetraenene 1, Azaindolizinen 2 und 3aH-Indazolen 3 werden beschrieben. aus einer Kombination von Höchst-und Tiefstfeld-Resonanzfrequenzen konnten die Strukturen 1 und 2 eindeutig unterschieden werden. Eine entsprechende Analyse wurde für 3 vorgenommen. Inkrementabschätzungen führten zu meist guter Übereinstimmung mit den gemessenen Spektren. Aus den Strichspektren kann der durch die verschiedenen Substituenten hervorgerufene Einfluß auf die chemischen Verschiebung von 1 - 3 werden kurz diskutiert.
    Additional Material: 3 Ill.
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  • 92
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2120-2122 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2095-2114 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Substituenteffects in Pericyclic Reactions: The Cycloheptatriene-Norcaradiene-Problem, investigated in C-7-Monosubstituted CompoundsCharacteristic features of the cycloheptatriene-norcaradiene potential curves can be simulated by using methyl cations, which are stabilized by heterofunctional groups and bound to C-7: 1. The potential curve corresponding to low energy cycloheptatriene is realized for the 7-bis(alkylamino)methyl cation 9a 2. Cycloheptatriene and norcaradiene are energetically comparable in the case of the 7-alkoxy(amino)methyl cations. At room temperature 9b - e and 10b - e form a fast dynamic equilibrating system. 3. Norcaradiene 10f comprises the lower minimum of the potential curve for the 7-(1,3-dioxolan-2-ylium) cation. In 10f the substituent is in the exo-position. Using variable temperature 1H-n.m.r., thermodynamic parameters are determined for the equilibria 9b - e ⇋ 10b - e. The influence of C-7-substituents on the cycloheptatriene-norcaradiene equilibrium is discussed and visualized using the MO-model.
    Notes: Methylkationen, stabilisiert durch nachbarständige Alkoxy-oder Alkylaminogruppen und gebunden an C-7, ermöglichen es, drei charakteristische Lagen des Cycloheptatrien-Norcaradien-Gleichgewichtes zu simulieren: 1Mit energieniedrigem Cycloheptatrien-Niveau im 7-Bis(alkylamino)methyl-Kation 9a.2Mit nahezu energiegleichen Cycloheptatrien- und Norcaradien-Grundzuständen in den 7-Alkoxy(amino)methyl-Kationen 9b-e ⇋ 10b - e. 3. Mit energieniedrigem Norcaradien-Grundzustand in der 7-(1,3-Dioxolan-2-ylium)-Verbindung 10f. In 10f ist der Substituent exo-ständig. Thermodynamische Daten der schnellen und reversiblen Gleichgewichte 9b - e ⇋ 10b - e werden bestimmt. Die C-7-Substituentenbeeinflussung des Cycloheptatrien-Norcaradien-Gleichgewichtes wird diskutiert und durch das MO-Modell beschrieben.
    Additional Material: 7 Ill.
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  • 94
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2169-2175 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Easy Way for the Preparation of Organylfluorophosphoranes RnPF5-nOrganylfluorophosphoranes can easily be synthesized by reaction of phosphines or chlorophosphines with CCl4 and HF-donors, especially phenylcarbamoyl fluoride.
    Notes: Eine einfache Synthese der Organylfluorphosphorane beruht auf der Umsetzung von Phosphinen und Chlorphosphinen mit CCl4 und HF-Donatoren, vorzugsweise Phenylcarbamoyl-fluorid.
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  • 95
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2215-2237 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Cyclopropenones with enamines, 2. Methylphenyl- and Phenylcyclopropenone and EnaminesThe reaction of methyphenylcyclopropenone (2) with enamines 4a-d and phenycyclopropenone (3) with enamines 4a, c, h at 20°C leads to 2-azoniabicyclo[3.1.0]hex-3-en-3-olates 6, which are isomerized thermally to 2,4-pentadienamides 8. These are also formed directly from 2, 3 and enamines 4 at 80 °C and are accompained in some cases (enamines 4g, h) by β-enaminoketones (5a - c). The constitution and configuration of these „1:1-adducts“ is derived from spectral and chemical evidence. The reaction of 3 with enamines 4 yields as main products „2:1-adducts“ for which the structure of spiro-lactones 20, 21 is assumed on the basis of spectroscopic and chemical data. Some aspects of the mode of formation of these products are discussed.
    Notes: Die Reaktion von Methylphenylcyclopropenon (2) mit den Enaminen 4a - d und Phenyl-cyclopropenon (3) mit den Enaminen 4a, c, h bei 20 C führt zu 2-Azoniabicyclo[3.1.0]hex-3-en-3-olaten 6, die thermisch zu 2,4 -Pentadienamiden 8 isomerisieren. Diese werden bei 80 °C auch direkt aus 2,3 und Enaminen 4 gebildet und sind in einigen Fällen (Enamine 4g, h) von β-Enaminoketonen (5a-c) begleitet. Konstitution und Konfiguration dieser „1:1-Addukte“ wird aus spektroskopischen Kriterien und chemischen Reaktionen abgeleitet. Bei der Umsetzung von 3 mit Enaminen 4 entstehen als Hauptprodukte „2:1-Addukte“ für die aufgrund spektroskopischer und chemischer Befunde die Struktur von Spirolactonen 20, 21 anzunehmen ist. Einige Aspekte zum Bildungsmechanismus dieser Produkte werden diskutiert.
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  • 96
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2186-2214 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Cyclopropenones with Enamines, 1 Diphenylcyclopropenone and EnaminesDiphenylcyclopropenone (1) reacts with the enamines 9 at 0-20°C to yield the 2-azoniabicyclo[3.1.0]hex-3-en-3-olates 10, whereas at 80°C the main products of the reaction are the 2,4-pentadienamides 25; compounds 10 are isomerized to the amides 25 at 20°C. The structure of the betaines 10 is deduced from their spectral data, their C-protonation (leading to 17), their O-alkylation (leading to 19), and their ring opening reactions with nucleophiles such as water, alcohols, and amines (leading to 20, 23, 24). The structure of the amides 25 is proven by means of spectral data and independent synthesis of the tetrahydro derivatives 26. The reaction of 1 with some enamines 9 produces as by-products the β-enamino ketones 30 and α-amino cyclopentenones 31, which are isomeric with 25. Their structure is confirmed by means of spectra and chemical degradation reactions. Some aspects of the mechanism of the reaction of diphenylcyclopropenone with enamines are discussed on the basis of the constitution of the products 10, 25, 30, and 31.
    Notes: Die Reaktion von Diphenyclyclopropenon (1) mit den Enaminen 9 führt bei 0-20°C zu den 2- Azoniabicyclo[3.1.0]hex-3-en-3-olaten 10, bei 80°C zu den 2,4-Pentadienamiden 25 als Hauptprodukten die Verbindungen 10 werden bei 80°C zu den Amiden 25 isomerisiert. Die Struktur der Betaine 10 wird aus ihren spektroskopischen Daten, ihrer C-Protonierung (zu 17), ihrer O-Alkylierung (zu 19) und ihrer Ringöffnung mit nucleophilen Agentien wie Wasser, Alkoholen und Aminen (zu 20, 23, 24) bewiesen. Der Konstitutionsbeweis der Amide 25 wird über ihre Spektren und über die unabhängige Synthese von Tetrahydroderivaten 26 geführt. Als Nebenprodukte der Reaktion von 1 mit einigen Enaminen 9 werden zu 25 isomere β-Enaminoketone 30 und α-Aminocyclopentenone 31 isoliert. Deren Konstitution wird durch Spektren und Abbaureaktionen gesichert. Aufgrund der ermittelten Konstitutionen 10, 25, 30, 31 werden einige Aspekte des Mechanismus der Reaktion von Diphenylcyclopropenon mit Enaminen erörtert.
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  • 97
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2284-2294 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Synthesis of Purinenucleoside-6-sulfonates6(1H)-Purinethone-9-(β-D-ribofuranosid) (1), the corresponding 5′-monophosphate 7, and the 5′-triphosphate 8 as well as 2-amino-6(1H)- purinethione-9-(β-D-ribofuranoside) (2) and 2-amino-6(1H)-purinethione-9-(β-D-2′-deoxyribofuranoside) (3) have been converted to the sulfonates 4,9,10,5, and 6 by reaction with sulfite ions in the presence of oxygen. The sulfonates 4 and 5 reacted in aqueous ammonia with good yields to give adenosine and 2,6-diaminopurine-9-(β-D-ribofuranoside), respectively. 4 and 9 react with aziridine to form 6-(1-aziridinyl)purine-9-(β-D-ribofuranoside) (15) and the corresponding 5′-monophosphate 16. 5 and 6 fluoresce with high quantum yields on excitation in the near u. v. It was shown by means of fluorescence spectroscopy, absorption spectroscopy, and comparison with authentic material that irradiation of 1, 2 and 3 by light of the wavelength 235 nm in the presence of oxygen affords the purinenucleoside-6-sulfonates 4, 5 and 6.
    Notes: 6(1H)-Purinthion-9-(β-D-ribofuranosid) (1), das entsprechende 5′-Monophosphat (7) und 5′-Triphosphat (8) sowie 2-Amino-6(1H)-purinthion-9-(β-D-ribofuranosid) (2) und 2-Amino-6(1H)-purinthion-9-(β-D2′-desoxyribofuranosid) (3) wurden durch Reaktion mit Sulfitionen in Gegenwart von Sauerstoff quantitativ in die entsprechenden Sulfonsäurederivate 4,9,10,5,6 übergeführt. Die Sulfonate 4 und 5 ließen sich bei Raumtemperatur mit wäßrigem Ammoniak in guten Ausbeuten zu Adenosin bzw. 2,6-Diaminopurin-9-(β-D-ribofuranosid) umsetzen. 4 und 9 reagierten mit Aziridin zu 6-(1-Aziridinyl)purin-9-(β-Dribofuranosid) (15) bzw. dem 5′-Monophosphat 16. 5 und 6 fluoreszieren mit hoher Quantenausbeute im langwelligen ultravioletten Licht. Mit Hilfe der Fluoreszenzspektroskopie, Absorptions-spektroskopie und durch Vergleich mit authentischem Material konnte die Bildung der Purinnucleosid-6-sulfonate 4, 5 und 6 auch bei der Bestrahlung von 1, 2 und 3 mit Licht der Wellenlänge 325 nm in Gegenwart von Sauerstoff nachgewiesen werden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2326-2328 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2-Propyl-cis-perhydroquinolin-5α-olReaction of 1,3-cyclohexanedione with 1-chloro-3-hexanone (2), followed by reductive amination yields 2-propyl-1,2,3,4,5,6,7,8-octahydro-5-quinolinon (4). On hydrogenation with Pt in acetic acid 2-propyl-cis-perhydroquinolin-5α-ol (5) is obtained.
    Notes: Ausgehend von 1,3-Cyclohexandion wurde durch Umsetzung mit 1-Chlor-3-hexanon (2) und nachfolgende reduktive Aminierung das 2-Propyl-1,2,3,4,5,6,7,8-octahydro-5-chinolinon (4) erhalten. Hieraus entsteht bei der Hydrierung mit Pt in Eisessig 2-Propyl-cis-perhydrochinolin-5α-ol (5).
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2345-2361 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies of Electron-Depleted Thiocarbonyl Compounds, 2. Trithiocarbonate S,S-DioxidesEleven trithiocarbonate S,S-dioxides 1 were prepared by treatment of chlorodithioformates with sulfinic acid salts and their properties investigated. In the reaction of methyl chlorodithioformate with sodium methanesulfinate, methyl (methylsulfonyl)(methylthio)methyl trithiocarbonate (4a) is formed instead of the expected 1. Compounds 4 can also be obtained by reduction of 1 with sulfinates, thiophenols, or tetrabutylammonium borohydride. Sodium diethyl methylmalonate is thioacylated by S′-phenyl S-p-tolyl trithiocarbonate S,S-dioxide (1i) to yield diethyl methyl(phenylthiothiocarbonyl)malonate(13), while the less bulky phenyllithium attacks 1i in a nucleophilic manner at the thiono sulfur to yield S′,S″-diphenyl S-p-tolyl trithioorthoformate S,S-dioxide (15). Inverse addition of Grignard solutions to 1 produces the 1-sulfonyl -1,2,2-trithioethylenes 19.
    Notes: Durch Umsetzung von Chlordithioformiaten mit Sulfinsäuresalzen wurden elf Trithiocarbonat-S.S-dioxide 1 dargestellt und auf ihre Eigenschaften untersucht. Bei der Umsetzung von Methyl-chlordithioformiat mit Natrium-methansulfinat bildet sich statt des erwarteten 1 Methyl-[(methylsulfonyl)(methylthio)methyl]-trithiocarbonat (4a). Die Verbindungen 4 erhält man auch bei der Reduktion von 1 mit Sulfinaten, Thiophenolen oder Tetrabutylammoniumboranat. Natrium-methylmalonsäure-diäthylester wird von S′-Phenyl-S-p-tolyl-trithiocarbonat-S,S-dioxid (1i) zu Methy(phenylthiothiocarbonyl)malonsäure-diäthylester (13) thioacyliert, während das weniger sperrige Phenyllithium 1i nucleophil am Thionschwefel unter Bildung von S′.S″-Diphenyl-S-p-tolyl-trithioorthoformiat-S,S-dioxid (15) angreift. Inverse Addition von Grignard -Verbindungen an 1 führt zu den 1-Sulfonyl-1,2,2-trithioäthylenen 19.
    Additional Material: 5 Tab.
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  • 100
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic Dicarboxylic Acid Esters, III. Reaction of Dimethyl 4,5-Dihydro-2,3-furandicarboxylates with 1,2-Diamines.  -  Synthesis of 3-(5-Alkyl-2-2oxotetrahydro-3-furanylidene)-2-quinoxalinones, -2-pyrazinones, and -1,4-diazepine-2-onesTreatment of the dihydrofurandicarboxylic acid esters 4a-c with 1.2-diamines does not result in normal ester aminolysis but in ring cleavage followed by lactonization. According to the diamine used the quinoxalinones 14, 15a-c, the pyrazinones 11-c, and the diazepinones 16a, c are obtained. The independent synthesis of the compounds 11a, 14a, 15a by condensation of the different diamines with α-ethoxalyl-γ-butyrolactone as well as the tabulated i. r. and n. m. r. data confirm the proposed structures.
    Notes: Dihydrofurandicarbonsäureester vom Typ 4a-c reagieren mit 1,2-Diaminen nicht im Sinne einer normalen zweifachen Ester-Aminolyse, sondern unter Ringöffnung und anschließender Lactonisierung. Entsprechend dem eingesetzten Diamin erhält man die Chinoxalinone 14.15a-c, die Pyrazinone 11a-c sowie die Diazepinone 16a, c. Die unabhängigen Synthesen der jeweiligen Grundkörper 11a, 14a, 15a durch Kondensation der verschiedenen Diamine mit α-Äthoxalyl-γ-butyrolacton, wie auch die aufgeführten IR- und NMR-Daten bestätigen die angenommenen Strukturen.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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