EP0782560A1

EP0782560A1 - Fullerene derivatives as synthetic components, process for their production and their use

Info

Publication number: EP0782560A1
Application number: EP95932672A
Authority: EP
Inventors: Carsten Bingel
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1994-09-19
Filing date: 1995-09-06
Publication date: 1997-07-09
Also published as: DE4433245A1; JPH10506106A; WO1996009275A1

Abstract

The present invention concerns novel fullerene derivatives of the formula (I) in which the symbols and indices mean: F - a fullerene radical of the formula C20+2m, where m = 2 to 100; R1 - an aryl radical which may be substituted by 1 to 5 substituents; R2 - a XOIX radical in which X = H, OH, Cl, Br, OR, NH¿2?, NHR or NRR'; and n - a natural number from 1 to 10+m, with m = 2 to 100; a process for their production and their use.

Description

description

Fullerene derivatives as building blocks, processes for their preparation and their use.

Fullerenes are cage-shaped carbon allotropes of the general formula (C _{20 +} 2r 'where m is a natural number. They contain twelve five- and any number, but at least two six-membered rings of carbon atoms. Although this class of compounds was only detected by Kroto and Smalley in 1985 (Nature 318 (1985) 162) and Krätschmer and Huffman first reported on the representation of macroscopic amounts of C _{60 in} 1990 (Nature 347 (1990) 354), such compounds quickly met with broad interest and were the subject of numerous research work within a very short time (see e.g. GS Hammond, VJ Kuck (Editors); Fullerenes, American Chemical Society, Washington DC 1992 and Accounts of Chemical Research, March 1992 edition).

Extensive investigations have already been undertaken for targeted derivatization, in particular of C ₆₀ and C ₇₀ (see, for example, R. Taylor, DRM Walton, Nature 363 (1993) 685 and A. Hirsch, Angew. Chem. 105 (1993) 11). In various derivatization attempts it was possible to isolate defined C ₆₀ monoadducts.

Cyclopropane derivatives were obtained, for example, by the reaction of fullerenes in 1.3 dipolar cycloadditions with diazomethane derivatives (see, for example, F. Wudl et al., Acc. Chem. Res. 25 (1992) 157 and F. Diederich et al., Helv. Chem. Acta 76 ( 1993) 1231), in [2 + 1] carbene additions with nucleophilic glycosylidene carbenes (see e.g. A. Vasella et al., Angew. Chem. 104 (1992) 1383) and by reaction with stabilized σ-halocarbanions (see e.g.

ERSÄΓZBLAΠ (RULE 26) C. Bingel, Chem. Ber. 126 (1993) 1957). In contrast to the reaction of diazomethane derivatives with C ₆₀ (see, for example, F. Diederich et al., Helv. Chem. Acta 76 (1993) 1231), the reaction of σ-halocarbanions with fullerenes (see, for example, C. Bingel, Chem. Ber. 126 (1993) 1957) uniformly to 6-6 ring methano fullerene derivatives.

The object of the present invention was the synthesis of defined fullerene derivatives which have a broad spectrum of structural units with functional groups which can be implemented as versatile, easily accessible building blocks with a large number of compounds to give new fullerene-containing substances and which have the physical properties of the fullerene derivatives, such as solubility and polarity.

It has now surprisingly been found that, for example, a-halocarbanions of substituted σ-haloacetic acid derivatives can be reacted with fullerenes to give new fullerene derivatives.

The invention therefore relates to fullerene derivatives of the formula I

in which the symbols and indices have the following meaning:

F is a fullerene radical of the formula C _{20 +} 2m mi m = 2 to 100; R ¹ is an aryl radical which is optionally substituted by 1 to 5 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ³ , O (C = O) R, SO ₃ H, SO ₂ CI, F , Cl, Br, NO ₂ and / or CN can be substituted, where R is a straight-chain or branched C ₂ to C ₂₀ alkyl group in which one or more CH ₂ groups by -C «C-, -CH = CH- , -O-, -S-, -COO-,

ERSA7ZBLÄTT (RULE 26) -O (C = O) -, -SiR ⁵ ₂ -, -CO- and / or phenylenediyl can be replaced, where R ^{5 is} phenyl or C- to C ₁₂ alkyl, and R ^{3 can be the} same or different from R. and as R is defined, or -CβC-R or -CH = CHR, where R has the above meaning; ² is a COX radical, where X = H, OH, Cl, Br, OR ⁴ , NH ₂ , NHR or NRR ³ , where R ^{4 is} either defined as R or is selected from the following structures:

Table 1

wherein Q ¹ , Q ² , Q ³ and Q ^{4 are} independently CH, N or CF; Q ¹ is preferably CH or N; and Q ² , Q ³ and Q ⁴ = CH;

and n is a natural number from 1 to 10 + m, with m = 2 to 100. Compounds of the formula I in which the symbols and indices have the following meaning are preferred:

F is a fullerene radical of the formula C _{20 + 2m} with m = 20, 25, 28, 29;

R ¹ is an aryl radical, preferably a C ₆ -C ₁₄ aryl radical, which is optionally substituted by 1 to 3 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ³ , O (C = O) R , SO ₃ H, SO ₂ CI, F, Cl, Br, NO ₂ and / or CN can be substituted, where R is a straight-chain or branched C ₂ to C ₂₀ alkyl group in which one or more CH ₂ groups are replaced by - C «C-, -CH = CH-, -O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ -, -CO- and / or phenylenediyl can be replaced, whereby R ^{5 is} phenyl or C until C _{6 is} alkyl, and R ^{3 may be the} same or different from R and is defined as R;

R ² is a COX radical, where X = OH, Cl, OR ⁴ , NH ₂ , NHR or NRR ³ , where R ^{4 is} either defined as R or is selected from the following structures:

and n is a natural number from 1 to 18.

Compounds of the formula I in which the symbols and

Indices have the following meaning:

F is a fullerene radical of the formula C _{20+ 2m} with m = 20 or 25;

R ¹ is a C ₆ -C ₁₄ aryl radical, preferably a phenyl or benzyl radical, which may be substituted by 1 substituent R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ³ , O (C = O) R, F, Cl, Br, NO ₂ or CN can be substituted, where R is a straight-chain or branched C ₂ to C ₂₀ alkyl group in which one or more CH ₂ groups are substituted by -C «C-, -CH = CH -, -O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ , -CO- and / or phenylenediyl can be replaced, where R ^{5 is} phenyl or C ₁ to C alkyl , and R ^{3 may be the} same or different from R and is defined as R;

R ² is a COX radical, where X = OH, OR ⁴ , NHR or NRR ³ , where R ^{4 is} either defined as R or is selected from the following structures:

and n is a natural number from 1 to 6.

ERSÄΓZBLÄΓT (RULE 26) Compounds of the formula I in which the symbols and indices have the following meaning are very particularly preferred:

F is a fullerene radical of the formula C _{20 + 2m} with m = 20 or 25;

R ¹ is phenyl;

R ² is a COX radical, where X = OH, OR ⁴ , NH ₂ , NHR or NRR ³ , where R is a straight-chain and / or branched C ₂ to C ₂₀ alkylene group, in which one or more CH ₂ groups pass through -C «C-, -CH = CH-, -O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ - and / or -CO- can be replaced, where R ^{5 is} phenyl or C * to C ₄ alkyl, and R ^{3 can be} identical or different from R and how R is defined and R ^{4 is} either as R defined or is selected from the following structures:

and n is 1 or 2.

The invention further relates to a process for the preparation of fullerene derivatives of the formula I, in which a fullerene of the general formula C _{20+ 2m} , where m can assume the values mentioned above, in an inert, aprotic, organic solvent with a compound of the general formula II

wherein R ¹ , R ² and n are as defined above, and

Y is -Cl, -Br, I, -OSO ₂ Ar, OSO ₂ alkyl, OSO ₂ CF ₃ or OSO ₂ C ₄ F ₉ , in the presence of a base in the temperature range from -78 ° C to 180 ° C.

I I

A variety of solvents can be used as the inert, aprotic, organic reaction medium (see R. S. Ruoff et al. J. Phys. Chem. 97, 3379 (1993)), but aromatic solvents, such as e.g. Toluene, benzene and / or chlorobenzene used.

The choice of base depends on the pKa value and the sensitivity of the C-H acidic compound to the base used.

Preferred bases are alkali metal hydrides, alcoholates, amides, amines, amidines, guanidines and / or phosphazene bases.

The above-mentioned reaction preferably takes place in a temperature range from 0 to 110 ° C., particularly preferably at room temperature (15-30 ° C.).

For the preparation of compounds of the formula I with n = 1, the stoichiometry of the starting compounds is preferably carried out in a temperature range from -78 ° C. to + 50 ° C., particularly preferably at 0 ° C. to 50 ° C. A high degree of substitution and thus a large value for n is achieved by using excess CH-acidic compound of the formula II and a sufficient amount of base and, if appropriate, heating to above 100 ° C. to accelerate the reaction. However, the compounds of the formula I obtainable by the process according to the invention can also be prepared in a well-defined manner by subsequent reactions, for example an ester of the formula I to give the corresponding acid of the formula! is saponified or an alcohol of the formula I is reacted with an acid to give an ester of the formula I or an ester of the formula I is reacted with an amine to give the corresponding amide of the formula I.

A process is preferred in which a compound of the formula I which contains a reactive ester of the COR ⁴ type, where R ⁴ can assume the meaning of the structures shown in Table 1, with an alcohol or amine, preferably a primary or secondary amine, is converted into a new fullerene derivative.

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 derivatives can also be used.

The fullerenes can be produced by producing fullerene soot in an arc process with subsequent extraction with a non-polar, organic solvent, such as e.g. in WO 92/04279, can be obtained as raw fullerenes. The further fine separation can be carried out by column chromatography.

Some of the fullerenes used are also commercial products.

As cyclopropanation reagents, commercially available, substituted σ-haloacetic acid derivatives can be used, or the compounds of formula II used can be obtained by known chemical processes, such as, for example, the reaction of an acid halide with a hydroxylamide or a hydroxyaromatic or heteroaromatic to form a reactive ester. The fullerene derivatives of the formula I according to the invention serve, inter alia, as starting products for the production of new, fullerene-containing derivatives and can be used for the production of optoelectronic components.

The invention is illustrated by the examples.

List of abbreviations

CDCI3 Deuterotrichloromethane

CS ₂ carbon disulfide

DBU 1,8-diazabicyclo [5.4.0] undec-7-en h hours

MS (FAB) mass spectroscopy (fast atom bombardment) medium (IR) or multiple (NMR)

R Ratio of Fronts in Thin Layer Chromatography s Singlet (NMR) or strong (IR)

SiO ₂ silica gel for chromatographic purposes

All reactions were carried out in an argon atmosphere; the further processing was not carried out under protective gas.

example 1

To a solution of 200 mg (0.27 mmol) of C ₆₀ in 100 ml of toluene

61.8 mg (0.27 mmol) σ-bromophenylacetic acid, methyl ester and 60 mg

(0.54 mmol) potassium tert-butoxide was added. After stirring at 22 ° C. for 6 hours, 5

Drop of 1 molar sodium hydrogen sulfate solution added, the

Reaction mixture dried with magnesium sulfate, filtered and concentrated to half.

After chromatography on silica gel (0.062 - 0.2 mm) with toluene / hexane 1: 3 to

4: 1 was 80 mg (34%)

obtained as a microcrystalline solid. R _f (SiO ₂ ; toluene) = 0.43

MS (FAB): 868 (MM 90%), 720 (100%)

^ -NMR (360 MHz, CDCI ₃ ): δ = 8.10 (m, 2H), 7.54 (m, 3H), 3.96 (s, 3H)

¹³ C NMR (90.5 MHz, CDCI ₃ ): δ = 167.20; 147.48, 146.34, 145.54, 145.26, 145.21, 145.21, 145.18,

144.77, 144.77, 144.74, 144.56 (1C), 144.51, 144.41, 143.95, 143.76,

143.16 (1 C), 143.08. 143.03, 143.03, 142.98, 142.96 (IC), 142.44, 142.23,

142.18, 142.11, 141.01, 141.01, 138.33, 137.89, 137.87, 132.50, 132.36,

129.38, "128.73, 75.65, 55.91, 53.77. (1 signal of the fullerene residue was not found.)

Example 2

321 mg (1.2 mmol) of (1-chloro-1-phenylacetoxy-) succinimide and 183 mg (1.2 mmol) of 1, 8-diazabicyclo were added to a solution of 1.1 g (1.5 mmol) of C ₆₀ in 500 ml of toluene [5.4.0 ] undec-7-en (DBU) given. After 72 h at 30 ° C., the reaction mixture was filtered and the solution was concentrated to half. After chromatography on silica gel (120 g; 0.063-0.2 mm) with toluene, 360 mg (31%, based on the CH acidic compound)

obtained as a microcrystalline solid.

R _f (SiO ₂ ; toluene) = 0.15

MS (FAB): 951 (MM 30%), 918 (30%), 809 (70%), 765 (100%), 720 (70%)

¹ H-NMR (360 MHz, CS ₂ / CDCI ₃ ): δ - 8.13 (m, 2H), 7.57 (m, 3H), 2.39 (s, 4H)

¹³ C-NMR (100 MHz, CS ₂ / CDCI ₃ ): δ = 166.34 (2C = O), 161.75 (1 C = O), 145.28 (1C), 145.25, 144.96,

144.91, 144.91, 144.9, 144.82, 144.58, 144.51, 144.5 (1 C), 144.41, 144.32 (2 Sig.), 144.32 (2 Sig.), 144.1 (1 C), 143.65, 143.40, 142.86, 142.64 (3 Sig .), 142.58, 142.51, 141.93, 141.82, 141.82, 141.46, 140.66 (2 sig.), 139.06, 138.34, 132.37, 130.20, 129.5, 128.55, 73.37, 51.0, 25.51

C ₇₂ H ₉ NO ₄ (951.87): calc .: C 90.9, H 1.0, N 1.5; found: C 92.0, H 1.0, N 1.6.

Example 3

78.7 mg (0.27 mmol) of σ-chlorophenylacetic acid (4-nitrophenyl ester) and 41 mg (0.27 mmol) of DBU were added to a solution of 200 mg (0.27 mmol) of C ₆₀ in 100 ml of toluene. After stirring at 21 ° C. for 6 h, the solution was filtered and concentrated to half. After chromatography on silica gel (0.063-0.2 mm) with toluene / hexane 1: 2 to 1: 0, 108 mg (41%)

obtained as a microcrystalline solid.

R _f (SiO ₂ ; toluene / i-hexane 1: 1) = 0.3

MS (FAB): 975 (MM 50%), 720 (100%)

¹ H NMR (360 MHz, CDCI ₃ ): δ - 8.30 (m, 2H), 8.22 (m, 2H), 7.61 (m, 3H), 7.36 (m, 2H).

¹³ C-NMR (90.5, MHz, CDCI ₃ ):

6 - 164.41, 155.17, 146.69, 145.95 (1C), 145.71, 145.39, 145.36,

145.33, 145.29, 145.27, 145.04, 144.86, 144.80, 144.80, 144.68, 144.65 (1C), 144.55, 144.51 (1C), 143.93, 143.79, 143.21, 143.11, 143.09, 143.06, 143.06, 143.04, 142.36, 142.24, 142.18, 142.09, 141.19, 141.13, 138.52, 137.77, 132.44, 131.50, 129.94, 129.09, 125.40, 122.36, 75.08, 54.93.

Example 4

75 mg (0.079 mmol) of the activated ester from Example 2 was reacted in 75 ml of toluene with 16 mg (0.079 mmol) of 11-aminoundecanoic acid and 12 mg (0.079 mmol) of DBU. After a reaction time of 24 h, the reaction mixture was acidified with 0.01 ml of glacial acetic acid and filtered. After chromatography on silica gel (50 g, 0.063-0.2 mm) with toluene and toluene / acetic acid 20: 1, 39 mg (57%) were used instead of the expected amide

obtained as a solid.

R _f (SiO ₂ ; toluene / acetic acid 20: 1) = 0.28.

MS (FAB): 854 (MM 50%), 810 (M - CO ₂ , 100%), 710 (70%).

Example 5

48 mg (0.05 mmol) of the activated ester from Example 2 were reacted with an amino sugar in 25 ml of toluene for 5 hours at 100 ° C. The dark precipitate was filtered off, washed with toluene and then with methanol and dried. 28 mg (48%)

won.

MS (FAB): 1156 (MM 30%), 810 (50%), 729 (100%).

SPARE BLADE (RULE 26) Example 6

48 mg (0.05 mmol) of the activated ester from Example 2 were reacted in 25 ml of toluene for 2 days at 20 ° C. with 9 mg (0.05 mmol) of bis [3- (dimethylamino) propyl] amine. The reaction product was chromatographed on silica gel (10 g, 0.063-0.1 mm; 52.5 ml methylene chloride / methanol 20: 1, 53.75 ml methylene chloride / methanol / triethylamine 40: 2: 1 and 55 ml methylene chloride / methanol / triethylamine 20: 1: 1) . The fractions with the clean product [R _{ (SiO ₂ , CH ₂ Cl ₂ / MeOH / NEt ₃ 20: 1: 1) = 0.20] were spiked with the same volume of toluene and methylene chloride, methanol and triethylamine were removed on a rotary evaporator. The partially precipitated product was dissolved by adding methylene chloride and quaternized by adding 1 ml of methylene iodide. The brown precipitate of the bisammonium salt was separated from the solvent, washed with toluene and dried in an oil pump vacuum. 39 mg (59%)

receive.

MS (FAB): 1039 (M ^Θ -CH ₃ , 10%), 720 (100%), 526.6 (M ^{θ Θ} , 25%)

Example 7

Analogously to Example 6, 19 mg (0.02 mmol) of the activated ester from Example 2 in 10 ml of toluene were reacted with 9.3 mg (0.02 mmol) of a bile acid methyl ester derivative. After chromatography on silica gel (10 g, 0.063 - 0.2 mm, 100 ml methylene chloride, 50 ml CH ₂ CI ₂ / MeOH 50: 0.3, 15 50 ml CH ₂ CI ₂ / MeOH 50: 0.6, 51.5 ml CH ₂ CI ₂ / MeOH 50: 1.5) were 6 mg (23%)

receive.

R _f (SiO ₂ , CH ₂ CI ₂ / MeOH 20: 1) = 0.45

MS (FAB): 1301 (M ^θ , 100%), 720 (60%).

Example 8

200 mg (0.21 mmol) of the activated ester from Example 2 were in 150 ml

Toluene reacted for 5 hours at 50 ° C with 106 mg (0.21 mmol) of a bile acid β-t-butyl ester derivative.

After chromatography on silica gel (1) 100 g, 0.063-0.2 mm, 800 ml toluene,

300 ml methylene chloride, 400 ml CH ₂ CI ₂ / MeOH 20: 0.4, 300 ml CH ₂ CI ₂ / MeOH

20: 0.6 and 100 ml CH ₂ CI ₂ / MeOH 20: 1;

(2) 40 g, 0.063-0.1 mm, 800 ml CH ₂ CI ₂ / MeOH 20: 0.2, 200 ml CH ₂ CI ₂ / MeOH

20: 1; 173 mg (61%)

won.

R _f (SiO ₂ , CH ₂ CI ₂ / MeOH 20: 1) = 0.36

MS (FAB): 1343 (M ^θ , 40%), 810 (30%), 720 (100%)

¹ H-NMR (360) MHz, CDCI ₃ ): δ = 8.08 (m, 2H), 7.54 (m, 3H). 6.77 (1 NH), 3.96 (br.s, 1H), 3.83 (br. D, J = 2.5 Hz, 1 H), 3.59 (m, 2H), 3.48-3.43 (m, 3H), 2.30-1, 10 (m, 24H + 2 OH), 1.42 (s, 9H), 0.95 (d, J = 6.4 Hz, 3H), 0.90 (s, 3H), 0.66 (s, 3H).

¹³ C-NMR (90 MHz, CDCI ₃ ): δ - 173.54 (C = O), 166.02 (C = O), 147.20, 147.16, 146.87, 146.86, 145.56 (2C), .145.26 (4C), 145.15 (2C ), 145.14 (2C), 145.09 (2C), 144.85, 144.75 (2C), 144.71 (4C), 144.56, 144.45 (2C), 144.33 (2C), 143.97, 143.96, 143.73 (2C). 143.17, 143.10, 143.09, 142.99 (5C), 142.85, 142.84, 142.28, 142.26, 142.23 (2C), 142.14 (2C), 142.06 (2C), 140.92 (4C), 138.96, 138.94, 138.08 (20,133.83, 131.94, 129.30 , 128.97, 79.92, 76.36, 76.35, 74.96, 73.00, 68.51, 66.15, 57.85, 47.42, 46.66, 42.13, 40.70, 39.65, 36.62, 35.12, 35.05, 34.38, 33.79, 32.60, 31.00, 30.46, 28.69, 28.15 (3C ), 27.44, 26.26, 24.65, 23.23, 23.19, 17.41, 12.57. Example 9

10 ml of trifluoroacetic acid were added at 20 ° C. to a solution of 50 mg (0.037 mmol) of the fullerene derivative from Example 8 in 20 ml of methylene chloride. After 35 min. methylene chloride and trifluoroacetic acid were distilled off in vacuo, the residue was washed with diethyl ether and dried in an oil pump vacuum. 54 mg of crude product were obtained. After chromatography on silica gel (10 g, 0.063-0.1 mm, with methylene chloride / methanol / acetic acid 20: 0.4: 0.05 to 20: 0.8: 0.05), 14 mg (30%)

won.

R _f (SiO ₂ "CH ₂ CI ₂ / MeOH / AcOH 20: 0.4: 0.05) = 0.13

MS (FAB): 1287 (M ^θ , 90%), 720 (100%).

^ -NMR (360 MHz, CDCI ₃ ): δ = 8.06 (m, 2H), 7.53-7.42 (m, 3H), 7.30 (t, J = 5.2 Hz, 1 NH), 3.90 (br.

1 H). 3.77 (br., 1 H), 3.53 (m, 2H), 3.45-3.39 (m, 2H), 3.33 (m, 1H), 2.3-1, 1 (m, 24H), 0.92 (d, J = 6.4 Hz, 3H), 0.85 (s, 3H), 0.62 (s, 3H). Example 10

To a solution of 1 g (1.19 mmol) of C ₇₀ in 700 ml of toluene, 318 mg (1.19 mmol) of (1-chloro-1 phenylacetoxy-) succinimide and 181 mg (1.19 mmol) of DBU were added. After stirring at 22 ° C. for 36 h, the reaction mixture was filtered and the solution was concentrated to half.

After chromatography on SiO ₂ (250 g, 0.063 - 0.2 mm) with toluene, 640 mg (50%)

obtained as a microcrystalline solid. R _f (SiO ₂ ; toluene) = 0.17.

MS (FAB): 1071 (M ^θ , 70%), 930 (100%), 840 (50%);

C ₈₂ H ₉ NO ₄ (1071.98): calc .: C 91.9 H 0.8 N 1.3 found: C 93.7 H 0.8 N 1.3

Claims

Claims:

Fullerene derivatives of the formula I,

in which the symbols and indices have the following meaning:

F is a fullerene radical of the formula C _{20 + 2m} with m = 2 to 100; R ¹ is an aryl radical which is optionally substituted by 1 to 5 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ³ , O (C = O) R, SO ₃ H, SO ₂ CI, F , Cl, Br, NO ₂ and / or CN can be substituted, where R is a straight-chain or branched C ₂ to C ₂₀ alkyl group in which one or more CH ₂ groups by -CC-, -CH = CH-, - O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ -, -CO- and / or phenylenediyl can be replaced, where R ^{5 is} phenyl or C to C ₁₂ alkyl, and R ^{3 may be the} same or different from R and as R is defined, or -C «CR or -CH = CHR, where R has the above meaning; is a COX radical, where X = H, OH, Cl, Br, OR ⁴ , NH ₂ , NHR or NRR ³ , where R ^{4 is} either defined as R or is selected from the following structures:

wherein Q ¹ , Q ² , Q ³ and Q ^{4 are} independently CH, N or CF; Q ¹ is preferably CH or N; and Q ² , Q ³ and Q ⁴ = CH; and n is a natural number from 1 to 10 + m, with m = 2 to 100.

Fullerene derivatives according to claim 1, wherein the symbols and indices of

Formula I have the following meaning:

F is a fullerene radical of the formula C _{20 + 2m} with m = 20, 25, 28, 29;

R ¹ is an aryl radical which is optionally substituted by 1 to 3 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ³ , O (C = O) R, SO ₃ H, SO ₂ CI, F , Cl, Br, NO ₂ and / or CN can be substituted, where R is a straight-chain or branched C ₂ to C ₂₀ alkyl group in which one or more CH ₂ groups by -C * C-, -CH = CH- , -O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ -. -CO- and / or phenylenediyl can be replaced, wherein R ^{5 is} phenyl or C ₁ to C _{6 is} alkyl, and R ^{3 may be the} same or different from R and is defined as R; R ² is a COX radical, where X = OH, Cl, OR ⁴ , NH ₂ , NHR or NRR ³ , where R ^{4 is} either defined as R or is selected from the following structures:

and n is a natural number from 1 to 18.

3. Fullerene derivatives according to claim 1 or 2, wherein the symbols and indices of the formula I have the following meaning: F is a fullerene radical of the formula C _{0 + 2m} with m = 20 or 25; R ¹ is an aryl radical which is optionally substituted by 1 substituent R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ³ , O (C = O) R, F, Cl, Br, NO ₂ and / or CN can be substituted, where R is a straight-chain or branched C ₂ to C ₂₀ alkyl group in which one or more CH ₂ groups are represented by -C = C-, -CH = CH-, -O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ , -CO- and / or phenylenediyl can be replaced, where R ^{5 is} phenyl or C * to C ₄ alkyl, and R ^{3 is the} same or different from R can be and how R is defined; R ² is a COX radical, where X = OH, OR ⁴ , NHR or, NRR ³ , where R ^{4 is} either defined as R or is selected from the following structures:

and n is a natural number from 1 to 6.

Fullerene derivatives according to at least one of claims 1 to 3, wherein the symbols and indices of the formula I have the following meaning: F is a fullerene radical of the formula C _{0 + 2m} with m = 20 or 25; R ¹ is phenyl;

R ² is a COX radical, where X = OH, OR ⁴ , NH ₂ , NHR or NRR ³ , where R is a straight-chain or branched C ₂ to C ₂₀ alkyl group in which one or more CH ₂ groups are represented by -C - "C-, -CH = CH-, -O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ - and / or -CO- can be replaced, where R ⁵ Phenyl or C until C _{4 is} alkyl and R ^{3 can be} identical or different from R and as R is defined and R ^{4 is} either as R is defined or is selected from the following structures:

and n is 1 or 2.

Process for the preparation of fullerene derivatives of the formula I.

in which a fullerene of the general formula C _{20 + 2m} , where m = 2 to 100, in an inert, aprotic, organic solvent with a compound of the general formula II

γ

in which

R ^{1 is} an aryl radical which is optionally substituted by 1 to 5 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ³ . O (C = O) R, SO ₃ H, SO ₂ CI, F, Cl, Br, NO ₂ and / or CN can be substituted, where R is a straight-chain or branched C ₂ to C ₂₀ Is alkyl group in which one or more CH ₂ groups are replaced by -C βC-, -CH = CH-, -O-, -S-, -COO-, -O (C = O) -, -SiR ⁵ ₂ - , -CO- and / or phenylenediyl can be replaced, where R ^{5 is} phenyl or C- to C ₁₂ alkyl, and R ^{3 can be} identical or different from R and as R is defined, or -C «CR or - CH = CHR, where R has the above meaning; R ^{2 is} a COX radical, where X = H, OH, Cl, Br, OR ⁴ , NH ₂ , NHR or NRR ³ , where R ^{4 is} either defined as R or is selected from the following structures:

wherein Q ¹ , Q ² , Q ³ and Q ^{4 are} independently CH, N or CF; Q ¹ is preferably CH or N; and Q ² , Q ³ and Q ⁴ = CH; and Y is -Cl, -Br, I, -OSO ₂ Ar, OSO ₂ alkyl, OSO ₂ CF ₃ or OSO ₂ C ₄ F ₉ , in the presence of at least one base in a temperature range from -78 ° C to 180 ° C. . >. Process according to Claim 5, characterized in that toluene, chlorobenzene and / or benzene is used as the organic solvent.

'. Process according to Claim 5 or 6, characterized in that alkali metal hydrides, alcoholates, amides, amines, amidines, guanidines and / or phosphazene bases are used as the base.

8. The method according to at least one of claims 5 to 7, characterized in that one carries out the reaction in a temperature range from 0 ° C to 110 ° C.

9. The method according to claim 8, characterized in that one carries out the reaction at room temperature.

10. Use of the fullerene derivatives according to at least one of claims 1 to 4 for the production of optoelectronic components.