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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3490-3514 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1H NMR Shifts in the Molecular Planes of Anisotropic CO, CN, and CC Double BondsSynthetic procedures are given for fluorenes with 2,7- and 1,8-dimethyl as well as 2-fluoro and 2,7-difluoro substituents. Analysis and comparison of the NMR spectra provides evidence of downfield shifts for protons situated in the planes of doubly bonded moieties with reference to compounds devoid of such double bonds. Tetralin and indan derivatives lead to corresponding conclusions. The importance of conjugation and of electric field effects is assessed by protonation studies.
    Notes: Die Synthese von Fluorenderivaten mit 2,7- und 1,8-Dimethyl- sowie 2-Fluor- und 2,7-Difluor-Substituenten wird beschrieben. Durch Analyse und Vergleich ihrer NMR-Spektren zeigt sich, daß 1H-Atomkerne in Doppelbindungsebenen bei geringeren Magnetfeldstärken absorbieren als in Vergleichsverbindungen ohne entsprechende Doppelbindung. Modellverbindungen mit Tetralin- und Indan-Struktur führen zum gleichen Schluß. Die Bedeutung konjugativer Substituenteneinflüsse und elektrischer Feldeffekte wird anhand von Verschiebungsänderungen bei der Protonierung beurteilt.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 2116-2131 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2-Methyl-1-phenyl-1-propenyllithium. A vinyllithium Derivative Showing Catalyzed TransmetalationFull preparative and kinetic details are given for the apparent vinyl-to-allyl anion rearrangement1)of the title compound 1. The rapid and quantitative formation of the allyllithium derivative 7 is shown to be catalyzed by 2-methyl-1-phenyl-1-propene (2). An intermolecular transmetalation mechanism with de-aggregation and ionization steps is suggested to explain the orders of reaction, parameters of activation, and solvent dependency.
    Notes: Die rasche und vollständige Umwandlung der Vinyllithium-Verbindung 1 in die Allyllithium-Verbindung 7 wird 1H-NMR-spektroskopisch verfolgt und durch chemische Umsetzungen belegt. Diese scheinbare Umlagerungsreaktion erfolgt unter katalytischer Mitwirkung des 2-Methyl-1-phenyl-1-propens(2). Aus den Reaktionsordnungen, Aktivierungsparametern und der Solvensabhängigkeit wird auf einen intermolekularen Ummetallierungsmechanismus mit deaggregierten und ionisierten Zwischenstufen geschlossen.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 1592-1599 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vinyl-Benzyl-Isomerisierung und Elektrocyclisierungen bei Lithiumderivaten des o-Tolylstilbens(Z)-2-(2-Methylphenyl)-1,2-diphenylvinyllithium (1) lagert sich in THF-Lösung zu 1-[2-(Lithiomethyl)phenyl]-1,2-diphenylethen (2) um. Die Benzyllithiumverbindung 2 kann hierbei zwar nicht direkt beobachtet werden, ist aber wegen ihrer unabhängigen Bildung bei der Metallierung von 1-[2-Ethoxymethyl)phenyl]- (5) und 1-(2-Methylphenyl)-1,2-diphenylethen (7) mit den gleichen Folgeprodukten zwangsläufige Zwischenstufe. 2 cyclisiert unter reversiblem Angriff auf den syn-ständigen Phenylkern zum Cyclohexadienid-Anion 3 mit siebengliedrigem Ring. 3 zeigt Koaleszenzphänomene im Protonenresonanzspektrum und isomerisiert bei thermodynamischem Reaktionsabschluß zum 1,2-Diphenyl-1-indanid-Anion 10.
    Notes: (Z)-2-(2-Methylphenyl)-1,2-diphenylvinyllithium (1) isomerizes in THF solution to give 1-[2-(lithiomethyl)phenyl]-1,2-diphenylethene (2). Although 2 cannot be observed directly in this case, its intermediacy becomes evident from the independent preparation by metallation of 1-[2-(ethoxymethyl)phenyl]- (5) and 1-(2-methylphenyl)-1,2-diphenylethene (7), with formation of the same sequential products from all three sources. 2 cyclizes by reversible attack on the syn-phenyl group to give a cyclohexadienide anion 3 containing a seven-membered ring. 3 exhibits 1H NMR coalescence phenomena and rearranges under thermodynamic control to the 1,2-diphenyl-1-indanide anion 10.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 1581-1591 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Conformational ortho-Effect ino-Tolylstilbenes and their vinyllithium Derivatives1,2)Geometrical isomers of stilbene derivatives with an additional, o-substituted phenyl moiety at the CC double bond (5, 6, 13) are prepared and structurally assigned. The isomer with the two phenyl groups in trans-position is favoured in equilibrium (conformational ortho-effect). For the vinyllithium derivative (19/20), a strong solvent dependency of 1H NMR shifts and of the rate of equilibration if found.
    Notes: Geometrische Isomere von Stilbenderivaten mit o-substituiertem Phenyl als zusätzlichem Substituenten an der CC-Doppelbindung (5, 6, 13) werden hergestellt und strukturell zugeordnet. Das Isomere mit trans-ständigen Phenylgruppen ist im Gleichgewicht begünstigt (konformativer ortho-Effekt). Beim Vinyllithiumderivat (19/20) hängen die 1H-NMR-Verschiebungen und die Geschwindigkeit der Gleichgewichtseinstellung stark vom Lösungsmittel ab.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 1600-1609 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1-Phenyl-2,2-di(o-tolyl)vinyllithium E/Z-Topomerization, Vinyl-to-Benzyl Isomerization, and Electrocyclization Reactions1,2)Diastereotopomerization of the methyl groups by carbanion inversion in the title compound 5 occurs slowly in boiling diethyl ether and rapidly in cooled THF solutions (NMR coalescence at -28°C). 5 in THF undergoes irreversible isomerization at ca. 0°C to give the benzyllithium derivative E-8. The seven-membered ring anion 13, exhibiting 1H NMR coalescence phenomena, is slowly formed from 8 in THF at room temperature in a kinetically controlled reaction. The thermodynamically controlled termination reaction at + 60°C produces the anion 16 by five-membered ring closure.
    Notes: Die Diastereotopomerisierung der Methylgruppen durch Carbanion-Inversion in der Titelverbindung 5 erfolgt in siedendem Diethylether langsam, in tiefgekühltem THF rasch (NMR-Koaleszenz bei -28°C). Bei a. 0°C isomerisiert 5 in THF irreversibel zum Benzyllithium-Derivat D-8. In kinetisch gesteuerter Reaktion bildet sich aus 8 in THF bei Raumtemperatur langsam das Anion 13 mit siebengliedrigem Ring, das Koaleszenzerscheinungen im Protonenresonanzspektrum zeigt. Der thermodynamisch kontrollierte Reaktionsabschluß bei + 60°C führt zum Anion 16 mit fünfgliedrigem Ring.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1980 (1980), S. 1207-1215 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Formation and Reactivity of Di-tert-alkyl Substituted PhenylalkenesMolecular rearrangements occur during the attempted syntheses of α-bromo-β,β-di-tert-alkylstyrenes; the resulting structures are elucidated. A hydrocarbon dimer with allenic structure accompanies the formation of the Grignard reagent from an α-bromostyrene with bulky substituents.
    Notes: Bei Versuchen zur Synthese von α-Brom-β,β-di-tert-alkylstyrolen laufen molekulare Umlagerungen ab; die Strukturen der Reaktionsprodukte wurden aufgeklärt. Bei einem sperrig substituierten α-Bromstyrol ist die Bildung der Grignardverbindung von der eines dimeren Kohlenwasserstoffs mit Allenstruktur begleitet.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0009-2940
    Keywords: Aggregations ; Complex, tert-butyl methyl ether ; diastereotopomerization, (EIZ) ; NMR, coupling, constants, HH, CH, CLi ; NMR, Lithiation shifts ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Improved preparations of 2,6-dimethylstyrene (5) and its α-bromo derivative (10) are described. The Br/Li exchange reaction of 10 provides single crystals of the title compounds 11 or 12, which were characterized as disolvated dimers by X-ray analyses. A similar dimer persists in diethyl ether, tert-butyl methyl ether, and toluene at all accessible temperatures, with significant lithiation NMR shifts (relative to 5) partially due to charge delocalization from the sp2-carbanionic center. Some NMR coupling constants are typical of the dimeric aggregate. The configurational (E,Z) lability is quantified in toluene solution.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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