Neben den Hauptabbauwegen des Etofenamats bei Versuchstieren und Menschen (Hydroxylierung, Esterspaltung und Konjugation) wurde in der Etherspaltung ein metabolischer Nebenweg gefunden. Nach peroraler Gabe von Etofenamat konnte bei Hunden 5-Hydroxyflufenaminsaure-P-hydroxyethylester (3) aus Faces isoliert und mittels MS und NMR identifiziert werden. In Milch einer mit Etofenamat peroral behandelten Ziege wurde eine Substanz in Spuren mittels GLC nachgewiesen, deren Retentionszeit dem Flufenaminslure-0-hydroxyethylester (2) entspricht. Ether Cleavage, a Side Route of Etofenamate Metabolism in AnimalsIn addition to the main route of etofenamate metabolism in animals and men (hydroxylation, esterolysis and conjugation) ether cleavage was found to be a metabolic side route. P-Hydroxyethyl-5-hydroxyflufenamate (3) was isolated from faeces of dogs after peroral administration of etofenamate and was identified by mass and NMR spectroscopy. In milk of a goat, which got etofenamate by the oral route, a trace metabolite was detected which in GLC showed a retention time like that of f3-hydroxyethyl flufenamate (2). : R = H
The through-space interaction of separated n-systems that are partly doped with electrons is of interest for theories of bonding ['] and for the material sciences.[21 The model dianthryl compounds la-c can serve as efficient electron storage devices;'31 their ions exhibit n-system interaction~'~] that are similar to those in the multilayered phanes."' As part of our studies directed toward the preparation of "polyelectrophoric" hydrocarbons,[61 we describe here the synthesis and reduction of the new compounds Id, 2a,b, and 3. Two questions arise: Is the electronic interaction between the anthracene moieties in 1 also possible for longer bridges (n = 1 l)? Are the electron-transfer properties of la-c also evident in the higher homologues, e.g., 3, with more than two redox groups?1,11 -Di(9-anthryl)-3,6,9-trioxaundecane 2aI7l was prepared by reaction of the trioxaundecyleneditoluenesulfonate 7b with the species 5 (2 equiv.) (obtained from 9,10-dihydroanthracene and nBuLi), followed by dehydrogenation of the tetrahydrodianthryl system."] The X-ray structure analysis of 2a reveals a close approach of the anthracene moieties (preference of the gauche over the anti conformations of the C C bonds in the chain[' iO1).['ll The C-9/C-9' separation (ca. 10 A) is significantly smaller than that expected for polymethylene chains with the C C anti conformation.The synthesis of the hydrocarbon Id, which corresponds to the polyether Za, was achieved in an analogous manner. On account of the poor accessibility of 7, n==5, 2b was prepared from 7a and 2-(9-anthryl)ethoxide. In analogy to the synthesis of Id and 2a, 9,10-bis[3-(9,10-dihydro-9-anthryl)propyl]anthracene 4 was prepared from 5 and 9,lObis(3-bromopropyl)anthracene 6c[IZ1 (tetrahydrofuran, -80°C) in 83% yield. Deprotonation of 4 (nBuLi/tetramethylethylenediamine, cyclohexane, 80°C) followed by oxidation with cadmium chloride afforded the product 3, which contains three separated anthracene The new compounds Id, 2a,b, and 3 were reduced with alkali metals to the paramagnetic radical anions as well as to the polyanions. The distribution of spin density among the anthracene moieties in the radical anions (localization in one fragment or delocalization over all fragments) serves as an indication of the extent of through-space interaction. The most important experimental criteria are the size and multiplicity of the hyperfine coupling constants determined by ESR or ENDOR spectroscopy.The coupling constants of the radical anion Ido"/K@ [aH [mg=0.261 (H-1,8), 0.136 (H-2,7), 0.168 (H-3,6), 0.282 (H-4,5),0.510 (H-lo), 0.250 (a-CH,), 0.029 (0-CH,)] are the same as those in the 9-ethylanthracene radical anion. The spin density remains localized in one of the n-systems, as expected from the separation of the anthracene moieties. This result is independent of temperature and is valid for the solvent system dimethoxyethane (DME)/hexamethylphosphoric triamide (HMPT) as well as for 2-methyltetrahydrofuran (MTHF). As expected, solvent-separated ion pairs are present in DMEIHMPT; MTHF, o...
Bei der Konfigurationszuordnung hilft der Anisotropieeffekt der SulfinylgrupperX1: DaB die Methylprotonen von 4a (6=2.51, s) und die ortho-Arylprotonen von 4b (6=7.93, m) bei relativ tiefem Feld absorbieren, zeigt, daI3 der Sauerstoff der SO-Gruppe diesen Substituenten nahe ist. d. h. die C=S-Bindung ist E-konfiguriert. Dagegen scheint bei den Anilinderivaten 4c die Z-Form zu dominieren (siehe Tabelle 1). 9 Abb. 1. ORTEP-Plot der Struktur von 4b im Kristall. Die Schwingungsellipsoide entsprechen einer 50proz. Wahrscheinlichkeit. Wichtige Bindungslsngen [A] und -winkel ["I: S2-Cl3 1.6290). S2-03 1.470(4); C13-S2-03 115.7(2) 191. Von 4b wurde eine Kristallstrukturanalyse durchgefuhrt. Im Kristall gibt es keine Konjugation zwischen den n-Systemen des Amidinteils und der C=S(O)-Bindung, denn die Ebenen Nl-C8-N2 und C14-C13-S2 stehen fast senkrecht (92.8') zueinander. Q VCH Verlagsge~ell~cha/r mhH. 0-6940 Wernherm. 1986 0044-8249/86/0505-0444 0 02.50/0 Angew Chem 98 (19861 Nr 5 IS] M. Daney. G . F. R. Lapouyade, H. Bouas-Lourent, Fr. Pat.-Anm. Lett. 21 (1980) 541. Angew. Cliem. 98 (1986) Nr. 5 0 VCH Verlagsgesellsrhafr mbH. 0-6940 Weinheim, 1986 0044-8249/86/0505-0445 S 02.50/0
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Prr$i~.wr Woljkung Liittkr a m 70. Gehurtstag gwidmetStapelformige n-Systeme wie mehrlagige Phane". 21 Die Synthese der doppellagigen Verbindung 3 beruht darauf, dal3 1 iiber das Dilithiumsalz 2 regioselektiv an den beiden zentralen C-Atomen alkyliert werden kann [5d. 'I.
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