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  • Benzocyclobutene  (1)
  • Benzocycloheptenedione  (1)
  • Chelates  (1)
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  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 921-926 
    ISSN: 1434-1948
    Schlagwort(e): Aluminium ; Chelates ; Lewis acids ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Sodium nitrite (NaNO2) dissolves readily in THF, when the methylene-bridged dialuminium compound R2Al-CH2-AlR2 [R = CH(SiMe3)2] 1 with two coordinatively unsaturated aluminium atoms is added. Compound 1 reacts as a chelating Lewis acid, and, as shown by a crystal structure deter-mination of the [Na([18]crown-6)(Et2O)]+ derivative 5c, a compound (5) is formed, in which one oxygen atom and the nitrogen atom of the nitrite ion are each coordinated by one aluminium atom to form a five-membered Al2CNO hetero-cycle. The second oxygen atom of the nitrite anion is not affected. Similarly, lithium nitrate (LiNO3) reacts with 1 to yield a THF soluble product (6a). Single crystals were obtain-ed of the [Li(N,N′,N′′-trimethyltriazinane)2]+ derivative 6c, whose structure shows each aluminium atom to be coordinated by one oxygen atom of the nitrate ion to give a six-membered Al2CNO2 heterocycle.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    ISSN: 1434-193X
    Schlagwort(e): Chromium ; Benzocyclobutene ; Dianionic Oxy-Cope Rearrangement ; Methoxyallene ; Benzocycloheptenedione ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Addition of carbon nucleophiles to (benzocyclobutenedione)tricarbonylchromium(0) (4) results in the formation of exo mono- and diadducts as well as 1,2-diketones as the consequence of proximal ring-opening reactions. In one case the unexpected formation of benzocycloheptenedione complexes is observed. Treatment of 4 with an excess of 1-ethoxy-1-lithioethene gives the product of a dianionic oxy-Cope rearrangement followed by an intramolecular aldol addition. This is also the case with lithiated methoxyallene, and as the result the first head-to-head coupling product 12 of two methoxyallene molecules is isolated in good yield. 12 is used as a diene in Diels-Alder cycloadditions, and its molecular structure is compared to that of the similar molecule 13, lacking the two exo methylene substitutents.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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