Browsing by Author "Agster, Wolfgang"

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    Nucleophile aromatische Substitution - ein neuer Weg zur Synthese von Biphenylen
    (1971) Effenberger, Franz; Nagel, Klaus; Agster, Wolfgang
    Die wichtigsten Methoden zur Darstellung von Biphenylen sind die über radikalische oder metallorganische Zwischenstufen verlaufenden Ullmann- und Gomberg-Reaktionen; daneben werden Biaryle bei der Benzidinumlagerung und der oxidativen Dimerisierung sowie bei Reaktionen uber Arin-Zwischenstufen gebildet. Bei der Umsetzung von Aminobenzolen (1) mit reaktiven Halogenaromaten (2) ist uns jetzt eine polare Aryl-Aryl-Verknüpfung durch nucleophile aromatische Substitution zu den Biphenylen (4) bis (6) gelungen.
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    Nucleophilic aromatic substitution : a new synthetic route to biphenyls
    (1971) Effenberger, Franz; Nagel, Klaus; Agster, Wolfgang
    The most important methods for preparation of biphenyls are the Ullmann and Gomberg reactions, which involve radical or organometallic intermediates; furthermore, biaryls are formed by benzidine rearrangement and oxidative dimerization, as well as in the course of reactions involving aryne intermediates.
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    Synthesis, structure, and spectral behavior of donor acceptor substituted biphenyls
    (1983) Effenberger, Franz; Agster, Wolfgang; Fischer, Peter; Jogun, Kurt H.; Stezowski, John J.; Daltrozzo, Ewald; Kollmannsberger- von Nell, Georg
    Reaction of the activated halonitrobenzenes 2a-f with the bis- and tris(dialkylamino)benzenes 1a-e affords, via a direct nucleophilic substitution, the highly substituted biphenyls 3a-o; the lesser substituted biphenyls 5 and 6 were prepared by an Ullmann reaction. All these biphenyls are deeply colored; the dark red color can be assigned to an intramolecular charge transfer. A crystal structure determination was carried out for 2,4,6-tripyrrolidino-2',4',6'-trinitrobiphenyl (3a): space group C2/c, a = 16.071 (2) A, b = 14.545 (1) A, c = 20.177 (2) A, {3 = 91.361 (9)°, Z = 8 (temperature ≈ 120 K). The dihedral angle between the two arene rings was found to be only 52.5°, despite the four bulky substituents in the o,o'-positions. With this far-from-orthogonal torsional angle about the biphenyl linkage, the strong intramolecular charge transfer from the π system of the donor into the π system of the acceptor arene becomes easily understandable. A PPP calculation with the torsional angles taken from the X-ray structure analysis satisfactorily reproduces the experimental absorption spectrum of 3a. The shift of the long-wavelength absorption between the individual biphenyls 3a-o, 5, and 6 likewise is accounted for satisfactorily by the calculation; it depends primarily on the intrinsic donor strength of the different NR2 moieties (pyrrolidino > dimethylamino > piperidino > morpholino). The IH NMR spectra (in dilute solution) likewise mirror this gradation in Nr2 donor capacity; they also show that steric hindrance at the biphenyl linkage is mainly the result of interaction between the o-dialkylamino groups and the C6 skeleton of the acceptor arene. This is borne out by the crystal structure analysis.