WO1997003975A1

WO1997003975A1 - Polyfullerene addition products, regioselective process for producing the same and their use

Info

Publication number: WO1997003975A1
Application number: PCT/EP1996/002960
Authority: WO
Inventors: Carsten Bingel
Original assignee: Hoechst Aktiengesellschaft
Priority date: 1995-07-18
Filing date: 1996-07-05
Publication date: 1997-02-06
Also published as: DE19526173A1

Abstract

Fullerene derivatives having formula (I) may be easily produced by a one-pot reaction and are suitable for example for synthesizing new fullerene derivatives and for producing optoelectronic components.

Description

description

Polyfullerene adducts, processes for their regioselective production and their use

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

Since a high potential of this substance class is expected, for example in the field of optoelectronics and active ingredient research, extensive studies on targeted derivatization, in particular of C ₆₀ and C ₇₀ , have already been undertaken (see, for example, R. Taylor, DRM Walton, Nature 1993, 363, 685 and A. Hirsch, Angew. Chem. 1993, 105, 1 189). In various derivatization attempts, it was possible to isolate defined monoadducts of C ₆₀ (see, for example, A. Hirsch, The Chemistry of the Fullerenes, Thieme, Stuttgart, New York, 1994).

Studies of regioselectivity in the case of multiple additions to fullerenes, in particular to C ₆₀ , are the subject of current fullerene research (see, for example, osmylation: JM Hawkins et al., J. Am. Chem. Soc. 1992, 1 14, 7954; 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). Diederich and co-workers published a paper on spacer-controlled bis and tris additions to C ₆₀ , whereby in a first addition C _{60 was} cyclopropanated with a bromomalonate derivative, each of which contained a diene in the alcohol residues that intramolecularly in a second reaction step, a thermal Diels-Alder Reaction, further reacted with C ₆₀ (L. Isaacs, RF Haldimann, F. Diederich, Angew. Chem. 1994, 106, 2424).

The object of the present invention is to provide polyadducts of fullerenes which have interesting properties for use in optoelectronics or in drug discovery.

It has now surprisingly been found that polyadducts of fullerenes can be prepared in good yields in a simple one-pot reaction in a highly regioselective manner.

The invention therefore relates to a fullerene derivative of the formula I

where the symbols and indices have the following meaning:

F: is a fullerene radical of the formula C _{(20 + 2m)} ^with rn = 2 to 100;

El, E4: are the same or different COOH, COOR, CONRR ¹ , CHO, COR,

CN, P (O) (OR) ₂ , SO ₂ R, N0 ₂ , H and R, where R, R ^1, identical or different, is a straight-chain or branched, optionally mono- or polysubstituted or substituted aliphatic radical (C ₁ to C ₂₀ ) in which one or more CH ₂ groups are represented by -C≡C-, -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by 0 or NR ³ , where R ³ is phenyl, (C ₁ -C ₂ o) ~ alkyl or benzyl, or R, R1 an aryl radical which is optionally substituted by 1 to 5 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, SO ₃ H, SO ₂ CI, F, Cl, Br, NO ₂ and / or CN can be substituted, where R and R ^{1 has} the meaning given above;

E2, E3: are identical or different -COO-, -CONR-, - (C = O) -, -P (O) (OR) (O-) and -SO ₂ -, where R has the meaning given above or is a benzyl or aryl unit which is optionally substituted by 1 to 4 further substituents R, OH, OR, NHCOR, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, SO ₃ H, SO ₂ CI, F , Cl, Br, NO ₂ and / or CN may be substituted, where R and R ^{1 has} the meaning given above; is equal to Formula II or Formula III,

in which the symbols and indices have the following meaning:

E5, E6: are defined like E2, E3;

E7: is defined like E1, E4;

A, B, D: are the same or different, each a linear or branched, optionally mono- or _{polysubstituted} or substituted aliphatic chain (C ^ to C _2υ ) '' ^{n of} the one or more CH ₂ groups by -C ≤ C -, -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ can, wherein R ³ is phenyl, (C ₁ -C ₂ o) alkyl or benzyl, optionally substituted by 1 to 3 substituents R, OH, OR, COOR, OCOR, S0 ₃ H, SO ₂ CI, F, Cl , Br, NO ₂ and CN can be substituted; C: symbolizes the carbon atom, which is also associated with the

Fullerene radical F in formula I is linked via a cyclopropane ring;

Y: is equal to CH, CR, C-FktGr., Boron, N, P and As, where R is as defined above and FktGr. represents a functional group, preferably OH, NRR ¹ , F, Cl, Br, I, CN, NO ₂ , CO ₂ R or COR; n: is a natural number from 0 to (20 + 2m) / 2, 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 residue of the formula C _{(20 + 2m} , with m = 20, 25, 28, 29,

32;

El, E4: are identical or different COOR, CONRR ¹ , COR, CN, H and R, where R, R ¹ identical or different is a straight-chain or branched, optionally mono- or polysubstituted or differently substituted aliphatic radical (C-, C ₂₀ ) in which one or more CH ₂ groups are represented by -C≡C-, -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, Phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ , where R ³ is phenyl, (C _r C ₂₀ ) alkyl or benzyl, or R, R1 are an aryl radical which may be replaced by 1 to 3 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = 0) R, F, Cl, Br, NO ₂ and / or CN can be substituted, where R and R ^{1 has} the meaning given above;

E2, E3: are identical or different -COO-, -CONR-, - (C = O) - and -SO ₂ -, where R has the meaning given above or denotes a benzyl radical or aryl radical, which may be replaced by 1 or 2 more Substituents R, OH, OR, NHCOR, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, F, Cl, Br, NO ₂ and / or CN can be substituted, where R and R ^{1 are} the same as above has the meaning mentioned; is equal to Formula II or Formula III,

where the symbols and indices have the following meaning:

E5, E6: are defined like E2, E3;

E7: is defined like E1, E4;

A, B, D: are the same or different, each a linear or branched, optionally mono- or polysubstituted or substituted aliphatic chain (C ₁ to C ₂₀ ), in which one or more CH ₂ groups are represented by -C ≡ C- , -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ , wherein R ³ is phenyl, {C., - C ₂₀ ) alkyl or benzyl, which may be substituted by 1 to 3 substituents R, OH, OR, COOR, OCOR, F, Cl, Br, NO ₂ and CN can; symbolizes the carbon atom, which is also linked to the fullerene radical in formula I via a cyclopropane ring;

Y: is equal to CH, CR, C-FktGr. and N, where R is as defined above and FktGr. represents a functional group, preferably OH, NRR ¹ , F, Cl, Br, I, CN, NO ₂ , CO ₂ R or COR; n: is a natural number from 0 to (20 + 2m) / 2.

Compounds of the formula I in which the symbols and indices have the following meaning are particularly preferred:

F: is a fullerene radical of the formula C ₆₀ and C ₇₀ ;

E1, E4: are identical or different COOR, CONRR1, COR, where R, R1 identical or different is a straight-chain or branched, optionally one or more times the same or different represent substituted aliphatic radical (C1 to C ₁₀ ) in which one or more CH ₂ groups by -C≡C-, -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ , where R ³ is phenyl, (C ^ C ^ J-alkyl or benzyl, or R, R1 are an aryl radical which may be substituted by 1 to 3 substituents R, OH, OR, NHCOR, COOR, CONH ₂ , CONHR, CONRR ¹ , 0 (C = O) R, Cl, NO ₂ and / or CN, where R and R ^{1 has} the meaning given above;

E2, E3: is the same or different -COO- or - (C = O) -; X: is equal to Formula II or Formula III,

where the symbols and indices have the following meaning:

E5, E6: is the same or different and is defined as E2, E3;

E7: is defined as El, E4;

A, B, D: are identical or different, each a linear or branched, optionally mono- or polysubstituted or substituted aliphatic chain (C- _| to C ₂₀ ), in which one or more CH ₂ groups by -C ≡C -, -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ can, wherein R ³ is phenyl, (CpC ^ -Alky! or benzyl, which may optionally be substituted by 1 substituent R, OH, OR, COOR, OCOR, F, Cl, Br, N0 ₂ and CN;

C: symbolizes the carbon atom, which is also associated with the

Fullerene radical in formula I is linked via a cyclopropane ring; Y: is equal to CH, CR, C-FktGr. and N, where R is as defined above and FktGr. represents a functional group, preferably OH, NRR ¹ , F, Cl, Br, I, CN, NO ₂ , CO ₂ R or COR; n: is a natural number from 0 to 6.

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 ₆₀ ;

E1, E4: is equal to COOR, where R is a straight-chain or branched, optionally mono- or polysubstituted or substituted aliphatic radical (C ₁ to C ₅ ), in which one or more CH ₂ groups are represented by -C ≡ C- , -CH = CH-, -COO-, -O (C = O) -, - CO-, and / or phenylenediyl up to every third CH ₂ unit can be replaced by O or NR ³ , where R ³ is phenyl, (C ^ C ^ J-alkyl or benzyl, or R is an aryl radical which is optionally substituted by 1 to 3 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O ) R, SO ₃ H, SO ₂ CI, F, Cl, Br, NO ₂ and / or CN can be substituted, where R and R ^{1 has} the meaning given above;

E2, E3: is equal to -COO-;

X: is the same as a linear aliphatic chain (C ₁ to C ₁₂ ) which is optionally substituted one or more times or the same or different and in which one or more CH ₂ groups are represented by -C ≡ C-, -CH = CH-, phenylenediyl and / or up to every third CH ₂ unit can be substituted by O.

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 formulas IV or V, where

the symbols and indices are as defined above, and L is Cl, Br, I, OSO ₂ Ar, OSO ₂ alkyl, OSO ₂ CF ₃ , OSO ₂ C ₄ F ₉ , in the presence of a base in the temperature range of -78 ° C up to 180 ° C is implemented.

Preferred is a method in which fullerene or a fullerene derivative as described above with a compound of the formula IV or V, where L is a hydrogen atom, in the presence of a base and an oxidizing agent, preferably halogen, particularly preferably bromine or iodine, in a stew reaction is implemented.

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 -20 ° C. to 30 ° C., particularly preferably in a temperature range from 0 ° C. to 5 ° C.

To prepare compounds of the formula I, the starting compounds C _{20 + 2m} and IV or V are each approximated, preferably with precise stoichiometry, in a concentration range from 0.2 to 3 mmol / dm ³ , preferably 0.25 to 0.5 mmol / dm ³ .

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, e.g. a t-butyl ester of the formula I is acid-cleaved to give the corresponding acid of the formula I.

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 can also be used.

The fullerenes can be obtained, for example, by producing fullerene soot in the arc process with subsequent extraction with a non-polar organic solvent, as described in WO 92/09279, as raw fullerenes. The further fine separation can be carried out by column chromatography.

Some of the fullerenes used are also commercial products.

Fullerene adducts can be obtained by adding various reagents to the double bonds of the fullerenes (see e.g. R. Tayler, D.R.M. Walton, Nature 363 (1993) 685 and A. Hirsch, Angew. Chem. 105 (1993) 1 1).

The σ-halo-CH-acidic or the acidic methylene compounds of the formula IV or V can be obtained by known chemical processes from simple or simple accessible chemical compounds. For example, σ, ω-diols are reacted with methyl malonate chloride to give corresponding bismalonates, which are converted in a one-pot reaction with fullerene, iodine and the base DBU to give compounds of the formula I, the fullerene bisadducts being partially highly regioselective depending on the chain length of the diol be formed.

The compounds of formula I according to the invention serve, for example, as building blocks for the synthesis of new fullerene derivatives or for the production of optoelectronic components.

The invention is illustrated by the following examples, without being restricted thereby.

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

example 1

47 mg (0.14 mmol) of the bismalonate were added to a solution of 100 mg (0.14 mmol) of C ₆₀ in 600 ml of toluene

^

70 mg (0.28 mmol) of iodine were added, and at 2 ° C. 85 mg (0.56 mmol) of DBU were added. After 1 h, 5 drops of 1 molar sodium hydrogen sulfate solution were added, the reaction mixture was dried with magnesium sulfate, filtered and concentrated to about 30 ml.

After chromatography on silica gel (110 g; 0.063-0.2 mm) with toluene / hexane (300 ml 2: 1), toluene (400 ml) and toluene / ethyl acetate (500 ml, 10: 1), the product-containing fractions were made up to about 10 ml concentrated and again chromatographed (20 g SiO ₂ ; 0.063-0.2 mm; toluene).

After removing the solvent, washing the residue with diethyl ether and drying in an oil pump vacuum, 60 mg (41%) of a 1: 3.5 regioisomer mixture (e: ice 3) were obtained.

1: 3.5 ice 3

R _f : (SiO ₂ , toluene) = 0.15

MS (FAB): 1054 (M ^θ , 75%), 720 (100%)

¹ H-NMR (360 MHz; CDCI ₃ ):

Main product: δ = 7.35, 7.17 (m, 4H), 6.04 (d, J = 1 1.3 Hz, 2H)), 5.00 (d,

J = 11.3 Hz, 2H), 4.09 (s, 6H)

By-product: δ = 7.65-6.9 (m, 4H), 5.87 (d, J = 1 1 Hz, 1 H), 5.73 (d, J = 1 1 Hz, 1 H), 5.08 (d, J = 1 1 Hz , 1 H), 4.88 (d, J = 1 1 Hz, 1 H), 4.05 (s, 3H), 4.03 (s, 3H)

Main product: ¹³ C-NMR (90 MHz, CDCI ₃ ): δ = 164.41, 163.83, 147.02, 146.45, 146.06, 145.86, 145.40, 145.36, 145.22, 145.06, 144.81, 144.42, 144.08, 143.21, 143.10, 142.97, 142.87, 142.30, 142.15, 142.01, 141.51 (2 sig.), 141.49 (2 sig.), 141.19, 141.07 (2 sig.), 138.22, 135.81 (2 sig.), 131 .76, 131.51, 130.54, 70.78, 70.51, 68.31, 53.89, 48.90.

Example 2

Analogously to Example 1, 44 mg (0.14 mmol) of the bismalonate were added to a solution of 100 mg (0.14 mmol) of C ₆₀ in 500 ml of toluene

71 mg (0.28 mmol) of iodine were added, and at 20 ° C 85 mg (0.56 mmol)

DBU added. After 40 min, 3 drops of 1 molar sodium hydrogen sulfate solution were added, the reaction mixture was dried with magnesium sulfate, filtered and concentrated to about 40 ml. After chromatography on silica gel (100 g; 0.063-0.2 mm) with toluene (800 ml) and toluene / ethyl acetate (210 ml, 10: 1), the product-containing fractions were concentrated to about 10 ml and chromatographed again (20 g SiO ₂ ; 0.063 -0.2 mm; 400 ml toluene and 150 ml toluene / ethyl acetate 40: 1). After removal of the solvent, washing of the residue with diethyl ether and drying in an oil pump vacuum, 54 mg (38%) of a 93: 7 regioisomer mixture (e: eis 3) were obtained.

R _f (SiO ₂ , toluene) = 0.09

MS (FAB): 1034 (M ^θ , 90%), 765 (90%), 720 (60%)

¹ H NMR (360 MHz, CDCI ₃ ): δ = 5.05 (m, 1 H), 4.48 (m, 1 H), 4.16 (m, 1 H), 3,963 (s, 3H), 3,961 (s, 3H) ), 3.76 (s, 1 H), 1 .8-0.9 (m, 8H) ¹³ C-NMR (90 MHz, CDCI ₃ ): δ = 164.19, 164.10, 163.75, 161.86, 148.18, 147.29, 147.25, 146.48, 146.46, 146.42, 146.31 (2C), 146.22, 146.13, 146.08, 146.04, 145.66, 145.52, 145.46, 145.35, 145.30, 145.20, 144.96, 144.86, 144.82, 144.68, 144.63, 144.61, 144.56, 144.48, 144.42, 144.16, 143.98 , 143.94, 143.76, 143.73, 143.67, 143.60, 143.53, 143.45, 143.43, 143.33, 143.25, 143.09, 143.07, 143.00, 142.90, 142.47, 142.17, 141.86, 141.68, 141.59, 140.85, 140.83 (2C), 140.80, 140.52, 139.71, 138.56, 138.47, 71.92, 71.86, 71.51, 70.27, 66.64, 65.77, 53.98, 53.85, 51.17, 30.1 1, 29.29, 25.95, 25.81.

Example 3

Analogously to Example 1, 42 mg (0.14 mmol) of the bismalonate were added to a solution of 100 mg (0.14 mmol) of C ₆₀ in 500 ml of toluene

71 mg (0.28 mmol) of iodine were added, and at 0 ° C 85 mg (0.56 mmol) of DBU were added. After 1 h, 5 drops of 1 molar sodium hydrogen sulfate solution were added, the reaction mixture was dried with magnesium sulfate, filtered and concentrated to about 45 ml.

After chromatography on silica gel (20 g; 0.063-0.2 mm) with toluene (50 ml) and toluene / ethyl acetate (250 ml, 100: 1 and 100 ml 10: 1), the product-containing fractions were concentrated to about 4 ml and chromatographed again ( 10 g SiO ₂ ; 0.063-0.2 mm; 600 ml toluene). After removing the solvent, washing the residue with diethyl ether and drying in an oil pump vacuum, 50 mg (35%) of the cis-2 regioisomer

receive.

R _f (SiO ₂ , toluene) = 0.06

MS (FAB): 1020 (M ^θ , 100%), 720 (70%) ¹ H-NMR (360 MHz, CDCI ₃ ): δ = 4.85 (m, 2H), 4.18 (m, 2H), 3.92 (s, 6H), 1.86 (m, 4H), 1.63 (br.m, 2H) .

¹³ C-NMR (90 MHz, CDCI ₃ ): δ = 163.55, 162.90, 148.95, 147.51, 147.48 (1 C), 147.33 (1 C), 146.13, 146.07, 145.81, 145.77, 145.69, 145.40, 145.24, 145.16, 145.07, 144.63, 144.50, 144.29, 144.20, 144.08, 143.62, 143.33, 142.87, 142.39, 141.27, 141.07. 139.78, 136.68 (1 C), 136.62, 136.19, 135.78 (1 C), 70.68, 67.17, 65.56, 53.69, 49.49, 27.18, 21.08.

Example 4

Analogously to Example 1, 40 mg (0.14 mmol) of the bismalonate were added to a solution of 100 mg (0.14 mmol) of C ₆₀ in 500 ml of toluene

71 mg (0.28 mmol) of iodine were added, and 85 mg (0.56 mmol) of DBU were added at 0 ° C. After 1 h, 5 drops of 1 molar sodium hydrogen sulfate solution were added, the reaction mixture was dried with magnesium sulfate, filtered and concentrated to about 50 ml.

After chromatography on silica gel (40 g; 0.063-0.2 mm) with toluene (400 ml) and toluene / ethyl acetate (300 ml, 200: 1), the product-containing last fractions were concentrated to about 5 ml and chromatographed again (20 g SiO ₂ ; 0.063-0.2 mm; 800 ml toluene). After removal of the solvent, washing of the residue with diethyl ether and drying in an oil pump vacuum, 32 mg (23%) of a regioisomer mixture in a ratio of 5: 38: 57 (e: cis-3: cis-2) were obtained by HPLC

receive.

R _f : (SiO ₂ , toluene) = 0.03-0.14

Example 5

Analogously to Example 1, 38 mg (0.14 mmol) of the bismalonate were added to a solution of 100 mg (0.14 mmol) of C ₆₀ in 500 ml of toluene

C (CCHHj ₂ D) r ₃ , and

71 mg (0.28 mmol) of iodine were added, and 85 mg (0.56 mmol) of DBU were added at 0 ^° C. After 1 h, 5 drops of 1 molar sodium hydrogen sulfate solution were added, the reaction mixture was dried with magnesium sulfate, filtered and concentrated to about 50 ml.

After chromatography on silica gel (15 g; 0.063-0.2 mm) with toluene (400 ml) and toluene / ethyl acetate (200 ml, 10: 1), after removing the solvent, washing the residue with diethyl ether and drying in an oil pump vacuum 36 mg (26 %) of a product mixture which, according to HPLC, shows 10% of a monoadduct and 85% of the cis-3 isomer

receive. R _f : (SiO ₂ , toluene) = 0.05

MS (FAB): 992 (M ^θ , 100%), 720 (60%)

¹ H-NMR (360 MHz, CDCI ₃ ): δ = 4.45 (m, 2H), 4.43 (m, 2H), 4.04 (s, 6H), 2.34 (m, 2H)

¹³ C-NMR (75 MHz, CDCI ₃ ): δ = 164.20, 163.99, 146.67, 146.50, 145.76, 145.55, 145.48, 145.33, 145.31, 144.99, 144.93, 144.59, 144.58, 144.39, 144.23, 143.79, 143.62, 143.50, 142.28, 142.27, 141.89, 141.83, 141.07, 140.87, 140.74, 140.59, 140.48, 140.43, 135.20, 129.49, 72.03, 68.81, 63.02, 53.81, 49.14, 25.98.

Example 6

71 mg (0.28 mmol) of iodine were added, and at 0 ° C 85 mg (0.56 mmol) of DBU were added. After 1 h, 5 drops of 1 molar sodium hydrogen sulfate solution were added, the reaction mixture was dried with magnesium sulfate, filtered and concentrated to about 50 ml.

After chromatography on silica gel (15 g; 0.063-0.2 mm) with toluene (400 ml) and toluene / ethyl acetate (150 ml, 10: 1), after removing the solvent, washing the residue with diethyl ether and drying in an oil pump vacuum 10 mg (7 %) of a product mixture which, according to HPLC, contains 42% of a monoadduct as the main bisadducts and 32% of the cis-3 isomer

contains, won.

R _f : (SiO ₂ , toluene) = 0.1

Example 7

Analogously to Example 1, 46 mg (0.14 mmol) of the bismalonate were added to a solution of 100 mg (0.14 mmol) of C ₆₀ in 480 ml of toluene

71 mg (0.28 mmol) of iodine were added, and at 0 ° C 85 mg (0.56 mmol) of DBU were added. After 1 h, 5 drops of 1 molar sodium hydrogen sulfate solution were added, the reaction mixture was dried with magnesium sulfate, filtered and concentrated to about 30 ml.

After chromatography on silica gel (1 2.5 g; 0.063 - 0.1 mm) with toluene

(500 ml) after removing the solvent, washing the residue with diethyl ether and drying in an oil pump vacuum 88 mg (60%)

Product mixture, which according to HPLC and NMR spectroscopy from two

Bisadducts, the trans-4 isomer and the e isomer in the ratio 56:44,

won.

Formula (MW): C ₇₅ H ₂₀ O ₈ (1048.977)

R _f (SiO ₂ , toluene): 0.14

MS (FAB): 1048 (M ^θ , 100%), 720 (30%)

trans-4 isomer:

¹ H-NMR 360 MHz, CDCI ₃ ): δ = 4.73 (m, 2H), 4.1 1 (m, 2H), 4.06 (s, 6H), 1.66

(m, 4H), 1.28 - 1.0 (m, 6H)

¹³ C-NMR (90 MHz, CÜCI ₃ ): δ = 164.19, 164.1 1, 148.30 (1 C), 147.10, 146.78 (1 C), 146.33, 146.17, 145.62, 145.54, 145.47, 145.39, 145.14, 145.01, 144.34 , 144.24, 144.16, 144.09, 143.44 (1 C), 143.36, 143.03, 142.92, 142.19, 142.15, 141.95, 141 .84 (1 C), 141.68 (4C), 141 .36, 140.34, 139.95, 138.85, 133.65, 71.45, 71 .08, 66.88, 53.94, 50.69, 34.1 1, 28.98, 26.71

e isomer:

¹³ C-NMR (90 MHz, CDCI ₃ ): δ = 164.02, 163.86, 163.79, 163.12, 148.86 bis

138.64: not all 56 fullerene signals resolved, 71.91, 71.85, 71.80, 70.63,

67.52, 67.34, 53.86, 53.84, 51.82, 29.07, 28.86, 28.45, 28.21, 26.42,

26.14

Example 8

Analogously to Example 1, 48 mg (0.14 mmol) of the bismalonate were added to a solution of 100 mg (0.14 mmol) of C ₆₀ in 480 ml of toluene

After chromatography on silica gel (12.5 g; 0.063-0.1 mm) with toluene (480 ml), after removing the solvent, washing the residue with diethyl ether and drying in an oil pump vacuum, 64 mg (43%) of a product mixture, which was determined by HPLC and NMR spectroscopy consists of two bisadducts, trans-4: I equals 1 1: 89,

won.

Formula (MW): C ₇₆ H ₂₂ O ₈ (1063.004)

R _f (SiO ₂ , toluene) = 0.14

MS (FAB): 1062 (M ^θ , 100%), 720 (25%)

e isomer:

¹ H-NMR (360 MHz, CDCI ₃ ): δ = 4.79 (t, d, J _aχ = 10.9 Hz; J _ab = 3.1 H, 1 H),

4.71 (m, 1H), 4.20-4.11 (m, 2H), 4.01 (s, 3H), 4.00 (s, 3H), 1.84-0.93 (m,

12H)

¹³ C-NMR (90 MHz, CDCI ₃ ): δ = 163.90, 163.82, 163.51, 163.26, 148.82, 147.31, 147.26, 146.97, 146.56, 146.52, 146.39, 146.38, 146.15, 146.13, 146.05, 145.73, 145.52, 145.40, 145.29, 145.25 (2C), 145.21, 145.06, 144.88, 144.87, 144.79, 144.68, 144.63, 144.59 (2C), 144.48, 144.29, 144.14, 144.07, 143.86, 143.82, 143.72, 143.65, 143.64 (2C), 143.63, 143.57, 143.54, 143.41, 143.09, 143.05, 143.01, 142.68, 142.44, 142.01, 141.84, 141.73, 141.65, 141.63, 141.55, 141.33, 140.56, 139.78, 139.75, 138.78, 71.79, 71.76, 71.59 , 70.46, 67.08, 66.94, 53.93, 53.88, 51.65 (2C), 29.00, 28.94, 28.91, 28.77, 26.03, 25.76

trans-4 isomer:

¹ H-NMR (360 MHz, CDCI ₃ ): δ = 4.59 (m, 2H), 4.26 (m, 2H), 4.06 (s, 6H),

1.84-0.93 (m, 12H)

¹³ C-NMR (90 MHz, CDCI ₃ ): δ = 164.23, 164.13, 148.21 to 134.66: not all 30 Fulier signals resolved, 71.25, 70.89, 67.48, 54.00, 50.75, 29.22, 28.77, 26.08

Claims

Claims:

1 . Fullerene derivative of the formula I,

where the symbols and indices have the following meaning:

F: is a fullerene radical of the formula C _{(20 + 2m)} with m = 2 to 100;

E1, E4: are the same or different COOH, COOR, CONRR ¹ , CHO, COR, CN, P (O) (OR) ₂ , SO ₂ R, NO ₂ , H and R, where R, R ^{1 are the} same or different straight-chain or branched, optionally mono- or polysubstituted or substituted aliphatic radical [C _λ to C ₂₀ ), in which one or more CH ₂ groups are represented by -C ≡ C-, -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ , where R ³ is phenyl, (C-pC ^ -Alkyl or benzyl, or R, R1 are an aryl radical which is optionally substituted by 1 to 5 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, SO ₃ H, SO ₂ CI, F, Cl, Br, NO ₂ and / or CN can be substituted, where R and R ^{1 has} the meaning given above;

E2, E3: are identical or different -COO-, -CONR-, -! C = O) -, -P (O) (OR) (O-) and -S0 ₂ -, where R has the meaning given above or is a benzyl or aryl unit which is optionally substituted by 1 to 4 further substituents R, OH, OR, NHCOR, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, SO ₃ H, SO ₂ CI, F , Cl, Br, N0 ₂ and / or CN may be substituted, wherein R and R ^{1 has} the meaning given above;

X: is equal to Formula II or Formula III,

in which the symbols and indices have the following meaning:

E5, E6: are defined like E2, E3;

E7: is defined like E1, E4;

A, B, D: are identical or different and each are a linear or branched aliphatic chain (C ₁ to C ₂₀ ) optionally substituted one or more times or differently or in which one or more CH ₂ groups are represented by -C = C- , -CH = CH-, -COO-, -O (C = 0) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ , where R ³ is phenyl, (C ^ C ^ -Alky! or benzyl, which is optionally substituted by 1 to 3 substituents R, OH, OR, COOR, OCOR, SO ₃ H, SO ₂ CI, F, Cl, Br, NO ₂ and CN can be substituted;

C: symbolizes the carbon atom, which is also linked to the fullerene radical F in formula I via a cyclopropane ring;

Y: is equal to CH, CR, C-FktGr., Boron, N, P and As, where R is as defined above and FktGr. represents a functional group, preferably OH, NRR ¹ , F, Cl, Br, I, CN, NO ₂ , CO ₂ R or COR; n: is a natural number from 0 to (20 + 2m) / 2, with m = 2 to 100.

2. Fullerene derivative according to claim 1, wherein the symbols and indices have the following meaning:

F: is a fullerene radical of the formula C _{(20 + 2m)} with m = 20, 25, 28, 29, 32;

E1, E4: are identical or different COOR, CONRR ¹ , COR, CN, H and R, where R, R ¹ identical or different is a straight-chain or branched, optionally mono- or polysubstituted or substituted aliphatic radical (C, to C ₂₀ ) represent in the one or more CH ₂ groups by -C ≡ C-, -CH = CH-, -COO-, -O (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ , where R ³ is phenyl, (C _} -C ₂₀ ) -Ml <y \ or benzyl, or R, R1 are an aryl radical which is optionally replaced by 1 to 3 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, F, Cl, Br, NO ₂ and / or CN can be substituted, where R and R ^{1 has} the meaning given above;

E2, E3: are identical or different -COO-, -CONR-, - (C = O) - and -SO ₂ -, where R has the meaning given above or denotes a benzyl radical or aryl radical, which may be replaced by 1 or 2 more Substituents R, OH, OR, NHCOR, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, F, Cl, Br, NO ₂ and / or CN can be substituted, where R and R ^{1 are} the same as above has the meaning mentioned;

X: is equal to Formula II or Formula III,

^

where the symbols and indices have the following meaning:

E5, E6: are defined like E2, E3;

E7: is defined like E1, E4;

A, B, D: are the same or different, each a linear or branched, optionally mono- or polysubstituted or substituted aliphatic chain (C ₁ -C ₂₀ ) in which one or more CH ₂ groups are represented by -C -C C -, -CH = CH-, -COO-, -0 (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ where R ³ is phenyl,

or is benzyl, which may optionally be substituted by 1 to 3 substituents R, OH, OR, COOR, OCOR, F, Cl, Br, NO ₂ and CN; C: symbolizes the carbon atom, which is also linked to the fullerene radical in formula I via a cyclopropane ring; is equal to CH, CR, C-FktGr. and N, where R is as defined above and FktGr. represents a functional group, preferably OH, NRR ¹ , F, Cl, Br, I, CN, NO ₂ , CO ₂ R or COR; n: is a natural number from 0 to (20 + 2m) / 2.

3. Fullerene derivative according to claim 1, wherein the symbols and indices have the following meaning:

F: is a fullerene radical of the formula C ₆₀ and C ₇₀ ;

E1, E4: are identical or different COOR, CONRR1, COR, where R, R1 identical or different represent a straight-chain or branched, optionally mono- or polysubstituted or differently substituted aliphatic radical (C1 to C ₁₀ ), in which one or more CH ₂ groups by -C ≡ C-, -CH = CH-, -COO-, -O (C = 0) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ Unit can be replaced by O or NR ³ , where R ³ is phenyl, (C 1 -C 4 -alkyl or benzyl, or R, R 1 is an aryl radical which is optionally substituted by 1 to 3 substituents R, OH, OR, NHCOR, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = O) R, Cl, NO ₂ and / or CN can be substituted, where R and R ^{1 has} the meaning given above;

E2, E3: is the same or different -COO- or - (C = O) -;

X: is equal to Formula II or Formula III,

where the symbols and indices have the following meaning:

E5, E6: is the same or different and is defined as E2, E3; E7: is defined like E1, E4;

A, B, D: are each the same or different, a linear or branched, optionally mono- or polysubstituted or substituted aliphatic chain (C-, to C ₂₀ ), in which one or more CH ₂ groups by -C ≡ C -, -CH = CH-, -COO-, -0 (C = O) -, -SiR ³ ₂ -, -CO-, phenylenediyl and / or up to every third CH ₂ unit can be replaced by O or NR ³ can, wherein R ³ is phenyl, (C _r C ₁₀ ) alkyl or benzyl, which may optionally be substituted by 1 substituent R, OH, OR, COOR, OCOR, F, Cl, Br, NO ₂ and CN;

C: symbolizes the carbon atom, which is also linked to the fullerene radical in formula I via a cyclopropane ring;

Y: is equal to CH, CR, C-FktGr., C-E5-C: -E7 and N, where R is as defined above and FktGr. represents a functional group, preferably OH, NRR ¹ , F, Cl, Br, I, CN, N0 ₂ , CO ₂ R or COR; n: is a natural number from 0 to 6.

4. Fullerene derivative according to claim 1, wherein the symbols and indices have the following meaning:

F: is a fullerene radical of the formula C ₆₀ ;

E1, E4: is the same as COOR, where R is a straight-chain or branched, optionally mono- or polysubstituted or substituted aliphatic radical (C ₁ to C ₅ ) in which one or more CH ₂ groups are represented by -C ≡ C- , -CH = CH-, -COO-, -O (C = O) -, - CO-, and / or phenylenediyl up to every third CH ₂ unit can be replaced by O or NR ³ , where R ³ is phenyl, (CpC ^ alkyl or benzyl, or R is an aryl radical which is optionally substituted by 1 to 3 substituents R, OH, OR, NHCOR, COOH, COOR, CONH ₂ , CONHR, CONRR ¹ , O (C = 0) R, S0 ₃ H, SO ₂ CI, F, Cl, Br, N0 ₂ and / or CN can be substituted, where R and R ^{1 has} the meaning given above;

E2, E3: is equal to -COO-; X: is equal to a linear aliphatic chain {C ^ to C ₁₂ ) which is optionally substituted one or more times or identically or differently and in which one or more CH ₂ groups are represented by -C≡C-, -CH = CH-, phenylenediyl and / or up to every third CH ₂ unit can be substituted by O.

5. A process for the preparation of fullerene derivatives according to claim 1, in which a fullerene of the general formula C _{20 + 2m} , where m can assume the values mentioned in claim 1, in an inert, aprotic, organic solvent with a compound of the general formulas IV or V, where

the symbols and indices are as defined in claim 1, and L is Cl, Br, I, OSO ₂ Ar, OSO ₂ alkyl, OSO ₂ CF ₃ , OSO ₂ C ₄ F ₉ , in the presence of a base in the temperature range from -78 "C to 180 ° C is implemented.

6. The method according to claim 5, characterized in that L is a hydrogen atom and that the reaction is carried out in the presence of a base and an oxidizing agent, preferably halogen, particularly preferably bromine or iodine.

7. The method according to claim 5, characterized in that toluene, benzene and / or chlorobenzene is used as solvent.

8. The method according to claim 5, characterized in that the base is selected from the group consisting of alkali metal hydrides, alcoholates, amides, amines, amidines, guanidines and / or phosphazene bases.

9. The method according to claim 5, characterized in that the

Reaction in a temperature range from -20 to 30 ° C, preferably from 0 to 5 ° C is carried out.

10. The method according to claim 5, characterized in that the fullerene and the compounds of the formulas IV or V each at the start of the reaction in a concentration range from 0.2 to 3 mmol / dm ³ , preferably 0.25 to 0.5 mmol / dm ³ available.

11. Use of fullerene derivatives according to claim 1 for the production of optoelectronic components.