ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • Inorganic Chemistry  (7,396)
  • LUNAR AND PLANETARY EXPLORATION  (3,213)
  • Biology
  • 2005-2009  (22)
  • 1980-1984  (6,720)
  • 1930-1934
Collection
Keywords
Language
Years
Year
  • 1
    Publication Date: 2021-05-19
    Description: L’étude porte sur l’évolution du pH et de la température au cours de la transformation artisanale du Cymbium, ainsi que sur les perspectives de valorisation du produit transformé. Les expérimentations menées au site de transformation artisanale de Joal ont permis de constater que : Après 12 heures de séjour en bac (1ère nuit), le Cymbium est encore en phase de rigor mortis. Le pH moyen affiché à l’issue de cette première nuit est de 7,6 ; donc proche de celui du mollusque vivant ; Le pH moyen du produit fini est légèrement acide et se situe entre 6,3 et 6,4. Donc le yeet de Joal est très peu fermenté ; Les difficultés de séchage notées sont dues : soit au manque de maîtrise des paramètres tels que, la température, l’humidité relative et la vitesse de l’air, soit à l’absence de protection du produit en cours de séchage contre les intempéries. Les essais sur les perspectives de valorisation montrent que : 47,64% du poids du Cymbium dépourvu de sa coquille font l’objet de rejets sous forme de rebuts (surtout en milieu industriel) ; Les enzymes végétales que sont, la bromélaïne, contenue dans le jus d’ananas, et la papaïne, contenue dans le latex de papaye, ainsi que les acides organiques contenus dans le vinaigre et le jus de citron, favorisent l’acidification et accélèrent la fermentation, tout en améliorant le goût, l’odeur et la texture du produit fini ; Les meilleurs résultats sont obtenus dans le cas de la fermentation sous température contrôlée, au laboratoire, où le pH du produit fini se situe entre 4,3 et 4,7. Enfin, sur l’ensemble de l’étude, il est prouvé que les rendements obtenus pour les produits ayant subi un processus de transformation complète (dans le cas des essais sur les perspectives de valorisation) sont faibles par rapport à ceux transformés à Joal. Ces rendements vont de : 2,88 à 28,57% pour le premier groupe de produits ct 31,4 à 58,3% pour le second groupe de produits.
    Description: Université Cheikh Anta Diop, Institut Universitaire de Pêche et d'Aquaculture, Dakar (Senegal)
    Description: Unpublished
    Description: cymbium; transformation artisanale; biologie; commercialisation; fermentation; séchage; température; pH; statistiques
    Keywords: pH ; Marketing ; Biology ; Fermentation ; Drying ; Temperature ; Processing fishery products ; Fermentation ; Biology ; Marketing ; Drying ; Temperature ; Statistics
    Repository Name: AquaDocs
    Type: Theses and Dissertations , Bachelor thesis
    Format: 132
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 2
    facet.materialart.
    Unknown
    American Association for the Advancement of Science (AAAS)
    Publication Date: 2009-11-07
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Vogel, Gretchen -- New York, N.Y. -- Science. 2009 Nov 6;326(5954):788-91. doi: 10.1126/science.326_788.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19892956" target="_blank"〉PubMed〈/a〉
    Keywords: *Academies and Institutes/economics/organization & administration ; Anthropology ; Biology ; Chemistry ; Germany ; Germany, East ; Physics ; Research Personnel ; Universities
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 3
    Publication Date: 2021-05-19
    Description: La creciente importancia que los recursos de calamar han adquirido en 105 últimos 30 años, los sitúa actualmente entre los más importantes recursos pesqueros del mundo. En consecuencia, paises tradicionalmente no explotadores o consumidores de productos de calamar, han orientado sus esfuerzos hacia el logro de un mejor conocimiento de las especies de cefalópodos que habitan su ambiente marino. En este sentido el aporte de disciplinas tales como la biología ha sido decisivo para desarrollar en forma exitosa pesquerías de calamar, entre otras.El programa de investigaciones del Instituto Nacional de Pesca para 1980 incluyó el estudio integral de la explotación de los calamares como un primer paso hacia el desarrollo de una pesquería del recurso. Este trabajo presenta los resultados de un estudio de los aspectos biológicos de la especie más importante del área: Illex argentinus y forma parte de una serie de tres documentos técnicos escritos por el autor referentes a recursos de calamar. Dichos documentos están relacionados con la tecnología de captura y la producción y comercialización del calamar en el Uruguay.
    Description: The growing importance of the squid resources during the last 30 years place them among the more important fish resources of the world. Therefore countries traditional1y non exploiters or consumers of squid products gave steps toward a better knowledge of the species of cephalopods inhabiting their marine environment. For instance, the contribution of subjects such as the biology lead to a successful development of squid fisheries, among others. The 1980 research program of the National Fisheries Institute included an integral study of the exploitation of the squids as a first step toward the development of a squid fishery. This paper presents the results of a study on the biological aspects of the principal species of the area: Illex argentinus. It is part of three technical reports written by the author on squid resources. These reports are fishery technology and production & marketing of squids in Uruguay.
    Description: Montevideo: Instituto Nacional de Pesca
    Description: Published
    Description: Illex argentinus, calamar, ZCP, biología, comportamiento, condiciones ambientales, desove, reproducción, relación de sexos, madurez sexual, crecimiento, frecuencia de longitudes, migraciones
    Keywords: Population structure ; Spawning ; Length ; Growth ; Biology ; Environmental conditions ; Spawning grounds ; Sex ratio ; Sexual maturity ; Reproduction ; Behaviour ; Biology ; Environmental conditions ; Population structure ; Spawning ; Spawning grounds ; Sex ratio ; Sexual maturity ; Reproduction ; Length ; Behaviour ; Migrations ; Growth
    Repository Name: AquaDocs
    Type: Report
    Format: 50
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 4
    facet.materialart.
    Unknown
    American Association for the Advancement of Science (AAAS)
    Publication Date: 2008-11-22
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Enserink, Martin -- New York, N.Y. -- Science. 2008 Nov 21;322(5905):1184-5. doi: 10.1126/science.322.5905.1184.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19023058" target="_blank"〉PubMed〈/a〉
    Keywords: Academies and Institutes/economics/*history ; Biology ; History, 20th Century ; Pathology ; Romania
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 5
    Publication Date: 2008-03-22
    Description: Minerals are more complex than previously thought because of the discovery that their chemical properties vary as a function of particle size when smaller, in at least one dimension, than a few nanometers, to perhaps as much as several tens of nanometers. These variations are most likely due, at least in part, to differences in surface and near-surface atomic structure, as well as crystal shape and surface topography as a function of size in this smallest of size regimes. It has now been established that these variations may make a difference in important geochemical and biogeochemical reactions and kinetics. This recognition is broadening and enriching our view of how minerals influence the hydrosphere, pedosphere, biosphere, and atmosphere.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Hochella, Michael F Jr -- Lower, Steven K -- Maurice, Patricia A -- Penn, R Lee -- Sahai, Nita -- Sparks, Donald L -- Twining, Benjamin S -- New York, N.Y. -- Science. 2008 Mar 21;319(5870):1631-5. doi: 10.1126/science.1141134.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Center for NanoBioEarth, Department of Geosciences, Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA 24061-0420, USA. hochella@vt.edu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/18356515" target="_blank"〉PubMed〈/a〉
    Keywords: Atmosphere ; Biology ; Geologic Sediments/chemistry ; Humans ; *Minerals/chemistry/metabolism ; *Nanoparticles ; Oceans and Seas ; Particle Size ; Solubility ; Thermodynamics
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 6
    Keywords: Biology ; Data processing ; Chemistry ; Chemistry, Physical organic ; Materials ; Nanotechnology
    ISBN: 9781402081897
    Language: English
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 7
    Keywords: Biochemistry ; Biology ; Data processing ; Biomedical engineering ; Chemistry ; Chemistry, Physical organic ; Materials
    ISBN: 9781402081842
    Language: English
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 8
    facet.materialart.
    Unknown
    American Association for the Advancement of Science (AAAS)
    Publication Date: 2007-05-26
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Marshall, Eliot -- New York, N.Y. -- Science. 2007 May 25;316(5828):1112.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/17525309" target="_blank"〉PubMed〈/a〉
    Keywords: Biology ; *Federal Government ; History, 21st Century ; Minnesota ; Nobel Prize ; Politics
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 9
    Publication Date: 2021-05-19
    Description: This journal is published by NIOF, Alexandria, Egypt
    Description: General pattern of gonadal development in female Trachinotus ovatus was divided into six maturity stages, which are; immature, maturing, nearly ripe, ripe, spawning and spent stages. The maximum value of gonadosomatic index (GSI) was attained in June and July. Total protein content in ovaries varied according to different maturity stages recording maximum value at immature ovaries and minimum at spawning and spent ovaries. The values of GSI in ovaries were inversely correlated to their total protein content at different maturity stages. Seven amino acids (proline, alanine, valine, methionine, isoleucine, leucine and histidine) were found to increase significantly in ripe ovary, followed by a significant decrease in both spawning and completely spent ovaries. While, arginine and threonine reached their maximum concentration in the spawning period. On the other hand, serine amino acid reached their minimum value in the ripe ovary. Total lipid contents of ovaries reached their minimal values at immature stage, while the maximum recorded value was at the nearly ripe gonad. The ovarian total lipid contents approximately followed the same manner of the GSI according to the different maturity stages except in spawning period. Many differences were detected in fatty acid concentrations in female Trachinotus ovatus ovaries in relation to different maturity stages. Eicosapentaenoic acid content varied according to the stage of sexual maturity. While, the maximum recorded value of arachidonic acid was at the ripe stage. Palmitic acid and oleic acid had the highest concentrations among fatty acids, while those with low concentrations were pentadecanoic acid and gadoleic acid.
    Description: NIOF
    Description: Published
    Keywords: Trachinotus ovatus ; Ovaries ; Total proteins and amino acids ; Total lipids and fatty acids ; Biology ; Fish
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed , Article
    Format: 1022334 bytes
    Format: 44919 bytes
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 10
    Publication Date: 2021-05-19
    Description: Thèse
    Description: Résumé : En Mauritanie, un constat clair met en évidence une tendance de sur-exploitation « en série» des stocks à haute valeur, des Mugilidés; le mulet jaune premièrement, puis ensuite le mulet noir et le mulet doré (espèces pouvant être considérées de substitution). L’exploitation intensive du mulet jaune à partir de 1996 a conduit au ciblage du mulet noir à partir de 1998 et puis, plus récemment encore, celui du mulet doré en 2001. L’absence d’une gestion rationnelle risque de conduire, dans moins de sept ans à la quasi-disparition de ces ressources (logiquement renouvelables). C’est dans ce contexte de baisses des rendements, auquel s’ajoute la dégradation des zones littorales par l’action anthropique sans cesse croissante, que ce travail a permis d’approfondir les connaissances scientifiques du domaine paralique en général, des zones de dilutions en particulier et d’étudier les structures démographiques (taille, âge, sex-ratio) et la reproduction (saison et aire de ponte) des trois Mugilidae les plus ciblés. Ce travail explique également, les stratégies d’occupation du littoral atlantique mauritanien en différentes périodes par ces trois poissons très côtiers, donc fortement affectés par les changements environnementaux et les diverses activités littorales (impacts des ouvrages construits dans cette zone). Il a montré l’existence de divergences dans les préférences de l’occupation des milieux par ces ressources et même leurs tolérances aux conditions climatiques pour l’accomplissement des différentes phases de leurs cycles de vie. On retrouve les adultes des trois espèces, avec des abondances saisonnières très marquées, sur la bande côtière de faible profondeur (moins de 30 m) en déplacement nord - sud pour la reproduction et sud - nord pour l’alimentation. La répartition en fonction du milieu et de l’âge montre une fois encore que les adultes de Liza aurata sont résidants au nord du Banc d’Arguin et dans la baie du Lévrier et n’effectuent que des migrations limitées dans cet espace, tandis que les juvéniles peuvent être emportés par les courants jusqu’à Nouakchott et même à l’embouchure. Quant aux adultes des Mugil cephalus et Mugil capurrii, ils accomplissent intégralement leur cycle de vie en mer et seuls les juvéniles pondus à la proximité du delta du fleuve rentrent dans l’estuaire pour rester environ deux ans et demi avant de regagner définitivement la mer à nouveau. Ce schéma n’exclu pas les possibilités de rencontrer, même accidentellement la L. aurata au bas delta du Sénégal ou bien évidemment les autres espèces dont les déplacements sont fortement liés aux conditions hydroclimatiques. Abstract : In Mauritania there is clear evidence of an overfishing tendency “in series” of high value stocks of Mugilidae; in decreasing degree of importance of the Common Grey Mullet, then the Narrow-head Grey Mullet and finally the Golden Gray Mullet (a species that can be considered as a surrogate species). The intensive exploitation of the Common Grey Mullet which began in 1996, has resulted in the targetting the Narrow-head Grey Mullet since 1998 and more recently the exploitation of the Golden Grey Mullet in 2001. In a time frame of less than seven years, the absence of rational management risks the near complete disapearance of these resources (resources otherwise renewable). To this situation of decreasing yields, which is worsen by the degradation of the coastal zone due to an ever increasing antropic pollution, that this study aims to increase our scientific knowledge of confined systemes, of dilution zones and of population structure (size, age, sex-ratio) and reproduction (spawing areas and season) of the three most targetted Mugils. This study also explains the utilisation strategies of the Mauritanian Atlantic coast during different time periods by these three very coastal fish, which are subjected to environmental changes and diverse coastal activities (impacts of construction in this zone). This study shows the existance of diverging habitat use and tolerances to climatic conditions during the different life cycle phases. We find adults of the three species to have very marqued seasonal abondances, on the shallow coastal band (of less than 30 m) in displacement north-south for reproduction and south-north for feeding. The spacial and age distribution of Liza aurata adults show once again that they are residents of the northern bank of Arguin and of the Bay of Lèvrier and that they undergo limited migrations in this zone. However, the juveniles of this species may be transported by currents as far as Nouakchott incluing the river mouth. In contrats, adults of Mugil cephalus and Mugil capurri undego their entire life cycle at sea with only juveniles spawned in proximity of river deltas entering the estuaries to remain about two and a half years before returning definitevely to the sea. This present schema dosen’t exclude the accidental possibility of finding L. aurata in the lower Senegal delta or in other areas where their displacements are closely linked to hydroclimatique conditions.
    Description: IMROP
    Description: Unpublished
    Description: Aménagement, 〈Mugil cephalus〉 ,〈 Liza aurata〉, 〈 Mugil capurrii〉, Dynamique d’exploitation, Ecobiologie, Reproduction, Mugilidés
    Keywords: Distribution ; Biology ; Legislation ; Reproduction ; Biology ; Distribution ; Ecological distribution ; Exploitation ; Abundance ; Legislation ; Reproduction ; Stock identification ; Zonal distribution
    Repository Name: AquaDocs
    Type: Theses and Dissertations , Master thesis
    Format: 760008 bytes
    Format: 509155 bytes
    Format: 1415534 bytes
    Format: 388171 bytes
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 11
    facet.materialart.
    Unknown
    Alexandria: National Institute of Oceanography and Fisheries
    Publication Date: 2021-05-19
    Description: This journal is published by NIOF, Alexandria, Egypt
    Description: The effect of metrifonate on the immunity of the exposed fish are evaluated through the determination of the antibody titer and mortality rate during the challenge trial. In the chronic toxic exposure to metrifonate by dose 0.17mg/liter for 8 weeks, the more clear signs were darkness of fish color with hemorrhagic patches & loosing of scale at end of the trial the color return to normal. Determination of some blood parameters revealed significant decrease of white blood cell count, as there were lymphopenia and nueutrophilia during the chronic exposure to metrifonate. Phagocytic assay revealed a significant decrease in both phagocytic activity (PA) and phagocytic index(PI).Hypoproteinami hypoglobulinaemia and hypoalbuminaemia were observed. The challenge trial indicted that, the metrifonate decrease the immunity of exposed fish.. The using of biogen“R” as a growth promoter in fish diet minimized the toxicity of metrifonate.
    Description: NIOF
    Description: Published
    Description: Immunosuppressive, Metrifonate, Oreochromis niloticus
    Keywords: Biology ; Biology ; Immunology
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed , Article
    Format: 128656 bytes
    Format: 53690 bytes
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 12
    Publication Date: 2021-05-19
    Description: L’étude du cycle sexuel de l’Anchois montre que la principale période de reproduction s’étend d’avril à octobre. Celle-ci serait sous la dépendance principale de l’élévation de la température de surface. La croissance, abordée à l’aide des marques supposées journalières sur les otolithes, donne des résultats jugés satisfaisants jusqu’à 10 cm L.F. Par contre, ceux concernant les tailles supérieures devront être confirmés.
    Description: IMROP
    Description: Published
    Description: Anchois, Reproduction, Biologie, Croissance, Cycle sexuel, Otolithes, Engraulis encrasicolus
    Keywords: Growth ; Otoliths ; Biology ; Sexual maturity ; Sexual reproduction ; Biology ; Growth ; Otoliths ; Sexual maturity ; Sexual reproduction
    Repository Name: AquaDocs
    Type: Refereed , Article
    Format: 1044342 bytes
    Format: 741617 bytes
    Format: 600783 bytes
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 13
    Keywords: Bioinformatics ; Biology ; Data processing ; Biotechnology ; Computer software ; Data structures (Computer science) ; Genetic engineering
    ISBN: 9782287339097
    Language: English
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 14
    Unknown
    Dordrecht : Springer
    Keywords: Biology ; Data processing ; Biomedical engineering ; Chemistry
    ISBN: 9781402035876
    Language: English
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 15
    Publication Date: 2021-05-19
    Description: Etude réalisée dans le cadre des activités de recherche de l’Institut National des Sciences et Technologies de la Mer (INSTM)
    Description: Unpublished
    Keywords: Répartition sexuelle ; Thon rouge ; Biométrie morphologique ; Scombridés ; Ressources pélagiques ; Biologie ; Pelagic fish ; Biology ; Biometrics
    Repository Name: AquaDocs
    Type: Theses and Dissertations , Master thesis
    Format: 2291528 bytes
    Format: 1348297 bytes
    Format: 2113072 bytes
    Format: 4231912 bytes
    Format: 284744 bytes
    Format: 2552779 bytes
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 16
    facet.materialart.
    Unknown
    Alexandria: NIOF
    Publication Date: 2021-05-19
    Description: In a second study of electromicroscopic analysis of ultrastructural organelles of coho salmon muscle showed a significant increase in lipid droplet density in the largest stages compared with the smallest fish. The opposite was observed with the mitochondria where its density decreased in the large sized fish. An apparent decrease in capillary density with increasing body mass was also observed. These finding may imply a possible additional role of lipid depot as fish grew from parr to smolt.
    Description: Published by NIOF, Alexandria
    Description: Published
    Keywords: Ultrastructure ; Cohosalmon ; Lipid droplets ; Salmon ; Biology ; Fish
    Repository Name: AquaDocs
    Type: Journal Contribution , Non-Refereed , Article
    Format: 5918970 bytes
    Format: 49546 bytes
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 17
    Publication Date: 2021-05-19
    Description: Study of microscopic structural changes of red and white muscle of coho salmon, Oncorhynchus kisutch, through different developmental stages and through transition from parr to smolt revealed developmental variation in fibre size where white fibres were larger than red ones. The increase in fibre area, characterizing all stages of development, was associated with reduction in both fibre and capillary densities. In large fish the reduction in red muscle capillary density was 10 fold lesser than that of white muscle.
    Description: Published by NIOF, Alexandria
    Description: Published
    Keywords: Oncorhynchus kisutch ; White fibres ; Red fibres ; Biology ; Salmon ; Biology ; Fish
    Repository Name: AquaDocs
    Type: Journal Contribution , Non-Refereed , Article
    Format: 575920 bytes
    Format: 44785 bytes
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 18
    Publication Date: 2021-05-19
    Description: Il y a des annexes
    Description: Résumé : La biologie de la langouste rose des côtes mauritaniennes est aujourd’hui bien connue. Nous avons cependant rappelé les traits marquants. Sur le plan de la pêche, de 1963 à 1988, le stock de la langouste rose a connu trois phases d’exploitation. Après une phase de surexploitation entre 1963 et 1970-1971, le stock de langouste rose de Mauritanie a pu se reconstituer grâce à une réduction importante du nombre de langoustiers. Ceci c’est traduit à partir de 1971 par une augmentation sensible des captures et aussi de la PUE. Mais le dédoublement du nombre de ces derniers en 1987 et 1988 a fait chuter les P.U.E de 50% ce qui est un signe d’effondrement du stock à nouveau.
    Description: Abstract : Biology of Mauritanian pink lobster is known. However we presented some important aspects of specie’s biology. On fisherie’s plan, between 1963 and 1988, the stock of Mauritanian pink lobster went through three phases of exploitation. Like this, after an over exploitation phase between 1963 and 1970-1971. The stock of the pink lobster of Mauritania was reconstituted little by little owing to an important reduction enabled a significant increase in the number of catches and the C.P.U.E. But doubling in the number of beats in 1987 and 1988 reduced the C.P.U.E. by 50%, which again contributed to the breaking down of stock.
    Description: IMROP
    Description: Published
    Keywords: Pêche ; Etat des stocks ; Mauritanie ; Biologie ; Fishing ; Langouste rose ; Biology ; Palinurus mauritanicus ; Mauritania ; Status of stocks ; Pink lobster ; Lobster culture
    Repository Name: AquaDocs
    Type: Journal Contribution , Non-Refereed , Article
    Format: 289877 bytes
    Format: 579974 bytes
    Format: 570207 bytes
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 19
    Publication Date: 2021-05-19
    Description: Thèse pour l’obtention du grade de Docteur de l’Université de Bretagne Occidentale spécialité océanologie biologique
    Description: RESUME: Les eaux océaniques mauritaniennes sont au carrefour d'eaux froides et salées provenant du Nord, et d'autres chaudes et moins salées du Sud. L'interaction de ces eaux est à l'origine d'un régime hydrologique à 4 saisons: une saison froide de janvier à mai, une saison de transition froide-chaude de juin à juillet, une saison chaude d'août à octobre et enfin une saison de transition chaude – froide de novembre à décembre. La présente étude met en relation ces variations hydrologiques saisonnières, la distribution et la biologie de Mustelus mustelus. La distribution spatiale et temporelle de M. mustelus sur le plateau continental mauritanien a été suivie en analysant les données récoltées au cours de 20 campagnes de prospections scientifiques, 13 hauturières et 7 côtières, réparties sur les 4 saisons hydrologiques qui caractérisent cette zone géographique. La population d'émissoles est concentrée au Nord du Cap Timiris. L'espèce ne semble pas effectuer de migration latitudinale, mais un déplacement côte - large et inversement a été mis en évidence. Durant la saison froide, cette espèce à affinité tropicale est repoussée vers la côte, dans la Baie du Lévrier et le Nord Est du Banc d'Arguin par les basses températures venant du Nord qui persistent sur le plateau continental mauritanien de janvier à mai. Ce sont surtout les mâles matures qui rejoignent alors, pour l'accouplement, les femelles, de distribution plus côtière. Entre juin et octobre, avec le réchauffement des eaux, les mâles commencent à se déplacer vers des eaux plus profondes. Mais dès le début du refroidissement, un nouveau mouvement vers la côte s'amorce. Un échantillonnage mensuel des débarquements de la Pêche Artisanale a permis de collecter, en 2 ans, 2510 séries de données individuelles exploitées pour les études de l'alimentation, de la reproduction et de la croissance. L'étude des contenus stomacaux n'a pas montré de différence significative entre les femelles et les mâles, l'analyse a été faite sans distinction des sexes. Le nombre d'estomacs vides est de 10,3 % des estomacs examinés. La distribution Nord de M. mustelus pourrait être liée à l'abondance des principales proies de l'espèce, les bernard-l'hermites (Anomoures). En effet, ces proies qui seraient abondantes dans sa zone de répartition sont dominantes aussi bien en termes de nombre que de poids et d'occurrence dans les contenus des estomacs examinés. Les proies secondaires sont des Poissons, des Mollusques et des Annélides. Ainsi, l'émissole serait une espèce opportuniste qui se nourrit principalement de proies les plus vulnérables et accessoirement de proies de capture plus difficiles. L'étude du régime alimentaire chez l'émissole lisse en Mauritanie témoigne d'un comportement en rapport étroit avec le fond. La distribution différentielle des deux sexes influence le sex ratio qui est en faveur des femelles dans la zone côtière et des mâles dans la zone hauturière. La taille de première maturité sexuelle de M. mustelus en Mauritanie est de 67 cm pour les mâles et 72 cm pour les femelles. Chez les femelles, l'activité vitellogénique est continue et dure toute l'année chez les femelles matures (y compris gestantes) sauf en période de fécondation, période pendant laquelle elle est arrêtée. Le nombre d'ovocytes vitellogèniques de grand diamètre (supérieur ou égal à 10 mm) atteint un maximum en mai dans l'unique ovaire droit présent chez les émissoles lisses. La chute de leur nombre dans l'ovaire en juin et juillet annonce l'ovulation. Les mâles s'accouplent avec les femelles entre janvier et mai; les spermatozoïdes sont alors stockés dans le tiers inférieur des glandes nidamentaires jusqu'à la période de fécondation (juillet-août). L'organogenèse dure jusqu'aux mois d'octobre – novembre; elle aboutit alors à des embryons qui ressemblent morphologiquement aux adultes, au-delà de ces mois, le développement embryonnaire se limite à une augmentation de taille et de poids. Les embryons sortent de leurs capsules, les réserves vitellines se résorbent et sont remplacées par le placenta. Chez les femelles, la durée de la gestation est de 7 à 10 mois. Les femelles commencent à mettre bas à partir de février, la parturition se poursuit jusqu'en juin, mois pendant lequel les rares femelles encore gestantes mettent bas. A la naissance les juvéniles ont des tailles comprises entre 240 et 320 mm. La fécondité utérine maximale observée au cours de cette étude est 13 embryons; la moyenne est de 4 embryons par portée. Les bandes de croissances observées dans des coupes de vertèbres de femelles de 45 à 99 cm et de mâles de 50 à 85 cm de longueur totale ont été utilisées pour l'estimation de l'âge des poissons. Les données d'âge et de longueur ont permis d'établir les équations de croissances selon les modèles de Von Bertalanffy et de Holden. Ces modèles conduisant à des résultats différents; celui de Von Bertalanffy a été retenu en raison de sa flexibilité qui rend son application plus courante dans les pêcheries. Les paramètres de ce modèle sont, pour les femelles K=0,21, L∞=113,4 et t0=-2,03, pour les mâles K=0,26; L∞=91,3 et t0= -2,43. Les femelles ont donc des croissances plus rapides que les mâles et les âges à la première maturité sexuelle sont de 2,6 ans pour les mâles et de 2,8 pour les femelles. #
    Description: ABSTRACT: Mauritanian coastal waters are crossroads between cold and salted northern waters, and warmer and less salted southern waters. The interaction of these waters is at the origin of four hydrological seasons: cold (January to May), cold-to-warm transition (June-July), warm (August to October) and warm-to-cold transition (November-December). The present study connects these seasonal hydrological variations with the distribution and biology of Mustelus mustelus. Spatial and temporal distribution of M. mustelus on the Mauritanian continental shelf was followed while analyzing data collected during 20 scientific campaigns, 13 deep-sea and 7 coastal, distributed over the 4 hydrological seasons which characterize this geographical area. Smoothound sharks population is concentrated North of Cape Timiris. The species does not seem to carry out of latitudinal migration, but a coast to deep sea displacement - and conversely a deep sea to coast - was found. During the cold season, this species with tropical affinity is pushed back towards the coast, in Baie du Lévrier and Northeast of the Banc d’Arguin by cold water temperatures coming from the North which persist on the Mauritanian continental shelf from January to May. Mature males then join, for the coupling, females, which are of more coastal distribution. Between June and October, with the reheating of water, males start to move towards deeper water. But from the very start of cooling, a new movement towards the coast starts. A monthly sampling of the artisanal fishery catches made it possible to collect, in 2 years, 2,510 individual specimen data for the study of food, reproduction and growth. The study of stomach contents did not show a significant differences between females and males. The analysis was made regardless of gender. The number of empty stomachs is 10,3 % of the examined stomachs. The Northern distribution of M. mustelus could be related to the abundance of the principal prey species, the hermit crab (Anomoura). Indeed, these preys which would be abundant in its zone of distribution are dominant in terms of number, biomass and occurrence in the contents of the examined stomachs. The secondary preys are of fish, molluscs and annelids. Thus, smoothound shark would be an opportunist species which feeds mainly on the most vulnerable preys and incidentally on more difficult preys of capture. The study of the smoothound shark diet in Mauritania testifies to a behavior in close connection with the bottom. The differential distribution of the two sexes influences the sex ratio which is in favor of females in the coastal zone and males in the deep-sea zone. Size at first sexual maturity of M. mustelus in Mauritania is 67 and 72 cm for males and females, respectively. For females, the vitellogenic activity is continuous year-round for mature females (including gestating ones), except during the period of fecundation. The number of vitellogenic ovocytes of large diameter (greater or equal to 10 mm) reaches a maximum in May in the single right ovary of the smoothound shark. The fall of their number in June and July announces ovulation. Males couple themselves with females between January and May; spermatozoids are then stored in the nidamental glands lower third until the period of fecundation (July-August). Organogenesis lasts until October - November; it then leads to embryos which resemble to the adults morphologically. Afterwards, the embryonic development is limited to an increase in size and weight. The embryos leave their capsules, vitellogenic reserves reabsorb and are replaced by the placenta. Gestation period is 7 to 10 months for females. The females start to put low as from February, parturition continues until June, month during which the rare still gestating females give birth. With birth the youthful ones have sizes ranging between 240 and 320 mm. The maximum observed fecundity during this study is 13 embryos; the average is of 4 embryos per litter. Growth bands observed in cuts of vertebrae on females and males of total length ranging from 45 to 99 cm and from 50 to 85 cm, respectively, were used to estimate fish age. Age and length data made it possible to establish growth equations according to Von Bertalanffy and Holden’s models. These models lead to different results; Von Bertalanffy model was retained because of its flexibility which makes its application more current in fisheries. The parameters of this model are K=0.21, L∞=113.4 for females and t0= -2.03, and K=0.26 L∞=91.3 and t0 = -2.43 for males. The females tend to grow faster than males and the age at the first sexual maturity is 2.6 and 2.8 years for males and females, respectively.
    Description: IMROP
    Description: Unpublished
    Keywords: Mauritania ; Croissance ; Biologie ; Biology ; Physical environment ; Mauritanie ; Ecology ; Fecundity ; Growth ; Emissole lisse ; Alimentation ; Smouthound shark ; Mustelus mustelus ; Fécondité ; Reproduction ; Milieu physique ; Ecologie ; Distribution ; Shark fisheries
    Repository Name: AquaDocs
    Type: Theses and Dissertations , Master thesis
    Format: 590258 bytes
    Format: 258762 bytes
    Format: 363146 bytes
    Format: 366462 bytes
    Format: 244523 bytes
    Format: 566375 bytes
    Format: 290251 bytes
    Format: 369083 bytes
    Format: 371620 bytes
    Format: 268691 bytes
    Format: 189212 bytes
    Format: 260731 bytes
    Format: 400881 bytes
    Format: 515266 bytes
    Format: 169101 bytes
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 20
    facet.materialart.
    Unknown
    CNROP - AtlantNIRO -MEIPP-sa, 2001 plaquette de vulgarisation
    Publication Date: 2021-05-19
    Description: Le présent prospectus donne une courte caractéristique biologique des principales espèces pêchées dans la Zone Economique Exclusive Mauritanienne et des engins utilisés pour la pêche, ainsi que les informations relatives à leur composition chimique, à la valeur nutritive de la matière première, et à ses caractéristiques avec les possibilités de sa transformation en différents produits. Les informations présentées pourront être utiles aux producteurs pour le choix de la matière première et des possibilités de sa valorisation
    Description: IMROP / AtlantNIRO / MEIPP-sa
    Keywords: Fishery resources ; Valorisation produits ; Composition chimique ; Biologie ; Ressources halieutiques ; Biology ; Valeur nutritive ; Fish processing ; Transformation des produits ; Engins de pêche ; Food value ; Fishing gear ; Fish species ; Processing fishery products
    Repository Name: AquaDocs
    Type: Other
    Format: 5190937 bytes
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 21
    Publication Date: 2021-05-19
    Description: L’étude porte sur l’exploitation, la biologie et la dynamique du poulpe (Octopus vulgaris, Cuvier) des eaux mauritaniennes. La répartition spatio-temporelle dans la région du Cap Blanc ne semble être liée ni à la taille, ni au sexe, mais varie au cours de l’année. L’analyse de l’état actuel de la pêcherie basée sur les congélateurs céphalopodiers met en évidence une augmentation de l’effort de pêche et la poursuite de chute des p.u.e. La composition des captures révèle une progression du pourcentage des individus de poids inférieur à 200 grammes (« poulpo »). L’étude biologique montre qu’il existe deux saisons de reproduction par an (mai-juillet et septembre-novembre) qui engendrent deux recrutements, l’un en mai et l’autre à partir de septembre. La croissance pondérale a été obtenue sur les des distributions de fréquences de poids. Une transformation des poids en longueurs a permis de déterminer les paramètres de l’équation de VON BERTALANFFY pour chaque cohorte. Après détermination des coefficients de mortalité naturelle et par pêche, les résultats obtenus par le modèle global et le modèle de RICKER sont discutés. La mise en œuvre d’un modèle global montre que le niveau actuel des captures est proche de la prise maximale équilibrée et que l’effort de pêche ne doit pas être augmenté. //
    Description: This study deals with the exploitation, the biology and the dynamics of common octopus (Octopus vulgaris, Cuvier) in Mauritanian waters. In the Cap Blanc region, the spatio-temporal distribution appears to be independent of the length and sex but variable through the year. The analysis of the present state of the fishery reveals an increase of the fishing effort and continuous decrease of the catch per unit effort. An increase of the small individuals, with weight under 200 g (“poulpo”), can be seen from catches composition. The biological study shows that there are two spawning seasons (May-July and September-November) which allow two recruitments in May and September. The growth parameters of the VON BERTALANFFY equation are calculated from the transformed weights in lengths. The calculated mortality coefficients are used in a RICKER’s model of yield per recruit and the results are discussed. The use of a generalized production model shows that the present catch is very close to the maximum sustainable yield. Therefore, one would aware to prevent an increase of the fishing effort.
    Description: IMROP
    Description: Unpublished
    Keywords: Reproduction ; Common octopus ; Population dynamics ; Environnement ; Dynamique de population ; Exploitation ; Environment ; Poulpe ; ZEE Mauritanienne ; Distribution ; Mauritanian Exclusive Economic Zone ; Biologie ; Croissance ; Growth ; Octopus vulgaris ; Biology ; Octopus fisheries
    Repository Name: AquaDocs
    Type: Theses and Dissertations , Master thesis
    Format: 118750 bytes
    Format: 225579 bytes
    Format: 214223 bytes
    Format: 133209 bytes
    Format: 283528 bytes
    Format: 300477 bytes
    Format: 671556 bytes
    Format: 198088 bytes
    Format: 549732 bytes
    Format: 143768 bytes
    Format: 858590 bytes
    Format: 210451 bytes
    Format: 255821 bytes
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 22
    facet.materialart.
    Unknown
    American Association for the Advancement of Science (AAAS)
    Publication Date: 2005-12-24
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉New York, N.Y. -- Science. 2005 Dec 23;310(5756):1880-5.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/16373539" target="_blank"〉PubMed〈/a〉
    Keywords: Astronomical Phenomena ; Astronomy ; Biology ; Brain/growth & development ; Brain Diseases/genetics ; Climate ; Earth (Planet) ; Evolution, Planetary ; Humans ; Nuclear Reactors ; Plant Development ; Plants/genetics ; Potassium Channels ; *Research ; Systems Theory
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2337-2350 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hetero-π-Systems, 7. SilabenzeneFlash pyrolysis of silacyclohexadiene derivatives 5k, 5m, and 7b yields silabenzene (1), which can be isolated in an argon matrix at 10 K. 1 exhibits characteristic IR and UV spectra. By photoexcitation a mutual interconversion between silabenzene (1) and dewarsilabenzene (2) can be achieved.
    Notes: Durch Kurzzeitpyrolyse der drei Silacyclohexadien-Derivate 5k, 5m und 7b läßt sich Silabenzol (1) erzeugen und in einer Argonmatrix bei 10 K isolieren. 1 zeichnet sich durch charakteristische IR- und UV-Spektren aus. Mittels photochemischer Anregung ist eine gegenseitige Umwandlung zwischen Silabenzol (1) und Dewarsilabenzol (2) zu erreichen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2452-2463 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemistry of 1,3,5-TristyrylbenzeneDepending on the reaction conditions the irradiation of the title compound 1 yields the cyclophane 5, the pyrene derivative 6, or the polycondensed aromatic system 9. An X-ray analysis was performed for 5, representing a new type of cyclophane in which two benzene rings are bridged again by rings.
    Notes: In Abhängigkeit von den Reaktionsbedingungen erhält man bei der Belichtung der Titelverbindung 1 das Cyclophan 5, das Pyrenderivat 6 oder das polykondensierte aromatische System 9. Für den neuen Cyclophantyp 5, bei dem zwei Benzolringe selbst wieder durch Ringe verbrückt sind, wurde eine Röntgenstrukturanalyse durchgeführt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2469-2478 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclopropenes as Complex Ligands: η4-Vinylketene Complexes of Manganese, Vanadium, and Cobalt; Preparative and X-ray Crystallographic ResultsThe reaction of 1,2,3-triphenylcyclopropene with (η5-C5H5)Mn(CO)3, (η5-C5H5)V(CO)4, (η5-C5H5)Co(CO)2 and Co2(CO)8 yields via ring opening and carbonylation the new compounds LMn(C5H5)CO (1), LV(C5H5)(CO)2 (2), LCo(C5H5) (3, 4) and L2Co2(CO)4 (6) (L = η4-C3Ph3HCO), respectively. In the reaction with (η5-C5H5)Co(CO)2 additionally the formation of 2,3-diphenylindenone (5) is observed. The X-ray structures of 1, 3 and 5 have been determined.
    Notes: Die Umsetzung von 1,2,3-Triphenylcyclopropen mit (η5-C5H5)Mn(CO)3, (η5-C5H5)V(CO)4, (η5-C5H5)Co(CO)2 und Co2(CO)8 ergibt unter Ringöffnung und Carbonylierung die neuen Verbindungen LMn(C5H5)CO (1), LV(C5H5)(CO)2 (2), LCo(C5H5) (3, 4) bzw. L2CO2(CO)4 (6) (L = η4-C3Ph3HCO). Bei der Reaktion mit (η5-C5H5)Co(CO)2 wird außerdem die Bildung von 2,3-Diphenylindenon (5) beobachtet. Die Röntgenstrukturen von 1, 3 und 5 wurden bestimmt.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2495-2503 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 1401). Boron, Aluminium, and Gallium Halide Adducts of a Tetraaminodiboron CompoundThe tetraamino diboron compound 1 adds trihalides EX3 (E = B, Al, Ga, X = Cl, Br, I) to yield 1:1- and 1:2-coordination compounds. The BBr3 adduct 1b is thermally stable and shows nonfluxional behaviour in solution in contrast to the AlCl3 and GaCl3 adducts. The 1:2 adducts are nonfluxional and, according to NMR spectra, only the meso-form is present. The structure of the 1:1-adducts was ascertained by an X-ray structure determination of 1g. The single crystal contained R configurated molecules. A change from planar to the envelope conformation of the diazaborolidine ring occurs on adduct formation.
    Notes: Die Tetraaminodibor-Verbindung 1 lagert die Trihalogenide EX3 (E = B, Al, Ga; X = Cl, Br, I) zu 1:1- bzw. 1:2-Koordinationsverbindungen an. Von diesen zeigt nur das thermisch stabilere BBr3-Addukt 1b in Lösung im Gegensatz zu den AlCl3- und GaCl3-Addukten kein fluktuierendes Verhalten. Die 1:2-Addukte sind starr, und nach NMR-Spektren bildet sich nur die meso-Form. Die Struktur der 1:1-Addukte wurde durch Röntgenstrukturanalyse von 1g gesichert; die Einkristalle enthielten ein R-konfiguriertes Molekül. Durch die Addition nimmt der sonst planare Diazaborolidin-Ring Briefumschlag-Konformation an.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2504-2509 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 1411). Unexpected Formation of a Bis(amino)borane: Synthesis and Structure of Bis(benzyl-tert-butylamino)boraneThe reaction of BCl3 with 3 molar equivalents of lithium benzyl-tert-butylamide produces the bis(amino)borane 2 in 29% yield. According to an X-ray structure determination the compound crystallizes in the monoclinic system, space group C2/c, and the molecule possesses almost C2 symmetry. The mean BN bond lenght is 142 pm, and the C2N planes are twisted by an average of 23.8° versus the HBN2 plane.
    Notes: Die Umsetzung von BCl3 mit 3 mol Lithium-benzyl-tert-butylamid liefert mit 29% Ausbeute das Bis(amino)boran 2. Nach Röntgenstrukturanalyse der monoklin in der Raumgruppe C2/c kristallisierenden Verbindung besitzt das Molekül nahezu C2-Symmetrie. Der durchschnittliche BN-Abstand beträgt 142 pm, und die C2N-Ebenen sind gegen die HBN2-Ebenen um durchschnittlich 23.8° verdrillt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 28
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2479-2494 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 139. Addition Compounds of Alkylhalogenoboranes with 1,3,2-Diazaborolidines: Structure, Stability, and Exchange ReactionsReactions of alkylhalogenoboranes RnBX3 - n (n = 0 - 2) with the 1,3-dimethyl-1,3,2-diazaborolidines 1 - 4 yield stable 1:1 addition compounds 1a - e, 2a, 3a - d, 4a irrespective of the boron substituents. Coordination of the borane moiety occurs at a ring N atom. An X-ray structure determination of the BCl3-adduct 3a shows two enantiomers in the asymmetric unit, envelope ring conformation, and strong π-bonding between the non-coordinated B an N atoms. - Equilibria of the 1:1 adducts with their ring cleavage products and their behaviour towards a second mol of BX3 was studied. In this case, replacement of the ring-BR group occurs. In contrast, haloboranes react with the 2-(dimethylamino)diazaborolidine 5 with R2N-substituent exchange while diborane yields in the first instance the (dimethylamino)borane adduct 5a.
    Notes: Umsetzungen von Alkylhalogenboranen RnBX3 - n (n = 0 - 2) mit den 1,3-Dimethyl-1,3,2-diazaborolidinen 1 - 4 führen unabhängig vom Bor-Substituenten zu stabilen 1:1-Additionsverbindungen 1a - e, 2a, 3a - d, 4a, wobei die Koordination über ein N-Atom des Fünfrings erfolgt. Die Röntgenstrukturanalyse des BCl3-Addukts 3a zeigt zwei enantiomere Formen in der asymmetrischen Einheit, “envelope”-Ringkonformation und eine starke π-Rückbindung des Ringbors zum nicht koordinierten Stickstoff. - Gleichgewichte der 1:1-Additionsverbindungen mit ihrem Ringöffnugsprodukt sowie ihr Verhalten gegenüber einem zweiten mol Lewis-Säure wurden untersucht. Hierbei wird die Ring-BR-Gruppe verdrängt. Im Gegensatz dazu tauscht das 2-(Dimethylamino)diazaborolidin 5 mit Halogenboranen den R2N-Substituenten aus, während die Umsetzung mit Diboran zunächst ein wenig stabiles (Dimethylamino)boran-Addukt 5a liefert.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 29
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2527-2530 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal Ketene Compounds, XXII. Anionic η2-Ketenyl Complexes of Molybdenum and TungstenAnionic η2-ketenyl complexes [NR4′]{η5-C5H5(CO) (CN)M[η2-O=C=C—R]} [M = molybdenum: 3a, b; M = tungsten: 4a - c] are formed by ligand substitution on neutral η2-ketenyl compounds as well as by reaction of dicarbonyl(η5-cyclopentadienyl)carbyne complexes with tetraalkylammonium cyanides.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 30
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminyl Oxides (Nitroxides), XXXV. The Tricyclic Dimer of a Vinyl Aminyl Oxide (Vinyl Nitroxide) and its Isomerization to give a 2,4,7,9-Tetraoxa-5,10-diazatetracyclo[4.4.2.03,12.08,11]dodecaneVinyl aminyl oxide 6 is formed by oxidation of hydroxylamine 3 via the intermediates 4 and 5. Dimerization of 6 yields the tricyclic compound 8. In solution dissoziation of 8 occurs at approximately 40°C, four bonds being cleaved to afford radical 6. By prolonged heating in various solvents as well as by proton catalysis at room temperature 8 is rearranged to give the tetracyclic isomer 9, the structure of which has been confirmed by X-ray analysis.
    Notes: Das Vinylaminyloxid 6 entsteht bei der Oxidation des Hydroxylamins 3 über die Zwischenstufen 4 und 5. 6 dimerisiert unter Bildung der tricyclischen Verbindung 8. 8 dissoziiert in Lösung bereits bei etwa 40°C unter Spaltung von vier Bindungen in das Radikal 6. Durch längeres Erhitzen in verschiedenen Lösungsmitteln, aber auch unter Protonenkatalyse bei Raumtemperatur, wird 8 in ein tetracyclisches Isomeres 9 umgewandelt. Die Struktur von 9 wurde durch Röntgenstrukturanalyse ermittelt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 32
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1-22 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 3-Metalated Enamines, X. Formation and Reactivity of 1-(Diethoxyphosphoryl)-1-(dimethylamino)allyl Anions1-Phosphorylenamines 8 and 10 react regio- and stereoselectively after deprotonation as anions 8A and 10A with silylating and alkylating reagents to give homologous (E)-1-phosphorylenamines 13, 15, 19 - 32. These can be hydrolyzed to give the corresponding carboxylic acids alkylated at C-3. Deprotonation of 10 occurs always on the methyl group cis to the phosphoryl group. The primarily formed anion isomerizes rapidly about the C-1 - C-2 bond. The highly regio- and stereoselective deprotonation allows the controlled introduction of up to three different alkyl groups. The results of NMR spectroscopic investigations of 8A and 10A are discussed.
    Notes: Die 1-Phosphorylenamine 8 und 10 reagieren nach Deprotonierung als Anion 8A und 10A regio-und stereoselektiv mit Silylierungs- und Alkylierungsmitteln zu homologen (E)-1-Phosphorylenaminen 13, 15, 19 - 32. Diese lassen sich zu den entsprechenden in 3-Stellung alkylierten Carbonsäuren hydrolysieren. Bei 10 erfolgt die Deprotonierung stets an der zur Phosphorylgruppe cis-ständigen Methylgruppe. Anschließend isomerisiert das primär gebildete Allyl-Anion rasch um die C-1 - C-2-Bindung. Diese hohe Regio- und Stereoselektivität der Deprotonierung gestattet die gezielte Einführung von bis zu drei verschiedenen Alkylgruppen. Die Ergebnisse der NMR-spektroskopischen Untersuchung von 8A und 10A werden diskutiert.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 33
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2839-2849 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chromoionophores, 51). Chromoionophores with Azulene Units as Chromophores and π-Donor ComponentsThe synthesis and spectroscopic investigation of a series of new chromoionophores with azulene as chromophore and of suitable reference compounds are described. Cations complexed by the ionophore influence the chromophore, causing downfield shifts in the 1H NMR spectra and ion-selective changes in the absorption spectra. It is concluded that the chromophore can interact with the cations via carboxylic oxygen atoms or directly via the π-electrons of the azulene unit. Crystalline complexes of the azulene ligands 6 and 7 with alkali and alkaline-earth metal salts are synthesized. The geometry of the 7 · KSCN complex is examined by X-ray structure analysis.
    Notes: Synthese und spektroskopische Untersuchung einer Reihe von neuen Chromoionophoren mit Azulen als Farbträger und von geeigneten Vergleichsverbindungen werden beschrieben. Die Beeinflussung des Chromophors durch im Ionophorteil komplexierte Kationen verursacht in Lösung 1H-NMR-Tieffeldverschiebungen und ionenselektive Veränderungen in den Elektronenspektren. Daraus wird gefolgert, daß der Chromophor über Carboxyl-Sauerstoffatome oder direkt über die π-Elektronen des Azulens mit den Kationen in Wechselwirkung treten. Kristalline Komplexe der Azulen-Liganden mit Alkali- und Erdalkalimetallsalzen werden hergestellt. Die Geometrie des 7 · KSCN-Komplexes wird durch Röntgenstrukturanalyse ermittelt.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 34
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2875-2885 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Unsaturated Aldehyde Dimethylhydrazones with Electrophilic ReagentsCrotonaldehyde dimethylhydrazone (1) is substituted at C-3 by electrophiles such as chlorine, bromine, iodine, arylsulfenyl chloride, phenylsulfinyl chloride, and nitronium tetrafluoroborate to form the products 10a  -  c, 18a, b, 25, and 26. In contrast, from 1 and p-nitrobenzoyl chloride the dienehydrazide 3 is obtained. Acrolein dimethylhydrazone reacts with diazoacetic ester to give the cyclopropane derivative 29. Isoxazole 32 is obtained from 28 and p-chlorobenzonitrile oxide.
    Notes: Crotonaldehyd-dimethylhydrazon (1) wird durch elektrophile Reagenzien wie Chlor, Brom, Iod, N-Chlorsuccinimid, Arylsulfenylchlorid, Phenylsulfinylchlorid oder Nitryl-tetrafluoroborat and C-3 unter Bildung der Produkte 10a  -  c, 18a, b, 25 und 26 substituiert. Bei Einwirkung von p-Nitrobenzoylchlorid auf 1 erhält man dagegen das Dienhydrazid 3. Acrolein-dimethylhydrazon (28) reagiert mit Diazoessigester zum Cyclopropanderivat 29, mit p-Chlorbenzonitriloxid zum Isoxazolin 32.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 35
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2886-2899 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Partially Substituted Tetrazenes (Me3E)nN4H4 - n (E = Si, Ge, Sn): Preparation, Characterization, and Thermolysis1)Partially substituted tetrazenes (Me3E)nN4H4 - n (E = Si, Ge, Sn) can be prepared by protolysis of higher substituted tetrazenes (Me3E)oN4H4 - o (O 〉 n) or by silylation, germylation, or stannylation of lower substituted tetrazenes (Me3E)mN4H4 - m (m 〈 n). The obtained tetrazenes (Tab. 1) are colorless compounds; they have 2-tetrazene constitution, and trans-tetrazene configuration. The tetrazene (Me3Si)2N  -  N = N  -  NHX (X = H or GeMe3) isomerize by heating in dilute solution into (Me3Si)XN  -  N = N  -  NH(SiMe3). The thermolysis of (Me3Si)2N  -  N = N  -  NH(SiMe3) leads mainly to Me3SiN3 and (Me3Si)2NH (t140°C1/2140°C = 3/4 h), of (Me3Si)2N  -  N = NH2 to Me3SiN3 and Me3SiNH2 (concentrated solution; t140°C1/240°C ca. 1/4 h), and of (Me3Si)HN  -  N = N  -  NH(SiMe3) to N2 and (Me3Si)2N  -  NH2 (dilute solution; t140°C1/2140°C 〉 1 h) or to NH3 and (Me3Si)2NH (concentrated solution; t140°C1/2 〈 1 h).
    Notes: Teilsubstituierte Tetrazene (Me3E)nN4H4 - n (E = Si, Ge, Sn) können durch Protolyse höher substituierter Tetrazene (Me3E)oN4H4 - o (O 〉 n) oder durch Silylierung, Germylierung bzw. Stannylierung niedriger substituierter Tetrazene (Me3E)mN4H4 - m (m 〈 n) dargestellt werden. Die gewonnenen Tetrazene (Tab 1) sind farblose Verbindungen: sie haben 2-Tetrazen-Konstitution und trans-Tetrazen-Konfiguration. Die Tetrazene (Me3Si)2N  -  N = N  -  NHX (X = H oder GeMe3) isomerisieren sich in verdünnter Lösung beim Erhitzen in (Me3Si)XN  -  N = N  -  NH(SiMe3). Die Haupttermolyse von (Me3Si)2N  -  N = N  -  NH(SiMe3) führt zu Me3SiN3 und (Me3Si)2NH (t140°C1/2140°C = 3/4 h), von (Me3Si)2 (Me3Si)2N  -  N = NH2 zu Me3SiN3 und Me3SiNH2 (konzentrierte Lösung; t140°C1/240°C ca. 1/4 h) und von (Me3Si)HN  -  N = N  -  NH(SiMe3) zu N2 und (Me3Si)2N  -  NH2 (verdünnte Lösung; t140°C1/2140°C 〉 1 h) oder zu NH3t140°C und (Me3Si)2NH (Konzentrierte Lösung; t140°C1/2140°C 〈 1 h).
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 36
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2900-2909 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Assignment of Configuration of Larger Bicyclo[n.1.0]alkyl Amines: The Hexahydro-1-azepinyl Residue as „Stereo Indicator“The temperature dependency of the 1H NMR spectra of the hexahydro-1-azepinylbicyclo[9.1.0]-dodecanes 3a  -  f is investigated. The ΔG≠-values of the hexahydroazepine dynamics permit an easy assignment of the endo-amino configuration in 3a  -  f. Starting from 3a, which is synthesized via the enaminosulfonium salt 7, the derivatives 3b  -  f are obtained by nucleophilic substitutions. Normally the cis-configuration of the bicyclo system is not changed during these reactions. However, reaction of the cis-compound 3a with hexahydroazepine leads either to a cis-aminal 3e or to a trans-aminal 4e depending on the conditions of the reaction.
    Notes: Die aus der Temperaturabhängigkeit der 1H-NMR-Spektren der Hexahydro-1-azepinylbicyclo [9.1.0]dodecan-Derivate 3a  -  f ermittelten ΔG≠-Werte der Hexahydroazepinyl-Dynamik ermöglichen eine einfache Festlegung der endo-Amino-Konfiguration. Die Verbindungen 3b  -  f werden aus 3a über eine Folge nucleophiler Substitutionen erhalten; 3a ist über das Enaminsulfonium-Salz 7 zugänglich. Normalerweise bleibt die cis-Konfiguration des Bicyclosystems bei den Substitutionen erhalten. Jedoch führt die Umsetzung der cis-Verbindung 3a mit Hexahydroazepin  -  abhängig von den Reaktionsbedingungen  -  zu einem cis-Aminal 3e oder einem trans-Aminal 4e.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 37
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2910-2927 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Aminobicyclo[n.1.0]alkanes, I Thermolysis of Aminobicyclo[n.1.0]alkanes with a Dimedone MoietyFrom the bicyclic aminals 4 and dimedone (5) derivatives 6 are obtained, which give different types of products upon thermolysis depending on the ring size of the bicyclus. The bicycloheptane and -octane compounds 6b, c lead to diacylated enamines 8b, c by protonation of the cyclo-propane ring. Contrarily, an elimination of morpholine takes place in 6a, d, e containing a bicyclohexane, -undecane, or -dodecane ring. There are formed derivatives with an exo-methylenefuran unit, which has a Z-configuration in 17a and an E-configuration in 16d, e. 16e the product of a kinetically controlled reaction, rearranges via the Z-isomer 17e to give the furan 18e by heating in morpholine. A methylenebicyclo[n.1.0]alkane 14 is discussed to be an intermediate in the formation of 16d, e and 17a, respectively.
    Notes: Aus den bicyclischen Aminalen 4, und Dimedon (5) werden Derivate 6 erhalten, die in Abhängigkeit von der Ringgröße des Bicyclus unterschiedliche Thermolyseprodukte ergeben. Die Bicycloheptan- und -octanverbindungen 6b, c, führen unter Protonierung des Cyclopropanrings zu Diacylenaminen 8b, c. Eine Eliminierung von Morpholin wird dagegen bei 6a, d, e mit einem Bicyclohexan-, -undecan- bzw. -dodecan-Ring beobachtet. Dabei entstehen Verbindungen mit einem exo-Methylenfuran-Strukturelement, das bei 17a in der Z- und bei 16d, e in der E-Konfiguration vorliegt. 16e, das kinetisch kontrollierte Reaktionsprodukt, kann durch Erhitzen in Morpholin über das Z-Isomere 17e zum Furan 18e umgelagert werden. Die Beteiligung einer Methylenbicyclo-[n.1.0]alkan-Zwischenstufe 14 beim Entstehen von 16d, e bzw. 17a wird diskutiert.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 38
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 172-186 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Radical Ions, 55. The One-Electron Oxidation of Tetrahedrane to Cyclobutadiene Radical CationTetra-tert-butyltetrahedrane, on one-electron oxidation using AlCl3 in CH2Cl2, opens to form tetra-tert-butylcyclobutadiene radical cation, which can also be generated under identical reaction conditions from tetra-tert-butylcyclobutadiene itself. The assignments of the ESR and ENDOR spectra are supported by deutero substitution of one tert-butyl group and by MNDO hypersurfaces for the thermal and for the oxidative structural changes of both C4 skeletons. The feasible formation of a valence isomeric tert-butyl(tri-tert-butylcyclopropenyl)carbene radical cation is discussed.
    Notes: Tetra-tert-butyltetrahedran öffnet sich bei Einelektronen-Oxidation mit AlCl3 in CH2Cl2 zum Tetra-tert-butylcyclobutadien-Radikalkation, das unter gleichen Reaktionsbedingungen auch aus Tetra-tert-butylcyclobutadien erzeugt werden kann. Die Zuordnungen der ESR- und ENDOR-Spektren werden durch Deutero-Substitution einer tert-Butyl-Gruppe sowie durch MNDO-Hyperflächen für die thermischen und oxidativen Strukturänderungen der beiden C4-Gerüste gestützt. Die mögliche Bildung eines valenzisomeren tert-Butyl(tri-tert-butylcyclopropenyl)carben-Radikalkations wird diskutiert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 222-233 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Dynamic Behaviour of PentamethylcyclopentadienylphosphanesBy reaction of pentamethylcyclopentadienyl(Me5cp)-lithium with halogenophosphanes the Me5cp-phosphanes 1 - 5, 7, 8, 11, 12, 14, 15, and 19 - 24 are synthesized. Substitution reactions with the Me5cp-halogenophosphanes 7 and 14 lead to the Me5cp-phosphanes 6, 9, 10, 13, and 16 - 18. These molecules posses a fluxional structure owing to 1,5-sigmatropic rearrangements of the particular phosphorus group. It is demonstrated by 1H dnmr investigations and lineshape analyses, that the ligands at phosphorus influence drastically the speed of these rearrangements (activation energies between 5 and 31 kcal/mol).
    Notes: Durch Umsetzung von Pentamethylcyclopentadienyl(Me5cp)-lithium mit Halogenphosphanen werden die Me5cp-Phosphane 1 - 5, 7, 8, 11, 12, 14, 15 und 19 - 24 hergestellt. Substitutionsreaktionen an den Me5cp-Halogenphosphanen 7 und 14 führen zu den Me5cp-Phosphanen 6, 9, 10, 13 und 16 - 18. Diese Moleküle besitzen eine fluktuierende Struktur aufgrund von 1,5-sigmatropen Umlagerungen der jeweiligen Phosphorgruppierung. Durch 1H-NMR-Untersuchungen und Linienformanalysen wird gezeigt, daß die phosphorständigen Liganden die Geschwindigkeit dieser Umlagerungen drastisch beeinflussen (Aktivierungsenergien zwischen 5 und 31 kcal/mol).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 40
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polyspiranes, 7. Cascade Rearrangements, 2: From Polyspiranes to Polycycles - Sixfold 1,2-Shifts in Functionalized Pentaspiro[2.0.2.0.2.0.2.0.2.1]hexadecanesThe pentaspirohexadecanes 3a, b may be rearranged to 8a, b via 7a, b, which are potential precursors of the [6.4]coronane 1. 7a and 8a were benzoylated to give 7d and 8e, respectively, the molecular structures of which were determined by X-ray analysis. 7a, b and 8a, b adopt the all-cis-configuration. 7a and 7b contain axial hydroxyl groups. The overall rearrangements of 3a, b may thus be described in terms of sixfold 1,2-shifts with inversion at both the migration origins and termini.
    Notes: Die Pentaspirohexadecane 3a, b können über 7a, b in 8a, b umgelagert werden. 7a, b sind potentielle Vorläufer des [6.4]Coronans 1. 7a und 8a wurden zu 7d bzw. 8e benzoyliert, die Molekülstrukturen von 7d und 8e röntgenographisch bestimmt. 7a, b und 8a, b sind all-cis-konfiguriert, 7a und 7b enthalten die Hydroxylgruppe axial gebunden. Die Gesamtumlagerungen von 3a, b können demnach als sechsfache 1,2-Verschiebungen unter Inversion am jeweiligen Ausgangs- und Endpunkt der Umlagerung beschrieben werden.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 41
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 187-202 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Gas Phase Reactions, 40. Selenoformaldehyde: Highly Correlated Wave Function and Photoelectron Spectroscopic EvidenceA systematic search for the unknown molecule selenoformaldehyde, H2C = Se, starts with the precalculation of its ionization pattern from ab-initio-PNO-CI and CEPA wave functions. The selenium precursors H3CSeSeCH3, H3CSeCN, H3CSeCl, and (H2CSe)3 are pyrolyzed in a flow system under PE spectroscopic real-time analysis: Applying “computerized spectra stripping” to the PE spectra of the pyrolysis mixtures, an ionization pattern can be extracted which correlates satisfactorily with the quantum chemical prediction for H2C = Se. To further support the assignment, selenoacetaldehyde, CH3CH = Se, and selenocarbonyl difluoride, F2C = Se, are prepared by thermal monomerization of ((H3C)HCSe)3 and (F2CSe)2, respectively.
    Notes: Nach dem unbekannten Molekül Selenoformaldehyd, H2C = Se, wird systematisch gesucht, beginnend mit der Vorausberechnung seines Ionisationsmusters aus ab-initio-PNO-CI-und CEPA-Wellenfunktionen. Als Selen-Ausgangsverbindungen werden H3CSeSeCH3, H3CSeCN, H3CSeCl und (H2CSe)3 im Gasstrom unter PE-spektroskopischer Echtzeit-Analytik pyrolysiert: Aus den Pyrolysegemisch-Spektren läßt sich durch Spektren-Subtraktion mit Hilfe eines Rechners ein Ionisationsmuster herausschälen, das mit der quantenchemischen Voraussage für H2C = Se zufriedenstellend korreliert. Zur weiteren Stützung der Spektrenzuordnung werden Selenoacetaldehyd, CH3CH = Se, und Selenocarbonyldifluorid, F2C = Se, durch thermische Monomerisierung von ((H3C)HCSe)3 und (F2CSe)2 dargestellt.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 42
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 234-245 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Na⊕ Complexation of New Multidentate Polyether Ligands - Rapid Estimation of Complexation Constants by 23Na NMR SpectroscopyA new 23Na NMR method for fast and simple estimation of Na⊕ complex stabilities is reported and applied to various polyether ligands. Syntheses of the new coronands and podands amongst the employed substrates are given.
    Notes: Eine neue 23Na-NMR-Methode zur raschen und zuverlässigen Abschätzung der Komplexstabilitäten für Na⊕ wird beschrieben und an Polyetherliganden unterschiedlicher Struktur erprobt. Synthesen von neuen Kronenverbindungen und Podanden, die als Meßliganden dienen, werden mitgeteilt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 43
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Hindered Alkenes, IV. Preparation of Some Octamethylcycloalkylidenecycloalkanes and Related CompoundsSixteen “tied back” derivatives of tetra-tert-butylethene of type 4 were prepared via the thiadiazoline and selenadiazoline routes, resp. Strain in 4 increases with increasing number of ring members. The compounds 4m, n, p, and q represent the alkenes of highest fragmentation strain prepared so far, and the limit for the utility of the present synthetic methods. The causes for the failure of these methods in the synthesis of yet more highly strained alkenes are discussed.
    Notes: Mit Hilfe der Thiadiazolin- und Selenadiazolin-Methode wurden 16 neue überbrückte Derivate des Tetra-tert-butylethens vom Typ 4 dargestellt. Mit wachsender Ringgliederzahl nimmt die Spannung in 4 zu. Die Grenzen der erwähnten Synthesewege liegen für die Alkene bei 4m, n, p und q; sie stellen die Alkene höchster Fragmentierungsspannung dar, die bisher isoliert wurden. Die Ursachen für das Versagen dieser Methoden bei der Synthese sterisch noch stärker gehinderter Alkene werden diskutiert.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 44
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 344-354 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemical Reactions of Transition Metal Olefin Complexes, 8. Photochemical Addition of 6-Substituted Pentafulvenes to Tricarbonyl(η6-8,8-dimethylheptafulvene)chromium(0)Under photochemical conditions 6-substituted pentafulvenes (2a - d) displace one CO ligand from tricarbonyl(η6-8,8-dimethylheptafulvene)chromium(0) (1) with formation of a C - C bond between C-6 of a fulvene and C-1 of the heptafulvene ligand leading to substituted dicarbonyl-[η5:3-(cyclopentadienediyl)(isopropylidenecycloheptadienediyl)methane]chromium complexes (3a - 5c). In all cases two diastereomeric complexes are formed, which are separated by column chromatography. They differ in the location of the η3-enyl systems. In 3a, d the enyl system encompasses C-1′ to C-3′, in 4a, b, d C-1′, C-7′, and C-8′, and in 5b, c C-3′ to C-5′ in the isopropylidenecycloheptadienediyl residue. The structures of the complexes 3a - 5c were derived from the spectra.
    Notes: 6-Substituierte Pentafulvene (2a - d) verdrängen unter photochemischen Bedingungen aus Tricarbonyl(η6-8,8-dimethylheptafulven)chrom(0) (1) einen CO-Liganden unter Ausbildung einer C - C-Bindung zwischen C-6 eines Fulvens und C-1 des Heptafulven-Liganden. Es resultieren substituierte Dicarbonyl[η5:3-(cyclopentadiendiyl)(isopropylidencycloheptadiendiyl)methan]-chrom-Komplexe (3a - 5c), und zwar stets in zwei Diastereomeren, die sich säulenchromatographische trennen lassen. Sie unterscheiden sich in der Stellung des η3-Enyl-Systems. In 3a, d umfaßt das Enyl-System C-1′ bis C-3′, in 4a, b, d C-1′, C-7′ und C-8′ und in 5b, c C-3′ bis C-5′ im Isopropylidencycloheptadiendiyl-Rest. Die Konstitutionsformeln von 3a - 5c wurden spektroskopisch abgeleitet.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 45
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Mechanism of the Thermal Rearrangement of Bicyclo[2.2.0]hexane: Dispiro[cyclopropane-1,2′-bicyclo[2.2.0]hexane-3′,1′′-cyclopropane] and Analogously Substituted Derivatives as New Model CompoundsUpon thermolysis the 2,3-diazabicyclo[2.2.2]oct-2-enes 10a-c yield only the thermodynamically more stable 1,5-hexadienes, namely 11, 13, and 15, respectively. Upon photolysis, however, remarkable proportions of the new bicyclo[2.2.0]hexane derivatives 2 (66%), 4 (29%), and 3 (58%), respectively, are formed besides the hexadienes; the by-product (2%) from 10a most probably is the hexalin 12, as it would arise from an intermediate diradical by neighboring group participation of both three-membered rings. The thermolyses of 2, 3, and 4 follow first order rate laws and yield 11, 13, and 15. According to the kinetic data, which best fit a two-step mechanism, the diradical from 2 is stabilized purely electronically by 25.8 kJ/mol with respect to the diradical from 4.
    Notes: Die 2,3-Diazabicyclo[2.2.2]oct-2-ene 10a-c ergeben bei der Thermolyse nur das jeweils thermodynamisch stabilere 1,5-Hexadien, nämlich 11, 13 bzw. 15. Bei der Photolyse entstehen daneben in beachtlichen Anteilen von 66, 29 und 58% die neuen Bicyclo[2.2.0]hexan-Derivate 2, 4 bzw. 3; dem Nebenprodukt (2%) aus 10a kommt höchstwahrscheinlich die Konstitution des Hexalins 12 zu, wie es aus einem intermediären Diradikal durch Nachbargruppenbeteiligung der beiden Dreiringe entstehen müßte. Die Thermolyse von 2, 3 und 4 folgt Zeitgesetzen 1. Ordnung und führt zu 11, 13 und 15. Nach den kinetischen Daten, die am besten mit einem zweistufigen Verlauf zu vereinbaren sind, ist das 1,4-Diradikal aus 2 gegenüber dem aus 4 rein elektronisch um 25.8 kJ/mol stabilisiert.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 46
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal π-Complexes of Benzene Derivatives, XXIV1). 1H NMR Coordination Shift and Ring Current Quenching in Sandwich Complexes as Studied for Bis(η6-[10]paracyclophane)chromium(0)The title compound was prepared by means of metal atom-ligand vapor cocondensation. Its most conspicuous feature, the well defined disposition of 20 methylene groups in the periphery of the title complex is employed to gauge via 1H NMR the coordination induced quenching of the aromatic ring current in arenes.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 376-382 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (η3-Cycloalkenyl)(η5-cyclopentadienyl)nickel ComplexesReaction of nickelocene (1) with isopropylmagnesium chloride (2) and the five- to eight-membered 1,3-cycloalkdienes 3 - 6 leads to the (η3-cycloalkenyl)(η5-cyclopentadienyl)nickel complexes 7 - 10. Mechanistic investigations of the reaction involving 1,4-cyclohexadiene (11) indicates that the homolytic cleavage of the Ni - C bond in an initially formed (η3-3-cycloalkenyl)-nickel complex occurs faster than isomerization, via β-elimination, to the η3-cycloalkenyl form.
    Notes: Durch Umsetzung von Nickelocen (1) mit Isopropylmagnesiumchlorid (2) und den fünf- bis achtgliedrigen 1,3-Cycloalkadienen 3 - 6 werden die (η3-Cycloalkenyl)(η5-cyclopentadienyl)nickel-Komplexe 7 - 10 erhalten. Aus mechanistischen Untersuchungen mit 1,4-Cyclohexadien (11) folgt, daß die homolytische Spaltung der Ni - C-Bindung in primär gebildeten (η1-3-Cycloalkenyl)nickel-Komplexen rascher als deren Isomerisierung über β-H-Eliminierung zu den η5-Cycloalkenyl-Formen sein muß.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 48
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 383-388 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Addition of Organomagnesium Halides to C = C Bonds, XVII. Reactions of Organomagnesium Halides with (Trimethylsilyl)ethyleneEthyl- (2), isopropyl- (3), and the 2-alkenylmagnesium halides 4 and 15 add with 〉 95% regioselectivity to the C = C bond of (trimethylsilyl)ethylene (1) to give the 1:1 adducts 5 - 7 and 16 which upon hydrolysis are converted into the (trimethylsilyl)hydrocarbons 8 - 10 and 17. In the case of 15, addition is accompanied by inversion of the 2-butenyl to the 1-methylallyl group to give 16.
    Notes: Ethyl- (2), Isopropyl- (3) und die 2-Alkenylmagnesiumhalogenide 4 und 15 addieren sich zu 〉 95% regioselektive an die C = C-Bindung in (Trimethylsilyl)ethylen (1) zu den 1:1-Addukten 5 - 7 und 16, aus denen durch Hydrolyse die (Trimethylsilyl)kohlenwasserstoffe 8 - 10 und 17 erhalten werden. Bei 15 erfolgt bei der Addition Inversion des 2-Butenyl- zum 1-Methylallyl-Rest unter Bildung von 16.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 445-454 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on Diazo Compounds and Azides, XLIII1). 1,2-Dewarpyridazines - Suitable Precursors for the Generation of Azacyclobutadienes?Heating of the (diazomethyl)cyclopropenes 9b and c yields the pyridazines 10b and c as main products. The formation of the carbenes 11b and c, which decompose into the acetylenes 12 and 13, competes with the isomerization reaction. The pyridazine 10d is obtained immediately by electrophilic diazoalkane substitution of 6 with the cyclopropenylium salt 8; 9d can be established as intermediate by IR spectroscopy. The irradiation of the pyridazines 10a - d (10a is described in literature) leads to the stable 1,2-Dewarpyridazines 15a - d. The flash pyrolysis of 15b, conducted exemplarily, affords the fragment pairs 16 and 13b as well as 12 and 20. Their formation is in agreement with the intermediacy of the valence tautomeric azacyclobutadienes 17 ⇄ 18.
    Notes: Erhitzen der (Diazomethyl)cyclopropene 9b und c liefert die Pyridazine 10b und c als Hauptprodukte. Mit der Isomerisierungsreaktion konkurriert die Bildung der Carbene 11b und c, die in die Acetylene 12 und 13 zerfallen. Das Pyridazin 10d wird unmittelbar durch elektrophile Diazoalkansubstitution von 6 mit dem Cyclopropenyliumsalz 8 erhalten; 9d kann IR-spektroskopisch als Zwischenstufe nachgewiesen werden. Die Bestrahlung der Pyridazine 10a - d (10a ist literaturbekannt) führt in guten Ausbeuten zu den stabilen, 1,2-Dewarpyridazinen 15a - d. Die für 15b beispielhaft ausgeführte Blitzpyrolyse, liefert die Fragmentpaare 16 und 13b sowie 12 und 20. Deren Bildung legt das intermediäre Auftreten der valenztautomeren Azacyclobutadiene 17 ⇄ 18 nahe.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 50
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallcarbonyl-Synthesen, XVI1). Metall-Metall-Mehrfachbindungen: Synthese, Molekül- und Kristallstruktur von Tri-μ-carbonylbis([η5-pentamethylcyclopentadienyl)mangan](Mn ≡ Mn) - die erste Mangan-Mangan-DreifachbindungPhotolyse des Halbsandwich-Mangan-Komplexes (η5-C5Me5)Mn(CO)3 (1) in Tetrahydrofuran (THF) führt ohne Nebenreaktionen zum Solvenskomplex (η5-C5Me5)Mn(CO)2(THF) (2). Dieser ist im festen Zustand im deutlich unter 0°C liegenden Temperaturbereich haltbar, erleidet aber spontane CO-Eliminierung bei Raumtemperatur; dabei bildet sich der neue Zweikernkomplex (η5-C5Me5)2Mn2(μ-CO)3 (3). Während Elementaranalyse, Infrarot- und Massenspektren sowie die 1H- und 13C-NMR-Spektren dieser Verbindung eine hochsymmetrische dreifach Carbonylverbrückte Struktur zuweisen, stützt eine Einkristall-Röntgenstrukturanalyse das Vorliegen der ersten bisher bekannten Mangan-Mangan-Dreifachbindung (dMn - Mn 217.0(1) pm). Eine verbesserte Darstellung von Tricarbonyl(η5-pentamethylcyclopentadienyl)mangan (1) wird beschrieben.
    Notes: Photolysis of the manganese half-sandwich complex (η5-C5Me5)Mn(CO)3 (1) in tetrahydrofuran (thf) cleanly yields the solvent complex (η5-C5Me5)Mn(CO)2(thf) (2). Compound 2 is stable as solid at temperatures well below 0°C but undergoes spontaneous elimination of carbon monoxide at ambient temperature with concomitant formation of the novel dinuclear complex (η5-C5Me5)2-Mn2(μ-CO)3 (3). While elemental analysis, infrared and mass spectroscopy as well as the 1H NMR and 13C NMR spectra unequivocally demonstrate this compound to adopt a highly symmetrical triply carbonyl-bridged structure, a single-crystal X-ray diffraction study supports the presence of the first triple bond between manganese atoms (dMn - Mn 217.0(1) pm). An improved synthesis of tricarbonyl(η5-pentamethylclopentadienyl)manganese (1) is also described.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 51
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3297-3302 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Oxidative Ether Cleavage with p-Nitroperbenzoic AcidThe reaction of p-nitroperbenzoic acid in chloroform with alkyl ethers (1a, 2a) leads by selective attack at C-H bonds in α-position to the ether oxygen to hemiacetals, which decompose to aldehydes and alcohols, yielding carboxylic acids. Secondary alkoxy groups as in 3a, 4a furnish Baeyer-Villiger oxidation products of initially formed ketones. Kinetic measurements with substituted benzyl methyl ethers show a Hammett reaction constant ρ = -0.9, which is in accordance with the observed relatively small discrimination between secondary and tertiary C-H bonds. The results are compared with similar hydroxylations of alkanes and with monooxygenase reactions and point to oxenoid transition states. Radical reactions as found with some alkanes are not observed, which is shown by the small amounts of nitrobenzene (≤10%) formed during the reaction. 13C-NMR shifts of several ethers and oxidation products are reported.
    Notes: p-Nitroperbenzoesäure reagiert mit Alkylethern (1a, 2a) in Chloroform selektiv an einer C-H-Bindung in α-Position zum Ethersauerstoff zu Halbacetalen, die in Aldehyde und Alkohole zerfallen. Diese ergeben dabei Carbonsäuren. Bei 3a, 4a mit sekundären Alkoxyresten entstehen über Ketone Folgeprodukte der Baeyer-Villiger-Oxidation. Kinetische Messungen mit substituierten Benzylmethylethern ergeben eine Hammett-Reaktionskonstante ρ = -0.9, welche in Einklang mit der beobachteten relativ geringen Differenzierung zwischen Angriff an sekundären und tertiären C-H-Bindungen steht. Die Ergebnisse werden mit entsprechenden Hydroxylierungen von Alkanen sowie mit Monooxygenasen-Reaktionen verglichen und sprechen für oxenoide Übergangszustände. Radikalisch verlaufende Reaktionen wie bei einigen Alkanen werden kaum beobachtet, wie die geringfügige Bildung von Nitrobenzol (≤10%) zeigt. 13C-NMR-Verschiebungen von verschiedenen Ethern und Oxidationsprodukten werden angegeben.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 52
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermolabile Hydrocarbons, XXV1). Relationships between Thermal Stability, Strain, and Structure of 1,1′-Diphenyl-1,1′-bicycloalkylsThe products and activation parameters of the thermolysis reaction of the title hydrocarbons 1a (n = 4-8) and 1b (n = 12) were determined. Strain enthalpies and structural data of the compounds 1a and of the radicals 2a, which are generated on thermolysis, were obtained from force field calculations. For 1a (n = 8) a crystal structure analysis was carried out.  -  The importance of i-strain action is estimated from the relationship between ΔG≠ of the thermolysis reaction and the strain enthalpy of 1 from which the ring strain of the corresponding cycloalkane was substracted as a correction factor. In addition, a linear correlation between ΔG≠ and the change in strain enthalpy (MM2 results) in the course of the dissociation process was found. The large variation in ΔS≠ can be rationalized by consideration of the change in internal mobility (MM2 results) during the dissociation process.
    Notes: Die Produkte und Aktivierungsparameter der Thermolyse der Kohlenwasserstoffe 1a (n = 4-8) und 1b (n = 12) wurden bestimmt. Die Spannungsenthalpien und Strukturdaten der Verbindungen 1a und der beim thermischen Zerfall entstehenden Radikale 2a wurden durch Kraftfeldberechnungen ermittelt. Für 1a (n = 8) wurde eine Kristallstrukturanalyse durchgeführt.  -  Die Beziehungen zwischen ΔG≠ der Thermolyse und den um die Ringspannung korrigierten Spannungsenthalpien gestatten eine quantitative Analyse der i-strain-Wirkung. Außerdem wird eine lineare Korrelation zwischen ΔG≠ und der Änderung an Spannungsenthalpie im Dissoziationsprozess nach Kraftfeldrechnungen aufgezeigt. Stark unterschiedliche Aktivierungsentropien werden durch die Änderung der inneren Beweglichkeit im Zuge des Dissoziationsprozesses, die aus Kraftfeldrechnungen abschätzbar ist, verständlich.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 53
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 54
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3325-3329 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,2,4,4-Tetramethyl-3-methylenbicyclo[3.2.1]oct-6-enDie sterisch anspruchsvolle Titelverbindung 1 wurde in einer Eintopfreaktion aus Cyclopentadien und 2,4-Dimethyl-3-[(trimethylsilyl)methyl]-3-penten-2-ol (5) in Gegenwart von Titantetrachlorid/N-Methylanilin hergestellt. 2,2,4,4-Tetramethylbicyclo[3.2.1]oct-6-en-3-on (4) wurde vereinfacht im 15-g-Maßstab dargestellt.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 55
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3331-3339 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Complexes of Instable Ylides, IV1). Novel Ylidic Chelate Ligands with the Sequence CPNP as Structural Moiety in Tetracarbonylchromium ComplexesThe sulfur ylide complex (CO)5Cr[CH2S(O)Me2] (1) reacts with iminobis(phosphanes) 3a, b to yield five-membered metallacycles 4a, b, in which the novel ylides H2C=PPh2-NR-PPh2 are incorporated as chelate ligands. The reaction of (CO)4Cr[CH2S(O)Me2]2 (5) with (Ph2P)2NH (3d) leads to salt-like 7, which can be protonated and methylated at the nitrogen atom.
    Notes: Der Schwefelylid-Komplex (CO)5Cr[CH2S(O)Me2] (1) reagiert mit den Iminobis(phosphanen) 3a, b zu den fünfgliedrigen Metallacyclen 4a, b, welche die neuartigen Ylide H2C=PPh2-NR-PPh2 als Chelatliganden tragen. Die Umsetzung von (CO)4Cr[CH2S(O)Me2]2 (5) mit (Ph2P)2NH (3d) führt zum salzartigen Komplex 7, der sich am Stickstoffatom protonieren wie auch methylieren läßt.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 56
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kinetic and Mechanistic Investigations of Transition Metal Complex Reactions, XV1). Transition Metal Sulfur Ylide Complexes, XX2). Kinetic Evidence of [(CO)5Cr=CH2] in the Reaction of Pentacarbonyl[(dimethyloxosulfonio)-methanide]chromium(0) with Tertiary PhosphanesPentacarbonyl[(dimethyloxosulfonio)methanide]chromium(0), (CO)5Cr[CH2S(O)Me2] (1), reacts with tertiary phosphanes PR3 (2) (R = Ph, C6H4OMe-(p), C6H4Me-(p), C6H4Cl-(p)) to give pentacarbonyl(phosphonium ylide)chromium(0) complexes, (CO)5Cr[CH2PR3] (3), and dimethyl sulfoxide according to the first-order rate law. The reaction rate is independent on the type of the phosphane. The activation parameters for the reaction in 1,1,2-trichloroethane in the temperature range 39.6 to 68.0°C are ΔH≠ = 28.1 kcal · mol-1 and ΔS≠ = 12.7 cal · mol-1 · K-1. The reaction is initiated by irreversible dissociation of OSMe2 from 1. Addition of 2 to the carbene carbon of the resulting pentacarbonylmethylenechromium, [(CO)5Cr=CH2], yields 3 in a fast succeeding step. A mechanism involving rate determining dissociation of the Cr=CH2 bond can be excluded. These results represent the first evidence of a neutral, electrophilic carbonylmethylene complex.
    Notes: Pentacarbonyl[(dimethyloxosulfonio)methanid]chrom(0), (CO)5Cr[CH2S(O)Me2] (1), reagiert mit tertiären Phosphanen PR3 (2) (R = Ph, C6H4OMe-(p), C6H4Me-(p), C6H4Cl-(p)) nach dem Geschwindigkeitsgesetz erster Ordnung zu Pentacarbonyl(phosphorylid)chrom(0)-Komplexen, (CO)5Cr[CH2PR3] (3), und Dimethylsulfoxid. Die Reaktionsgeschwindigkeit ist von der Art des Phosphans unabhängig. Die Aktivierungsparameter für die Reaktion in 1,1,2-Trichlorethan im Temperaturbereich von 39.6-68.0°C sind ΔH≠ = 28.1 kcal · mol-1 und ΔS≠ = 12.7 cal · mol-1. K-1. Die Reaktion wird durch irreversible Dissoziation von OSMe2 vom Komplex 1 eingeleitet. An das Carbenkohlenstoffatom des resultierenden Pentacarbonylmethylenchroms, [(CO)5Cr=CH2], addiert sich dann 2 in einem raschen Folgeschritt unter Bildung von 3. Ein Mechanismus über einen geschwindigkeitsbestimmenden Cr-CH2-Bindungsbruch kann ausgeschlossen werden. Diese Ergebnisse sind der erste Nachweis eines neutralen elektrophilen Carbonylmethylen-Komplexes.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 57
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3365-3373 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zum Bau von 2-Azaallenium-KationenEntsprechend einer Röntgenstrukturanalyse kristallisiert das 2-Azaallenium-hexachloroantimonat 23 in der Topologie eines Allens (Geometrie 1a) und nicht eines 2-Azaallyl-Kations (1b). Ab-initio-Molekülorbital- (3-21 G Basissatz) und semiempirische MNDO-Rechnungen für das unsubstituierte 2-Azaallenium-Kation und einige mono- und disubstituierte Derivate (24) bestätigen die experimentellen Befunde: In vielen Fällen ist die Allengeometrie 24a stabiler als die 2-Azaallylium-Form 24b. Elektronenspendende Substituenten verringern den Energieunterschied zwischen 24b und 24a. Ein diaminosubstituiertes Allylium-Kation 24b ist energetisch stabiler als die entsprechende Allenium-Form 24a. Ganz allgemein sind substituierte 2-Azaallenium-Kationen um das zentrale Stickstoffatom sterisch flexibel. Verbindung 23 wurde nach einer neuen Synthese hergestellt.
    Notes: According to an X-ray structural analysis, the 2-azaallenium hexachloroantimonate 23 crystallizes with the topology of an allene (geometry 1a) and not of a 2-azaallyl cation (1b). Ab initio molecular orbital calculations (3-21 G basis set) and semiempirical MNDO calculations for the unsubstituted 2-azaallenium cation and for some mono- and disubstituted derivatives (24) confirm the experimental results: In many cases the allenium geometry 24a is more stable than the 2-azaallylium form 24b. Electron-releasing substituents reduce the energy difference between 24b and 24a. With two amino substituents the allylium geometry 24b is energetically preferred to the allenium form 24a. In general, substituted 2-azaallenium salts are sterically flexible around the central nitrogen atom. Compound 23 was synthesized by a new method.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 58
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 682-693 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Addition of Aldehydes to Activated Double Bonds, XXXIV1). Addition of Aldehydes to Cyclic α-Methylene KetonesThe thiazolium salt-catalyzed addition of aldehydes to the cyclic α-methylene ketones 3, 4, 7, 8, 48, and 49 leads to γ-diketones 9 - 22, 50 - 53; some of them were converted into unsaturated ketones 23 - 28, pyrroles 29 - 34, 37 - 43, and furans 35, 36, 44 - 46. The α-methylene ketones were synthesized by retro Diels-Alder reaction of the corresponding norbornene compounds 1, 2, 5, 6, 47.
    Notes: Die Thiazoliumsalz-katalysierte Addition von Aldehyden an die cyclischen α-Methylenketone 3, 4, 7, 8, 48 und 49 führt zu γ-Diketonen 9 - 22, 50 - 53, aus denen einige ungesättigte Ketone 23 - 28, Pyrrol- 29 - 34, 37 - 43 und Furanderivate 35, 36, 44 - 46 synthetisiert wurden. Die Darstellung der α-Methylenketone erfolgte durch Retrospaltung entsprechender Norbornenderivate 1, 2, 5, 6 und 47.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 59
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 666-671 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (Z)-/(E)-2,2,2',2'-Tetraethoxy-Δ3,3'(2H, 2'H)-bi[phenanthro[9,10-b]furan], II1). Synthesis and Structure Determination of some Phenantro-condensed O-HeterocyclesIn the absence of water the proton- or bromine-catalyzed isomerization of the pure diastereomers 1 leads to a mixture of the Z/E-isomers 2a. Acidic hydrolysis of these two diastereomers yields fumaric ester 4, which readily undergoes thermal cyclizitation to give coumarin 5a. - Direct acidic hydrolysis of the Z/E-isomers 1 forms orthoester 3 and fumaric ester 4. - Alkaline hydrolysis of coumarin 5b gives salt 5c, which on acidification forms carboxylic acid 5d. Heating of 5d in the presence of thionyl chloride leads to coumarino-coumarin 6. - Heating of coumarin 5b gives the furo-coumarin 7. 7 is also formed on heating of coumarino-coumarin 6 in the presence of water.
    Notes: Unter Ausschluß von Wasser führt die Protonen- bzw. Brom-katalysierte Isomerisierung der reinen Diastereomeren 1 zu dem Z/E-Isomerengemisch 2a. Die saure Hydrolyse dieser beiden Diastereomeren liefert den Fumarsäurediester 4, der thermisch zu dem Cumarin 5a cyclisiert. - Bei der direkten sauren Hydrolyse der Z/E-Isomeren 1 isoliert man den Orthoester 3 und den Fumarsäurediester 4. - Die alkalische Hydrolyse des Cumarins 5b gibt das Salz 5c, das durch Ansäuern die Carbonsäure 5d liefert. Beim Erhitzen von 5d in Thionylchlorid erhält man das Cumarino-cumarin 6. - Bei der thermischen Belastung entsteht aus dem Cumarin 5b das Furocumarin 7. In Anwesenheit von Wasser bildet sich 7 auch beim Erhitzen des Cumarino-cumarins 6.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 60
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azaborolinyl Complexes, X1). Synthesis and Properties of (1-tert-Butyl-2-methyl-η-1,2-azaborolinyl)carbonylmanganese and-molybdenum Complexes1-tert-Butyl-2-methyl-1,2-azaborolinyllithium (1) reacts with [CH3CN)3Mn(CO)3]PF6 to give (1-tert-butyl-2-methyl-η-1,2-azaborolinyl)tricarbonylmanganese (2). Neutral 1-tert-butyl-2-methyl-1,2-azaboroline (3) and Mo(CO)6 form π-ally(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)-dicarbonylmolybdenum (4). The formation of the allyl group is due to the decomposition of an azaborolinyl ring under the reaction conditions. 2 and 4 are characterized by mass, IR, and NMR spectra. 4 could be investigated by X-ray analysis. Orthorhombic, space group Pbca, Z = 8, a = 1697.4(9), b = 1441.8(5), c = 1219.4(7) pm. The chirality of the azaborolinyl ring causes the formation of enantiomers which exist as a racemate in the crystal.
    Notes: 1-tert-Butyl-2-methyl-1,2-azaborolinyllithium (1) reagiert mit [(CH3CN)3Mn(CO)3]PF6 zum (1-tert-Butyl-2-methyl-η-1,2-azaborolinyl)tricarbonylmangan (2). Neutrales 1-tert-Butyl-2-methyl-1,2-azaborolin (3) und Mo(CO)6 bilden π-Allyl(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)-dicarbonylmolybdän (4). Die Bildung der Allygruppe ist auf den Zerfall eines Azaborolin-Ringes unter den Reaktionsbedingungen zurückzuführen. 2 und 4 werden durch Massen-, IR- und NMR-Spektren charakterisiert. Von 4 konnte eine Röntgenstrukturanalyse durchgeführt werden: orthorhombisch, Raumgruppe Pbca, Z = 8, a = 1697.4(9), b = 1441.8(5), c = 1219.4(7) pm. Die Chiralität des Azaborolinyl-Ringes bedingt die Bildung von Enantiomeren, die im Kristall als Racemat vorliegen.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 61
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 694-701 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diazadiene als Steuerliganden in der Katalyse, 51). Synthese chiraler Diazadiene R* - N = CR' - CR' = N - R*Die im Prinzip einfache Kondensationsreaktion von Glyoxal (als Hydrat) und 2,3-Butandion mit primären Aminen führt leider bei aliphatischen Aminen mit tertiärem bzw. sekundärem α-Kohlenstoff oftmals zu unerwünschten Additionsprodukten. Unter speziellen Synthesebedingungen können mit (R)-1-Phenylethylamin (1) und (1S,2S,3S,5R)-3-(Aminomethyl)pinan die gewünschten Diimine (Diazadiene (dad): R* - N = CR' - CR' = N - R*, R' = H, CH3) 4, 6 - 8 erhalten werden. Aus (S)-2-Amino-1-butanol (3) werden je nach Dion-Komponente ein Morpholinomorpholin 9 bzw. ein Bioxazolidin 10 gebildet, die von elektronenreichen Metallen in ihrer isomeren Form als Diazadiene gebunden werden ((dad)Mo(CO)4 11 und 12). Die offenkettige dad-Form ist durch O-Silylierung (14, 15) stabilisierbar. Die (dad)Eisen(0)-katalysierte Dimerisierung von Butadien zu 4-Vinyl-1-cyclohexen mit diesen dad-Liganden ergibt Enantiomerenüberschüsse e.e. bis zu 16%.
    Notes: The condensation of glyoxal (as hydrate) or 2,3-butanedione with primary amines is, in principle, a simple reaction. Unfortunately, aliphatic amines with secondary or tertiary α-carbons often give unwanted addition products. Under special reaction conditions the desired diimines (diazadienes (dad): R* - N = CR' - CR' = N - R*, R' = H, CH3) 4, and 6 - 8 are obtained from (R-1-phenyl-ethylamine (1) and (1S,2S,3S,5R)-3-(aminomethyl)pinane (2). Depending on the dione, a morpholinomorpholine 9 and a bioxazolidine 10 are formed from (S)-2-amino-1-butanol (3), which are bound by electron-rich metals in their isomeric dad form ((dad)Mo(CO)4 11 and 12). The acyclic dad structure is stabilized by O-silylation (14, 15). The (dad)iron(0) catalyzed dimerization of butadiene with these controlling ligands to 4-vinyl-1-cyclohexene occurs with an enantiomeric excess up to 16%.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 62
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Application of High-Resolution Solid State NMR Spectroscopy for the Determination of the Ring-Chain TautomerismThe structure of the benzaldehyde derivatives 1 and 2 showing ring-chain tautomerism was investigated by NMR spectroscopy in the solid state and in solution. Difficulties in preparing single crystals, low solubility, and the presence of solvent in the crystal prevent an X-ray analysis and other spectroscopic methods. The structural problem was solved by C-13 CP-MAS NMR spectroscopy. 2-[2-(Methylamino)ethyl]-3-nitrobenzaldoxime (1) exists in the chain form in the crystal but is in equilibrium with the cyclic isomer in solution. Two different types of crystals were obtained from the aminoethenylbenzaldehyde derivative 2, one of them containing the chain the other the cyclic form of 2. Signal assignments in the solid state result from comparison with the spectra in solution, which have been partially assigned by 2D 1H 13C NMR shift correlation.
    Notes: Die Struktur der Benzaldehyd-Derivate 1 und 2, die Ring-Ketten-Tautomerie zeigen, wird durch NMR-Spektroskopie im festen und gelösten Zustand untersucht. Schwierigkeiten beim Züchten von Einkristallen sowie die Schwerlöslichkeit bzw. die Anwesenheit von Kristallösungsmittel verhinderten die Anwendung der Röntgenstrukturanalyse und anderer spektroskopischer Methoden. Mit Hilfe von C-13-CP-MAS-NMR-Spektren wird das Strukturproblem lösbar. In 2-[2-(Methyl-amino)ethyl]-3-nitrobenzaldoxim (1) liegt im Kristall die offene Form vor, die in Lösung mit dem cyclischen Tautomeren 1b im Gleichgewicht steht. Vom Aminoethenylbenzaldehyd-Derivat 2 lassen sich zwei verschiedene Kristalle gewinnen, in denen alternativ die offene und die cyclische Struktur vorliegt. Zur Signalzuordnung werden die Festkörper-NMR-Spektren mit den z. T. durch 2D-1H-13C-NMR-Verschiebungskorrelation zugeordneten C-13-Spektren verglichen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 63
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 710-724 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Asymmetric Catalyses, 121). New Optically Active P,N Ligands and Their Use in Rh-Catalyzed Asymmetric Hydrogenation and HydrosilylationNew P,N-ligands 2, 4 and 5 were prepared by Schiff base condensation of (2-formylphenyl)diphenyl- and tris(2-formylphenyl)phosphane with (R)-(+)-1-phenylethylamine and ethylenediamine. (R)-(+)-aminphos (6) was obtained by hydrogenation of the C = N bond in (R)-(+)-iminphos (2). The new imine ligands form stable chelate complexes. The pseudotetrahedral CpFe(CO)[R)-(+)-iminphos]PF6 was separated into the diastereoisomes with respect to the Fe configuration. The square planar Rh[(R)-(+)-iminphos]2X is obtained as a cis/trans mixture. The isolated Rh complexes and the combinations [Rh(COD)Cl]2/2, 4, and 6, respectively, were used as catalysts for the homogeneous hydrogenation of (Z)-α-(acetylamino)cinnamic acid and for the hydrosilylation of acetophenone with diphenysilane. The optical yield of 1-phenyl-ethanol, the product of hydrolysis of the hydrosilylation, increases with increasing ligand excess, decreasing catalyst concentration, and decreasing temperature.
    Notes: Neue P,N-Liganden 2, 4 und 5 wurden durch Schiffbasenkondensation von (2-Formylphenyl)diphenyl- und Tris(2-formylphenyl)phosphan mit (R)-(+)-1-Phenylethylamin und Ethylendiamin dargestellt. (R)-(+)-aminphos (6) wurde durch Hydrierung der C = N-Bindung in (R)-(+)-iminphos (2) erhalten. Die neuen Imin-Liganden bilden stabile Chelatkomplexe. Das pseudotetraedrische CpFe(CO)[(R)-(+)-iminphos]PF6 wurde in die Diastereomeren bezüglich der Fe-Konfiguration getrennt. Das quadratisch-planare Rh[(R)-(+)-iminphos]2X fällt als cis/trans-Gemisch an. Die isolierten Rh-Komplexe und die Kombinationen [Rh(COD)Cl]2/ 2, 4 bzw. 6 wurden als Katalysatoren für die homogene Hydrierung von (Z)-α-(Acetylamino)zimtsäure und für die Hydrosilylierung von Acetophenon mit Diphenylsilan eingesetzt. Die optische Ausbeute an 1-Phenylethanol, dem Hydrolyseprodukt der Hydrosilylierung, steigt mit zunehmendem Ligandenüberschuß, mit abnehmender Katalysatorkonzentration und mit abnehmender Temperatur.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 64
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 725-731 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Macrocyclic Quaternary Ammonium Salts, IV1). Catalysis of Nucleophilic Aromatic Substitutions by Azide as NucleophileThe macrotricyclic ammonium salt 2 indeed catalyzes the bimolecular nucleophilic substitution of the halonitroarenes 3 - 7 by azide. The kinetic analysis supports the view that azide anion is included into the molecular cavity of the anion host 2 prior to the rate limiting substitution step. The desolvation experienced by the anionic guest on the invasion of the cavity from free solution is credited for the augmentation of reactivity observed which is greater than with micellar cetyltrimethylammonium bromide (CTAB). Compared to this, the influence of the leaving group on the reactivity is small. The far reaching analogy to natural enzymes qualifies 2 to be a totally synthetic low molecular weight enzyme model comparable to the cyclodextrins.
    Notes: Das macrotricyclische Ammoniumsalz 2 ist in der Lage, die bimolekulare nucleophile Substitution der Halogennitroaromaten 3 - 7 mit Azid zu katalysieren. Die kinetische Analyse stützt die Vorstellung, daß das Azid-Anion in die Molekülhöhle des Anionenwirtes 2 aufgenommen wird und dort im geschwindigkeitslimitierenden Schritt die Substitution vollzieht. Die Desolvatation des Gastanions beim Übertritt aus freier Lösung in die hydrophobe Umgebung der Höhle erklärt die beobachtete Reaktivitätssteigerung, die größer ist als in micellarem Cetyltrimethylammoniumbromid (CTAB). Der Einfluß der Austrittsgruppe auf die Reaktivität ist demgegenüber gering. Wegen der Analogie im Wirkprinzip zu den natürlichen Enzymen kann man 2 als synthetisches niedermolekulares Enzymmodell den Cyclodextrinen an die Seite stellen.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 65
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 840-849 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of Adamantyl-Substituted Methyleneaziridines1)The thermolysis of the 1,1-dibromocyclopropanes 3b, c in the presence of primary amines produced the 3,3-disubstituted N-alkyl(2-bromo-2-propen)amines 2b, c. These as well as 2a afforded the 1-alkyl-2-alkylideneaziridines 4 on 1,3-dehydrobromination with sodium amide in liquid ammonia. The isopropylideneaziridine 4b crystallizes monoclinically as a racemate in the space group P21/n with four molecules per cell. The angle between the plane of the three-membered ring and the 1-adamantyl nitrogen bond is 55.4°. Some structural parameters of 4b are discussed.
    Notes: Die Thermolyse der 1,1-Dibromcyclopropane 3b, c in Gegenwart primärer Amine ergab die 3,3-disubstituierten N-Alkyl(2-brom-2-propen)amine 2b, c. Daraus sowie aus 2a wurden die 1-Alkyl-2-alkylidenaziridine 4 durch 1,3-Dehydrobromierung mit Natriumamid in flüssigem Ammoniak erhalten. 4b kristallisiert als Racemat monoklin in der Raumgruppe P21/n mit vier Molekülen pro Elementarzelle. Die Bindung zum Substituenten am Stickstoffatom ist um 55.4° aus der Dreiringebene ausgelenkt. Einige Strukturparameter von 4b werden diskutiert.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 66
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 856-858 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reduction of Oximes with Sodium Borohydride in the Presence of Transition Metal CompoundsThe reduction of oximes with sodium borohydride in the presence of NiCl2 · 6 H2O and MoO3 was investigated. The combination of NaBH4 with NiCl2 · 6 H2O converted the unsaturated oximes through exhaustive reduction into saturated amines (Table 1). The C = C double bond remains preserved if the reduction is carried out in the presence of MoO3 (Table 2). The stereo-chemistry of the reduction in the presence of NiCl2 · 6 H2O is distinctivly different from that of MoO3.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 67
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 68
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 859-861 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of γ- and δ-Lactones via Radical CC-Bond Formation ReactionLactones 5 and 6 can be synthesized via solvomercuration of alkenes 1 and reductive CC-bond formation with acrylonitrile.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 69
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1013-1025 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermolabile Hydrocarbons, XXIV1). Hexacyclopropylethane - Structure, Thermochemistry, and Stability2)The preferential conformation of hexacyclopropylethane (5) has S6 symmetry according to X-ray analysis and force field calculations (MM2). The central bond ist 163.6 pm long (MM2: 161.5 pm). From the heat of combustion and heat of sublimation a heat of formation δHf°(g) = 111.5 kcal · mol-1 is obtained which could not be reproduced by the MM2 force field. An unusually high torsion constant is made responsible for this. A resonance energy of 3.7 kcal · mol-1 for the tricyclopropylmethyl radical (4) is derived from the activation parameters of the thermolysis reaction of 5.
    Notes: Hexacyclopropylethan (5) besitzt nach Kristallstrukturanalyse und Kraftfeldrechnungen (MM2) eine Vorzugskonformation mit S6-Symmetrie und eine zentrale Bindungslänge von 163.6 pm (MM2: 161.5 pm). Die thermochemisch bestimmte Bildungsenthalpie δHf°(g) = 111.5 kcal ⋅ mol-1 läßt sich durch das Kraftfeld MM2 nicht reproduzieren, wofür eine ungewöhnlich hohe Torsionskonstante im Kraftfeld verantwortlich gemacht wird. Aus den Aktivierungsparametern der Thermolyse von 5 und der Spannungsenthalpie läßt sich für das Tricyclopropylmethyl-Radikal (4) eine Resonanzstabilisierung von 3.7 kcal ⋅ mol-1 ableiten.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 70
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1034-1038 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [1-(Arylcarbonyloxy)alkyl]phosphonium Salts, 31). Reductive C-Acylation of Aromatic AldehydesThe phosphonium salts 5 are synthesized from aldehydes 1, arenecarbonyl chlorides 2 and triphenylphosphane (4), and can then be deprotonated to 7. 7 react as acyl anion equivalents with aromatic aldehydes 9 forming enol esters 10, which are transformed to alkanones 11. The new aldehyde 9 → alkanone 11-transformation is characterised as a reductive C-acylation of aromatic aldehydes.
    Notes: Aus Aldehyden 1, Arencarbonsäurechloriden 2 und Triphenylphosphan 4 entstehen die Phosphoniumsalze 5, die zu 7 deprotoniert werden. 7 reagiert wie Acylanionäquivalente mit aromatischen Aldehyden 9 zunächst zu Enolestern 10, aus denen die Alkanone 11 hergestellt werden. Die neuartige Aldehyd 9 → Keton 11-Umwandlung wird als reduktive C-Acylierung der Aldehyde 9 charakterisiert.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 71
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1026-1033 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Substituent Effects on the C - C bond Strength, 61). TetracyclopropylsuccinonitrileThe heat of formation of the title compound 5 was obtained from the heat of combustion and the heat of sublimation. The activation parameters for the thermal decomposition of 5 were measured by reaction kinetics. A resonance energy of 7.8 kcal⋅mol-1 is obtained for the α-cyanodicyclopropylcarbinyl radical from the known relationship between strain enthalpy and free enthalpy of activation. Due to dicyclopropylcarbinyl stabilisation this value is 2.5 kcal⋅mol-1 higher than expected for a simple α-cyanoalkyl radical. Structural data for 5 were obtained from force field calculations (MM2).
    Notes: Die Bildungsenthalpie der Titelverbindung 5 wurde thermochemisch, die Aktivierungsparameter ihrer Thermolyse wurden reaktionskinetisch bestimmt. Aus dem bekannten Zusammenhang zwischen Spannungsenthalpie und Aktivierungsenthalpie leitet sich für das α-Cyandicyclopropylcarbinyl-Radikal (6) eine Resonanzenergie von 7.8 kcal⋅mol-1 ab. Durch Dicyclopropylcarbinyl-Stabilisierung ist dieser Wert 2.5 kcal⋅mol-1 höher als für einfache α-Cyanalkyl-Radikale erwartet. Die Struktur von 5 wurde mit der Kraftfeldmethode (MM2) berechnet.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 72
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1039-1051 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Chemistry of the Cluster SRuCo2(CO)9SRuCo2(CO)9 (2) results in good yield by heating of stoichiometric amounts of Co2(CO)8 and Ru3(CO)12 in the presence of ethyl mercaptan under synthesis gas pressure. In 2 up to three CO ligands can easily be replaced by PMe2Ph and up to two CO ligands by AsMe2MCp(CO)3 (M = Cr, Mo, W). The monosubstituted derivates SRuCo2(CO)8L with L = PMe2Ph (3) or L = AsMe2MCp(CO)3 (6 - 8) appear as two isomers, of which we assume substitution at ruthenium for the one formed first and subsequent transfer of the ligand to cobalt. The tetranuclear complexes SRuCo2(CO)8 - AsMe2MCp(CO)3 (6 - 8) undergo metal exchange upon heating under CO to yield the chiral clusters SRuCoMCp(CO)8 (12 - 14, M = Cr, Mo, W). Of these the Mo and W compounds are better accessible by reaction between 2 and [MCp(CO3]2. From SruCoMoCp(CO)8 (13) and optically active phosphane ligands mixtures of diastereoisomers SRuCoMoCp(CO)7L (18: L = ( - )-PMePrPh; 19: L = PPh2O( - )-Menthyl result. During the formation of 19 a slight enrichment of the ( - )-diastereoisomer occurs. The diastereoisomers can be separated chromatographically, but not yet reconverted to the pure enantiomers 13.
    Notes: SRuCo2(CO)9 (2) entsteht in guter Ausbeute beim Erhitzen stöchiometrischer Mengen von Co2(CO)8 und Ru3(CO)12 in Gegenwart von Ethylmercaptan unter Synthesegas-Druck. In 2 lassen sich bis zu drei CO-Liganden durch PMe2Ph und bis zu zwei CO-Liganden durch AsMe2MCp(CO)3 (M = Cr, Mo, W) leicht ersetzen. Die Monosubstitutionsderivate SRuCO2(CO)8L mit L = PMe2Ph (3) bzw. L = AsMe2MCp(CO)3 (6 - 8) treten in Form von zwei Isomeren auf, bei denen wir für das zuerst gebildete Substitution am Ruthenium und anschließend Wanderung des Liganden zum Cobalt annehmen. Die Vierkernkomplexe SRuCo2(CO)8 - AsMe2MCp(CO)3 (6 - 8) unterliegen beim Erhitzen unter CO einem Metallaustausch zu den chiralen Clustern SRuCoMCp(CO)8 (12 - 14, M = Cr, Mo, W). Von diesen sind die Mo- und W- Verbindungen besser durch Umsetzung von 2 mit [MCp(CO)3]2 zugänglich. Aus SRuCoMoCp(CO)8 (13) und optisch aktiven Phosphanliganden entstehen Diastereomerengemische SRuCoMoCp(CO)7L (18: L = (-)PMePrPh; 19: L = PPh2O(-)-Menthyl). Bei der Bildung von 19 tritt eine geringe Anreicherung des (-)-Diasteromeren ein. Die Diasteromeren sind chromatographisch zu trennen, jedoch bisher nicht in die reinen Enantiomeren 13 zurückzuverwandeln.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 73
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1250-1254 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Simple Synthesis of Primary Amines via their N,N-Bis(trimethylsilyl) DerivativesPrimary halogen compounds 1 or the corresponding tosylates react with sodium bis(trimethylsilyl)amide (2) in hexamethyldisilazine to form N,N-bis(trimethylsilyl)amines 3, which are converted into the amine hydrochlorides 5 by treatment with aqueous HCl.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 74
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 75
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1465-1475 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azo Bridges from Azines, IV1). Intramolecular [2 + 2] Photocycloaddition of Parallel C=C and N=N BondsThe parallel C=C and N=N bonds in the rigid molecules 1 - 10 photocyclize nearly quantitatively, forming 1,2-diazetidines 11 - 20. Their structure is confirmed by spectroscopic methods and for 13 by X-ray analysis. Radiation induced denitrogenation, the normal reaction for similar compounds without neighbouring C=C bonds, is suppressed even with the sensitive derivatives of 2,3-diazabicyclo[2.2.1]heptene. Photocyclization of 6, carrying two neighbouring C=C bonds, includes only the norbornene bond.
    Notes: In den starren Molekülen 1 - 10 reagieren die benachbarten parallelen C=C- und N=N-Bindungen nahezu quantitativ unter Photocyclisierung zu den 1,2-Diazetidinen 11 - 20, deren Struktur spektroskopisch und für 13 durch Kristallstrukturanalyse bewiesen wird. Die in Abwesenheit der C=C-Bindung beobachtete Photo-Denitrogenierung unterbleibt selbst bei den empfindlichen Derivaten des 2,3-Diazabicyclo[2.2.1]heptens. Photocyclisierung von 6 mit zwei zur N=N-Bindung benachbarten C=C-Bindungen tritt nur mit der Norbornendoppelbindung ein.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 76
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1583-1590 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (Disilylamino)phosphanes (Rf)2P - N(SiMe3)2 - Precursors for PN3S2 RingsThe reactions of the (disilylamino)phosphanes (Rf)2P - N(SiMe3)2 (Rf = CF3, C2F5) with S3N2Cl2 lead to new cyclophosphadithiatriazenes of composition (Rf)2PN3S2 (1a, b) with elimination of Me3SiCl and S8. By-products are (Rf)2P(Cl) = NSiMe3 (2a, b). Reaction of 1a, b with norbornadiene yields 1:1 adducts 3a, b. The X-ray structure analysis of 3a (Rf = CF3) is reported. When 1a is allowed to stand for several days a crystalline compound of composition [(CF3)2PN2S]2 (4) is formed. The X-ray structure analysis shows that 4 contains an eight-membered ring with 1,3-P(CF3)2 groups.
    Notes: Aus den (Disilylamino)phosphanen (Rf)2P - N(SiMe3)2 (Rf = CF3, C2F5) und S3N2Cl2 werden unter Abspaltung von Me3SiCl und S8 neue Cyclophosphadithiatriazene der Zusammensetzung (Rf)2PN3S2 (1a, b) erhalten. Als Nebenprodukte treten Phosphanimide (Rf)2P(Cl) = NSiMe3 (2a, b) auf. 1a, b bilden mit Norbornadien 1:1-Addukte 3a, b. Die Röntgenstrukturanalyse von 3a (Rf = CF3) wird mitgeteilt. Aus 1a bildet sich nach mehrtägigem Stehenlassen eine kristalline Verbindung [(CF3)2PN2S]2 (4), deren Röntgenstrukturbestimmung einen achtgliedrigen Ring mit 1,3-P(CF3)2-Gruppen zeigt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 77
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1935-1939 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Hydrogenation of Substituted 1,1-CyclopropanedicarbonitrilesOn catalytic hydrogenation of 2-butyl-, 2,2-dimethyl-, and 2,2,3-trimethyl-1,1-cyclopropane-dicarbonitrile (1 - 3) ring-opening at the C-1 - C-3 bond occurs as predicted by the rule of Musso et al.2). Two highly substituted cyclopropanes (10, 12) gave no hydrogenolytic ring fission.
    Notes: Bei der katalytischen Hydrierung von 2-Butyl-, 2,2-Dimethyl- und 2,2,3-Trimethyl-1,1-cyclopropandicarbonitril (1 - 3) findet entsprechend der Regel von Musso et al. 2) Ringöffnung an der C-1 - C-3-Bindung statt. Zwei hochsubstituierte Cyclopropane (10, 12) gaben keine hydrogenolytische Ringspaltung.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 78
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1052-1060 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azaborolinyl Complexes, XIII. Synthesis and Properties of Bis(1-tert-butyl-2-methyl-η3-1,2-azaborolinyl)nickelThe reaction of 1-tert-butyl-2-methyl-1,2-azaborolinyllithium (1) with NiBr2 leads to the sandwich complex bis(1-tert-butyl-2-methyl-η3-1,2-azaborolinyl)nickel (2). For the first time it is noticed that the azaborolinyl ring does not serve as η5 but as η3 ligand. The 1H NMR spectrum shows the existence of two isomers (2a,b), one of them could be investigated by X-ray analysis. As a result only the three ring carbon atoms possess binding distances to the nickel atom, whereas boron and nitrogen do not show any covalent interactions with the metal. The position of the signals of the ring protons in the 1H NMR spectrum differs characteristically from the position in other azaborolinyl sandwich complexes and in π-allyl compounds.
    Notes: Die Reaktion von 1-tert-Butyl-2-methyl-1,2-azaborolinyllithium (1) mit NiBr2 führt zum Sandwichkomplex Bis(1-tert-butyl-2-methyl-η3-1,2-azaborolinyl)nickel (2). Erstmals wird beobachtet, daβ der Azaborolinyl-Ring nicht als η5-, sondern als η3-Ligand dient. Das 1H-NMR-Spektrum zeigt das Vorliegen von zwei Isomeren (2a,b), von denen eines röntgenstrukturanalytisch untersucht werden konnte. Danach haben nur die drei Ringkohlenstoffe bindende Abstände zum Nickelatom, während Bor und Stickstoff keine kovalenten Wechselwirkungen mit dem Metall zeigen. Die Lage der Ringprotonen-Signale im 1H-NMR-Spektrum weicht charakteristisch von der Lage in anderen Azaborolinyl-Sandwichkomplexen und in π-Allylverbindungen ab.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 79
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1077-1082 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Struktur von as-Triazinochinazolinen, IDie 3-(Methylthio)-6-R-1,2,4-triazin-5(2H)-one 1 - 6 wurden durch Cyclokondensation mit Anthranilsäure in die 3-R-2H-as-triazino[3.2-b]chinazolin-2,6(1H)-dione 8 - 13 übergeführt. Reaktion von 2-Methyl-3-(methylthio)-6-phenyl-1,2,4-triazin-5(2H)-on (23) mit Anthranilsäure ergab 1-Methyl-3-phenyl-2H-as-triazino[3,4-b]chinazolin-4,6(1H)-dion (29) über das Zwischenprodukt 26. N-Methylanthranilsäure setzte sich mit 2 und 5 zu den 11-Methyl-3-R-2H-as-triazino-[3,2-b]chinazolin-2,6(11H)-dionen 36 und 38 um.
    Notes: 3-(Methyltio)-6-R-1,2,4-triazin-5(2H)-ones 1 - 6 have been converted into the 3-R-2H-as-tri-azino[3,2-b]quinazoline-2,6(1H)-diones 8 - 13 upon cyclocondensation with anthranilic acid. Reaction of 2-methyl-3-(methylthio)-6-phenyl-1,2,4-triazin-5(2H)-one (23) with anthranilic acid gave 1-methyl-3-phenyl-2H-as-triazino[3,4-b]quinoazoline-4,69 (1H)-dione (29) via the intermediate 26. N-Methylanthranilic acid and 2 or 5 afforded the 11-methyl-3-R-2H-as-triazino[3,2-b]quinazoline-2,6(11H)-diones 36 and 38, respectively.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 80
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1259-1261 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Simple Synthesis of 5-Cyano-2-pyridinecarboxylic Acid and its AmideThe title compounds 3 and 2 (X = CN) are prepared in good yields by regioselective carbamoylation of 3-cyanopyridine in a Minisci reaction and by consecutive amide hydrolysis with amyl nitrite in HCl-saturated acetic acid. The observed regioselectivity apparently remains confined to carbamoyl and possibly acyl radicals and to - M-effect substituents in 3-position.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 81
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Methylene Complexes, XLIII. Three- and Four-membered Dimetallacycles Having Sulfur Dioxide, Selenium, Chlorogold, and a Silver Diazoalkane as Molecular Building BlocksAs a very good π-ligand, sulfur dioxide adds under mild conditions (-80… +25°C) in fast and clean reactions to metal-metal double bonds with formation of stable 1:1 adducts that exhibit bridging sulfur dioxide ligands. Starting from the doubly bridged metal-metal double bonds of the dinuclear organorhodium- and -cobalt complexes 1a, b, 3, and 5, the novel μ-SO2 complexes 2a, b, 4, and 6, respectively, are formed. In some of these reactions, the coordination mode of the former bridging ligands changes to terminal. The first known μ-(thioformaldehyde S,S-dioxide-C,S) complexes 8a, b are achieved by means of clean electrophilic ring expansion reactions when sulfur dioxide inserts into the μ-methylene complexes 7a and 7b, respectively. Elemental selenium (9a), carbonyl(chloro)gold (9b), and the silver diazoalkane 9c form the three-membered metallacycles 10a - c upon treatment with 1a.
    Notes: Schwefeldioxid addiert sich als vorzüglicher π-Ligand unter schonenden Reaktionsbedingungen (-80… +25°C) rasch und übersichtlich an Metall-Metall-Doppelbindungen unter Bildung beständiger 1:1-Addukte, in denen stets SO2-Brücken vorliegen. Ausgehend von den zweifach verbrückten Metall-Metall-Doppelbindungen der zweikernigen Organorhodium- und cobalt-Komplexe 1a, b, 3 und 5 entstehen unter teilweiser Konstitutionsisomerisierung der Brückenliganden die neuen μ-SO2-Komplexe 2a, b, 4 bzw. 6. Durch glatt verlaufende elektrophile Ringerweiterungsreaktionen der μ-Methylen-Komplexe 7a, b sind die ersten μ-(Thioformaldehyd-S,S-dioxid-C,S)-Komplexe 8a, b zugänglich. Mit elementarem Selen (9a), Carbonyl(chloro)gold (9b) und dem Silberdiazoalkan 9c bildet 1a die dreigliedrigen Ringsysteme 10a - c.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 82
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mechanistic Investigations with the Aid of Isotopic Labeling, VIII. Investigations of the Reaction Pathway to Pyrrolo[2,3-d]pyrimidines from 4-Benzoyl-5-phenyl-2,3-furandione and Aryl Isocyanates4-Benzoyl-5-phenyl-2,3-furandione (1) reacts with aryl isocyanates to yield the pyrrolo[2,3-d]-pyrimidines 4 and the 2,3-pyrrolediones 2; using alkyl isocyanates the corresponding 2,3-pyrrolediones 2e - g are formed exclusively. The formation of 4 and 2 includes [4+2]cycloaddition steps and decarboxylation processes and should proceed via the (α-iminobenzyl)furandiones 6 and the (α-iminobenzyl)pyrrolediones 5 as probable intermediates. This is shown by chemical reactions, by an X-ray structure determination of 4e, and by the results of 14C-labeling. The reaction pathway of the thermolysis of 4 leading to the compounds 3 and 5 is additionally elucidated.
    Notes: 4-Benzoyl-5-phenyl-2,3-furandion (1) reagiert mit Arylisocyanaten zu den Pyrrolo[2,3-d]pyrimidinen 4 und den 2,3-Pyrroldionen 2. Bei Verwendung von Alkylisocyanaten entstehen ausschließlich die entsprechenden 2,3-Pyrroldione 2e - g. Die Bildung von 4 bzw. 2 umfaßt [4+2]-Cycloadditions- sowie Decarboxylierungsschritte und sollte über (α-Iminobenzyl)furandion- (6) und (α-Iminobenzyl)pyrroldion- (5) Zwischenstufen verlaufen. Dies konnte durch chemische Umsetzungen, eine Röntgenstrukturanalyse von 4e sowie mittels 14C-Markierung gezeigt werden. Das Entstehen der Thermolyseprodukte 3 und 5 aus 4 wird erklärt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 83
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1378-1392 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bildungsgeschwindigkeit und Charakterisierung von MagnesiumanthracenAufgrund kernresonanzspektroskopischer Untersuchungen (1H- und 13C-NMR) ist Magnesium im aus THF kristallisierbaren Magnesiumanthracen ⋅ 3 THF (2a) an den 9,10-Positionen des Anthracens gebunden. Die Bildungsgeschwindigkeit von 2a aus Magnesium und Anthracen ist in THF bei 60°C sowohl zur Anthracenkonzentration als auch zur Magnesiumoberfläche, bei 25°C nur zur Magnesiumoberfläche proportional. Magnesium, Anthracen und THF stehen mit 2a in einem temperaturabhängigen, reversiblen Gleichgewicht (Gl. 6), wobei tiefe Temperaturen die Bildung von 2a begünstigen. Bei erhöhten Temperaturen reagiert 2a mit dem Lösungsmittel unter Ringöffnung von THF und Einschiebung von Butylenoxy-Einheiten in die Mg - C-Bindungen, so daß nach Hydrolyse die Alkohole 6 bzw. 7 erhalten werden.
    Notes: 1H and 13C NMR studies on magnesium anthracene ⋅ 3 THF (2a), which can be recrystallized from THF, indicate that magnesium has the strongest interaction with the 9,10-positions of anthracene. While the rate of formation of 2a from magnesium and anthracene in THF at 60°C is proportional to both anthracene concentration and magnesium surface area, at 25°C it is proportional only to magnesium surface area Magnesium, anthracene and THF exist in a temperature dependent, reversible equilibrium with 2a (eq. 6), the formation of 2a being favoured at lower temperatures. At higher temperatures 2a reacts with the solvent to produce ring opening of THF and insertion of butyleneoxy units in the Mg - C bonds, so that on hydrolysis the alcohols 6 and 7 are obtained.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 84
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1393-1399 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermischer Zerfall von 1,2-Oxathiolan in der GasphaseDer cyclische Sulfensäureester 1,2-Oxathiolan (1) zersetzt sich thermisch (400 - 450 K) über 3-Mercaptopropanal (2) unter Verlust von H2S ausschließlich zu Acrolein (3). Experimente mit isotopenmarkierten Verbindungen weisen auf ein 1,2-Oxathiolan-Thietan-1-oxid-Gleichgewicht (1 ⇌ 4).
    Notes: The cyclic sulfenic ester 1,2-oxathiolane (1) decomposes thermally (400 - 450 K) exclusively to give acrolein (3) via 3-mercaptopropanal (2) by loss of hydrogen sulfide. Isotopic labelling experiments reveal the presence of a 1,2-oxathiolane-thietane 1-oxide equilibrium (1 ⇌ 4).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 85
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1455-1464 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azo Bridges from Azines, III. Unexpected Formation of a Compounds with Parallel C=C and N=N Bonds2)Dialdehyde 5 reacts with hydrazine at pH 〉 7 to form the trimeric azine 6Tr, at pH 〈 4, however, to yield unexpectedly 8, which contains parallel C=C and N=N bonds in close proximity. The complex reaction is clarified. 8 is characterized by structure proving reactions and its spectroscopic data.
    Notes: Der Dialdehyd 5 reagiert mit Hydrazin bei pH 〉 7 zu dem trimeren Azin 6Tr, bei pH 〈 4 unerwartet zu 8, das parallel benachbarte C=C- und N=N-Bindungen besitzt. Der komplexe Reaktionsverlauf wird aufgeklärt. 8 wird durch struktursichernde Reaktionen und spektroskopische Daten charakterisiert.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 86
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1424-1435 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Reaction of 2-Pyrrolecarbaldehyde with Hetero-substituted Ethenes3H-Pyrrolizines 1 have been obtained from reactions of 2-pyrrolecarbaldehyde with ethenylphosphonates 2 and the phosphane oxide 5, respectively, the ratio of products depending on the structure of the educts. On varying the reaction conditions a controlled synthesis of both isomers 1e/f was achieved. Pyrrolizines, formed in a reaction of 2 pyrrolecarbaldehyde with ethenyl phenyl sulfone (3), could not be isolated since the reaction proceeded to give more complex pyrrolizine derivatives and the cyclazine 11. A mechanism is proposed for this multistep reaction. N-Alkylation of 2-pyrrolecarbaldehyde with dihaloalkanes has been carried out using phase transfer catalysis.
    Notes: Umsetzungen des 2-Pyrrolcarbaldehyds mit Ethenylphosphonaten 2 und dem Phosphanoxid 5 führten zu 3H-Pyrrolizinen 1, wobei das Mengenverhältnis der gebildeten Isomeren von der Struktur der Edukte abhängt. In einem Falle (1e/1f) gelang die gezielte Synthese beider Isomeren durch Variation der Reaktionsbedingungen. Die aus 2-Pyrrolcarbaldehyd und Ethenylphenylsulfon (3) entstandenen Pyrrolizine 1e/f reagieren weiter unter Bildung komplexer Pyrrolizinderivate und des Cyclazins 11. Für diese Mehrstufenreaktion wird ein Mechanismus vorgeschlagen. Unter Phasentransfer-Bedingungen gelingen Alkylierungen des 2-Pyrrolcarbaldehyds mit Dihalogenalkanen.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 87
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1436-1454 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Evidence for a Radical Chain Mechanism for the Knabe Reaction of 1,2-Dihydro-2-methylpapaverineA free radical chain mechanism is proposed for the Knabe reaction and the accompanying elimination reaction on account of their nonintegral reaction order and of successful inhibition experiments. 3,4-Dimethoxybenzyl radicals are the chain carrying species. Battersby's synthesis of N-methylpavine (19) from 1,2-dihydro-2-methylpapaverine (9) is dependent on the presence of formic acid as radical chain inhibitor. In the presence of inhibitors 1-benzyl-1,4-dihydro-2-methyl-isoquinolinium ions like 10 are persistent species whose chemistry can now be investigated.
    Notes: Die Knabe-Reaktion von 1,2-Dihydro-2-methylpapaverin (9) und die begleitende Eliminierungsreaktion wurden durch ihre gebrochene Reaktionsordnung und durch die Möglichkeit der Inhibition als Radikalkettenreaktionen erkannt, deren kettentragendes Radikal das 3,4-Dimethoxybenzylradikal ist. Die Synthese von N-Methylpavin (19) aus 1,2-Dihydro-2-methylpapaverin (9) ist an die Anwesenheit von Ameisensäure als Inhibitor der Radikalketten gebunden. Durch Zusatz von Inhibitoren können nun Immoniumionen 10 und analoge Verbindungen stabilisiert und ihre Chemie untersucht werden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 88
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1497-1512 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Amino Acids, 21,2). N-Acetyl α,β-Didehydro α-Amino Acid Esters from α-Azidocarboxylic Acid Esters and Acetic Anhydride by Nitrogen Elimination with Rhenium Catalystsα-Azidocarboxylic acid esters 2 react with acetic anhydride in presence of catalytic amounts of rhenium heptasulfide and - if necessary - by addition of hydrochloric acid to give N-acetyl 3 or/and N,N-diacetyl-α,β-didehydro-α-amino acids esters 4 in very good yields. Exclusively monoacetylated products 3 are formed if water ist added before work up.
    Notes: Beim Erwärmen von α-Azidocarbonsäureestern 2 in Acetanhydrid/Essigsäure in Gegenwart katalytischer Mengen Rheniumheptasulfid und gegebenenfalls unter Zugabe von Chlorwasserstoff entstehen in sehr guten Ausbeuten N-Acetyl- 3 und/oder N,N-Diacetyl-α-β-didehydro-α-amino-säureester 4. Durch Zugabe von Wasser vor der Aufarbeitung erfolgt partielle Deacetylierung unter ausschließlicher Bildung der N-Monoacetylverbindungen 3.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 89
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic Compounds, VI1) Formation of Isomers upon Acylation of Compounds Having a 1-Aryl-4-methyl-5H-2,3-benzodiazepine SkeletonAcetylation of 1-(3,4-dimethoxyphenyl)-5-ethyl-7,8-dimethoxy-4-methyl-5H-2,3-benzodiazepine (1)2,3 in hot acetic anhydride yields the isomers 2a and 3a in equal proportions. Acetylation of 1 in the presence of pyridine led exclusively of 2a5), that of 1 ⋅ HCl (4)2,6) in hot acetic anhydride solely to 3a. 2a and 3a mutually fail to interconvert. However, 3a may be prepared from 2a via 5. While 3a was resistant against aqueous hydrolysis, at the same conditions 2a was converted into 7a by ring fission. 2b, 3b, and 7b were synthesized by applying propionic anhydride, and 3c from 4 by using benzoic anhydride. 13C-labelled 1 (17) and 3a (18) were prepared to assign the 13C-NMR signals of 3a. Furthermore, some additional examples are presented for the acetylation of 5H-2,3-benzodiazepines and their salts (22 - 26).
    Notes: Bei der Acetylierung von 1-(3,4-Dimethoxyphenyl)-5-ethyl-7,8-dimethoxy-4-methyl-5H-2,3-benzodiazepin (1)2,3) mit heißem Acetanhydrid werden die Isomeren 2a und 3a im Verhältnis von ≍ 1:1 gebildet. Die Acetylierung von 1 in Gegenwart von Pyridin führt ausschließlich zu 2a5), die des Hydrochlorids von 1(4)2,6) in heißem Acetanhydrid ausschließlich zu 3a. 2a und 3a können nicht ineinander umgewandelt werden, doch kann 3a aus 2a über 5 dargestellt werden. Während 3a beständig gegen wäßrige Hydrolyse ist, wird unter denselben Bedingungen 2a durch Ringöffnung in 7a übergeführt. Mittels Propionsäureanhydrid wurden 2b, 3b und 7b und mittels Benzoesäureanhydrid 3c synthetisiert. Für die Zuordnung des 13C-NMR-Spektrums von 3a wurden 13C-markiertes 1 (17) und 3a (18) hergestellt. Für die Acetylierung von 5H-2,3-Benzodiazepin-Basen und ihrer Salze werden noch weitere Beispiele angegeben (22 - 26).
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 90
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1523-1541 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminierung, III. Trimethylsilanol als austretende Gruppe, V. Silylierung-Aminierung von Hydroxy-N-heterocyclenDurch Silylierung-Aminierung lassen sich Hydroxy-N-heterocyclen (z. B. 18, 21, 26 u. a.) bequem in einer Einstufen-Eintopfreaktion aminieren (→ 20, 23 - 25 etc.). Aromatische Hydroxy-N-heterocyclen werden durch Silylierung in aktivierte und lipophile Zwischenprodukte vom Typ 3, 8 umgewandelt, die sich in situ mit Ammoniak, primären oder sekundären Aminen zu den entsprechenden mono-, bis- und tris-aminierten Produkten (5, 10) umsetzen. Die Additions-Eliminierungsreaktion von Aminen an O-silylierte Heterocyclen ist Lewissäure-katalysiert und verläuft gewöhnlich in hohen Ausbeuten, falls die austretende Gruppe Trimethylsilanol in situ durch überschüssiges Silylierungsmittel in Hexamethyldisiloxan umgewandelt wird. Anwendungsbreite und Grenzen dieser einfachen Methode werden diskutiert.
    Notes: Hydroxy N-heterocycles such as 18, 21, 26, and others are efficiently aminated in a one-step/one-pot procedure by silylation-amination to give 20, 23 - 25 etc. Silylation converts aromatic hydroxy N-heterocycles into activated and lipophilic intermediates of type 3, 8 which react in situ with ammonia, primary or secondary amines to form the corresponding mono-, bis- or tris-aminated products (5, 10). This addition-elimination of amines to O-silylated heterocycles in Lewis acid-catalyzed and proceeds usually in high yields if the leaving group trimethylsilanol is converted in situ by excess silylated agent into hexamethyldisiloxane. Scope and limitations of this simple procedure are discussed.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 91
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1765-1800 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polyfunctionalised Cyclohexanes from Dianhydrodeoxyinositols. cis-Deoxy-1,3(1,4)-inosadiamines from BenzeneA ca. 9:1 mixture (yield 87 - 90%) of the stereoisomeric (1α,2α,6α)-/(1α,2β,6α)-2-bromo-7-oxabicyclo[4.1.0]hept-3-enes (7a/8a) is obtained via controlled NBS bromination of 4,5-epoxycyclohexene (5). 7a/8a are quantitatively equilibrated in the presence of tetraalkylammonium bromides (the equilibrium being controlled by the polarity of the solvent (3:7 in acetonitrile)) and are isolated pure by chromatography. Through selective halogen substitution (7b/8b, 9b - d/10b - d) and ammonolysis the allylic epoxy alcohols 9a/10a are obtained in high yields. Stereospecific epoxidation of 7a/8a yields the (1α,2α,3α,5α,7α)-/(1α,2β,3α,5α,7α)-diepoxy bromides 12a/14a. The latter are equilibrated quantitatively to mixtures favoring either one in the ratio of ca. 9:1 (CCl4) and 1:9 (CH3CN), respectively. Upon SN2 substitution with ammonium acylates (→ 13b,c/15b,c) and ammonolysis the naturally not occurring dianhydrodeoxyinositols 13a/15a are isolated in practically quantitative yields. The usefulness of 13a/15a and of various derivatives for the stereoselective synthesis of cis-1,4- and cis-1,3-disubstituted cyclohexanetriols is exemplified by reactions with monovalent (H2O, HI, NaN3) and divalent nucleophiles (NH2NH2, CH3NHNH2). I.a. the cis-deoxy-1,3-inosadiamines 1 (2-deoxystreptamine)/2 and the cis-deoxy-1,4-inosadiamines 3/4 become available in high yields.
    Notes: Durch kontrollierte NBS-Bromierung von 4,5-Epoxycyclohexen (5) wird in 87 - 90proz. Ausbeute ein ca. 9:1-Gemisch der (1α,2α,6α)-/(1α,2β,6α)-2-Brom-7-oxabicyclo[4.1.0]hept-3-ene (7a/8a) erhalten. Diese können in Gegenwart von Tetraalkylammoniumbromiden verlustfrei und je nach Polarität des Lösungsmittels zu unterschiedlichen Gemischen (3:7 in Acetonitril) äquilibriert und chromatographisch rein isoliert werden. Durch selektive Halogensubstitution (7b/8b, 9b - d/ 10b - d) und Ammonolyse werden in hohen Ausbeuten die Allylepoxyalkohole 9a/10a zugänglich. Über die stereospezifische Epoxidierung von 7a/8a gewinnt man die (1α,2α,3α,5α,7α)-/(1α,2β,3α,5α,7α)-Diepoxybromide 12a/14a, die sich ebenfalls verlustfrei äquilibrieren (ca. 9:1 in CCl4, ca. 1:9 in CH3CN) und mit Ammoniumacylaten über 13b,c/15b,c praktisch quantitativ in die natürlich nicht vorkommenden Dianhydrodesoxyinosite 13a/15a überführen lassen. Die Brauchbarkeit von 13a/15a und diverser Derivate für die stereoselektive Synthese cis-1,4- bzw. cis-1,3-disubstituierter Cyclohexantriole wird durch Umsetzung mit monovalenten (H2O, HI, NaN3) und divalenten Partnern (NH2NH2, CH3NHNH2) exemplarisch belegt. U.a. werden dadurch die cis-Desoxy-1,3-inosadiamine 1 (2-Desoxystreptamin)/2 und die cis-Desoxy-1,4-inosadiamine 3/4 totalsynthetisch in hohen Ausbeuten zugänglich.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 92
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensed Ring Systems, XVI1). Synthesis, Crystal and Molecular Structure of a 1,4-Bridged Dewar-Benzene of the [6.2.2]Propellane Series with Conformational EnantiomerismStarting from 3,4:5,6-dibenzo-10,13-dithia[6.3.3]propella-3,5-diene (1) racemic 3,4:5,6-dibenzo-[6.2.2]propella-3,5,9,11-tetraene (7) is prepared. Its constitution is established by X-ray structure analysis. An enantiomeric enrichment of 7 has been achieved by chromatography on triacetyl cellulose; its halflife at 20°C is about 100 h.
    Notes: Ausgehend von 3,4:5,6-Dibenzo-10,13-dithia[6.3.3]propella-3,5-dien (1) wird das racemische 3,4:5,6-Dibenzo[6.2.2]propella-3,5,9,11-tetraen (7) hergestellt. Seine Konstitution wird röntgenstrukturanalytisch bewiesen. Durch Chromatographie an Triacetylcellulose konnte eine Anreicherung der Enantiomeren von 7 erreicht werden, deren Halbwertszeit bei 20°C ca. 100 h beträgt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 93
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1885-1895 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: About the Silylation of 1-tert-Butyl-1-sila-2,4-cyclohexadienes in the 2-, 4-, and 6-Position1-Sila-2,4-cyclohexadiene (1) reacts with tert-butyllithium to give 1-tert-butyl-1-sila-2,4-cyclohexadiene (3), which is transferred to 1-tert-butyl-1-chloro- (2) and 1-tert-butyl-1-methoxy-1-sila-2,4-cyclohexadiene (4) by substitution reactions. Silylation reactions at the pentadiene systems 2, 3, and 4 lead to the mono (5, 6, 7)-, bis (8, 9)-, and tris-trimethylsilylated (10) 1-tert-butyl-1-sila-cyclohexadienes. The 1H, 13C, and 29Si NMR data of the compounds are described.
    Notes: 1-Sila-2,4-cyclohexadien (1) reagiert mit tert-Butyllithium zu 1-tert-Butyl-1-sila-2,4-cyclohexadien (3), welches durch Substitutionsreaktionen in 1-tert-Butyl-1-chlor- (2) und 1-tert-Butyl-1-methoxy-1-sila-2,4-cyclohexadien (4) übergeführt werden kann. Silylierungsreaktionen an den Pentadiensystemen 2, 3 und 4 führen zu den mono(5, 6, 7)-, bis(8, 9)- und tris(trimethylsilyl)-substituierten (10) 1-tert-Butyl-1-silacyclohexadienen. Die 1H-, 13C- und 29Si-NMR-Daten der Verbindungen werden beschrieben.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 94
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1920-1925 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrochemical Syntheses, XX1). The Syntheses of S4N4 and (S5N5)ClThe cathodic reduction of S3N3Cl3 in 0.1 M (Ph3P=N=PPh3)[PF6]/CH2Cl2 or 0.15 M (Bu4N)-[BF4]/CH2Cl2 yields S4N4 at room temperature and (S5N5)Cl at - 20°C with current efficiencies of 90% and 49%, respectively.
    Notes: Die kathodische Reduktion von S3N3Cl3 in 0.1 M (Ph3P=N=PPh3)[PF6]/CH2Cl2 oder 0.15 M (Bu4N)[BF4]/CH2Cl2 ergibt bei Raumtemperatur S4N4 und bei - 20°C (S5N5)Cl mit Stromausbeuten von 90% bzw. 49%.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 95
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diazadienes as Controlling Ligands in Homogeneous Catalysis, VII1). Catalytic Synthesis and Structure of a Cyclooctatetraene with Twofold Vicinal Substitution - 1,4,5,8-Tetrakis[(p-tolyloxy)methyl]-1,3,5,7-cyclooctatetraeneThe catalytic reaction of 2-propynyl p-tolyl ether (propargyl p-tolyl either) with the diazadiene nickel complex 4 gives a highly symmetrical cycloocatetraene derivative 2. 1H NMR and 13C NMR spectra do not allow to distinguish between three possible substitution patterns (1,3,5,7; 1,4,5,8; 1,2,5,6). Double bond and substituent positions were determined by an X-ray structural analysis. The encountered pattern with a twofold vicinal substitution (1,4,5,8) was hitherto unknown for catalytically prepared cycloocatatetraenes. At the same time, 2 is the first cyclotetramer of a propargylic ether.
    Notes: Die katalytische Umsetzung von 2-Propinyl-p-tolylether (Propargyl-p-tolylether) mit dem Diazadien-nickelkomplex 4 führt zu einem hochsymmetrischen Cyclooctatetraenderivat 2. 1H-NMR- und 13C-NMR-Spektren erlauben aus Symmetriegründen keine Unterscheidung zwischen drei möglichen Substitutionsmusten (1,3,5,7; 1,4,5,8; 1,2,5,6). Durch eine Röntgenstrukturanalyse wurden die Substituentenstellung und die Lage der Doppelbindungen bestimmt. Das gefundene, doppelt vicinale 1,4,5,8-Substitutionsmuster war für katalytisch dargestellte Cyclooctatertraene bis jetzt unbekannt; zugleich ist 2 das erste Cyclotetramere eines Propargylethers.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 96
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclische β-Enaminoester, 341). Neue Typen von Spiro-Verbindungen durch Additions- und Ringschlußreaktionen von 3-(2-Imidazolidinyliden)- und 3-(Tetrahydro-2(1H)-pyrimidinyliden)dihydro-2(3H)-furanonen mit Acrylsäure-methylester und Acetylendicarbonsäure-dimethylesterDie 2(3H)-Furanone 1a - e reagieren mit Acrylsäure-methylester in Benzol- oder Dioxanlösung in einer Additions- und Cyclokondensations-Sequenz zu den Spiro-Verbindungen 2a - e. 1a, b ergeben mit Acetylendicarbonsäure-dimethylester die Additionsprodukte 3a, b; hingegen resultieren aus 1c - e in einer verwandten Additions-Cyclokondensationssequenz die Spiro-Verbindungen 4a - c.
    Notes: The 2(3H-furanones 1a - e react with methyl acrylate in benzene or dioxane solution to afford the spiro compounds 2a - e in an addition and cyclocondensation reaction sequence. With dimethyl acetylenedicarboxylate 1a, b give merely the addition products 3a, b, while 1c - e yields the spiro compounds 4a - c in a related addition-cyclocondensation step.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 97
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2761-2778 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Photochemical Elimination of Nitrogen from 1-(1-Alkenyl)-4-tert-butyl-1,4-dihydro-5H-tetrazol-5-ones. Competition between Addition of Methanol and Cyclization of a Dipolar IntermediateThe 4-tert-butyl-1-vinylterazolones 12a - c and the tetrazolones 13 and 14 are synthesized from the 5-chlorotetrazole 7 and the tetrazolone 9 via several routes. Bis(benzonitrile)palladium dichloride catalyses the O → N-Claisen rearrangement 8 → 11, the allyl → vinyl rearrangements 11a → 12b and 11b → 12c, as well as the equilibration 13 → 14. On 254 nm photolysis of the vinyltetrazolones 12 nitrogen is extruded and cyclic and/or acylic products of primary photo-intermediates are formed: In [D3]acetonitrile as solvent, 77% of 1-tert-butylimidazolone 16 arises from 12a, while the tetrazolones 12b, c produce only complex mixtures. In methanol as solvent, the methanol adduct 20a (23%) of the intermediate imidazolone 15a and the acyclic N-(1,2-dimethoxyethyl)urea 22a (32%) are obtained besides 45% of 16. In contrast, from 12c in methanol the corresponding urea 22c is formed almost quantitatively as the only product. In [D4]methanol solution of (E,Z)-12b a ratio of 4-methoxyimidazolidinone 20 b to the diastereomeric ureas 22 b of 22: 78 is observed. With decreasing amounts of [D4]methanol in [D4]methanol/[D3]acetonitrile mixtures, the imidazolidinone 20 b increases at the expense of the ureas 22 b. A 20 b: 22 b ratio of 98: 2 is reached in [D3]acetonitrile containing 3-6% [D4]methanol. This indicates a competition between the cyclization (affording 20 b via 15 b) and the methanol addition (producing 22 b via 21 b) of a dipolar photo-intermediate. The structure of the photo-products are confirmed by independent synthesis of 16 and by their high field proton and carbon-13 NMR spectra.
    Notes: Aus dem 5-Chlortetrazol 7 und dem Tetrazolon 9 werden auf verschiedenen Wegen die 4-tert-Butyl-1-vinyltetrazolone 12a - c sowie die Tetrazolone 13 und 14 hergestellt. Bei der 254-nm-Photolyse der 1-Vinyltetrazolone 12 erhält man in Abhängigkeit von Struktur und Reaktionsbedingungen das Imidazolon 16, die 4-Methoxyimidazolidinone 20 und/oder die N-(1,2-Dimethoxyalkyl)harnstoffe 22. Die Ergebnisse sprechen für eine Konkurrenz zwischen Cyclisierung (→ 15b → 20b) und Methanol-Addition (→ 21b → 22b) einer dipolaren Photozwischenstufe. Die Struktur der Photoprodukte wird durch unabhängige Synthese von 16 sowie Hochfeld-1H-und 13C-NMR-Spektren bewiesen.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2779-2784 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of New 1,2,6-Thiadiazines and 1,3,2,4-DithiadiazinesThe synthesis of some new benzo- and benzothieno-substituted 1,2,6-thiadiazin-3-ones 4a - c, 9a - f by cyclisation of dialkylsulfur diimides 1a - c with halide substituted acid chlorides 2 and 5a - c is described. Analogous cyclisation of the sulfonyl chloride 6 with 1a - d leads to 1,3.2,4-dithiadiazines 10a - d.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2785-2789 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions with Allylidenephosphoranes, IV. An Easy Synthesis of Cyclopentadienones (Cyclones)The allylidenephosphoranes 2 react with α-ketocarbonyl chlorides 3 readily to afford the cyclopentadienones 4 and their Diels-Alder dimers 5. With an excess of 2a, 4a undergoes competitive Michael additions yielding a mixture of 4-allylidene-2-cyclopentenone 6 and 4-(1-propenyl)-2-cyclopentenone 7.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...