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  • 1
    ISSN: 1434-4475
    Keywords: Azafulvenes ; Biladienes-ac ; Bilatrienes-abc ; DDQ ; Synthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Substituted azafulvenes were generated by dehydrogenation of 5′-methyl-substituted pyrromethenones withDDQ and characterized by UV- and1H-NMR-spectroscopy. Their electrophilic properties were demonstrated using several quenchers and furthermore they were used for a synthesis of verdinoid bile pigments (which easily can be converted to rubinoid systems by the action of NaBH4) with nearly any desired unsymmetrical alkyl substitution patter: The azafulvene spezies was generated by the action ofDDQ on a 5′-methylpyrromethenone and was quenched by an 5′-unsubstituted pyrromethenone. The resulting rubinoid adduct was dehydrogenated immediatly byDDQ — yields were good to high.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 118 (1987), S. 813-821 
    ISSN: 1434-4475
    Keywords: Tautomerisation ; Biladienes-ac ; Biladienes-ab ; Rubin → violintautomerisation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract On the catalysis by strong acids rubins (biladienes-ac) are found to undergo a tautomerisation yielding violins (biladienes-ab). This new and first interconversion reaction between biladiene chromophores can be used to direct the synthesis of rubins or violins starting from the same educts: the condensation of pyrromethenones with formaldehyde yields rubins in case of trifluoroacetic acid and violins when HBr is used as the condensating agent. The mechanistic implications are discussed.
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  • 3
    ISSN: 1434-4475
    Keywords: Bile pigments ; Bilatrienes-abc ; Biladienes-ac ; Photoisomerization, mechanism of ; Triplet energy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Studies of heavy atom effects as well as sensitization and quenching experiments with several model compounds suggested that in pyrromethenones and biladienes-ac the photoisomerization at exocyclic double bonds proceeds predominantly via the singlet path on direct irradiation. The energy of the triplet state of pyrromethenones and arylmethylenepyrrolinones was estimated by sensitization experiments to be in the region from 140 to 160 kJ/mol. On sensitization the reaction follows the triplet path. With bilatrienes-abc the situation is complicated by the fact that in homogenous phase there is only unidirectional isomerization but there is evidence that the direct process proceeds also via the singlet path. These experiments are supported by calculations using theFormosinho theory of radiationless deexcitation.
    Type of Medium: Electronic Resource
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