New Synthetic Routes to Alkyl‐Substituted and Functionalized Perylenes

Flüssigkristalline Coronenderivate mit außergewöhnlichen Fluoreszenzeigenschaften

“…[5] Zur Funktionalisierung und Alkylierung von Perylen 1 hat sich die Kupplung von 3,9(10)-Dibromperylen mit unterschiedlichen terminalen Alkinen bewährt, deren Dreifachbindungen anschlieûend katalytisch hydriert werden. [4] Es lag nahe, diese Aryl-Ethinyl-Verknüpfung auf die Funktionalisierung von N,N'-Dialkyl-1,7-dibrom-3,4;9,10-tetracarbonsäurediimiden 6 zu übertragen. Dabei ergab sich jedoch eine völlig überraschende Reaktionssequenz, die zu den neuen Verbindungen 8 führt (Schema 1).…”

Liquid Crystalline Coronene Derivatives with Extraordinary Fluorescence Properties

“…For the workup, the mixture was added to ice-cooled, dilute HCl and extracted with CHCl 3 . The organic layer was dried over MgSO 4 , and the product precipitated from CH 3 OH to afford orange 8 b in quantitative yield (500 mg).…”

“…The functionalization and alkylation of perylene (1) was achieved by coupling 3,9(10)-dibromoperylene with various terminal alkynes and subsequent catalytic hydrogenation of the triple bonds. [4] It appeared logical to apply this aryl ± ethynyl coupling to the functionalization of the N,N'-dialkyl-1,7-dibromo-3,4:9,10-bis(dicarboximide)s 6. However, a very surprising reaction sequence was observed which led to the novel compounds 8 (Scheme 1).…”

“…The commercially available perylene-3,4;9,10-tetracarboxylic dianhydride (4) is subjected to a twofold bromination with elemental bromine in 100 % sulfuric acid to provide 5 (90 ± 95 %), which is then converted into 6 a and 6 b (88 ± 95 %) with cyclohexylamine or noctylamine, respectively. [5] The palladium(0 0)-catalyzed [4] reactions of 6 with 1-alkynes in the presence of bases such as triethylamine afforded the expected bis(alkynyl)-substituted perylene-3,4:9,10-bis(dicarboximide)s 7 a ± e in high yields (85 ± 95 %). Treatment of 7 with strong, nonnucleophilic bases such as 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) triggers a cyclization reaction of unknown mechanism to yield almost [*] quantitatively the yellow title compounds 8 with various substituents at the resulting phenyl rings.…”

Synthesis and Properties of Oligonucleotides Involving a Perylene Unit Linked to a 2′-Deoxyribose Residue

“…The synthesis of the sugar-perylene unit was achieved as follows: first, the perylene was monobrominated by reaction with N-bromosuccinimide, [2,3] then a Sonogashira [4] reaction between the brominated perylene and propargyl alcohol gave the perylene with a hydroxylated linker. The latter was then glycosylated by reaction with 2 0 -deoxy-3,5-di-O-(4-toluoyl)-a-D-erythro-pentofuranosyl chloride to give the perylene sugar unit as the anomer mixture.…”