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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' Zeitschrift für analytische Chemie 330 (1988), S. 457-458 
    ISSN: 1618-2650
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 432-434 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das durch Bromierung von 3.3-Diphenyl-1.2.4.5-tetrahydro-3H-3-benzosilepin (1) mit N-Brom-succinimid entstehende 1.5-Dibrom-Derivat 2 läßt sich mit 1.5-Diazabicyclo[4.3.0]-nonen-(5) (3) zu 3.3-Diphenyl-3H-3-benzosilepin (4) dehydrobromieren. Die Pyrolyse des Silepins 4 führt zu Naphthalin.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 105 (1972), S. 2101-2103 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 3.3-Dimethyl-3H-3-benzosilepin and 3H-3-BenzosilepinThe reaction of 3.3-dichloro-3H-3-benzosilepin (1) with methyl lithium leads to 3.3-dimethyl-3H-3-benzosilepin (2). 2 is reduced with tris-(tert.-butoxy)-lithium aluminium hydride to 3H-3-benzosilepin (3). 2 and 3 are investigated by i.r. and n.m.r. spectroscopy and by mass spectrometry.
    Notes: Die Umsetzung von 3.3-Dichlor-3H-3-benzosilepin (1) mit Methyllithium führt zu 3.3-Dimethyl-3H-3-benzosilepin (2). Die Reduktion von 2 mit Tris-[tert.-butyloxy]-lithiumaluminiumhydrid ergibt 3H-3-Benzosilepin (3). 2 und 3 wurden IR- und NMR-spektroskopisch sowie massenspektrometrisch untersucht.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 3314-3318 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluorinated, Methoxylated and Differently Substituted 3H-3-BenzosilepinsThe reaction of 3,3-dichloro-3H-3-benzosilepin (1) with sodium fluoride, sodium methoxide and phenyl lithium leads to 3,3-difluoro- (2), 3,3-dimethoxy- (3), 3,3-diphenyl- (4) and 3-chloro-3-phenyl-3H-3-benzosilepin (5). - 3-Chloro-3-methyl-1,2,4,5-tetrahydro-3H-3-benzosilepin (7) has been brominated with N-bromosuccinimide in the positions 1 and 5, to form the dibromo product 8 which has been transformed into 3-chloro-3-methyl-3H-3-benzosilepin (9) via dehydrobromination. - The preparation of 5 in the same manner as 9 - through bromination of 3-chloro-3-phenyl-1,2,4,5-tetrahydro-3H-3-benzosilepin (6) and dehydrobromination - was not successful. Compound 7 has been transformed into bis(3-methyl-1,2,4,5-tetrahydro-3H-3-benzosilepin-3-yl) ether (10) by hydrolysis.
    Notes: Bei der Reaktion von 3,3-Dichlor-3H-3-benzosilepin (1) mit Natriumfluorid, Natriummethylat und Phenyllithium entstehen 3,3-Difluor- (2), 3,3-Dimethoxy- (3), 3,3-Diphenyl- (4) und 3-Chlor-3-phenyl-3H-3-benzosilepin (5). - 3-Chlor-3-methyl-1,2,4,5-tetrahydro-3H-3-benzosilepin (7) wird mit NBS in 1- und 5-Stellung bromiert, aus dem resultierenden Dibrom-Derivat 8 wird durch Dehydrobromierung das 3-Chlor-3-methyl-3H-3-benzosilepin (9) gebildet. 3-Chlor-3-phenyl-1,2,4,5-tetrahydro-3H-3-benzosilepin (6) kann nicht in der gleichen Weise zu 5 dehydriert werden. - 7 wird hydrolytisch in Bis(3-methyl-1,2,4,5-tetrahydro-3H-3-benzosilepin-3-yl)-ether (10) übergeführt.
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  • 5
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Intramolekulare Wechselwirkungen und behinderte Rotation in Tropinon-urethanen: Eine kombinierte PE-, ET- und DNMR-spektroskopische UntersuchungEine kürzlich postulierte 1,5-nNnO through-space-Wechselwirkung im Azabicyclo-[2.2.2]octanon 1 wurde mit Hilfe des isomeren Tropinon-urethans 3 experimentell bestätigt. In 3 verschwindet aus topologischen und lokalsymmetrischen Gründen das entsprechende Matrixelement 〈nN | H | nO〉. Die kombinierte Anwendung der Photoelektronen- (PES) und Elektronentransmissionsspektroskopie (ETS) läßt die deutliche Unterscheidung zwischen Einflüssen auf symmetrische π- bzw. antisymmetrische π*-Orbitale zu. Es wurde beobachtet, daß die Urethangruppe NCO2CH3 in 4 einen induktiven Effekt ausübt, der praktisch mit dem des O-Atoms in 7 übereinstimmt. Die temperaturabhängigen NMR-Spektren von 3, 4 und 6 lassen sich mit behinderter N—CO-Rotation deuten und nicht, wie im Fall von 6 behauptet, mit einer O—CO-Rotation. Es zeigt sich, daß die CC-Doppelbindung in Dehydrotropinon 4 die Rotationsbarriere erhöht, was durch die lokale Symmetrie und Topologie dieses Tropinongerüstes erklärbar ist. Dieser Effekt ist im Einklang mit den Ergebnissen der PES- und ETS-Messungen.
    Notes: A recently proposed direct 1,5-nNnO through-space interaction in the azabicyclo-[2.2.2]octanone 1 has been confirmed experimentally by investigating the isomeric tropinone urethane 3. In 3 the corresponding homoconjugative matrix element 〈nN | H | nO 〉 vanishes by reasons of topology and local symmetry The combined application of photoelectron (PE) and electron transmission (ET) spectroscopy allows the distinct differentiation between influences upon symmetric π and antisymmetric π* orbitals. It has been found that the urethane group NCO2CH3 in 4 exerts an inductive effect virtually identical with that of the oxygen atom in 7. The variable temperature NMR spectra of 3, 4 and 6 have been interpreted in terms of hindered N — CO rotations and not, as has been claimed in the case of 6, as O — CO rotation. The CC double bond in dehydrotropinone 4 turns out to increase the rotational barrier, a phenomenon which is explained by the local symmetry and topology of this tropinone skeleton and is further supported by the PES and ETS measurements.
    Additional Material: 5 Ill.
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  • 6
    ISSN: 0009-2940
    Keywords: Cycloadditions, dipolar ; Electron-transmission spectroscopy ; Norbornane systems ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of six 7-substituted norbornadienes with seven sulfonyl azides has been investigated. The products consist of either the novel azatetracyclic system 1 or the stereoisomeric bicycles 2 or of a mixture of them. The chemical behaviour of 1 has been studied. Mechanistically the results may be rationalized within the frame of the Mazzocchi-Houk model. The theoretical predictions of this model, concerning the π*and σ* energies, were confirmed experimentally by using electron-transmission spectroscopy.
    Additional Material: 7 Ill.
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  • 7
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