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WO1996027596A1 - Diazafulleroids, method of preparation and use thereof - Google Patents

Diazafulleroids, method of preparation and use thereof Download PDF

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Publication number
WO1996027596A1
WO1996027596A1 PCT/EP1996/000707 EP9600707W WO9627596A1 WO 1996027596 A1 WO1996027596 A1 WO 1996027596A1 EP 9600707 W EP9600707 W EP 9600707W WO 9627596 A1 WO9627596 A1 WO 9627596A1
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Prior art keywords
formula
alkyl group
bisazafulleroids
aryl
fullerene
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PCT/EP1996/000707
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German (de)
French (fr)
Inventor
Maurizio Prato
Fred Wudl
Thomas Grösser
Andreas Hirsch
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Hoechst Aktiengesellschaft
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Publication of WO1996027596A1 publication Critical patent/WO1996027596A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/18—Bridged systems

Definitions

  • Fullerenes are cage-shaped carbon allotropes of the general formula
  • an open 5-6 ring-bridged azafulleroid is formed from the 6-6-bridged triazole (see, for example, M. Prato et al., J. Am. Chem Soc. 1 993, 1 1 5, 1 148).
  • the object of the present invention is to synthesize defined fullerene derivatives which contain structural units with such functional groups, which on the one hand has the physical properties such as
  • the invention therefore relates to bisazafulleroids of the formulas (I) and (II)
  • R 1 , R 2 independently of one another H, a straight-chain or branched C 1 -C 20 alkyl group, a C 6 -C 14 aryl-C 1 -C 10 alkyl group or a C 6 -C 14 aryl group, wherein in one or more of the alkyl group is not
  • the invention further relates to a process for the preparation of the compounds of the formula (I) and / or (II) according to the invention, as shown in scheme 1.
  • Solvent preferably a high boiling aromatic solvent such as e.g. 1, 2-dichlorobenzene or 1-chloronaphthalene in which the fullerene or the monoazafulleroid of the formula (V) dissolves well, at a temperature of 50 ° C. to 200 ° C., preferably 100 ° C. to 160 ° C.
  • the compounds of formula (I) and / or (II) can also by thermolysis of a mono-6-6
  • a process for the preparation of the compounds of the formula (I) and / or (II) is preferred, in which a fullerene derivative of the formula (VI) is thermolyzed at a temperature of 100 ° C to 1 60 ° C, preferably 1 10 ° C to 1 20 ° C.
  • the compounds of the formula (VI) are preferably obtained from the monoazafulleroid of the formula (V) with one equivalent of the azide of the formula (IM) in one of the abovementioned inert solvents at a temperature from 0 ° C. to 80 ° C., preferably 20 ° C. to 30 ° C manufactured.
  • Monoazafulleroids can be prepared from fullerenes and azides of the formula (III) according to syntheses known from the literature (see, for example, M. Prato et al., J. Am.
  • Pure C 60 and / or C 70 are preferably used as fullerenes, but also raw fullerenes which contain a mixture of C 60 and C 70 as main components. However, all other known fullerenes or
  • Fullerene adducts are used.
  • the fullerenes can be produced, for example, by producing fullerene carbon black in the
  • Arc processes with subsequent extraction with a non-polar organic solvent, as described in WO 92/09279, can be obtained as crude fullerenes.
  • the further fine separation can be carried out by column chromatography.
  • Fullerene adducts can be obtained by adding various reagents to the double bonds of the fullerenes (see, for example, R. Tayler, D.R.M. Walton, Nature 363 (1 993) 685 and A. Hirsch, Angew. Chem. 1 05 (1993) 1 1).
  • the compounds of the formula (I) and / or (II) according to the invention serve, for example, as building blocks for the synthesis of new fullerene derivatives or for the production of optoelectronic components or pharmaceuticals Active substances.
  • UV / Vis (cyclohexane): ⁇ max [nm] 702 (br), 538 (br), 456 (sh), 435 (sh), 327,

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  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention concerns bis-azafulleroids of formula (I) and/or (II) in which the symbols are defined as follows: F is a fullerene entity of the formula C20+2m in which m = 2 to 100; R1, R2, independently of each other, are H, a straight-chain or branched-chain C¿1?-C20- alkyl group, a C6-C14 aryl/C1-C10 alkyl group or a C6-C14 aryl group, whereby one or more non-neighbouring CH2 groups in the alkyl group may be replaced by -C≡C-, -CH=CH-, -O-, -S-, -COO-, -SiR2- and/or -CO-, the alkyl and the aryl, independently of each other, may be substituted one or more times by in an identical or different manner OH, OR?3, COOR1, OCOR1¿, F, Cl, Br, NO¿2?, CN, NHCOR?3 or NR3COR3¿ groups and the aryl may be substituted by R3, R3 being a C¿1?-C6 alkyl group. The invention also concerns a process for preparing such compounds and their use.

Description

Beschreibung  description
Bisazafulleroide, Verfahren zu ihrer Herstellung und deren Verwendung Bisazafulleroids, process for their preparation and their use
Fullerene sind käfigförmige Kohlenstoffallotrope der allgemeinen Formel Fullerenes are cage-shaped carbon allotropes of the general formula
(C20 + 2m), wobei m eine natürliche Zahl ist. Sie enthalten zwölf Fünf- sowie beliebig viele, mindestens aber zwei Sechsringe aus Kohlenstoffatomen. Obwohl diese Verbindungsklasse erst 1985 von Kroto und Smalley nachgewiesen wurde (Nature, 1985, 318, 1 62) und Krätschmer und Huffman erstmals 1990 über die Darstellung makroskopischer Mengen an C60 berichteten (Nature 1990, 347, 354), sind solche Verbindungen sehr schnell auf ein breites Interesse gestoßen und wurden innerhalb kürzester Zeit Gegenstand zahlreicher Forschungsarbeiten (siehe z.B. G.S. Hammond, V.J. Kuck (Editors), Fullerenes, American Chemical Society, Washington DC 1992 und Accounts of Chemical Research, (C 20 + 2m ), where m is a natural number. They contain twelve five- and any number, but at least two six-membered rings made of carbon atoms. Although this class of compounds was only detected by Kroto and Smalley in 1985 (Nature, 1985, 318, 1 62) and Krätschmer and Huffman first reported the display of macroscopic amounts of C 60 in 1990 (Nature 1990, 347, 354), such compounds are very fast met with great interest and was the subject of numerous research projects within a very short period of time (see, for example, GS Hammond, VJ Kuck (Editors), Fullerenes, American Chemical Society, Washington DC 1992 and Accounts of Chemical Research,
Märzausgabe 1 992). March edition 1 992).
Da man ein hohes Potential dieser Stoffklasse, beispielsweise im Bereich der Optoelektronik und der Wirkstofforschung erwartet, wurden bereits Since a high potential of this substance class, for example in the field of optoelectronics and drug research, is expected, have already been
umfangreiche Untersuchungen zur gezielten Derivatisierung, insbesondere von C60 und C70, unternommen (siehe z.B. R. Taylor, D.R.M. Walton, Nature 1993, 363, 685 und A. Hirsch, Angew. Chem. 1993, 105, 1 1 89). In verschiedenen Derivatisierungsversuchen gelang es, definierte Monoaddukte von C60 zu isolieren (siehe z.B. A. Hirsch, The Chemistry of the Fullerenes, Thieme, extensive studies on targeted derivatization, in particular of C 60 and C 70 , have been carried out (see, for example, R. Taylor, DRM Walton, Nature 1993, 363, 685 and A. Hirsch, Angew. Chem. 1993, 105, 1 1 89). In various derivatization attempts it was possible to isolate defined monoadducts of C 60 (see e.g. A. Hirsch, The Chemistry of the Fullerenes, Thieme,
Stuttgart, New York, 1 994) . Stuttgart, New York, 1 994).
Untersuchungen zur Regioselektivität bei Mehrfachadditionen an Fullerene, insbesondere C60, sind Gegenstand der derzeitigen Fullerenforschung (siehe z.B. Osmylierung: J.M. Hawkins et al. , J . Am. Chem. Soc. 1 992, 1 14, 7954; Studies on regioselectivity in the case of multiple additions to fullerenes, in particular C 60 , are the subject of current fullerene research (see, for example, osmylation: JM Hawkins et al., J. Am. Chem. Soc. 1 992, 1 14, 7954;
Cyclopropanierung: A. Hirsch, I . Lamparth, H.R. Karfunkel, Angew. Chem. Int. Ed. Engl. 1994, 33, 437; Hydroborierung: C.C. Henderson et al., Angew. Chem. Int. Ed. Engl. 1994, 33, 786). Cyclopropanation: A. Hirsch, I. Lamparth, HR Karfunkel, Angew. Chem. Int. Ed. Engl. 1994, 33, 437; Hydroboration: CC Henderson et al., Angew. Chem. Int. Ed. Engl. 1994, 33, 786).
Um das Problem der aufwendigen chromatographischen Trennung z.B. To solve the problem of complex chromatographic separation e.g.
verschiedener Bisaddukte zu umgehen, wurde das Konzept der Spacer- kontrollierten Fernfunktionalisierung auf die Fullerenchemie angewendet (siehe z.B. F. Diederich et al., Angew. Chem. Int. Ed. Engl. 1994, 33, 2434). Bei der wichtigen Reaktionsklasse der Cycloadditionen findet der Angriff stets an einer elektronenarmen 6-6-Ring-Doppelbindung des Fullerens statt. To bypass various bis-adducts, the concept of spacer-controlled remote functionalization was applied to fullerene chemistry (see e.g. F. Diederich et al., Angew. Chem. Int. Ed. Engl. 1994, 33, 2434). In the important reaction class of cycloadditions, the attack always takes place on an electron-deficient 6-6 ring double bond of the fullerene.
Im Falle der Addition eines Azides an C60 bildet sich nach Abspaltung von N2 aus dem zunächst entstandenen 6-6-überbrückten Triazol ein geöffnetes 5-6-Ring überbrücktes Azafulleroid (siehe z.B. M. Prato et al., J. Am. Chem. Soc. 1 993, 1 1 5, 1 148). In the case of addition of an azide to C 60 , after the N 2 has been split off, an open 5-6 ring-bridged azafulleroid is formed from the 6-6-bridged triazole (see, for example, M. Prato et al., J. Am. Chem Soc. 1 993, 1 1 5, 1 148).
Aufgabe der vorliegenden Erfindung ist es, definierte Fullerenderivate zu synthetisieren, die Struktureinheiten mit solchen funktionellen Gruppen enthalten, wodurch sich einerseits die physikalischen Eigenschaften wie The object of the present invention is to synthesize defined fullerene derivatives which contain structural units with such functional groups, which on the one hand has the physical properties such as
Löslichkeit und Polarität verbessern und wodurch andererseits weitere chemische Umsetzungen zu neuen Fullerenderivaten ermöglicht werden. Improve solubility and polarity and, on the other hand, enable further chemical conversions to new fullerene derivatives.
Es wurde nun überraschend gefunden, daß sich Bisazafulleroide hoch It has now surprisingly been found that bisazafulleroids are high
regioselektiv herstellen lassen, indem Monoazafulleroide erneut mit organischen Aziden umgesetzt werden. Have it produced regioselectively by reacting monoazafulleroids again with organic azides.
Gegenstand der Erfindung sind daher Bisazafulleroide der Formeln (I) und (II) The invention therefore relates to bisazafulleroids of the formulas (I) and (II)
Figure imgf000004_0001
in der die beiden Stickstoffatome entweder geminal über ein sp2-Kohlenstoffatom oder vicinal über eine Ethylenbrucke miteinander verbunden sind und weiterhin jede Struktur zwei geöffnete 5-6 Ring überbrückte
Figure imgf000004_0001
in which the two nitrogen atoms are connected either geminally via an sp 2 carbon atom or vicinally via an ethylene bridge and each structure also bridged two open 5-6 rings
Azafulleroidstrukturelemente aufweist und worin die Symbole folgende Azafulleroid structural elements and wherein the symbols follow
Bedeutung haben: Have meaning:
F: ein Fullerenrest der Formel C20 + 2m mit m = 2 bis 100; F: a fullerene radical of the formula C 20 + 2m with m = 2 to 100;
R1 , R2: unabhängig voneinander H, eine geradkettige oder verzweigte C1-C20- Alkylgruppe, eine C6-C14-Aryl-C 1-C10-alkylgruppe oder eine C6-C14- Arylgruppe, wobei in der Alkylgruppe eine oder mehrere nicht R 1 , R 2 : independently of one another H, a straight-chain or branched C 1 -C 20 alkyl group, a C 6 -C 14 aryl-C 1 -C 10 alkyl group or a C 6 -C 14 aryl group, wherein in one or more of the alkyl group is not
benachbarte CH2-Gruppen durch -C≡C-, -CH = CH-, -O-, -S-, -COO-, -SiR2- und/oder -CO- ersetzt sein können, Alkyl und Aryl unabhängig voneinander ein- oder mehrfach gleich oder verschieden durch OH, OR3, COOR1 , OCOR1 , F, Cl, Br, NO2, CN, NHCOR3 oder NR3COR3 sowie Aryl durch R3 substituiert sein können und R3 eine C1-C6-Alkylgruppe ist. Adjacent CH 2 groups can be replaced by -C≡C-, -CH = CH-, -O-, -S-, -COO-, -SiR 2 - and / or -CO-, alkyl and aryl independently - or several times the same or different by OH, OR 3 , COOR 1 , OCOR 1 , F, Cl, Br, NO 2 , CN, NHCOR 3 or NR 3 COR 3 and aryl may be substituted by R 3 and R 3 is a C 1 -C 6 alkyl group.
Bevorzugt sind Verbindungen der Formel (I) und/oder (II), in der die Symbole folgende Bedeutung haben: Compounds of the formula (I) and / or (II) in which the symbols have the following meaning are preferred:
F: ein Fullerenrest der Formel C20 + 2m mit m = 20, 25, 28 und/oder 29. F: a fullerene radical of the formula C 20 + 2m with m = 20, 25, 28 and / or 29.
Besonders bevorzugt sind Verbindungen der Formel (I) und/oder (II), in der die Symbole folgende Bedeutung haben Compounds of the formula (I) and / or (II) in which the symbols have the following meaning are particularly preferred
F: C60 und/oder C70. F: C 60 and / or C 70 .
Ganz besonders bevorzugt sind Verbindungen der Formel (I) und/oder (II), in der die Symbole folgende Bedeutung haben: F: C60 R1 , R2: unabhängig voneinander H, eine geradkettige oder verzweigte C^ -CQ-Compounds of the formula (I) and / or (II) in which the symbols have the following meaning are very particularly preferred: F: C 60 R 1 , R 2 : independently of one another H, a straight-chain or branched C ^ -CQ-
Alkylgruppe oder eine Phenyl-C 1-C6-alkylgruppe, wobei in der Alkylgruppe eine oder mehrere nicht benachbarte CH2-Gruppen durch -O-, -COO- oder -SiR2 ersetzt sein können, Alkyl und Phenyl unabhängig voneinander ein- bis dreifach gleich oder verschieden durch OH, OR4, COOR4, OCOR4, F, Cl, Br, NO2 oder CN sowie Phenyl durch R4 substituiert sein können und R4 Methyl oder Ethyl ist. Alkyl group or a phenyl-C 1 -C 6 -alkyl group, where one or more non-adjacent CH 2 groups in the alkyl group can be replaced by -O-, -COO- or -SiR 2 , alkyl and phenyl independently of one another can be substituted three times the same or different by OH, OR 4 , COOR 4 , OCOR 4 , F, Cl, Br, NO 2 or CN and phenyl by R 4 and R 4 is methyl or ethyl.
Weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Verbindungen der Formel (I) und/oder (II), wie in Schema 1 dargestellt. The invention further relates to a process for the preparation of the compounds of the formula (I) and / or (II) according to the invention, as shown in scheme 1.
Zur Herstellung der Verbindungen der Formel (I) und (II) wird ein Fulleren der Formel C20 + 2m, worin m = 2 bis 100 ist, oder bevorzugt ein davon To produce the compounds of the formula (I) and (II), a fullerene of the formula C 20 + 2m , where m = 2 to 100, or preferably one of them
abstammendes Monoazafulleroid der Formel (V), mit 1 bis 10 Äquivalenten, bevorzugt 2 bis 3 Äquivalenten im Falle eines Fullerenes bzw. 1 Äquivalent im Falle eines Monoazafulleroids der Formel (V), eines Azides der Formel (III) derived monoazafulleroid of formula (V), with 1 to 10 equivalents, preferably 2 to 3 equivalents in the case of a fullerene or 1 equivalent in the case of a monoazafulleroid of the formula (V), an azide of the formula (III)
R-N3 (III) wobei R die gleiche Bedeutung wie R1 und R2 hat, in einem inerten RN 3 (III) where R has the same meaning as R 1 and R 2 , in an inert
Lösungsmittel, bevorzugt einem hochsiedenden aromatischen Lösungsmittel wie z.B. 1 ,2-Dichlorbenzol oder 1 -Chlornaphthalin in dem sich das Fulleren bzw. das Monoazafulleroid der Formel (V) gut löst, bei einer Temperatur von 50°C bis 200°C, bevorzugt 100°C bis 1 60°C umgesetzt. Die Verbindungen der Formel (I) und/oder (II) können aber auch durch Thermolyse eines Mono-6-6 Solvent, preferably a high boiling aromatic solvent such as e.g. 1, 2-dichlorobenzene or 1-chloronaphthalene in which the fullerene or the monoazafulleroid of the formula (V) dissolves well, at a temperature of 50 ° C. to 200 ° C., preferably 100 ° C. to 160 ° C. The compounds of formula (I) and / or (II) can also by thermolysis of a mono-6-6
überbrückten Triazolfullerenderivates der Formel (IV) in geringen Ausbeuten gewonnen werden. bridged triazole fullerene derivatives of the formula (IV) can be obtained in low yields.
Bevorzugt ist ein Verfahren zur Herstellung der Verbindungen der Formel (I) und/oder (II), bei dem ein Fullerenderivat der Formel (VI )
Figure imgf000007_0001
bei einer Temperatur von 100°C bis 1 60°C, bevorzugt 1 10°C bis 1 20°C, thermolysiert wird. A process for the preparation of the compounds of the formula (I) and / or (II) is preferred, in which a fullerene derivative of the formula (VI)
Figure imgf000007_0001
is thermolyzed at a temperature of 100 ° C to 1 60 ° C, preferably 1 10 ° C to 1 20 ° C.
Die Verbindungen der Formel (VI) werden bevorzugt aus dem Monoazafulleroid der Formel (V) mit einem Äquivalent des Azids der Formel (IM) in einem der obengenannten inerten Lösungsmitteln bei einer Temperatur von 0°C bis 80°C, bevorzugt 20°C bis 30°C hergestellt. The compounds of the formula (VI) are preferably obtained from the monoazafulleroid of the formula (V) with one equivalent of the azide of the formula (IM) in one of the abovementioned inert solvents at a temperature from 0 ° C. to 80 ° C., preferably 20 ° C. to 30 ° C manufactured.
Monoazafulleroide lassen sich aus Fulleren und Aziden der Formel (III) nach literaturbekannten Synthesen herstellen (siehe z. B. M. Prato et al., J. Am. Monoazafulleroids can be prepared from fullerenes and azides of the formula (III) according to syntheses known from the literature (see, for example, M. Prato et al., J. Am.
Chem. Soc. 1 993, 1 1 5, 1 1 48) . Chem. Soc. 1 993, 1 1 5, 1 1 48).
Als Fullerene werden bevorzugt reines C60 und/oder C70 eingesetzt aber auch Rohfullerene, die als Hauptkomponenten ein Gemisch aus C60 und C70 enthalten. Es können aber auch alle anderen bekannten Fullerene bzw. Pure C 60 and / or C 70 are preferably used as fullerenes, but also raw fullerenes which contain a mixture of C 60 and C 70 as main components. However, all other known fullerenes or
Fullerenaddukte eingesetzt werden. Fullerene adducts are used.
Die Fullerene können beispielsweise durch Herstellung von Fullerenruß im The fullerenes can be produced, for example, by producing fullerene carbon black in the
Lichtbogenverfahren mit anschließender Extraktion mit einem unpolaren organischen Lösungsmittel, wie in WO 92/09279 beschrieben, als Rohfulleren gewonnen werden. Die weitere Feinauftrennung kann säulenchromatographisch erfolgen. Arc processes with subsequent extraction with a non-polar organic solvent, as described in WO 92/09279, can be obtained as crude fullerenes. The further fine separation can be carried out by column chromatography.
Die eingesetzten Fullerene sind zum Teil auch Handelsprodukte. Some of the fullerenes used are also commercial products.
Fullerenaddukte lassen sich durch Addition verschiedener Reagenzien an die Doppelbindungen der Fullerene erhalten (siehe z. B. R. Tayler, D.R.M. Walton, Nature 363 ( 1 993) 685 und A. Hirsch, Angew. Chem. 1 05 ( 1993) 1 1 ) . Fullerene adducts can be obtained by adding various reagents to the double bonds of the fullerenes (see, for example, R. Tayler, D.R.M. Walton, Nature 363 (1 993) 685 and A. Hirsch, Angew. Chem. 1 05 (1993) 1 1).
Die erfindungsmäßigen Verbindungen der Formel (I ) und/oder (II) dienen beispielsweise als Bausteine für die Synthese neuer Fullerenderivate oder zur Herstellung von optoelektronischen Bauteilen oder pharmazeutischen Wirkstoffen. The compounds of the formula (I) and / or (II) according to the invention serve, for example, as building blocks for the synthesis of new fullerene derivatives or for the production of optoelectronic components or pharmaceuticals Active substances.
Die Erfindung wird im folgenden durch folgende Beispiele näher erläutert, ohne dadurch beschränkt zu werden. The invention is illustrated below by the following examples, without being restricted thereby.
Beispiel 1 example 1
Eine Lösung von C60 (500 mg, 0,694 mmol) und Azidoessigsäuremethylester (80 mg, 0,695 mmol) wurde 12 Stunden in 1-Chlornaphthalin (15 ml) bei 60°C gerührt. Das Reaktionsgemisch wurde durch Flash-Chromatographie A solution of C 60 (500 mg, 0.694 mmol) and methyl azidoacetate (80 mg, 0.695 mmol) was stirred for 12 hours in 1-chloronaphthalene (15 ml) at 60 ° C. The reaction mixture was by flash chromatography
(SiO2/Toluol) aufgetrennt, wobei C60 (270 mg, 0,375 mmol), Spuren des (SiO 2 / toluene), where C 60 (270 mg, 0.375 mmol), traces of
Monoazafulleroids und das 6-6 überbrückte Triazolin-C60-Derivat (165 mg, 0,198 mmol, 62 % bezogen auf umgesetztes C60) erhalten wurden. Monoazafulleroids and the 6-6 bridged triazoline-C 60 derivative (165 mg, 0.198 mmol, 62% based on converted C 60 ) were obtained.
Eine Lösung des 6-6 überbrückten Triazolin-C60-Derivates (200 mg, 0,239 mmol) in 1,2-Dichlorbenzol (15 ml) wurden bei 100°C für 25 Minuten gerührt. Das Reaktionsgemisch wurde durch Flash-Chromatographie (SiO2/Toluol) aufgetrennt und ergab C60 (38 mg, 22 %), das Monoazafulleroid (53 mg, 24 %) und die Produkte der Formel (I) und (II) mit R = CH2CO2Me (32 mg, 15 %), wobei das Produkt der Formel (I) das Hauptprodukt darstellt. A solution of the 6-6 bridged triazoline-C 60 derivative (200 mg, 0.239 mmol) in 1,2-dichlorobenzene (15 ml) was stirred at 100 ° C. for 25 minutes. The reaction mixture was separated by flash chromatography (SiO 2 / toluene) and gave C 60 (38 mg, 22%), the monoazafulleroid (53 mg, 24%) and the products of the formula (I) and (II) with R = CH 2 CO 2 Me (32 mg, 15%), the product of formula (I) being the main product.
1H-NMR (CS2/C6D6 (20 %), 250 MHz): δ = 5,20 (d, J = 17 Hz, 1H), 4,32 (d, 1 H-NMR (CS 2 / C 6 D 6 (20%), 250 MHz): δ = 5.20 (d, J = 17 Hz, 1H), 4.32 (d,
J = 17 Hz, 1H), 3,69 (s, 3H), J = 17 Hz, 1H), 3.69 (s, 3H),
13C-NMR (CS2/C6D6 (20 %), 62,9 MHz): δ = 169,81, 161,00, 147,83, 13 C-NMR (CS 2 / C 6 D 6 (20%), 62.9 MHz): δ = 169.81, 161.00, 147.83,
147,20, 145,82, 145,59, 145,29, 145,25, 144,95, 144,92, 144,58, 144,51, 147.20, 145.82, 145.59, 145.29, 145.25, 144.95, 144.92, 144.58, 144.51,
144,39, 144,30, 144,11, 143,85, 143,70, 142,85, 142,60, 142,02, 141,89,144.39, 144.30, 144.11, 143.85, 143.70, 142.85, 142.60, 142.02, 141.89,
140,04, 139,93, 139,33, 137,60, 135,61, 134,93, 132,71, 132,53, 131,35,140.04, 139.93, 139.33, 137.60, 135.61, 134.93, 132.71, 132.53, 131.35,
52,30 (CH2), 51,83 (CH3). 52.30 (CH 2 ), 51.83 (CH 3 ).
UV/Vis (Cyclohexan):λmax [nm] = 702 (br), 538 (br), 456 (sh), 435 (sh), 327,UV / Vis (cyclohexane): λ max [nm] = 702 (br), 538 (br), 456 (sh), 435 (sh), 327,
259, 212. 259, 212.
FD-MS: m/z = 894 (M+) Beispiel 2 FD-MS: m / z = 894 (M + ) Example 2
Analog zu Beispiel 1 wurde das Produkt der Formel (I) mit R = Analogously to Example 1, the product of formula (I) with R =
CH2OCH2CH2SiMe3 gewonnen. CH 2 OCH 2 CH 2 SiMe 3 obtained.
1H-NMR (CDCI3, 600 MHz): δ = 5,56 (d, J = 9,4 Hz, 1H), 5,41 (d, J = 1 H-NMR (CDCI 3 , 600 MHz): δ = 5.56 (d, J = 9.4 Hz, 1H), 5.41 (d, J =
9,4 Hz, 1H), 4,14 (td, J = 9,5 & 7,1 Hz, 1H), 3,98 (td, J = 9,5 & 7,1 Hz,9.4 Hz, 1H), 4.14 (td, J = 9.5 & 7.1 Hz, 1H), 3.98 (td, J = 9.5 & 7.1 Hz,
1H), 1,67 (m, 2H), 0,15 (s, 9H) 1H), 1.67 (m, 2H), 0.15 (s, 9H)
13C-NMR (125 MHz, CDCI3): δ = 160,19 (1), 147,45 (2), 147,09 (2), 145,54 13 C-NMR (125 MHz, CDCI 3 ): δ = 160.19 (1), 147.45 (2), 147.09 (2), 145.54
(1), 145,36 (2), 144,96 (2), 144,86 (2), 144,62 (2), 144,59 (2), 144,21 (6),(1), 145.36 (2), 144.96 (2), 144.86 (2), 144.62 (2), 144.59 (2), 144.21 (6),
144,10 (1), 144,00 (2), 143,77 (2), 143,59 (2), 143,45 (2), 142,83 (2),144.10 (1), 144.00 (2), 143.77 (2), 143.59 (2), 143.45 (2), 142.83 (2),
142,33 (2), 141,81 (2), 141,74 (2), 140,28 (2), 139,59 (2), 139,42 (2),142.33 (2), 141.81 (2), 141.74 (2), 140.28 (2), 139.59 (2), 139.42 (2),
139,15 (2), 138,71 (2), 136,74 (2), 135,36 (2), 134,66 (2), 132,12 (2),139.15 (2), 138.71 (2), 136.74 (2), 135.36 (2), 134.66 (2), 132.12 (2),
132,93 (1), 130,54 (2), 82,89 (NHCH2O), 66,56 (OCH2), 18,21 (CH2Si) -1,24132.93 (1), 130.54 (2), 82.89 (NHCH 2 O), 66.56 (OCH 2 ), 18.21 (CH 2 Si) -1.24
(Si(CH3)3). (Si (CH 3 ) 3 ).
UV/Vis (CH2Cl2): λmax[nm] = 545, 430, 331, 261. UV / Vis (CH 2 Cl 2 ): λ max [nm] = 545, 430, 331, 261.
FAB-MS: m/z = 1011 (M+). FAB-MS: m / z = 1011 (M + ).

Claims

Patentansprüche: 1. Bisazafulleroide der Formel (I) und/oder (II) Claims: 1. Bisazafulleroids of formula (I) and / or (II)
Figure imgf000011_0001
Figure imgf000011_0001
worin die Symbole die folgende Bedeutung haben: where the symbols have the following meaning:
F: ein Fullerenrest der Formel C20 + 2m mit m = 2 bis 100; F: a fullerene radical of the formula C 20 + 2m with m = 2 to 100;
R1 , R2: unabhängig voneinander H, eine geradkettige oder verzweigte C1-C20- Alkylgruppe, eine C6-C14-Aryl-C1-C10-alkylgruppe oder eine C6-C14- Arylgruppe, wobei in der Alkylgruppe eine oder mehrere nicht R 1 , R 2 : independently of one another H, a straight-chain or branched C 1 -C 20 alkyl group, a C 6 -C 14 aryl-C 1 -C 10 alkyl group or a C 6 -C 14 aryl group, wherein in one or more of the alkyl group is not
benachbarte CH2-Gruppen durch -C≡C-, -CH = CH-, -O-, -S-, -COO-, -SiR2- und/oder -CO- ersetzt sein können, Alkyl und Aryl unabhängig voneinander ein- oder mehrfach gleich oder verschieden durch OH, OR3, COOR1 , OCOR1 , F, Cl, Br, NO2, CN, NHCOR3 oder NR3COR3 sowie Aryl durch R3 substituiert sein können und R3 eine C 1 -C6-Alkylgruppe ist. Adjacent CH 2 groups can be replaced by -C≡C-, -CH = CH-, -O-, -S-, -COO-, -SiR 2 - and / or -CO-, alkyl and aryl independently - or several times the same or different by OH, OR 3 , COOR 1 , OCOR 1 , F, Cl, Br, NO 2 , CN, NHCOR 3 or NR 3 COR 3 and aryl may be substituted by R 3 and R 3 is a C 1 -C 6 alkyl group.
2. Bisazafulleroide gemäß Anspruch 1 , dadurch gekennzeichnet, daß F ein Fullerenrest der Formel C20 + 2m ist, mit m = 20, 25, 28 und/oder 29. 2. bisazafulleroids according to claim 1, characterized in that F is a fullerene of the formula C 20 + 2m , with m = 20, 25, 28 and / or 29.
3. Bisazafulleroide gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß F C60 und/oder C70 ist. 3. bisazafulleroids according to claim 1 or 2, characterized in that FC 60 and / or C 70 .
4. Bisazafulleroide gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß 4. bisazafulleroids according to at least one of the preceding claims, characterized in that
F: C60 ist und Q: C 60 is and
R1 , R2: unabhängig voneinander H, eine geradkettige oder verzweigte C1-C6- Alkylgruppe oder eine PhenvI-C 1-C6-alkylgruppe, wobei in der Alkylgruppe eine oder mehrere nicht benachbarte CH2-Gruppen durch -O-, -COO- oder -SiR2 ersetzt sein können, Alkyl und Phenyl unabhängig voneinander ein- bis dreifach gleich oder verschieden durch OH, OR4, COOR4, OCOR4, F, Cl, Br, NO2 oder CN sowie Phenyl durch R4 substituiert sein können und R4 Methyl oder Ethyl ist. R 1 , R 2 : independently of one another H, a straight-chain or branched C 1 -C 6 -alkyl group or a PhenvI-C 1 -C 6 -alkyl group, one or more non-adjacent CH 2 groups in the alkyl group being denoted by -O- , -COO- or -SiR 2 can be replaced, alkyl and phenyl independently of one another, three to the same or different, by OH, OR 4 , COOR 4 , OCOR 4 , F, Cl, Br, NO 2 or CN and phenyl by R. 4 can be substituted and R 4 is methyl or ethyl.
5. Verfahren zur Herstellung von Bisazafulleroiden gemäß mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man ein Monoazafulleroid der Formel (V) 5. A process for the preparation of bisazafulleroids according to at least one of claims 1 to 4, characterized in that a monoazafulleroid of the formula (V)
Figure imgf000012_0001
Figure imgf000012_0001
mit einem Azid der Formel (III) R2-N3 (III) wobei F, R1 und R2 die oben genannten Bedeutungen haben, with an azide of the formula (III) R 2 -N 3 (III) where F, R 1 and R 2 have the meanings given above,
in einem inerten Lösungsmittel bei einer Temperatur im Bereich von 50°C bisin an inert solvent at a temperature in the range of 50 ° C to
200°C umsetzt. Implemented at 200 ° C.
6. Verfahren zur Herstellung von Bisazafulleroiden gemäß mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man ein Monoazafulleroid der Formel (V) 6. A process for the preparation of bisazafulleroids according to at least one of claims 1 to 4, characterized in that a monoazafulleroid of the formula (V)
Figure imgf000013_0002
Figure imgf000013_0002
mit einem Azid der Formel (III) with an azide of the formula (III)
R2-N3 (III) wobei F, R1 und R2 die obengenannten Bedeutungen haben, R 2 -N 3 (III) where F, R 1 and R 2 have the meanings given above,
in einem inerten Lösungsmittel bei einer Temperatur im Bereich von 0°C bisin an inert solvent at a temperature in the range of 0 ° C to
80°C zu einer Verbindung der Formel (VI) umsetzt, Converts 80 ° C to a compound of formula (VI),
Figure imgf000013_0001
Figure imgf000013_0001
und das Fullerenderivat der Formel (VI) bei einer Temperatur im Bereich von 100°C bis 1 60°C thermolysiert. and thermolysing the fullerene derivative of the formula (VI) at a temperature in the range from 100 ° C. to 160 ° C.
7. Verwendung der Bisazafulleroide der Formel (I) und/oder (II) gemäß mindestens einem der Ansprüche 1 bis 4 als Synthesebausteine. 7. Use of the bisazafulleroids of the formula (I) and / or (II) according to at least one of claims 1 to 4 as synthesis building blocks.
8. Verwendung der Bisazafulleroide der Formel (I) und/oder (II) gemäß mindestens einem der Ansprüche 1 bis 4 zur Herstellung optoelektronischer Bauteile oder zur Herstellung pharmazeutischer Wirkstoffe. 8. Use of the bisazafulleroids of the formula (I) and / or (II) according to at least one of claims 1 to 4 for the production of optoelectronic components or for the production of active pharmaceutical ingredients.
PCT/EP1996/000707 1995-03-06 1996-02-21 Diazafulleroids, method of preparation and use thereof WO1996027596A1 (en)

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