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  • 2000-2004
  • 1970-1974  (1,211)
  • 1920-1924
  • 1971  (1,211)
  • Organic Chemistry  (689)
  • Life and Medical Sciences  (463)
  • Atomic, Molecular and Optical Physics  (59)
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  • 2000-2004
  • 1970-1974  (1,211)
  • 1920-1924
Year
  • 101
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971) 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Type of Medium: Electronic Resource
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  • 102
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971), S. 181-194 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: In Bombyx mori the male is the homogametic sex, crossing over occurs only in males, and chiasmata are observed in spermatocytes, but not in oocyte nuclei. If the assembly of synaptonemal complexes is an essential prerequisite for genetic crossing over and chiasmata formation, then the nuclei of Bombyx spermatocytes should contain synaptonemal complexes. Synaptonemal complexes were found in spermatocytes from young four instar larvae. The structure of meiotic bivalents is described using micrographs taken with 100 and 1000 KV electron microscopes. These data together with that from the literature are used to construct a three-dimensional model of the synaptonemal complex and to suggest its method of origin and its function during crossing over.
    Additional Material: 9 Ill.
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  • 103
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971), S. 215-241 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Queen butterflies do not mate until the male has brushed the tufts of his scented, abdominal “hairpencils„ over the female's head and antennae. The trichogen cells located at the base of each hairpencil are secretory. Presumably, these cells produce the sex pheromone necessary for mating. The liquid secretion must move from a central, microvillus-lined vesicle through the cuticle of the hairs to coat numerous, free, cuticular „dust“ particles which adhere to the hairs' surface. The dust carries the secretion to or near the female's antennae. In the pupal stage the dust particles develop as outpocketings of the hair epicuticle. An amorphous matrix, probably protein epicuticle, is deposited in the outpocketings between the cuticulin layer and plasma membrane of the hair. Before the butterfly emerges from the pupa the matrix becomes enclosed by cuticulin, and the particles pinch off from the hair.
    Type of Medium: Electronic Resource
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  • 104
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Light microscopy of serially sectioned nasopalatine duct remnants in ventral rostral integument of four adult (2 ♂, 2 ♀) fin whales reveals: (1) a common structure in all, (2) blindly ending nasopalatine pits 4 to 9 mm deep, (3) solid epithelial duct remnants 12 to 15 mm long, (4) lack of chemoreceptor endings, and (5) an abundance of presumed mechanoreceptors, mostly of the Pacinian category on the adoral sides, but also including some thinly encapsulated and perivascular ones that extend into the abundant connective tissue papillae of the duct remnants. Comparative and evolutionary relations of these structures are discussed.
    Additional Material: 1 Ill.
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  • 105
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971), S. 281-313 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: A morphohistological study was carried out on the pineal organ in 15 species of teleosts belonging to 12 different families. In spite of a general similarity in pineal structure in different species, there is evident a systematic diversity. The majority of species possess saccular pineal organs containing photoreceptors as prominent parenchymal components. The close anatomical relationship of the pineal organs with the relatively thin cranial roof further supports the photosensory nature of this organ in most species. However, in certain species, particularly Corydoras aneus, apparent paucity of sensory cell outer segments, parenchymal proliferation, epithelial compactness and rich vascularization suggest specializations for a predominantly nonsensory and possibly secretory function. On the other hand, the preponderance of sensory cells in the pineal organ of Symphysodon aequifasciatus and Gyrinocheilus aymoneri indicates exceptional adaptitions for a predominantly photosensory role. The results are discussed in the light of existing electron microscopic and biochemical investigations which support a secretory function of fish pineal. The need for proper selection of species for future research on pineal function is emphasized.There is also evident a close anatomical relationship between the pineal organ, the dorsal sac and the third ventricle in various species. The possibility of intramural functional relationship of the pineal with these structures and the brain is suggested.The presence of intrapineal neurones and an afferent (pinealofugal) innervation in majority of species is described. The tractus pinealis enters the posterior commissure area. In rainbow trout, Salmo gairdneri, some branches, right and left, leave the posterior commissure and could be seen to move toward the habenular ganglia. Their destination remains unclear. In jack smelt, Atherinopsis californiensis, a major bundle of tract fibres follows the ventral aspect of the posterior commissure reaching what may be nuclei dorsomedialis-dorsolateralis. The possibility of direct connections with the fasciculus retroflexus is suggested. No evidence could be provided supporting existence of an efferent (pinealopetal) innervation of parenchymal cells in the pineal of species studied. It is pointed out that clarification of this aspect in future is important for a proper understanding of metabolic aspects of pineal organs in fishes.
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  • 106
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The structure, attachment and subsequent metamorphosis of larvae of the marine bryozoan Bugula neritina were studied by light and electron microscopy.Two points of larval anatomy are of special significance to proper interpretation of the metamorphosis: 1Two cytologically similar blastemal tissues, each laden with free ribosomes, occur as parts of the apical organ complex. The upper blastema directly contacts the larval surface, forming the non-ciliated rows of the apical organ. The lower blastema is internal and is oral to and contiguous with the upper blastema.2The epidermal tissues of the larva are joined in the following sequence, beginning at the aboral pole: a. apical organ complex; b. apical-connecting cell; c. infolded pallial sinus epithelium; d. vesicular-connecting cell; e. aboral vesicular epithelium; f. corona; g. oral vesicular epithelium; and i., j., and k. internal sac neck, wall and roof regions.The initial stages of metamorphosis involve a complex sequence of morphogenetic movements, including: 1eversion of the internal sac, permanently attaching the larva to the substrate;2inrolling of the aboral vesicular epithelium, corona, oral vesicular and ciliated epithelia, and neck region of the internal sac into the larval interior; concomitantly the pallial sinus epithelium evaginates;3loss of connection between the invaginated tissues and the surface;4fusion of the pallial sinus epithelium with the wall region of the internal sac, maintaining the integrity of the body surface;5retraction of the apical organ complex and invagination of the pallial sinus epithelium with the simultaneous elevation of the internal sac wall region to the aboral pole.At the conclusion of these events the preancestrular surface is covered by the wall and roof regions of the internal sac. Cells of the wall region form the epidermis of the body wall except for the attachment disc and secrete a cuticular exoskeleton that is secondarily calcified; the attachment disc is formed by the roof region of the internal sac.Internally, the ectodermal upper blastema differentiates into the lophophore and digestive tract of the ancestrular polypide, while the lower blastema forms the lining of the lophophoral coelom and the splanchnic (but not the somatic) lining of the visceral coelom. The visceral somatic peritoneum is formed from cells that may originate from the mesodermally derived pigmented cells of the larva to which they are similar in pigmentation and cytology. Such a composite derivation of a coelomic lining has not been described previously.
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  • 107
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Morphology 135 (1971) 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Type of Medium: Electronic Resource
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  • 108
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971), S. 479-487 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Smears of Orconectes virilis hemolymph were prepared by fixation in 10% formalin immediately upon withdrawal, and after an interval of 1, 5, or 15 minutes. These smears were then stained by a variety of histochemical means designed to identify a material which is released from both hyaline and granular cells during the coagulation process. Based upon reactions to various carbohydrate, lipid and protein tests, this material appears to consist of a glycoor muco-protein, and its localization and activity coincide with the „fibrin ferment“ described by Hardy (1892). Its release is probably initiated from the hyaline cells, followed shortly thereafter by a similar activity of the granulocytes. While it cannot be ascertained by the methods used in this study whether or not this material participates actively in clotting, its release is nevertheless coincidental with coagulation.
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  • 109
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 135 (1971), S. 13-50 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The ectethmoid-mandibular articulation in Melithreptus and Manorina (Meliphagidae: Aves) consists of the dorsal mandibular process fitting into and abutting against the ventral ectethmoid fossa; it forms a brace for the mandible. This articulation in Melithreptus is a typical diarthrosis with long folded capsular walls. The mandible, thus, has two separate articulations, each with a different axis of rotation. No other genus of Meliphagidae (except Ptiloprora) or any other avian family possesses a similar feature.The jaw and tongue musculature of Melithreptus are described. The two muscles opening the jaws are well developed, while those closing the jaws are small. The tongue muscles show no special developments.A large maxillary gland, presumably muscus secreting, covers the ventral surface of the jaw muscles. Its duct opens into the oral cavity just behind the tip of the upper jaw. The frilled tip of the tongue rests against the duct opening.The ectethmoid-mandibular articulation braces the adducted mandible against dorsoposteriorly directed forces. The mandible can be held closed without a compression force exerted by the mandible on the quadrate, permitting the bird to raise its upper jaw with greater ease and less loss of force. The tongue can be protruded through the slight gap between the jaws, moving against the duct opening and thus be coated with mucus. Presumably, these birds capture insects with their sticky tongue. Hence, the ectethmoid-mandibular articulation is an adaptation for this feeding method; it evolved independently in three genera of the Meliphagidae.The ectethmoid-mandibular articulation demonstrates that a bone can have two articulations with different axes of rotation, that the two articular halves can separate widely, and that articular cartilages can be flat and remain in contact over a large area. Its function suggests that the basitemporal articulation of the mandible found in many other birds has a similar function. And it demonstrates that in the evolution of the mammalian dentary-squamosal articulation, the new hinge did not have to lie on the same rotational axis as the existing quadrate-articular hinge.
    Additional Material: 16 Ill.
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  • 110
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Spermatozoa in the head of the epididymis of the flying squirrel have large cup-shaped acrosomal heads with two ventral ridges. The cytoplasmic droplet contains an ovoid body and a group of large granules. These structures may be related to the chromatoid body of spermatids. The spermatozoa form polarized cylindrical bodies with centrally placed tails and peripheral heads. The tips of acrosomes protrude into concavities of acrosomal cups of neighboring spermatozoa. Peripheral portions of acrosomes are in contact with microvilli (stereocilia) of epididymal cells. Polarized cylindrical bodies are present in five species of Sciuridae.
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  • 111
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 135 (1971), S. 153-163 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Fine structure of the carp torus longitudinalis was studied by electron and light microscopy and compared with the granular layer of the carp cerebellum. There are three types of cells in the torus longitudinalis, that is, small, medium-sized and large cells. From the small cells to the medium-sized cells, there is gradual transition in size and in the amounts of cell organelles. These cell profiles and the closely packed cell pattern in a part of the torus longitudinalis are quite similar to those in the granular layer of the cerebellum. Moreover, peculiar synaptic configurations of so-called “synaptic glomeruli” are found both in the torus longitudinalis and in the granular layer of the cerebellum. In the torus longitudinalis, unmyelinated nerve fibers are seen to have bulbous swellings along their course, most of which contain a mitochondrion, as do they in the carp tectum opticum.It is speculated that the torus longitudinalis may be partly related to the granular layer of the cerebellum and partly to the tectum opticum.
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  • 112
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: In muskellunge blastulae the yolk sac syncytium originally contains nuclei comparable in size to the blastomere nuclei from which the syncytial nuclei arose. By mitosis the originally diploid syncytial nuclei become numerous and crowded together. Continued synchronous mitosis of neighboring syncytial nuclei and the resultant crowding together of their spindles culminates in overlapping spindles, multipolar spindles, disorganized spindles, and the crowding together of large numbers of condensed chromosomes from contigous spindles. When such an aggregation of condensed chromosomes becomes enclosed within one nuclear membrane, a giant nucleus appears in the following interphase. It soon becomes postmitotic.
    Additional Material: 16 Ill.
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  • 113
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971), S. 383-397 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The typical eupyrene and atypical apyrene cycles of sperm differentiation in Bombyx mori were studied, with special attention to centriole number and behavior. Contrary to other reports, there is always only one centriole in the differentiating and in the mature sperm, thus confirming our previous findings that insect sperm has one centriole at the base of the flagellum, in contrast to two centrioles found in many other groups of animals. This numerical difference is discussed in an evolutionary context.
    Additional Material: 17 Ill.
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  • 114
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Examination of the cardiac anatomy of lizards of the family Varanidae revealed that much of the previous literature contained basic errors both in description and interpretation. These are corrected and terminology of various authors is standardized.The varanid ventricle is similar to that of most other lizards in not being elongated, in having the base at right angles to the longitudinal axis, and in having the vertical septum weakly developed. However, it is not a typical lacertilian heart in that it has a number of characteristic ophidian features such as a muscular cone surrounding the cavum latero-dorsale and a prominent twisting of the cava. It lacks a gubernaculum cordis and a cartilaginous rod in the septum aortico-pulmonale, both of which are present in many non-varanid lizards, but seldom occur in snakes. The location of the heart is more posterior in the body than is true of other lizards.
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  • 115
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971), S. 425-435 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Recent hypotheses about the mechanisms of adaptation of bone to impressed mechanical forces differ according to the extent to which tensile stresses are thought to be functionally important in bone. A pilot study of three anatomical regions by means of the photoelastic analogy suggests the possibility that net tension rarely exists in significantly large regions of bones during normal function.Thus the examination of two situations (opposite linear attachment of muscles to the lips of bony crests and opposite areal attachment of muscles to either side of thin bony plates) suggests that in rare cases where precise anatomical architecture is such that net tension may be present, then bone is not found; such regions consist of appropriate collagenous structures.In the third situation (opposite attachment of tendons to a sesamoid bone) where it would appear that net tension ought to exist, it is suggested that it is likely that it does not. Net tension probably occurs only in tendons running in tightly curved bony grooves: those very situations where sesamoid bones are not present.
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  • 116
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 134 (1971), S. 437-445 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The left and right afferent nerves to the corpus cardiacum contain approximately 50 and 90 axons, respectively, when they enter the gland. Both bifurcate within the gland, so that four nerves leave the corpus cardiacum. These, however, contain a total of 90 axons. Of the 50 axons unaccounted for 30 are believed to terminate in the corpus cardiacum and 20 in the corpus allatum. The corpus cardiacum contains 12 intrinsic neurosecretory cells which are disposed laterally with respect to the extrinsic axons. Many of these contain neurosecretory spheres and presumably originate in the brain. The intrinsic corpus cardiacum cells also contain neurosecretory granules, and they produce short cytoplasmic processes which interdigitate with the extrinsic axons.
    Additional Material: 7 Ill.
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  • 117
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 133 (1971), S. 1-15 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The pineal organ of the bluefin tuna was studied using light and electron microscopy. The pineal, an evagination in the diencephalic pallium, consists of a distal expanded end-organ and a stalk. A pineal nerve connects this end-organ to the habenular area of the diencephalon. The tissues above the pineal are modified for light transmission. Supporting cells are the most numerous type seen in the pineal tissue. The cytoplasm often contains glycogen, while the golgi apparatus is seldom seen. The plasma membrane is a complex of folded membranes interdigitating with adjacent cells. The sensory cells are characterized by a basal nucleus, a constricted neck region, and an ellipsoid region that is capped distally by lamellae. Sensory cells have the basic appearance of retinal photoreceptors. The lamellae are more disorganized than those of retinal rods, and some lamellae appear to be discharged from the cell.This study indicates that the pineal may function to deliver photoperiodic stimuli to the central nervous system, through the transmission of nerve impulses.
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  • 118
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    New York, NY : Wiley-Blackwell
    Journal of Morphology 133 (1971), S. 105-123 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The endodermal nerve nets of the scyphozoan jellyfish Phacellophora camtschatica and Cyanea capillata were stained with methylene blue. Small animals (3-7.5 cm in diameter) stained easily. The endodermal nerve net of both species is a synaptic net consisting of bipolar and some few tripolar nerve cells with unbranched neurites. The neurites terminate on other neurites. Very few free nerve endings were observed. The neurites have a diameter of 1/4-1/2 μ and there is no indication of the presence of neurites too fine to be followed in the light microscope.The gross appearance of the net changes with the size of the medusa. Staining 15-53 cm diameter animals showed that the nerve cells increase in size with the size of the animals, that the density of the nerve net decreases.The endodermal nerve net is very similar to our interpretation of the Diffuse Nerve Net of the ectoderm but without the typical primary sense cells. In both cases the appearance of branching neurites is interpreted as an artifact caused by neurites terminating on other neurites.
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  • 119
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Adult newts placed in an atmospheric environment of 85% oxygen, saturated humidity, and at a temperature of 20 ± 1°C survived particularly well a 44-day test period. They did not succumb to “oxygen toxicity” as has been frequently reported for other vertebrate species.Having established the newt's tolerance of high oxygen atmosphere, the effect of oxygen on growth and development in the regenerating newt limb was investigated. Under the atmospheric conditions described above, and under 92% oxygen, the regeneration of adult newt limbs appeared to be retarded during the first 25 days after amputation when compared with regenerating limbs of control animals kept under a normal atmosphere of 21% oxygen (air). Thereafter, little or no difference could be discerned between the regeneration of experimental and control limbs.It is known that molecular oxygen participates directly in the hydroxylation of proline to hydroxyproline in the synthesis of collagen. Sectioned regenerates stained specifically for collagen were examined to determine if collagen synthesis was induced in experimental animals. Two regeneration-inhibited limbs of oxygenated newts showed cicatrical repair of the apical limb stump 25 days after amputation. However, the majority of the experimental animals revealed no obvious increase in collagen fibers.These results contraindicate any marked “oxygen toxicity” affecting the life of the newts, or regeneration of their limbs. It is suggested that a change in collagen fiber type might have been induced by the high-oxygen atmosphere. Investigations to test this hypothesis are currently underway.
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  • 120
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The morphology of the Weberian ossicles of Astyanax mexicanus, an eyed river fish, and A. jordani, the Mexican blind cave fish, was investigated and the results were correlated with behavioral data on the auditory capacities of the two species. Several characteristics of the ossicles of the two species were inter-specifically significantly different while other characteristics varied as much intra-specifically as inter-specifically. The ascending arm of the scaphium was shorter in the blind fish than in the river fish and the ascending arm of the intercalarium was further from the distal end of the base of the bones in the blind fish than in the river fish.A previously unreported ligament between the scaphium and the sinus atrium impar was found in Astyanax. It was hypothesized that this connective tissue retained perilymphatic fluid within the inner ear, helped the ossicles return to an anterior position after moving posteriorly, and might protect the inner ear during intense acoustical stimulation.
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  • 121
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    Journal of Morphology 133 (1971), S. 241-251 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Changes with age in bone cortex of the rat were investigated by establishing histological parameters which could be quantitated to estimate age at death. Decalcified cross sections of mandible, femur and tibia were prepared from rats two to 120 days old, and measurements were made of: (1) number of osteons, (2) average number of lamellae per osteon, (3) average Haversian canal diameter, and (4) number of non-Haversian (primary) canals. Multiple regression techniques were used to estimate age at death from several combinations of these variables.With age, the number of osteons per unit area of bone and the number of lamellae per osteon increased, but Haversian canal diameter and the number of primary canals decreased. Multiple regression analyses indicated that age at death could be estimated to ± 3 days of the true value in 95% of the cases. Nomographs based on histological measurements of each bone were prepared which can provide accurate estimates of age between two and 120 days in the Sprague-Dawley female rat. It was concluded that microstructure of bone cortex can not only be quantitated to provide accurate estimates of age but it may also constitute a sensitive measure of the metabolic state of the organism. The techniques utilized should prove useful in anthropology as well in studies of bone aging.
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  • 122
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    Journal of Morphology 133 (1971), S. 253-271 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The distribution of glycogen, lipids and succinic dehydrogenase (SDH) in twitch and tonus fibers of several amphibians and birds is described, and the correlation of histochemical properties with fiber structure and function is discussed. Twitch and tonus fibers were identified histologically by the presence of Fibrillenstruktur and Felderstruktur respectively. The rectus abdominis, sartorius and semitendinosus were studied in Rana pipiens, Xenopus laevis and Necturus maculosus; the pectoralis major, pectoralis minor, anterior latissimus dorsi and posterior latissimus dorsi were investigated in Gallus gallus and Passer domesticus. Periodic acid-Schiff was used to stain for glycogen, Sudan Black B for lipids and Nitro BT for localization of SDH activity.In amphibian muscles, fibers with Fibrillenstruktur and Felderstruktur constitute the rectus abdominis. Except in one case, only Fibrillenstruktur fibers were seen in the sartorius and semitendinosus. In the avian muscles, fibers with Fibrillenstruktur comprise the pectoralis major, pectoralis minor and posterior latissimus dorsi, while fibers with Felderstruktur constitute the anterior latissimus dorsi. These types of muscle fibers showed no consistent pattern in the distribution of glycogen, lipids and SDH. The evidence precludes the use of such data alone for distinguishing twitch (Fibrillenstruktur) and tonus (Felderstruktur) fibers.
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  • 123
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    Journal of Morphology 133 (1971), S. 319-337 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The fine structure of the excretory tubes of the mesostigmatid mite Macrocheles muscaedomesticae were investigated. These paired tubes are partially ensheathed by fat body and invested throughout by a branching system of visceral muscles. The fine structure of the cells of the excretory tube is in general similar with only minor differences found throughout its length. The basal region of each epithelial cell of the excretory tube borders the hemocoel and is divided into many compartments by the extensive infolding of the plasma membrane. Mitochondria and vacuolar inclusions are often closely associated with these compartments. More than one morphological type of mitochondria was found distributed throughout the cells of the excretory tubes. The most commonly encountered type had well developed cristae and an electron dense matrix. Less commonly, mitochondria with somewhat poorly developed cristae and a translucent matrix often containing myelin-like figures of varying complexity were observed. It is suggested that they represent part of a normal process of mitochondrial degeneration. The apical region of the cell has a border composed of plate-like folds of the plasma membrane termed microlamellae. The lumen contains abundant granules of the excretory product.
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  • 124
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    Journal of Morphology 133 (1971), S. 375-386 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The fine structure of the developing gizzard of the chick embryo has been studied to define the sequence of events in cytodifferentiation of the epithelium and to look for morphological evidence of epithelio-mesenchymal interaction. During the fourth day of incubation epithelial cells begin to form mucous secretory granules, later massive glycogen deposits appear, and finally by day 8 numerous cell processes have formed. Tissue was prepared by a number of methods to stain material associated with cell surfaces. At the time induction is presumbably occurring such stainable material is abundant. Epithelial and mesenchymal tissue components when cultured transfilter show no inductive effects and stainable cell surface material is greatly reduced near the epithelium.
    Additional Material: 21 Ill.
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  • 125
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: An approximate 1:1 ratio of myelinated to unmyelinated fibers was established in counts from electron micrograph montages in nerves of the newt, Triturus (Notophthalmus) viridescens. The number of myelinated fibers correspond to the number counted with the light microscope after osmium fixation. Light microscope counts of silver impregnated sections yielded a value slightly higher suggesting that, except for bundles of unmyelinated fibers, the silver technique revealed mainly myelinated fibers. The results were used to reassess previous quantitative studies on the relation between number of nerve fibers and the control which nerves exert on regeneration. For a truer estimate of the number of axons affecting regeneration, fiber values previously reported should now be doubled to include the large number of unmyelinated fibers. However, calculations show that the unmyelinated fibers contribute less than 3% of the total neuroplasm in the peripheral nerve.Finally, counts made of Schwann cells and fibroblasts show that the latter are few in number.
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  • 126
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    Journal of Morphology 134 (1971) 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
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  • 127
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    Journal of Morphology 134 (1971), S. 1-19 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: A histological study was undertaken of the differentiation of the lymphomyeloid complex of larvae of the common leopard frog, Rana pipiens, reared at 18-21 °C. Immature lymphocytes are first recognised in the thymus and pronephros at stage I of Taylor and Kollros ('46). By the end of stage II, small lymphocytes are regularly found among the predominant larger lymphoid cells in the thymus, in which corticomedullary differentiation has begun. At this time, a few small lymphocytes are also apparent in the ventral cavity bodies, lymph gland, pronephros, mesonephros and intestine, but rarely occur in the spleen. During stages III and IV extensive development of these components of the lymphomyeloid complex occurs. The organs now contain large numbers of mature lymphocytes and have attained states of differentiation that remain essentially similar in subsequent larval stages. By stage V, small epithelium-associated lymphoid accumulations are abundant throughout the length of the gastrointestinal tract. The anlagen of the procoracoid body and bone marrow appear just prior to metamorphosis.The kidneys are the main sites of blood formation in the larva. Masses of granulocytes are also usually found in the abundant ventral cavity bodies. A consideration of the roles of each of the organs provides insight into the ontogeny of the immune system of the Anura in general.
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  • 128
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    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Each chemoreceptor sensillum of Limulus polyphemus consists of 6-15 bipolar neurosensory cells with distal processes confined within a single cuticular tubule as they extend to the outside environment. The cuticular tubule, which is enveloped by the cuticulo-tubal cell, opens proximally into a fluid-filled extracellular space through which the dendrite passes before entering the cuticular tubule. Between the neurosensory cells are one to three microvillar cells also exposed to the extracellular space. This space is enclosed by a sheath cell extending proximally from the inner opening of the cuticular tubule and enveloping the proximal portions of the dendrites, the distal portions of the microvillar cells, as well as the distal portion of some neurosensory cell bodies. Most of the remaining portions of the neurosensory cells and microvillar cells are enveloped by neuroglia. Tight junctions occur between the distal portions of the dendrites in or near the cuticular tubule. Each dendrite has a cilium-like segment located where it traverses the extracellular space with a 9 + 0 pattern of fibers. Septuplelayered junctions occur among the proximal portions of some dendrites and some neurosensory cell bodies of the same sensillum. The subjacent processes of the sensillum frequently course proximally as isolated axons before joining nerve bundles. In the chilarial and gnathobasal chemoreceptors these nerve bundles course proximally to neuropile clumps of a peripheral nerve plexus. The presence of numerous synaptic vesicles in the neuropiles suggests that chemical transmission may occur among “en passant” synapses formed by the axons. Proximally the neuropiles are joined to the central nervous system by relatively long nerves.
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  • 129
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    Journal of Morphology 133 (1971), S. 303-317 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: In the course of this investigation 24 fetuses of the Sprague-Dawley rats were used. Pregnant animals were sacrificed at 12, 14, 16, 18, and 20 days of gestation. The fetuses were removed and fixed in buffered formalin solution. The heads were dehydrated, embedded in paraffin, and the nasal cavities were sectioned serially. Light microscope observations were made on 10 to 15 μ thick sections stained with H and E, Mallory's trichrome stain, and Gomori's alkaline phosphatase stain. The 12 day old fetus possessed well developed olfactory depression with a thick epithelial covering. The olfactory fossa was still separated from the buccal cavity by a solid layer of young mesenchyme. In the 14 day old fetus the communication between the nasal and buccal cavities was established. The palatal shelves developed still vertically. All the turbinates and the nasal capsule were already differentiated. The glandular system was represented with the main and two to three accessory excretory ducts. During the sixteenth day of prenatal development, the sinus and the sinus related glands became for the first time evident. The ossification of the membranous parts of the lateral nasal wall was initiated. In the next two developing stages the maturation of the cartilage, the increasing ossification in the membrane, and the further differentiation of the glands were the major morphological changes in the formation of the lateral nasal wall.
    Additional Material: 5 Ill.
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  • 130
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The histogenetic and organogenetic capabilities of normal and lobeless embryos of Ilyanassa obsoleta are analyzed. Larvae developed from eggs in which the polar lobe was removed at the trefoil stage of first cleavage were studied in wholemount and section. None showed any evidence of eyes, statocysts, operculum, external shell, heart, or intestine. Sixty per cent of the wholemount larvae observed under polarized light exhibited internal masses of birefringent material resembling shell material. Of eight- to nine-day lobeless larvae studied as stained, sectioned material 100% possessed muscle tissue; 97.5% possessed velar tissue, digestive gland tissue, and style sac tissue; 52.5% possessed two or more style sac areas; 71% exhibited esophagus; 63% possessed stomach tissue; 37% exhibited stomodeal-like invaginations of the ectoderm; 31% exhibited a lightly staining ciliated area at the tip of the prevelar ectoderm; and 21% possessed glandular ectoderm resembling pedal or mantle gland tissue.The evidence presented suggests that the material of the polar lobe has an important role not only in cellular differentiation but also in the organization of tissue types into organs or organ primordia.
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  • 131
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    Journal of Morphology 134 (1971), S. 47-55 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: An electron microscopic investigation was made of the origin and morphology of the canal system that connects sister spermatocytes of larval Bombyx mori. Canal formation results from incomplete cleavages during the mitoses which immediately precede meiosis. We suggest the lip which surrounds each canal is derived from the contractile ring which is prevented from constricting completely by interaction with the midbody. Cells were found with as many as four canals which demonstrates that canal rims can persist through a number of mitotic cycles. Speculations are advanced as to the significance of these canals in restricting gonocytes from unlimited divisions.
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  • 132
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    Journal of Morphology 134 (1971), S. 91-103 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Adult and nymphal antennae of the cockroach, Leucophaea maderae, contain nine or more different morphological types of sense organs. There is no outwardly apparent sexual dimorphism in adult antennae. Nymphs are dificient in gross numbers of sensilla. Sense organs are classified morphologically by their similarity to known types of sensila and are assigned functions on this basis and preliminary electrophysiological data: Sensilla chaetica (A), thick-walled mechanoreceptive hairs in groups on the antennal base; S. chaetica (B), thick-walled setae which are tactile and probably chemoreceptive, occurring in the antennal base and flagellum; S. trichodea (A), thin-walled chemoreceptive hairs of the flagellum; S. trichodea (B), minute hairs on the scape and pedicel; S. basiconica, thin-walled chemoreceptive pegs, and S. coeloconica („pit-pegs“) of the flagellum; S. campaniformia and scolopidia, mechanoreceptors in the base and flagellum; plus Johnston's organ and/or connective chrodotonal organs in the pedicel. Calculations based on absolute counts of sensilla and their known innervation yield an estimate of about 3.3 × 104 sensilla and 105 cells per antenna.
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  • 133
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    Journal of Morphology 134 (1971), S. 131-140 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The carp, Cyprinus carpio, was found to have eight pairs of muscles inserting on the pharyngeal bones. These were the levator arcus branchialis V, retractor os pharyngeus superioris, retractor os pharyngeus inferioris, cleithropharyngeus superficialis, cleithropharyngeus profundus, coracobranchialis posterior, transversus ventralis V and subarcualis rectus communis. Complete morphological descriptions of the muscles are given along with relevant osteological information. The pharyngeal muscles function in mastication by moving the bones and their attached teeth against the chewing pad so that crushing and grinding of food occurs during occlusion. In addition, certain pharyngeal bone muscles enlarge the lumen of the posterior pharynx thereby admitting food to the region of the teeth and chewing pad. The homologies of some of these muscles are considered along with the historical details pertinent to the establishment of a suitable nomenclature for the pharyngeal bone muscles.
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  • 134
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    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The hypothalamus of the opossum (Didelphis virginiana), the armadillo (Dasypus novemcinctus mexicanus), and the cat (Felis domestica) was studied using Del Rio Hortega's silver carbonate technique, as modified by Scharenberg ('60). This technique demonstrates astrocytes, oligodendroglia, and neuronal perikarya, but does not impregnate microglia. The morphology of macroglia was observed in ten comparable nuclei in each of the three species. The subpial and subependymal areas were also examined.Astrocytes display more cell body angularity and have more processes in most hypothalamic regions of the cat when compared to similar regions of the opossum and armadillo.In the anterior hypothalamic nucleus, the ventromedial and the dorsomedial hypothalamic nuclei, and the medial mammillary nucleus of all three species, astrocytes send processes to neurons, but neuronal and astrocytic perikarya are usually not directly contiguous. However, oligodendrocytes in a perisomatic position on neurons are a consistent feature in these nuclei.A closer relationship appears to exist between astrocytes and neurons in the neurosecretory nuclei. In the supraoptic nucleus and paraventricular nucleus of all three species a basket-like structure, designated a „pericellular envelope“ was observed surrounding neuronal perikarya. This structure is composed of astrocytic and oligodendroglial cell bodies and processes, and is most highly developed in the cat.A dense astrocytic plexus was observed in the suprachiasmatic nucleus of the cat, and in the comparable nuclei of the armadillo and opossum. The most prominent macroglial cell type of the lateral hypothalamic and lateral mammillary nuclei of all three species is the interfascicular oligodendrocyte. The posterior hypothalamic nucleus of each species has many perisomatic oligodendrocytes, and in the armadillo and cat astrocytes are closely related to the larger neurons.A subpial plexus, consisting of a palisade of small glial cells with many processes, is present in the hypothalamus of the three species. Ependymal cells have long projecting processes throughout the length of the third ventricle in the armadillo hypothalamus, but such processes are only apparent in the region of the infundibular nucleus and median eminence in the opossum and cat.
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  • 135
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    Journal of Morphology 134 (1971), S. 243-257 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: This paper reports the demonstration, using fluorescence microscopy, of nucleolar DNA in two species of Drosophila. In Drosophila fulvimaculoides, the nucleolar DNA presents a variable morphology, suggestive of puffing activity. This material, which sometimes shows a banded structure like that of the polytene chromosomes, is shown not to be coextensive with the Y chromosome. Nucleolar DNA is demonstrated in Drosophila tumiditarsus also, and previous reports of an association of the dot chromosome with the nucleolus in this species are confirmed. The special usefulness of these two species for various sorts of investigation in pointed out.
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  • 136
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    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Striated visceral muscle cells are scattered singly or in small groups at the base of the intestinal cells of the mid-gut of Drosophila melanogaster larvae. Fibers less than 1 μ in diameter, designated as small, contain a single myofibril, few, if any, dyads and few mitochondria. Fibers of somewhat larger diameter contain dyads and more mitochondria. Both types of fiber have a perforate Z band which appears as discontinuous bodies in longitudinal sections and as a perforate sheet of dense rims and clear perforations in transverse sections. The Z rims contain filaments, 30 to 50 Å, oriented in the transverse direction. The number and arrangement of myofilaments and the ultrastructure of the Z band are consistent with the function of these muscles.
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  • 137
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    Journal of Morphology 135 (1971) 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
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  • 138
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    Journal of Morphology 135 (1971), S. 259-272 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The segmental anatomy of Harmothoë imbricata deviates from the plan of a typical errant polychaete only slightly. The body is partitioned into 37 nonmetameric segments and is covered by 15 pairs of elytra. The segmental musculature consists of paired dorsal and ventral longitudinal muscles, pairs of dorso-ventral muscles, and in places the external surface of the worm is covered by a sheet of circularly coursing muscle fibers subjacent to the cuticle. The dorsal tubercles, elytrophores, cirratophores and ventral cirri are moved by muscles derived from segmental and intrinsic parapodial muscles. From the anatomy it is surmised that the lateral bending of the worm during swimming is due to cycles of activity involving the longitudinal muscles (S-waves). During a cycle of parapodial stepping, parapodial levators and promotors raise a parapodium from the substrate and direct it forward (the recovery stroke), at which time the muscles of the aciculum and setal sacs withdraw the neuropodial setae. During the power stroke parapodial depressors and remotors bring the tip of the parapodium against the substrate, applying a forward thrust and the neuropodial setae are extended. At the conclusion of the power stroke, the recovery stroke begins anew.
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  • 139
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    Journal of Morphology 135 (1971), S. 309-321 
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Subcapsular cells lining the thymic stroma vary from low to high forms, while others have a hemocytoblastoid aspect. The purpose of the present study was to establish whether the transformation of the low forms into hemocytoblastoid subcapsular cells can be induced by an antigen. Rats given 10 Lf of diphtheria toxoid intramediastinally were killed at periods ranging from 3 to 24 hours later. Other rats were injected with 3H-thymidine at various intervals after the toxoid injection, and were killed one hour later. The observations revealed a rapid hemocytoblastoid transformation of subcapsular cells following administration of the toxoid. The transformation is detectable as early as three hours after the injection and can be completed after nine hours. Radioautography revealed that DNA duplication is initiated rapidly in the transforming subcapsular cells, since it can be completed 9 to 12 hours after the toxoid injection. Other observations suggested the transformation of reactive perithymic fibroblasts into subcapsular cells as well as the transformation of hemocytoblastoid fibroblasts and subcapsular cells into free hemocytoblastoid cells.
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  • 140
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 99-107 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polarography of Nickel (II) in the presence of DL-tryptophan has been studied in KNO3 supporting electrolyte. Nickel yields two irreversible steps which are due to the formation of two varieties of complex in sluggish equilibrium with each other. The reduction is an irreversible, kinetically controlled process as evidenced from cyclic voltammetry and i-t curves. Rate constants of the processes are evaluated. The effect of temperature is described.
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  • 141
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 108-114 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch potentiometrische bzw. photometrische pH-Titration wurden Protonierungskonstanten von 1-substituierten Butandion-(2,3)monoximen (1 und 2) und -dioximen (3) bestimmt. Die zu den Monoximen 1 und 2 gehörigen Anionen sind mesomeriestabilisiert. Bei den quaternären Ammoniumkationen 1a, 1b, 1d und 2g wird daher in erster Stufe die Oxim-, in zweiter Stufe die Ammoniumgruppierung deprotoniert. Für die lg cK11 bzw. lg cK12 der Verbindungen 1 und 2 besteht eine lineare Freie-Energie-Polare-Energie-Beziehung. Von den verschiedenen Protonierungsstufen der Dioxime 3 existieren Tautomere. Die von den Amindioximen 3 d, 3e und 3 f abgeleiteten quaternären Ammoniumkationen können daher in erster Stufe sowohl ein Ammonium- als auch ein Oximproton abspalten, und sie unterscheiden sich damit charakteristisch von 1 a, 1 b, 1 d und 2 g.
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  • 142
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus 2-Desoxyribose bildet sich in saurem Medium 3-Acetylacrolein. Dieses reagiert mit 3,5-Dihydroxytoluol (Orcin) im Sinne einer aldolartigen Aldehyd-Phenol-Kondensation über eine zwischengeschaltete Oxydation zu einer Reihe violetter und blauer Farbstoffe. Die Hauptkomponenten wurden präparativ dünnschichtchromatographisch dargestellt und als 9-(2-Acetylvinyl)-dimethyl-hydroxy-3-isoxanthone 2 und 1-(Dimethyl-3-isoxanthonyl)-2-[(dimethyl-dihydroxy-9-methyl-xanthenyl)-9]-äthylene 4 charakterisiert. Die Bildung von 4 erfolgt aus 2 und Orcin. Die Farbstoffe haben den Charakter von Säure-Base-Indikatoren mit stark pH-abhängigen Elektronenspektren. Sie sind in protonisierter Form die Träger der Farbreaktion (2: λmax = 575 nm; 4: λmax = 595 nm).
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  • 143
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 371-376 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation of acetylacetone with anthranilic acid in presence of piperidine as the condensing agent gives acetylacetoneanthranilic acid SCHIFF'S base (H2AA) which forms complexes with Zinc (II) and Palladium (II). The dissociation constants of H2AA have been determined by interpolation at half n̄ values and also by algebraic method which give the values 4.85 and 8.25 at 30° ± 1 °C for the dissociation constants. The stability constants of Zinc (II) and Palladium (II) complexes have been determined adopting CALVIN and MELCHIOR'S extension of BJERRUM'S method and the values of log k1 are found to be 2.92 and 3.97 respectively at 30° ± 1 °C. In these complexes 1:1 metal-ligand stoichiometry is observed.
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  • 144
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 411-421 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: It seems advisable to investigate polycondensation processes extended systematically from low to high conversion by carefully chosen model systems, considering the statistical data available on the processes themselves and the relationship between structure and properties of the resulting polymers. In a previous paper (Rev. Gén. Caoutchouc Plastiques, Éd. Plastiques, 4, (1967) 111) dealing with conventional crosslinking agents, the possibility was suggested to perform polycondensation processes approaching more closely the classical random distribution. This can be achieved with symmetrical monomers having functional groups well spaced out to avoid substitution effects and cyclisation. Cyclisation is also rendered more difficult by greater stiffness of the structure of the monomers. This paper shows by some examples that, in favourable cases, the deviation from the classical random distribution can be reduced to the limits of experimental error, thus enabling the physical properties to be compared with the results of comparatively simple model calculations.
    Notes: Es ist ratsam, Polykondensationsprozesse an äußerst sorgfältig gewählten Modellsystemen zu studieren, und zwar systematisch von niedrigeren nach höheren Umsätzen, und indem man die Kenntnis der Prozesse selbst, der resultierenden Struktur der Produkte, und deren strukturgebundenen physikalischen Eigenschaften gleichzeitig auf statistischer Basis vertieft. In einem früheren Bericht (Rev. Gén. Caoutchouc Plastiques, Éd. Plastiques, 4, 1967, 111) über bekannte organische und anorganische Netzformer wurde auf die Möglichkeit hingewiesen, Polykondensationssysteme zu entwickeln, die den reinen klassischen Zufallsverteilungen in viel besserer Näherung folgen. Hierzu wählt man symmetrische Monomere mit räumlich weit auseinanderliegenden Funktionen, um Substitutionseffekte und Ringschlüsse weitgehend zu vermeiden; weiterhin werden Ringschlüsse auch durch Steifheit der Monomerstruktur sehr erschwert. In diesem Vortrag wird an einigen Beispielen belegt, daß man so tatsächlich die Abweichungen vom klassischen (cyclenfreien) Zufallsmodell in günstigen Fällen erwartungsgemäß bis zur Grenze der Unmeßbarkeit zurückdrängen kann, und daß sich das deshalb lohnt, weil man dann physikalische Eigenschaften der Produkte mit relativ einfachen Modellrechnungen vergleichen kann.
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  • 145
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 422-446 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The non-equilibrium polycondensation is one of the processes developed in the efforts taken to discover new routes of syntheses in polymer chemistry. It applies to various routes of synthesis, such as polyrecombination, oxidative dehydropolycondensation, polycyclisation, polycondensation of dicarboxylic acids with diamines or bis-phenols and others.The characteristic features of the non-equilibrium polycondensation consist in the absence of reversible equilibrium reactions, high values of the equilibrium constants leading practically to the irreversibility of the process and, in contrast to equilibrium polycondensation, the possibility to prepare copolymers exclusively from monomers. In addition, it offers the essential advantages residing in the wider molecular weight distribution than that of polymers obtained by equilibrium polycondensation.The paper describes experimental results demonstrating the advantages of the non-equilibrium polycondensation. Various examples are presented that prove the non-equilibrium polycondensation a promising process for the synthesis of commercially valuable polymers.
    Notes: Die Entwicklung synthetischer Richtungen in der Polymerchemie führte zu einer Reihe neuer Syntheseverfahren, darunter auch der Nichtgleichgewichts-Polykondensation. Diese umfaßt die Polyrekombination, die oxydative Dehydropolykondensation, die Polycyclisierung, die Polykondensation von Dicarbonsäurechloriden mit Diaminen oder Bisphenolen u. a.Die Merkmale der Nichtgleichgewichts-Polykondensation sind: Fehlen reversibler Reaktionen während der Synthese; hohe Werte der Gleichgewichtskonstante und damit eine Nichtumkehrbarkeit des Prozesses sowie die Möglichkeit, im Gegensatz zur Gleichgewichts-Polykondensation Copolymere nur aus Monomeren zu erhalten.Ein wesentlicher Unterschied besteht auch in einer breiteren Verteilung der relativen Molekülmassen als bei Produkten, die durch Gleichgewichts-Polykondensation erhalten werden.Im Vortrag werden experimentelle Befunde mitgeteilt, die die genannten Besonderheiten der Nichtgleichgewichts-Polykondensation anschaulich illustrieren. An einer Reihe von Beispielen wird gezeigt, daß die Nichtgleichgewichts-Polykondensation ein aussichtsreiches Verfahren von praktisch wertvollen Polymeren ist.
    Additional Material: 18 Ill.
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  • 146
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 294-300 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,5-Diacyl-2-alkyl-diaminoguanidine 1 cyclisieren unter Wasserabspaltung zu 3-(Nα-Alkyl-Nβ-acylhydrazino)-5-aryl-1,2,4-triazolen 3. Die Cyclisierung der 1-Acyl-2-alkyl-5-carbamoyldiaminoguanidine 2 führt zu 2-Alkyl-3-[semicarbazido-(1)]-5-aryl-1,2,4-triazolen 5. Aus 3 und 5 lassen sich durch Säurehydrolyse die entsprechenden Hydrazinotriazole 4 und 6 darstellen.
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  • 147
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 301-308 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wurden hochtemperaturbeständige Azopigmente auf der Basis von 3-Amino-phthalsäureimid hergestellt. Durch Einführung von Chlorsubstituenten konnte die Lichtechtheit günstig beeinflußt werden. Die Migrationsechtheit wurde durch Molekülverdopplung entscheidend verbessert.
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  • 148
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 385-386 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 149
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 447-460 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The concept of tacticity, originally established for vinyl polymers, is shown to be valid also for condensation polymers if extended to include some particularities. From this point of view the preparation and properties of exclusively isotactic polyesters from lactic acid and substituted β-hydroxy propionic acid are described. Ditactic polyurethanes were prepared from tartaric acid esters. In contrast to tactic vinyl polymers, the condensation polymers obtained show optical activity.A special kind of steric regularity was found to be possible in polyesters and polyamides having built-in single bonds with hindered rotation. Thermal isomerisation of these polyesters may result in removal of their tacticity. The kinetics of this reaction were investigated.Cis-tacticity and trans-tacticity was observed to occur in condensation polymers having C=C or N=N double bonds in the backbone chain. The preparation of some of these polymers is reported, including experiments based on a photolytic polyreaction. The application of catalysts or light led to isomerisation at the double bonds.
    Notes: Der Begriff der Taktizität wurde ursprünglich nur für Vinylpolymere konzipiert; es wird gezeigt, daß er unter Berücksichtigung einiger Besonderheiten auch auf Polykondensate anwendbar ist. Unter diesem Gesichtspunkt werden Herstellung und Eigenschaften von rein isotaktischen Polyestern auf der Basis von Milchsäure und substituierten β-Hydroxypropionsäuren geschildert. Beispiele für ditaktische Polyurethane lassen sich von Weinsäure-Estern ableiten. Zum Unterschied von taktischen Vinylpolymeren sind diese genannten Polykondensate optisch aktiv.Eine besondere Art von sterischer Regelmäßigkeit ist bei Polyestern und Polyamiden durch den Einbau von drehungsbehinderten Einfachbindungen möglich. Bei diesen Polyestern kann die thermische Isomerisierung zum Verlust der Taktizität führen. Die Kinetik dieser Reaktion wird studiert.Cis-Taktizität oder trans-Taktizität kann bei Polykondensaten mit C=C- oder N=N- Doppelbindungen in der Hauptkette auftreten. Die Herstellung von einigen derartigen Polymeren wird beschrieben; unter anderem wird eine photolytische Polyreaktion erprobt. Durch Einwirkung von Katalysatoren oder Licht tritt Isomerisierung an den Doppelbindungen ein.
    Additional Material: 2 Ill.
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  • 150
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971) 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 151
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 561-568 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Herstellung von Estern aus Alkalisalzen verschiedener Carbonsäuren mit Alkylhalogeniden in Gegenwart von tertiären Aminen oder quartären Ammoniumsalzen wird am Modellbeispiel Natriumbenzoat/Benzylchlorid/Triäthylamin untersucht und die Abhängigkeit der Reaktion von verschiedenen Parametern bestimmt. Die Ergebnisse sind durch die Annahme einer zusätzlichen Reaktionsphase an der Festkörperoberfläche erklärbar. Als Katalysator wirkt das quartäre Ammoniumion, tertiäre Amine sind nur als Vorstufe anzusehen.
    Additional Material: 9 Ill.
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  • 152
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 594-601 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Arylidene-2-phenyl-2-imidazolin-5-ones 1 react with Grignard reagents in a boiling ether-benzene mixture to yield 4-diarylmethyl derivatives 2 together with their oxidation products 3 and 4. The exocyclic double bond in 5 also undergoes addition reaction with the same reagents to yield 4-triarylmethyl derivatives 6. Alkylation of 2 affords the 4-alkylimidazolones 7 and 8.
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  • 153
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 579-584 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acidity constants of 3-, 4- and 5-chloro-o-toluidinium ions have been measured at 25° in aqueous dioxane media containing 20, 45, 70 and 72 wt.% of 1.4-dioxane by pH metry. The necessary correction factors to convert pH meter readings into stoichiometric pH have been evaluated. The relation between the strength of anilinium ions and various solvent properties has been discussed. A HAMMETT type relation has been developed for correlating the acid strength of these disubstituted anilinium ions with HAMMETT's structural parameters.
    Additional Material: 3 Ill.
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  • 154
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 642-645 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenylazocarbonamide liefern nach N-Chlorierung mit tert.-Butylhypochlorit in Chloroform in einer Fragmentierungsreaktion kristallines Phenyldiazoniumchlorid 4 in hoher Ausbeute. Auch N-Chlor-cyclohexyl-azocarbonamid ist fragmentierbar.
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  • 155
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 686-698 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Umsetzung von o-Xylylendihalogeniden mit Ammoniak und einigen seiner Derivate (Benzylamin, N,N-Diphenylhydrazin, Carbonsäurehydrazide, Harnstoff, Cyanamid) liefert Isoindolin 2, 2-substituierte Isoindolin- und o-Xylylendiaminderivate.Eine neue Methode zur Darstellung von 2 aus o-Xylylendihalogeniden und Cyanamid wird beschrieben.
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  • 156
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 706-714 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of 4-arylazo-2-alkoxy-2-thiazolin-5-ones 4a-f with glycine or phenylhydrazine effects their conversion into 1-aryl-5-alkoxy-1 H-1,2,4-triazole-3-carboxylic acid derivatives 5a-j, with the loss of hydrogen sulfide. On the other hand, the reaction of the 2-ethoxy (4a-c) and the 2-isopropyloxy (4g-i) derivatives with strong basic amines involves the loss of an alkyl mercaptan to yield the N-substituted amines 7d-j of 1-aryl-Δ2-1,2,4-triazolin-5-one-3-carboxylic acids. The 2-benzyloxy derivatives 4d-f react with the same reagents to give the N-substituted amides 2a-g of 1-aryl-Δ2-1,2,4-triazolin-5-thione-3-carboxylic acids, with the loss of benzyl alcohol.Hetero-ring opening of 4, followed by recyclisation, occurs upon treatment with ethyl or phenyl magnesium halides to yield the triazolinethione derivatives 13 a-c.
    Additional Material: 2 Tab.
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  • 157
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 722-729 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird über Versuche zur Synthese von 1,3-Oxathiolium-Salzen aus S-Ketomethylen sowie o-Hydroxyphenyl-thiolester-Derivaten berichtet. Die Salze bilden sich nur bei der Einwirkung von starken Mineralsäuren (HClO4) auf o-Hydroxyphenyl-thiolester bzw. auf ihre zugehörigen Ausgangsverbindungen, während unter gleichen Bedingungen die entsprechenden S-Ketomethylenderivate nicht reagieren. Diese cyclisieren dafür aber in Gegenwart überschüssiger Thiosäuren zu 1,3-Dithiolium-Salzen, deren Struktur, ebenso wie die der 1,3-Oxathiolium-Salze, an Hand analytischer und spektroskopischer Daten gesichert wurde.
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  • 158
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 754-762 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: IR-Spektren von höheren und verzweigten Trialkylcyanosilanen bestätigen, daß diese wie das Trimethyl- und Triäthylcyanosilan aus Gemischen der Normal- und Isoform bestehen. Die Alkylgruppen haben auf die Lage der CN- und NC-Schwingungsbanden und auf das Verhältnis von Normal-: Isoform keinen Einfluß. In Bis-[dialkyl(iso)cyano]-disiloxanen, die durch Jodieren der betreffenden Dihydrogendisiloxane und anschließende Umsetzung mit Silbercyanid hergestellt wurden, tritt die Isoform stärker hervor.
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  • 159
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 768-772 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 160
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    Keywords: Chemistry ; Organic Chemistry
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    Topics: Chemistry and Pharmacology
    Additional Material: 4 Tab.
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  • 161
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 778-780 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 162
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 889-898 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Infrarotspektren von Butan-, Hexan,- Heptan-, Octan- und Decanarsonsäure sowie von Phenyl-, o-Methylphenyl-, p-Methylphenyl-, p-Äthylphenyl- und p-Diphenyl-arsonsäure werden im Bereich von 400-3500 cm-1 mitgeteilt und die Frequenzen zugeordnet. In den Spektren der Alkanarsonsäuren können im üblichen Erwartungsbereich keine As—C-Valenzschwingungen nachgewiesen werden. Die Bindung eines Phenylringes an den Arsonsäurerest macht die Spektren im Gebiet der AsO-Valenzfrequenzen unübersichtlich. Die Unterscheidung dieser Banden von den CH-out-of-plane-Schwingungen ist unsicher.
    Additional Material: 2 Ill.
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  • 163
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 905-916 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Der elektronenstoßinduzierte Abbau von Trimethylphenoxysilanen (H3C)3Si—O—C6H4R (R = —H und —Cl, —Br, —CH3, —NH2, —NO2 jeweils in ortho-, meta-und para-Stellung) wird beschrieben. Die Hauptfragmentierunsreaktion besteht in der Abspaltung eines Methylradikals vom Molekülion. Für die Ausbeute dieser Reaktion ergibt sich eine HAMMETT-Korrelation. Der Ausdruck lg [(I(M-15)/IM)R(I(M-15)/IM)H] nimmt mit steigendem Wert für die σ-Konstante zu. Diese Abhängigkeit wird auf der Grundlage der Quasi-Gleichgewichts-Theorie der Massenspektren als Folge des Substituenteneinflusses auf die Geschwindigkeit der Spaltungsreaktion und den Anteil der Molekülionen, der die zum Ablauf der Reaktion erforderliche Aktivierungsenergie besitzt, interpretiert. Zur Diskussion dieses Substituenteneffektes werden die mit der Elektronenstoßmethode bestimmten Ionisationspotentiale und die Aktivierungsenergien für die Spaltungsreaktion M+ → (M-15)+ + ·CH3 herangezogen.
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  • 164
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 935-939 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei Reaktion des L-α-Narcotins mit Bromcyan und nachfolgender Hydrolyse entsteht D-β-Narcotin, d.h. es tritt spezifische Inversion nur an C-1 ein. ROBINSON und Mitarbeiter hatten eine spezifische Inversion an C-9 mittels methanolischer Kalilauge verwirklicht. Durch Kombination beider Methoden lassen sich die vier Narcotin-Isomeren sowie die zwei Racemate herstellen.
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  • 165
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 969-976 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3 (5)-Amino-pyrazol liefert mit 1,3-Dicarbonylverbindungen R1COCH2COR2 5, 7-disubstituierte Pyrazolo[1,5-a]pyrimidine. Wenn R1 ≠ R2, erhält man definierte Bicyclen über substituierte 5-Vinylamino-1-p-toluolsulfonyl-pyrazole, z.B. 15, die aus 5-Amino-1-p-toluolsulfonyl-pyrazol, R1COCH2COR2 und katalytischen Mengen Aminsalzen gewonnen werden. Bei der Methylierung von 7-Hydroxy-5-methyl-pyrazolo [1, 5-a]pyrimidin 11 werden 4, 5-Dimethyl-(20a) und 1, 5-Dimethyl-pyrazolo [1, 5-a]pyrimidin- (7) (21a) isoliert. Ein O-Alkyl-Derivat von 11 wird aus 7-Chlor-5-methyl-pyrazolo [1,5-a]pyrimidin und C3H7ONa gewonnen. Die Strukturen 15, 20a und 21a werden durch Diskussion von τ- und J-Werten (1H-NMR-Spektren) für die Pyrazol-Protonen festgelegt.
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  • 166
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 167
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 956-968 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Addition verschiedener elektrophiler Agenzien an ω-Methoxyolefine wurde untersucht, um Aufschluß über eine Methoxygruppenbeteiligung zu erhalten. Eine derartige Beteiligung konnte bei der Addition von Chlor und Brom an 5-Methoxypenten-(1) nachgewiesen werden; hier entstehen zu 10-15% die entsprechenden 2-Halogenmethyltetrahydrofurane, und zu 50-60% tritt Umlagerung unter Verschiebung der Methoxygruppe ein. Die Addition von Chlor oder Brom an 6-Methoxyhexen-(1) liefert zu 15-20% die entsprechenden 2-Halogenmethyltetrahydropyrane, eine Methoxylgruppenwanderung ist nicht nachweisbar. Die Reaktion von Chlor oder Brom mit 4-Methoxybuten-(1) und mit 7-Methoxyhepten-(1) liefert ausschließlich 1, 2-Additionsprodukte.Bei der Anlagerung von Chlor an Allyl-methyl-äther erhält man außer 73% 2,3-Dichlor-1-methoxypropan infolge nebenher ablaufender Dreikomponentenreaktionen 12% 1,2,3-Trichlorpropan, 7% 1,3-Dimethoxy-2-chlorpropan und 8% 1, 2-Dimethoxy-3-chlorpropan. Bei der Addition von 2,4-Dinitrophenylsulfenylchlorid und von Quecksilberacetat an ω-Methoxyolefine tritt weder Umlagerung noch Ringschluß ein. Mit 2, 4-Dinitrophenylsulfenylchlorid entstehen nebeneinander Markownikow- und anti-Markownikow-Produkte, der Anteil des Markownikow-Produktes steigt mit wachsender Kettenlänge vom Allyl-methyl-äther bis zum 7-Methoxyhepten-(1).
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  • 168
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 993-998 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of ternary complexes of the type MAB (where M = Cu(II), Ni(II), Zn(II) or Cd(II); A = nitrilotriacetic acid and B = glycine, α-alanine or dl-aspartic acid) has been shown by potentiometric studies. The nature of titration curves indicates that the secondary ligand B is added stepwise to the initially formed metal nitrilotriacetates. The formation constants (log KMAB) and the free energies of formation (ΔF°) of the mixed complexes have been calculated at 25 ± 1 °C and m̈ = 0.10 (KNO3) at different pH values. The formation constants of the resulting 1:1:1 ternary complexes follow the order Cu(II) 〉 Ni(II) 〉 Zn(II) 〉 Cd(II).
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  • 169
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In conformity with the assumption that light fastness depends upon the electron density of the azo centre, it is now shown that condensation of the aldehyde function in p-aryl azo salicylaldehydes with hydroxylamine, semicarbazide, aniline, phenylhydrazine, 2,4-dinitrophenylhydrazine and ethylene diamine causes in most cases an increase in light fastness on nylon 6 as a result of the decreased electron attracting properties of the functions as compared with the aldehyde function. Aftertreatment of dyeings from arylazo salicylaldehydes or arylazo acetophenone with ethylene diamine causes a similar increase. Further confirmation of this observation is obtained in case of monoazo dyestuffs derived from salicylaldehyde and derivatives which contain the sulphonic acid group when applied as acid dyestuffs on Nylon 6. Application of the latter dyes on wool revealed an analogous tendency only in case of dyes derived from 2-naphthylamine-4, 8-disulphonic acid.
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  • 170
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1051-1059 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden die Elektronenanlagerungs-Massenspektren einer Reihe von 22,26-Epiminocholestanen verschiedenen Sättigungs- und Substitutionsgrades sowie unterschiedlicher Stereochemie an C-22 und C-25 vergleichend untersucht. Neben dem M-1-Peak wird als typischer Spaltprozeß bei dieser Verbindungsklasse Fragmentierung zwischen C-20 und C-22 beobachtet, die zu einem um 98 bzw. bei Acetylepiminocholestanen 140 Masseneinheiten unterhalb der Molmasse liegenden Peak führt. Eine Ausnahme bilden Δ22-ungesättigte Vertreter, bei denen eine solche Spaltung ausbleibt und die stattdessen einen charakteristischen, durch Ion-Molekül-Reaktion mit Sauerstoff resultierenden M + 14-Peak zeigen. Daneben tritt in allen Fällen Abspaltung von Wasser bzw. Acetyl auf.
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  • 171
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1070-1080 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Am Beispiel einfacher Methylverbindungen CH3X wurden aus Eigenvektoren und Eigenwerten von Allvalenzelektronenrechnungen in CNDO/2-Näherung Größen berechnet, die der 13C—H-, der geminalen H—H-Kopplungskonstante bzw. der 13C-chemischen Verschiebung der Methylgruppen proportional sein sollen. Die theoretischen Größen werden mit den entsprechenden experimentellen Werten verglichen. Güte und Grenzen der Näherungsverfahren werden diskutiert.
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  • 172
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1101-1109 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mit einem Allvalenzelektronen-SCF-Verfahren - der INDO-Methode - wird die Elektronenstruktur des Tri- und Pentamethincyanins untersucht. An ausgewählten Modellen wird für die möglichen geometrischen Anordnungen der Trimethincyanin-Einzelmoleküle in Doppelmolekülen die relative energetische Stabilität abgeschätzt. Die Berechnungen bestätigen die schon früher festgestellte starke Ladungsalternation und einen weitestgehenden Bindungsausgleich entlang der Polymethinkette. Die Elektronendichteverteilung wird duch die Zusammenlagerung von Trimethincyaninmolekülen zu Doppelmolekülen wenig verändert. Das Modell mit einer „mauerwerkartigen“ Anordnung erweist sich als das stabilste.
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  • 173
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1118-1124 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eine auf Acrylnitril und Hydrazin basierende Synthese von 3(5)-Hydroxy-pyrazol 5a durch Sulfinateliminierung aus 1-(p-Toluolsulfonyl)-pyrazolidon-(3) in nicht-wäßrigem Milieu wird beschrieben. Die Methylierung von 5a liefert Gemische von 5-Hydroxy-1-methyl-pyrazol 5b und 1,2-Dimethyl-pyrazolon-(3) 7. 5b wird chemisch eindeutig durch Sulfinateliminierung aus 2-Methyl-1-(p-toluolsulfonyl)-pyrazolidon-(3), 5-Hydroxy-1-cyclohexyl-pyrazol durch Dehydrieren von 2-Cyclohexyl-pyrazolidon-(3) gewonnen. Die Methylierung von 5a mit 2 Mol p-Toluolsulfonsäure-methylester in DMF liefert in guter Ausbeute 7, analog ergibt 3(5)-Hydroxy-5(3)-methyl-pyrazol 1,2,5-Trimethyl-pyrazolon-(3).
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  • 174
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 1125-1130 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenol und Anilin werden durch Rhodanamin 1 in para-Stellung rhodaniert, p-Toluidin in ortho-Stellung. Acetophenon ergibt unter Verbrauch von zwei Mol 1 2-Amino-4-phenyl-5-rhodano-thiazol 6. Von β-Dicarbonylverbindungen abgeleitete Enamine 7 a, b, c werden zu Rhodan-enaminen 8 a, b, c rhodaniert, aus denen leicht Amino-thiazole, das Dithiin 10 und das Thiazolon 11 erhalten werden können.
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  • 175
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 31-44 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Für die Synthese von heterologen Indanon-(2)-Derivaten werden eine Reihe von ortho-Bis-acetonitrilen und die entsprechenden Diessigsäuren und -ester, wie z. B. Pyrrol- und Thiophen-3, 4-bis-acetonitrile sowie-3,4-diessigsäureester dargestellt. Die DIECKMANN-Cyclisierung führt nur bei dem Thiophenderivat 8 in guter Ausbeute zum gewünschten Ketoester 18, dessen tautomere Formen NMR-spektroskopisch charakterisiert wurden. Aus 18 wird ein Thiophen-Analoges zum Indanon-(2) 19 in hoher Ausbeute erhalten. Dagegen ergibt die Pyrrolverbindung 12 bei gleicher Synthesenfolge nur Spuren des Heterologen 22. Das Ausbleiben des Ringschlusses beim Pyrrolabkömmling aus geometrischen Gründen wird als unwahrscheinlich angesehen.
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  • 176
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der gemeinsamen Einwirkung von Phenolen und N-Methylanilin auf Arylcyanate katalysieren die Phenole die N-Methylanilin-Addition zu Isoharnstoffen und N-Methylanilin die Phenol-Addition zu Kohlensäure-diesterimiden. Die Reaktionen verlaufen über sechsgliedrige übergangszustände und sind durch stark negative Aktivierungsentropien (≈ -43 cal/Mol · grd) gekennzeichnet. Substituenteneffekte wirken sich unterschiedlich aus. Bei substituierten Arylcyanaten ist die Elektrophilie der OCN-Gruppe, bei substituierten Phenolen die Stärke der Assoziate maßgebend für die Reaktionsgeschwindigkeit. In den letzteren Fällen lassen sich daher die Additionsgeschwindigkeiten durch lineare Beziehungen der Form lg k = a · Δ\documentclass{article}\pagestyle{empty}\begin{document}$ \widetilde{v} $\end{document}OH - b beschreiben.
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  • 177
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 115-128 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrazolidon-(3) und dessen C-Alkyl-Derivate werden am N-1 acetyliert und benzoyliert, Aus 1-Acyl-pyrazolidonen-(3) erhält man mit Dimethylsulfat in Wasser oder DMF 2-Methyl-1-acyl-pyrazolidone-(3), mit Benzylhalogeniden in Alkoholen oder Methyläthylketon 2-Benzyl-1-acyl-pyrazolidone-(3), dagegen mit Diäthylsulfat in Alkoholen, Methyläthylketon oder DMF das O-Äthyl-Derivat, z. B. 3-Äthoxy-1-benzyol-Δ-pyrazolin. Die N-2-substituierten 1-Acyl-pyrazolidone-(3) werden sauer zu 2-substituierten Pyrazolidonen-(3) hydrolysiert. Alle Strukturen sind durch kritische Diskussion des chemischen Verhaltens, der IR- und 1H-NMR. Spektren gesichert.Durch Cu-katalysierte saure Dehydrogenierung von 2-Methyl-pyrazolidon-(3) und von 2-Methyl-1-acetyl-pyrazolidon-(3) erhält man nahezu quantitativ 5-Hydroxy-1-methylpyrazol, entsprechend aus 2-Benzyl-pyrazolidon-(3) (8e) 5-Hydroxy-1-benzyl-pyrazol. Die Alkalispaltung von 8e liefert 1-(β-Carboxy-äthyl)-2-benzyl-hydrazin.
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  • 178
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Methyl-penten-(2)-al 1 erhält man durch Aldolkondensation von Propionaldehyd bei 150° an Calciumhydroxid in einer Ausbeute von 42%; bei 300° an 33 Gew.-% Kaliumhydroxid auf Bimsstein in einer Ausbeute von 57% d. Th.Die Kondensation von Propionaldehyd mit Formaldehyd bei 300% an Kaliumhydroxid bzw. Calciumhydrogenphosphat-Kontakten (optimale Katalysatorkonzentration: 10 Gew.-%) liefert 2-Methylacrolein 2 in Ausbeuten von 56-61% (berechnet auf eingesetzten Propionaldehyd).Das Temperaturoptimum beider Reaktionen wurde ermittelt.Der Vorteil dieser Verfahren liegt neben den guten Ausbeuten besonders bei den leicht und billig herzustellenden Katalysatoren. Die Zahl der Nebenprodukte ist gering.
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  • 179
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 153-160 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Als Modellreaktionen zur Aufklärung der Kinetik und des Mechanismus der Oxydation tertiärer C—H-Bindungen durch Permanganat in alkalischen Lösungen wurde die Oxydation von Diphenylessigsäure untersucht. Es wurde gezeigt, daß bis zu Laugenkonzentrationen von etwa 1 m ein Mechanismus unter direktem oxydativen Angriff des Permanganats auf die tertiäre C—H-Bindung überwiegt und im geschwindigkeitsbestimmenden Schritt eine H—übertragung erfolgt. Die Geschwindigkeitskonstante beträgt 3,3 · 10-3 1 mol-1 s-1 bei 20°C und der kinetische Deuteriumisotopieeffekt 7,8.Mit steigender Laugenkonzentration wird in zunehmendem Maße ein radikalischer Mechanismus unter Beteiligung von OH-Radikalen wirksam. Dies drückt sich in einer charakteristischen Zunahme der Geschwindigkeitskonstanten mit steigender Laugenkonzentration sowie in einer Abnahme des kinetischen Isotopieeffektes aus.Es wird eine Variante zur kinetischen Analyse der beiden Mechanismen angegeben und die Geschwindigkeitskonstante für die Reaktion der OH-Radikale mit der tertiären C—H-Bindung zu 1,4 · 107 1 mol-1 s-1 bei 20°C bestimmt.
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  • 180
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 229-235 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Alkyl-, 1-Cycloalkyl-, 1-Aralkyl-, 1-Aryl- und 1-Acyl-pyrazolidone-(3) liefern mit Formaldehyd und sekundären Aminen N-2-MANNICH-Derivate, deren Struktur durch kritische Diskussion ihrer 1H-NMR- und IR-Spektren festgelegt wird. Die hydrogenolytische Spaltung von 2-Morpholinomethyl-1-benzyloxycarbonyl-pyrazolidon-(3) 8c ergibt quantitativ 1-Benzyloxycarbonyl-pyrazolidon-(3) 6c.
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  • 181
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 205-210 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Aminomethylierung von α,ω-Dinitroalkanen entstehen symmetrische Bis-MANNICH-Basen, die nach Überführung in ihre Dihydrochloride zu Dinitroalkadienen thermolysiert werden. Zur Struktursicherung dienen NMR-Spektren und die Addition von p-Toluidin.
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  • 182
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 218-228 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Über entsprechende Phosphorsäure-monoamid-dichloride 5 werden Triamide 8 mit zwei Äthyleniminresten und dem Rest eines hydrophoben Amins synthetisiert, wobei als letzteres neben Heptyl-, Dodecyl-, Cyclohexyl- und β-Phenyl-äthylamin ein antimitotisches α-Phenyl-β-(4-alkoxy-phenyl)-äthylamin (1f, 1g) dient. Eine Methode zur Darstellung von (+)- und (-)-[α-Phenyl-β-(4-äthoxyphenyl)-äthyl]-amid-phosphorsäure-dichlorid 5h und 5i wird angegeben.Aus Phosphoryl-N-Lost-dichlorid 6 wird das Dimorpholid 9k und Bis-(β-phenyl-äthyl)-amid 9e, aus Thiophosphoryl-N-Lost-dichlorid 7 eine Reihe von Thiophosphoryl-N-Lost-diamiden 10 b, 10 d-g, 10i gewonnen. Die Stereoisomerie bei der Kombination von Thiophosphoryl-N-Lost mit zwei Resten der antimitotischen Amine 1f, 1g wird diskutiert. Aus der Diskussion der Cl⊖-Abspaltung u.a. folgt, daß Phosphoryl-N-Lost-diamide des Typs 9k desaktivierte N-Lost-Derivate sind, Thiophosphoryl-N-Lost-diamide dagegen nicht.
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  • 183
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 259-264 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclohexyl- und Butyl-dichlorarsine RAsCl2 reagieren mit Natrium im Molverhältnis 1:2 zu den Cyclopolyarsinen (RAs)n. Während die n-Butyl- und Isobutyl-cyclopolyarsine als pentamere Verbindungen vorliegen, konnten im Falle der Cyclohexyl-, tert.-Butyl- und sek.-Butyl-cyclopolyarsine tetramere Strukturen nachgewiesen werden. Die Molekülgröße wurde durch kryoskopische Molmassebestimmungen und in einigen Fällen auch durch Massenspektren und Röntgenstrukturuntersuchungen ermittelt. Am Beispiel des Tetra-tert.-butyl-cyclotetraarsins wird das chemische Verhalten gegenüber Alkalimetallen, Halogenen und Methyljodid näher studiert.
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  • 184
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 277-286 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acide Verbindungen werden durch Dimethylformamid-dimethylacetal entweder methyliert (Phthalimid, p-Toluolsulfonsäure-methylamid, Phenol, Benzoesäure, Dihexylphosphinsäure, Salzsäure) oder in Tetramethylammoniumsalze (Ditosylimid, 2,4,6-Trichlorphenol, Pikrinsäure, Trifluoressigsäure, Diphenylphosphinsäure) bzw. in Tetramethylformamidiniumsalze (p-Toluolsulfonsäure, Perchlorsäure) überführt. Entscheidend für den verschiedenartigen Ablauf der Reaktionen ist die Acidität der Ausgangsverbindung.
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  • 185
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 339-348 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Am Beispiel der p-Phenylendiamine wird gezeigt, daß mit dem einfachsten quantenchemischen Rechenverfahren, der HMO-Methode, eine Reihe photographischer Eigenschaften, wie Entwicklungsgeschwindigkeiten, Kupplungsgeschwindigkeiten u.a., in Abhängigkeit vom Substituenteneinfluß zufriedenstellend vorausgesagt werden können.
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  • 186
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 331-338 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wurden die integralen Intensitäten charakteristischer Absorptionsbanden im Infrarotgebiet sowie die Dipolmomente einiger substituierter Arylchlorkohlensäureester bestimmt. Die Wurzel aus den integralen Intensitäten wurde mit den HAMMET-Konstanten σ in Beziehung gebracht. So konnte gezeigt werden, daß elektronenaffine Gruppen einen besonderen Einfluß auf die Elektronenstruktur der Chlorkohlensäuregruppe ausüben, der sich vor allem an der Aryl-Sauerstoffbindung bemerkbar macht. Der Einfluß auf die Carbonylgruppe und die Acyl-Sauerstoffbindung ist klein, während der auf die C—Cl-Bindung noch geringer ist.
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  • 187
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971) 
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 188
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 357-370 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Zerfallsreaktionen der Tetraalkoxysilane Si[—O—(CH2)nCH3]4 (n = 0-4) und Si[—O—(CH2)nCH(CH3)2]4 (n = 0, 1, 2) bei Elektronenstoß in der Ionenquelle des Massenspektrometers werden wiedergegeben. Sie bestehen im Abbau der primär durch Fragmentierung aus dem Molekülionen gebildeten Ionen (Alkyl-O-)3Si+ und (Alkyl-O-)3Si—OCH2+. Diese Abbaureaktionen sind Folgen von Wasserstoffumlagerungen, in deren Verlauf Aldehyd- und Olefinabspaltungen miteinander konkurrieren. Im allgemeinen überwiegt die Olefinabspaltung. Die Besonderheiten dieser Reaktionen bei der Fragmentierung der verschiedenen Tetraalkoxysilane werden diskutiert.
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  • 189
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 377-384 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mit einer thermokinetischen Methode wurde an einer kontinuierlichen Strömungsapparatur die Kinetik der Cumolhydroperoxidzersetzung mit Schwefelsäure in einem äquimolaren Phenol-Aceton-Gemisch zwischen 40 und 60 °C untersucht. Außerdem wurde der Einfluß von Wasser und Acetophenon im gleichen Temperaturbereich kinetisch verfolgt. Weiterhin konnten die Aktivierungsparameter und die Reaktionsenthalpie ermittelt werden.
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  • 190
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 397-410 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The paper presents the essential rules underlaying the polycondensation of the title components in organic solvents in the presence of tertiary amines on heating or at comparatively low temperatures. With hydrogen chloride resulting as a low molecular reaction product the condensation proceeds under non-equilibrium conditions. Conducting the condensation at higher temperatures, however, may be accompanied by destructive exchange reactions of the polymer with the starting material or between the polymer molecules themselves, affecting the molecular weight of the polymers obtained. Investigations of the kinetics of polycondensation of terephthalic acid with 9,9-bis-(4-hydrophenyl)-fluorene and 4,4′-(hexahydro-4,7-methyleneindan-5-ylidine)-diphenol at 150 to 200°C in a solvent with high boiling point showed the polyesterification to proceed by an anionic mechanism with formation of acylium ions at the start of and during the reaction.The polycondensation of dicarboxylic acid chlorides with bisphenols was found to depend largely on the components and composition of the initial mixture, temperature and other factors involved. Particularly, the kind of medium chosen for the polycondensation process reflects in the supramolekular structure and, thereby, in the physical properties of the polymer obtained.The results of experiments carried out to clarify the importance of tertiary amines in the polyesterification reaction in solvents at low temperature suggest two catalytic mechanisms, a nucleophilic and a general basic one.
    Notes: Im Vortrag werden die wichtigsten Gesetzmäßigkeiten der Polykondensation von Dicarbonsäurechloriden mit Bisphenolen in einem organischen Lösungsmittel unter Erwärmen oder bei relativ niedrigen Temperaturen in Gegenwart eines tertiären Amins betrachtet. Im Hinblick auf das niedermolekulare Reaktionsprodukt-Chlorwasserstoff-ist die Polykondensation dann ein Nichtgleichgewichtsprozeß. Wird sie jedoch bei höherer Temperatur durchgeführt, so können destruktive Austauschreaktionen des entstehenden Polykondensats mit den Ausgangsstoffen und zwischen den Makromolekülen auflaufen, wodurch die Molmassenverteilung der Polyarylate beeinflußt wird.Aus Untersuchungen zur Kinetik der Polykondensation von Terephthalsäurechlorid mit 9,9-Bis-(4-hydroxyphenyl)-fluoren und 5,5-Di-(4-hydroxyphenyl)-perhydro-4, 7-methylenindan in einem hochsiedenden Lösungsmittel bei 150 bis 300 °C geht hervor, daß die Polyveresterung nach einem ionischen Mechanismus unter Bildung von Acylium-Ionen verläuft.Von Bedeutung für die Polykondensation von Dicarbonsäurechloriden mit Bisphenolen sind: Verhältnis und Natur der Ausgangsstoffe; Reaktionstemperatur und Art des Mediums. Die Natur des Mediums beeinflußt die Ausbildung der übermolekularen Struktur des Polykondensats.Für die Polyveresterung durch tertiäre Amine bei niedrigen Temperaturen wird eine nucleophile Katalyse und eine allgemeine Basenkatalyse diskutiert.
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  • 191
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    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 387-396 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: The theory of Flory is extended to include the polycondensation in solution. The rate of the process is shown to be affected by the reactivity of the functional groups and their accessibility, considered to be the probability of interactions resulting in reactions. The accessibility depends strongly on the degree of coiling of the reactants.Calculations were performed to test the concept of the dependence of the polycondensation in solution on the chain length of the polymer and the nature of the solvent. The activation energy was found to increase with the degree of coiling of the reactants.The model reaction of 2, 2-bis-(p-hydroxyphenyl)propane with phenyl chloroformate and the polycondensation of 2,2-bis-(p-hydroxyphenyl)propane with its bis-chloroformate were investigated in the mixed solvents nitrobenzene/decaline and nitrobenzene/p-dichlorobenzene. With the first solvent the polarity and the dissolving quality decrease with increasing content of decaline. In the second mixture only the polarity changes with the content of dichlorobenzene.The rate of the model reaction is hardly affected by the composition of the solvent mixture.In the polymer system the rate is likewise hardly affected if only the polarity of the solvent mixture is changed. Lower dissolving quality caused differences of the kinetic constants ranging over one order. The results seem to support the theoretical considerations.
    Notes: Es wird eine Erweiterung der FLORYschen Theorie für Polykondensationsreaktionen in Lösung vorgeschlagen. Danach wird die Prozeßgeschwindigkeit vor allem von zwei Faktoren beeinflußt, von der Reaktivität der funktionellen Gruppen und von ihrer Akzessibilität - der Wahrscheinlichkeit einer zur Reaktion führenden Wechselwirkung. Die Akzessibilität ändert sich ihrerseits stark mit dem Knäuelungsgrad der Reaktanten.Zur Prüfung der Konzeption, daß die Kinetik von Lösungspolykondensationsreaktionen von der Kettenlänge der Makromoleküle und von der Natur des Lösungsmittels abhängt, wurden Berechnungen vorgenommen. Sie ergaben, daß die Aktivierungsenergie von Polykondensationsreaktionen in Lösung mit dem Knäuelungsgrad der Reaktanten zunimmt.Experimentell untersucht wurde die Modellreaktion von 2, 2-Bis-(p-hydroxyphenyl)propan und Chlorkohlensäurephenylester sowie die Polykondensation von 2, 2-Bis-(p-hydroxyphenyl)propan mit dessen Bis-chlorkohlensäureester in den Lösungsmittelgemischen Nitrobenzol/Dekalin und Nitrobenzol/p-Dichlorbenzol. Im erstgenannten System sinken Polarität und Lösungsmittelgüte für das Polymere mit steigendem Dekalingehalt. In der zweiten Mischung ändert sich mit dem Dichlorbenzolanteil nur die Polarität.Die Geschwindigkeit der Modellreaktion wird durch die Zusammensetzung des Lösungsmittels kaum beeinflußt.Beim makromolekularen System wird die Reaktionsgeschwindigkeit ebenfalls nur gegeringfügig beeinflußt, wenn man allein die Polarität des Lösungsmittelgemisches verändert. Bei Verringerung der Lösungsmittelgüte dagegen treten Unterschiede in den kinetischen Konstanten von einer Größenordnung auf. Diese Ergebnisse scheinen die Richtigkeit der theoretischen Erörterungen zu bestätigen.
    Additional Material: 3 Ill.
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  • 192
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 461-483 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: Siloxane oligomers containing two hydroxyl, amino or anhydride groups were obtained by applying the reactions known to lead to Si—C bonds.Polycondensation of these monomers with suitable bifunctional reactants resulted in siloxane-modified polyesters, phenolformaldehyde resins, polyamides, polyestermides and polyimides the properties of which, such as softening point, solubility and thermostability were investigated. The siloxane containing polyimides proved to be soluble and melting polymers that resisted heating up to 400 degrees C in the presence of air oxygen.Polyimides of similar properties but being composed of different siliciumorganic units were obtained by polycondensation of an imide-containing bis-silanol with dichloro-Si compounds. This process eliminates the laborious preparations of siliciumorganic diamines.Condensation polymerisation of organic polymers with siliciumorganic polymers having one or two reactive functional groups in their molecules allow to prepare siloxane-modified block and graft polymers as well cross-linked products.
    Notes: Mit Hilfe der bekannten Reaktionen zur Knüpfung von Si—C-Bindungen haben wir oligomere Polysiloxane mit zwei Hydroxyl-, Amino- und Anhydridgruppen hergestellt:Durch Polykondensation dieser Monomeren mit geeigneten bifunktionellen Partnern wurde eine Reihe siloxanmodifizierter Polyester, Phenol-Formaldehydharze, Polyamide, Polyesterimide und Polyimide synthetisiert und einige ihrer Eigenschaften (z. B. Erweichungspunkt, Löslichkeit, Thermostabilität) untersucht. Die siloxanhaltigen Polyimide waren beispielsweise löslich, schmelzbar und in Gegenwart von Luftsauerstoff bis gegen 400 °C beständig.Polyimide mit ähnlichen Eigenschaften, aber verschiedenen siliciumorganischen Bauelementen waren durch Polykondensation eines imidhaltigen Bis-Silanols mit Dichlor-Si-Verbindungen zugänglich. Bei diesem Verfahren erübrigt sich die präparativ oft aufwendige Synthese der entsprechenden siliciumorganischen Diamine.Polykondensationsreaktionen von organischen mit siliciumorganischen Polymermolekülen, die eine oder zwei zur Reaktion miteinander befähigte funktionelle Endgruppen besitzen, ermöglichten den Aufbau von siloxanmodifizierten Block- und Pfropfcopolymeren sowie vernetzten Produkten.
    Type of Medium: Electronic Resource
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  • 193
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 529-545 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: Phosphorus-containing polymers are known to have valuable properties, primarily the ability of self-extinction. Most favorable results were obtained with substances including phosphorus and chlocrine in their molecules. However, up to now attention was given predominantly to polymers having C—O—P bonds.The present paper describes the synthesis of phosphorus and phosphorus and chlorine containing polymers with C—P bonds using methylol derivatives of phosphorus. Bis-(p-carbomethoxyphenoxymethyl) methylphosphinoxide was used as a phosphine oxide derivative. This phosphorus-containing dicarboxylic acid was reacted with glycols to give phosphorus-containing polyesters and copolyesters. With glycols in excess the reaction led to phosphorus-containing and mixed oligomers which after reaction with diisocyanates yielded polyurethanes, copolyurethanes and urethane block copolymers.Esterification of bis(hydroxymethyl)phosphonic acid with acrylic and methacrylic acid yielded monomers which, when subjected to polymerisation, gave phosphorus-containing polyesteracrylates and methacrylates and, in addition, could be copolymerised with acrylic and methacrylic acid.Mono- and dicondensation products of hypophosphorous acid with chloral, being considered as chlorine-containing methylol derivatives of phosphinic and phosphonic acids, led to polyurethanes.
    Notes: Bekanntlich neigen phosphorhaltige Polymere zum Selbstverlöschen. Die besten Ergebnisse wurden erzielt, wenn im Molekül gleichzeitig Phosphor und Chlor vorhanden sind. Meist wurde jedoch bis jetzt den phosphorhaltigen Polymeren mit C—O—P-Bindungen Aufmerksamkeit gewidmet.Von uns wurden Polymere mit C—P-Bindungen synthetisiert, die nur Phosphor oder gleichzeitig Phosphor und Chlor enthalten. Zu diesem Zweck wurden einige Methylolderivate des Phosphors herangezogen. Von Derivaten des Phosphintyps wurde Bis-(p-carbomethoxyphenoxymethyl)-methylphosphinoxid als phosphorhaltige Dicarbonsäure herangezogen. Durch Umsetzung dieser Säure mit Glykolen wurden phosphorhaltige Polyester und Copolyester dargestellt. Im Falle eines Überschusses der Glykole wurden auch phosphorhaltige und gemischte Oligomere erhalten, aus denen durch Reaktion mit Diisocyanaten Polyurethane, Copolyurethane und Blockpolyurethane synthetisiert werden konnten.Durch Veresterung von Bis-(hydroxymethyl)-phosphonsäure mit Acryl- und Methacrylsäure wurden polymerisierbare Monomere erhalten und dann in phosphorhaltige Polyesteracrylate und -methacrylate überführt sowie mit Acryl- und Methacrylsäure copolymerisiert.Mono- und Dikondensationsprodukte der hypophosphorigen Säure mit Chloral können als chlorhaltige Methylolderivate von Phosphin- und Phosphonsäuren aufgefaßt werden; sie wurden bei der Synthese von Polyurethanen verwendet.
    Additional Material: 11 Ill.
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  • 194
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 569-578 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polarographic behaviour of thio-acetic acid (RSH) at dropping mercury electrode (d.m.e.) has been investigated in presence of KNO3 in the pH range 2-10.5 at 30.0 ± 0.2°C in 50% alcoholic medium at 0.2 M ionic strength. Well defined anodic waves were obtained at all pH values in the concentration range studied. At pH 〈 2.2 and 〉 10.5 ill defined anodic waves were obtained. The effect of pH, concentration of RSH, temperature, drop time and alcohol on the wave characteristic and the mechanism of the reaction occurring at the surface of the mercury drop have been studied in detail. A small prewave was also observed at pH 9.1 and 10.5, which has been assigned adsorption characteristics. The reversibility of the reaction mechanism was confirmed by a number of methods. The wave is diffusion controlled and reversible involving one electron transfer process: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm RSH} + {\rm Hg}\rightleftharpoons{\rm RSH}g + {\rm H}^ + + {\rm e} $$\end{document}Mathematical and experimental evidence shows that the anodic wave of RSH at. d.m.e. does not correspond to formation of (RSSR) but to a mercury compound RSHg according to the above equation. The diffusion coefficient and temperature coefficient for (30-45°C) of id at pH 4.0 and 9.1 have been found to be 1.698; 1.965 × 10-6 cm2/sec and 1.08%; 1.20% per degree respectively. The dissociation constant pKa was found to be 4.25 by the plot of E1/2 vs. pH. The linearity of id with RSH concentrations provides a rapid and precise method for the determination of RSH down to 0.2 mM.
    Additional Material: 4 Ill.
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  • 195
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    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 614-625 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Titelverbindungen wurden NMR-, UV- und CD-spektroskopisch untersucht. An Hand der chemischen Verschiebung der Protonen des Zuckerrestes wurde für alle untersuchten N-β-D-Glucopyranoside eine anti-Konformation nachgewiesen. Das Vorzeichen der Cotton-Effekte der Glucopyranoside und Desoxyribofuranoside hängt außer von der Konfiguration wesentlich von der Struktur des Aglykons ab. Veränderungen in unmittelbarer Nähe des glykosidischen Stickstoffatoms (6-Azathymin- und Pyridazon-(3)-Derivate) führen zu einer Umkehr des Vorzeichens der Cotton-Effekte.
    Additional Material: 5 Ill.
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  • 196
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 602-606 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ausgehend von 2,4,6-Trichlor-5-methyl-pyrimidin läßt sich über 2,4,6-Trifluor-5-methyl-pyrimidin und 5-Methyl-2,4-dibenzyloxy-6-fluor-pyrimidin durch nachfolgende Abhydrierung der Benzylgruppen 6-Fluor-thymin in guter Ausbeute gewinnen. Die Verbindung ist im Gegensatz zu 6-Fluor-uracil in wäßriger Lösung stabil und daher als biologisch aktive Substanz einsetzbar. Mit NH3 oder Benzylamin reagiert 6-Fluor-thymin leicht zu 6-Amino- bzw. 6-Benzylamino-thymin.
    Additional Material: 1 Tab.
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  • 197
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    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 626-635 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von Brenzcatechincarbonat 1 mit Alkoholen, Aminen und Hydrazinen werden Kohlensäureester, Urethane, Harnstoffe, Semicarbazide und Carbohydrazide hergestellt. Durch thermische Zersetzung von N-Alkyl-carbamidsäure-(2-hydroxyphenyl)-estern 6 werden Alkylisocyanate gewonnen.
    Additional Material: 8 Tab.
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  • 198
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    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 667-677 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In der Umsetzung von N-Acyl- und N-Äthoxycarbonyl-α-aminoketonen 1 mit Nitrosierungsmitteln wurde eine neue Methode zur Darstellung von 3-Acyl-1,2,4-oxadiazolen 3 gefunden. Als instabile Zwischenverbindungen sind die α-Hydroximinoderivate von 1, die C,N-Diacyl-formamidoxime bzw. C-Acyl-N-äthoxycarbonyl-formamidoxime 2, anzunehmen, welche vermutlich aus den primär gebildeten N-Nitrosoderivaten von 1 entstehen.
    Additional Material: 2 Tab.
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  • 199
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3(1)H-Imidazo[4,5-h]chinoline sind interessante ampholytische Chelatbildner, da sie in koordinativ günstiger Position zu einer N-Donatorfunktion - auf Grund der Tautomerie dieser Verbindungen - eine acide NH-Gruppe enthalten. Durch Kondensation von 5, 7-Dinitro-8-amino-chinolin mit Carbonsäuren unter reduzierenden Bedingungen wurden verschiedene C-2-substituierte 3(1)H-Imidazo[4,5-h]chinoline erhalten, die in Abhängigkeit vom Carbonsäurerest C-5-amino- bzw. -hydroxysubstituiert sind. Die Kondensation von 5-Nitro-7,8-diamino-chinolin mit Carbonsäuren ergibt in Gegenwart von Polyphosphorsäure C-2-substituierte 5-Nitro-3(1)H-imidazo[4,5-h]chinoline. Die Konstitution der erhaltenen Verbindungen wird durch massenspektroskopische Untersuchungen bestätigt. An unterschiedlich 15N-markierten Verbindungen konnte der Fragmentierungsmechanismus verschiedener 3(1) H-Imidazo[4,5-h]chinoline aufgeklärt werden. Durch quantenchemische Berechnungen des 3(1)H-Imidazo[4, 5-h]chinolins und verschiedener Substitutionsprodukte konnten Hinweise über die Lage der Tautomeriegleichgewichte, die Säure-Base-Eigenschaften, das UV-Spektrum sowie über das reaktive Verhalten dieser Verbindungen erhalten werden.
    Additional Material: 13 Ill.
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  • 200
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 715-721 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetylation of 4-hydroxy-1-thiocoumarin 1 b in the presence of phosphorus oxychloride yields the 3-acetyl derivative 2, which condenses with aromatic aldehydes to give the corresponding 3-cinnamoyl derivatives 3 a-e, and yields 3-arylazo-4-hydroxy-1-thiocoumarins 4 a-d upon treatment with aromatic diazonium salts.Whereas treatment of 1 b with primary amines results in the formation of 4-substituted amino derivatives 5 a-c, 3-acetyl-4-hydroxy-1-thiocoumarin 2 reacts with the same reagents to yield the 3-α-alkyliminoethyl derivatives 7 a-c.Treatment of 1 b with phenylhydrazine affords the 4-phenylhydrazine derivative 5 d. On the other hand, 2 reacts with the same reagent to yield a mixture of the phenylhydrazone 9 and the pyrazolo-1-thiocoumarin 10.
    Additional Material: 1 Tab.
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