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http://dx.doi.org/10.18419/opus-1072
Autor(en): | Effenberger, Franz Agster, Wolfgang Fischer, Peter Jogun, Kurt H. Stezowski, John J. Daltrozzo, Ewald Kollmannsberger- von Nell, Georg |
Titel: | Synthesis, structure, and spectral behavior of donor acceptor substituted biphenyls |
Erscheinungsdatum: | 1983 |
Dokumentart: | Zeitschriftenartikel |
Erschienen in: | Journal of Organic Chemistry 48 (1983), S. 4649-4658. URL http://dx.doi.org./10.1021/jo00172a040 |
URI: | http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-42955 http://elib.uni-stuttgart.de/handle/11682/1089 http://dx.doi.org/10.18419/opus-1072 |
Zusammenfassung: | 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. |
Enthalten in den Sammlungen: | 03 Fakultät Chemie |
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