FULLERENE DERIVATIVES, METHODS OF PREPARING THEM AND THEIR USE

Fullerene derivatives, methods of preparing them and their use Fullerenes are cage-like carbon allotropes of the formula (c20+2m) (wl1®1® m = a natural number) . They contain twelve five-member ed rings and also any number, but at least two, six-membered rings of carbon atoms. Although this class of compound was discovered only in 1985 by Kroto and Smalley (Nature, 1985, 318, 162) and Kratschmer and Huffman only reported the preparation of macroscopic amounts of C60 in 1990 (Nature 1990, 347, 354), such compounds have very quickly attracted wide interest and within a very short time have become the subject of numerous research studies (see, for example, G.S. Hammond, V.J. Kuck (Editors), Fullerenes, American Chemical Society, Washington DC 1992 and Accounts of Chemical Research, March edition 1992). Since a high potential is expected of this class of substances, for example in the fields of optoelectronics and research on active compounds, efforts have already been made to form derivatives, in particular of C60 (see, for example, H. Schwarz, Angew, Chem. 1992, 104, 301 and F. Wudl et al. in G.S. Hammond, V.J. Kuck (Editors), Fullerenes, American Chemical Society, Washington DC 1992 and Accounts of Chemical Research, March edition 1992). Some experiments on forming derivatives succeeded in isolating defined products. Examples are the reactions of fullerenes in 1.3 dipolar cycloadditions with diazo compounds (e.g. F. Wudl et al.. Ace. Chem. Res. 1992, 25, 157) and also in [2 + 1) carbene additions with nucleophilic glycosylidenecarbenes (e.g. A. Vasella et al., Angew. Chem. 1992, 104, 1383). Further examples are the addition of nucleophiles such as organolithium and organomagnesium compounds 30152-2 (e.g. A. Hirsch et al., Angew. Chem. 1992, 104, 808). It was desirable to synthesize fullerene derivatives containing structural units having those functional groups which are known to have applications in the field of research on active compounds, which can also be utilized for the construction of new polymer materials and which improve the physical properties, such as solubility or polarity, of the fullerene derivatives. It has long been known that 1, 3-dicarbonyl compounds such as ma Ionic esters and /3-ketoesters have proven useful in the synthesis of active compounds (e.g. Organikum 16, intended edition 1966, pages 393, 413, 414). The linking of acid C-H compounds, such as ma Ionic esters or /3-ketoesters, with activated olefins is known as the Michael edition (e.g. Organikum 16, intended edition 1986, page 507). It has now been found that well-defined fullerene derivatives can be obtained by reacting fuller- enes, for example, with the anions of 2-halocarbonyl compounds. The invention provides a fullerene derivative of the formula I 06=0. in which the symbols and indices have the following meanings : Fu: is a fullerene radical of the formula C(20+2m) where m = 20, 25, 28, 29; E1, E2 : are identical or different and are each COOH, COOR, CONRR1, CHO, COR, CN, P (O) (OR) 2 and S02R, where R, R1 are each a straight-chain or branched, aliphatic radical (Cj to C20) which may be unsub- stituted or monosubstituted or polysubstituted by 30152-2 identical or different sub stituents, in which rad¬ ical up to every third CH2 unit can be replaced by O or NR4, where R4 is (Cj-Cjq)-alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsub- stituted or substituted by from 1 to 5 substituents R, OH, OR, COOR, OCOR, SO3H, S02C1, F, Cl, Br, N02 and CN C00\ , or together are .CRR COCK or are different from one another and are each COR, R or H, or are different from one another and are each COR/R or F/Cl/Br, where R is as defined above, or are different from one another and are each N02, R3 or H, where R3 is an unsubstituted, mono sub- stituted or polysubstituted aliphatic radical (C1 to C2o) ' n: is a natural number from 1 to 10 + m where m = 20, 25, 28, 29. - 3a - According to another aspect of the present invention, there is provided a fullerene derivative of the formula I , x where the symbols and indices have the following meanings: Fu is a fullerene radical of the formula C(2o+2m) wherein m = 20, 25, 28 or 29; E1 and E2 are: i) identical or different and are each COOH, COOR, CONRR1, CHO, COR, CN, P(O) (OR) 2 or SO2R, wherein R and R1 are each a straight-chain or branched, aliphatic radical (Ci to C20) which is unsubstituted, monosubstituted or polysubstituted by identical or different substituents, and in which aliphatic radical up to every third CH2 unit can be replaced by O or NR4, wherein R4 is (C1-C20) -alkyl or benzyl, or a benzyl radical or phenyl radical which is unsubstituted or substituted by from 1 to 5 substituents selected from R, OH, OR, COOR, OCOR, SO3H, SO2CI, F, Cl, Br, NO2 and CN; ii) together COO. , CRR1 COO iii) different from one another and each COR, R or H; iv) different from one another and each a) COR or R or b) F, Cl or Br, where R is as defined above; or v) different from one another and each NO2, R3 or H, wherein R3 is an unsubstituted, monosubstituted or polysubstituted aliphatic radical (Ci to C20) ; and n is a natural number from 1 to 10 + m where m = 20, 25, 28 or 29. 30152-2 - 3b - Preference is given to compounds of the formula I in which the symbols and indices have the following meanings : Fu: is a fullerene radical of the formula C(2o+2m) where m = 20, 25, 28, 29, E1, E2 : are identical or different and are each COOR, COR, P(0) (OR) 2, COOH, CN, where R is a straight-chain or branched, aliphatic radical (Ci to C20) which may be unsubstituted or monosubstituted or polysubstituted by identical or different substituents, in which radical up to every third CH2 unit can be replaced by 0 or NR4, where R4 = (C1-C20) -alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsubstituted or substituted by from 1 to 3 substituents R, OH, OR, COOR, OCOR, SO3H, SO2CI, F, Cl, Br, NO2 and CN, 30152-2 cock , or together are .C R R COO or are different from one another and are each COR, R or H, or are different from one another and are each COR/R or F/Cl/Br, ns is a natural number from 1 to 12. Particular preference is given to compounds of the formula I in which the symbols and indices have the following meanings: Fu: Cgg, C7q El / L2: COjR1 / C02R2 ; COjR1 / COR2 ; C02R1 / CN ; COAr/R1 or H; COAr/R1 or CI; C00\ . j C00x COR1 / COR2; PtOMOR/PiOMOR2; COOH / COOH; where R1 and R2 are identical or different and are each a straight-chain or branched alkyl radical {C- to C20) which may be unsubstituted or monosubstituted or polysubstituted by ident¬ ical or different substituents, in which rad- iS ical every third CH2 \anit can be replaced by O or NR4, where R4 = iC) -alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsubstituted or substituted by from 1 to 3 substituents OH, OMe, COjR1, OOCR1, SO3H, S02C1, F, Cl, Br, N02 and CN, and Ar is a phenyl radical which can likewise be substituted by 30152-2 from 1 to 3 substituents OH, OMe, Me, CCR1, OCOR1, SO3H, S02C1, F, Cl, Br, N02 and CN or can be substituted by a straight-chain or branched aliphatic radical (C-Cjo) , preferably cl-cio' which may be unsubstituted or monosubstituted or disubstituted by identical or different substituents COOR5, CONHR5, CONR, CONH2, CONR6, COOH, OH or OCOR5, COOAr, COOCHjAr, where R5 = Cj-Cg-alkyl, hydroxy- (C-Cg) -alkyl, carboxyCCj-Cg) -alkyl or (C-) -alkylcarboxyl- (Cj-Cg)-alkyl; R6 = Cn-Cn-alkylene in which up to every 3rd CH2 unit can be replaced by O and which together with the amide nitrogen forms a C12-C18 ring, and Ar is as defined above; n: is a natural number from 1 to 6. Very particular preference is given to compounds of the formula I in which the symbols and indices have the following meanings: Fu C50, C7o E1 / E2: C02Alkyl1 / COaAlkyl1 ; COjAlkyl1 / COAIkyl2 ; COAr / Ar ; COAr / Alkyl1 ; COAr / H where Alkyl1, Alkyl2 are each a straight-chain or branched alkyl radical having from 1 to carbon atoms in which up to every third CH2 unit can be replaced by O, and Ar is a phenyl group which can be substituted by a 30152-2 n: straight-chain or branched aliphatic radical (Cj-Cg) which may be unsubstituted or monosubstituted or disubstituted by identical or different substituents COOR5, CONHR5, CONRj, CONR6, COOH, OH or OCOR5, where R5 and R6 are as defined above, is 1 or 2. The straight-chain or branched aliphatic radical (C1-C20) R, R1 can be, for example, preferably monosubstituted or disubstituted by identical or different substituents OH, COOH, COOAr, CONRj, CONR6, OCOR5, COOCH2Ar, CONHCH2Ar, CONHAr, CONHR5, COOR5, halogen, CONH2, COCH2Ar, COAr, CO{C1-C6) -alkyl or CHO, where Ar, R5 and R6 are as defined above. The compounds of the invention having the formula I are prepared, for example, by cyclopropanation of fullerene with an a-halo-CH-acid compound in the presence of a suitable base (e.g. L.L. McCoy, J. Amer. Chem. Soc. 1958, 80, 6568) or by reaction of suitably functionalized cyclopropanated fullerene derivatives by known methods, with care having to be taken to ensure that the reagents used do not react with the electrophilic fullerene radical. The invention further provides the following process for preparing fullerene derivatives of the formula I (Pu } + c v * y v n lait 0;< .E' —'n Formula II Formula I (20+2m) where where Fu is a fullerene radical of the formula C, m = 20, 25, 28, 29, E1 and E2 are identical or different and are each COOH, 30152-2 COOR, CONRR1, CHO, COR, CN, P(0)(OR)2 and S02R, where R, R1 are each a straight-chain or branched aliphatic radical (C to C20) which may be unsubsti- tuted or monosubstituted or polysubstituted by identical or different substituants, in which radical up to every third CH2 unit can be replaced by O or NR4, where R4 is (C1-C20)-alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsubstituted or substituted by from 1 to substituents R, OH, OR, COOR, OCOR, SO3H, S02C1, F, Cl, Br, N02 and CN C00\ , or together are CRR co(r or are different from one another and are each COR, R or H, or are different from one another and are each COR/R or F/Cl/Br, or are different from one another and are each N02, R3 or H, where R3 can be an unsubstituted, monosub¬ stituted or polysubstituted aliphatic radical (Cjl to C20), X is -Cl, -Br, -I, -OS02Ar, OS02CF3, OS02C4F9, base:is alkali metal hydride, alkali metal hydroxide, alkoxide, amide, amine, guanidine n is a natural number from 1 to 10 + m where m = 20, 25, 28, 29. - 7a - According to yet a further aspect of the present invention, there is provided a process for preparing fullerene derivatives as described herein, which comprises reacting a fullerene of the formula C(2o+20m) (m = 20, 25, 28 or 29) in an aprotic organic solvent with a CH acid component of formula II II and with an alkali metal hydride, an alkali metal hydroxide, an alkoxide, an amide, an amine or a guanidine, in a temperature range from -780C to 180oC, wherein: E1 and E2 are: i) identical or different and are each COOH, COOR, CONRR1, CHO, COR, CN, P (O) (OR) 2 or S02R, wherein R and R1 are each independently a straight-chain or branched aliphatic radical (Ci to C20) which is unsubstituted, monosubstituted or polysubstituted by identical or different substituents, and in which aliphatic radical up to every third CH2 unit can be replaced by 0 or NR4, wherein R4 is (C1-C20) -alkyl or benzyl, or a benzyl radical or phenyl radical which is unsubstituted or substituted by from 1 to 5 substituents selected from R, OH, OR, COOR, OCOR, SO3H, SO2CI, F, Cl, Br, NO2 and CN; ii) together COO. /CRR coo ; iii) different from one another and each COR, R or H; iv) different from one another and each a) COR or R or b) F, Cl or Br; or v) different from one another and each NO2, R3 or H, wherein R3 is an unsubstituted, monosubstituted or polysubstituted aliphatic radical (d to C2o) ; and X is -Cl, -Br, -I, -OS02Ar, -OS02CF3 or -OSOzFg, where Ar is a phenyl radical. - 7b - Preference is given to a process for preparing compounds of the formula I, in which a fullerene of the formula C<2o+2m) (m = 20, 25, 28, 29) is reacted in an aprotic organic solvent such as toluene, chlorobenzene, benzene, CH2CI2 with compounds of the formula II in the presence of suitable bases in a temperature range from -78°C to 180oC, preferably from 0 to 1100C and in appropriate cases at room temperature (2 0-3 0°C). The selection of the base depends on the pKa and the sensitivity of the CH acid compound to the base used. The preparation of compounds of the formula I where n = 1 is carried out at approximate stoichiometry of the starting compounds, preferably in a temperature range from -780C to +50oC, particularly preferably at from 0oC to 500C. A higher degree of substitution and thus a greater value for n is achieved by using excess CH acid compound of the formula II and a sufficient amount of base and accelerating the reaction by heating, if appropriate, to above 1000C. However, the compounds of the formula I obtainable by the process of the invention can also be prepared in well- defined form by means of subsequent reactions by, for example, an ester of the formula I being saponified to give the corresponding acid of the formula I or an alcohol of the formula I being reacted with an acid to give an ester of the formula I or an ester of the formula I being reacted with an amine to give the corresponding amide of the formula I. The fullerene used is preferably pure Ceo and/or C70, but it is also possible to use crude fullerenes containing a mixture of Cg0 and C70 as main components. However, all other conceivable fullerenes or fullerene derivatives can also be used. The fullerenes can be obtained by preparation of fullerene black in an electric arc process with subsequent extraction using a nonpolar organic solvent (crude fullerene), as described, for example, in out by column chromatography. Some of the fullerenes used are also commercial products. The cyclopropanation reagents used can be, on the one 216124G hand, commercial a-halo CH acid compounds or the compounds of the formula II which are used can be obtained by methods known to the chemist, such as the halogenation of CH acid compounds or, for example, the Friedel-Crafts acylation of substituted aromatics using bromoacetyl halides. Ester and amide functions are obtained from the desired carboxylic acids and alcohols or amines by known methods. The compounds of the invention having the formula I are used, for example, in optoelectronic components. The invention is illustrated by the examples, Index of abbreviations CDCI3 CD2C12 CS2 DBU DMAP d Et20 HPLC h MS(FAB) m NaH q or quart quint Rf S Si02 t w deuterotrichloromethane dideuterodichloromethane carbon disulfide 1,8-diazobicyclo[5.4.0]undec-7-ene 4 -dime thy léuninopyridine doublet (NMR) or day(s) (indication of time) diethyl ether high-pressure liquid chromatography hours mass spectrometry (fast atom bombardment) medium (IR) or multiplet (NMR) sodium hydride quartet (NMR) quintet (NMR) ratio of fronts in thin-layer chromato- graphy singlet (NMR) or strong (IR) silica gel for chromatographic purposes triplet (NMR) weak (IR) 216124G Example 1 In a 250 ml nitrogen flask, 435 mg (0.60 mmol) of C60 were dissolved in 200 ml of toluene. 0.144 g (6.0 mmol) of NaH were introduced and 0.216 g (0.90 mmol) of diethyl bromomalonate was added thereto. The suspension was stirred for 6.5 h at room temperature, quenched with 8 drops of 1 molar H2S04 solution, dried with magnesium sulfate and filtered. According to HPLC, 65% of the C60 used had been reacted. Chromatography over silica gel (0.063 - 0.2 mm) using toluene/hexane 1:1 and toluene gave in microcrystalline form (0.238 g, 45%). Rf(Si02; toluene) = 0.50 MS(FAB): 87 8 (M+) IR (on KBr) : v [cm-1] = 2979 (w), 1745 (C = 0), 1428 (C60), 1295(m), 1266(m), 1234 (s), 1206(m), 1186 (Cgo), 1095(m), 1061(w). -NMR (360 MHz, CDCI3) : ô = 4.57 (q, J = 7.13 Hz, 4H) , 1.49 (t, J = 7.13 Hz, 6H). 13C-NMR (100 MHz, CDCI3) Ô = 163.55, 145.35, 145.26, 145.20, 145.18, 144.88, 144.69, 144.67, 144.60, 143.88, 143.08, 143.01, 142.99, 142.21, 141.92, 140.94, 139.03, 71.64, 63.37, 52.26, 14.22. Analysis calc. for C67H10O4 : C: 91.6% H: 1.1% found C: 92.4% H: 1.4% Example 2 The procedure of Example 1 was repeated, using 0.7 g (0.98 mmol) of Cg0, 0.2 9 g (1.2 mmol) of diethyl bromo¬ malonate and 0.23 g (9.6 mmol) of NaH in the reaction to give, after workup and chromatography over silica gel (0.063-0.2 mm), 0.33 g (39%) of monoadduct and - 11 C02Et (0.048 g, 4.7%). According to TLC, more than 1 isomer Rf(Si02; toluene) = from 0.19 to 0.24 MS(FAB): 103 6 (M+) Example 3 Under protective gas, 471 mg (0.654 mmol) of Cg0 in 200 ml of toluene were admixed with 207 mg (0.981 mmol) of dimethyl bromomalonate and 125 mg (0.821 mmol) of DBU and stirred for 4 h at room temperature. The reaction mixture was filtered and the solution was evaporated to a volume of 60 ml. According to HPLC 69% of C60 were reacted. Chromatography over Si02 (0.063-0.2 mm) using toluene/i-hexane 1:1, 2:1 and 3:1 gave (55x v~- CO,Me C02Me in microcrystalline form (249.3 mg, 44%) and in addition 114 mg (24%) of C60 were recovered. Rf(Si02; toluene) = 0.37 (toluene) MS(FAB): 850 (M~) -NMR (360 MHz, CDC1,/CS,): b = 4.06 (s) . Example 4 The procedure of Example 3 was repeated, with 0.137 g (0.190 mmol) of Cg0 in 58 ml of toluene being reacted with 88 mg (0.19 mmol) of didecyl bromomalonate and 29 mg (0.19 mmol) of DBU and stirred for 15 h at room temperature. According to HPLC, 75% of Cg0 were reacted. The reaction mixture was completely evaporated, the residue was extracted with diethyl ether (3 x 10 ml), the ether solution was filtered through silica gel and, after removal of the ether, chromatographed over SiOj (0.063-0.2 mm) using toluene/i-hexane 1:1 and 2:1. This gave 216124G OC10H21 0Ct0H21 as a brown viscous oil (66 mg, 31%). Rf(Si02; toluene/i-hexane 1:1) = 0.4 MS(FAB) : 1102 (M-) . H-NMR (360 MHz, CDCI3) : 6 = 4.47 (t, J = 6.5 Hz, 4H) , 1.82 (m, 4H), 1.43 (m, 4H) , 1.26 (m, 24H) , 0.82 (t, J = 6.0 Hz, 6H). 13C-NMR (100 MHz, CDCI3): Ô = 163.65, 145.39, 145.24, 145.17, 145.16, 144.86, 144.67, 144.65, 144.59, 143.87, 143.06, 143.00, 142.97, 142.19, 141.90, 140.93, 138.99, 71.70, 67.46, 52.47, 31.88, 29.61, 29.56, 29.33, 29.24, 28.61, 25.99, 22.68, 14.12 Example The procedure of Example 3 was repeated, with 943 mg (1.31 mmol) of C60 in 400 ml of toluene being reacted with 506 mg (1.31 mmol) of di(2-(2-methoxyethoxy)ethyl) bromomalonate and 199 mg (1.31 mmol) of DBU. After a reaction time of 18 h at room temperature, the reaction mixture was filtered and chromatographed over 50 g of silica gel (0.063-0.2 mm). C60 was eluted with toluene and the monoaddition product was eluted with 800 ml of toluene/diethyl ether 1:1. This gave 504 mg (37% based on -60 used) of monaddition product Rf(Si02; toluene/Et20 1:1) = 0.21 MS(FAB): 1026 (M", 40%), 720 (100%) H-NMR (360 MHz, CDCI3): ô = 4.64 (m, 4H) , 3.87 (m, 4H) , 3.67 (m, 4H), 3.53 (m, 4H), 3.36 (s, 6H). Example 6 The procedure of Example 3 was repeated, with 236 mg (0.33 nunol) of Ceo in 100 ml of toluene being reacted with 50 mg (0.33 mmol) of DBU and a solution of 74 mg (0.33 mmol) of 2, 2-dimethyl-5-bromo-4,6-diketo-l,3- dioxane in 2 ml of méthylène chloride. After a reaction time of 18 h at room temperature, the reaction mixture was filtered, evaporated to half its volume and chromatographed over 100 g of silica gel (0.063-0.2 mm). C50 was eluted with 3 00 ml of toluene/i-hexane 1:1 and the monoaddition product was eluted with 350 ml of toluene. After removal of the solvent, the black microcrystalline monoaddition product was washed with pentane and diethyl ether and dried in vacuo. This gave 60.2 mg (21%) of 0 .Me ©£C Rf(Si02; toluene) = 0.40 MS (FAB): 892 (M®, 20%), 804 (I-acetone, 25%), 760 (M®-acetone-C02, 55%), 720 (100%). -NMR (360 MHz, CDCI3) : 6 : 2.18 (s) "C-NMR (100 MHz, CDC12) : ô = 160.11(C = 0), 145.90, 145.66, 145.62(2C), 145.42, 145.15, 145.01(2C), 145.00, 144.40, 143.82, 143.57(2C), 143.50, 143.44, 142.64, 141.89, 141.75, 141.36, 106.34, 71.69, 44.74, 28.33 2 5 Example 7 The procedure of Example 3 was repeated, with 123 mg (0.17 mmol) of C60 in 50 ml of toluene being reacted with 51 mg (0.17 mmol) of di-tert-butyl bromomalonate and 26 mg (0.17 mmol) of DBU. After a reaction time of 4 h at 3 0 room temperature, the reaction mixture was filtered, evaporated to a volume of 2 0 ml and chromatographed over g of silica gel (0.063-0.2 mm). Using the eluant mixture toluene/i-hexane 1:1.5, Cso and the monoaddition product were eluted and separated from the polyaddition products. After removal of the solvent, the residue was taken up in méthylène chloride, with only small amounts of C60 being extracted together with the monoaddition product, and the méthylène chloride solution was evaporated to 5 ml. The chromatographic separation over 80 g of silica gel (0.063-0.2 mm) using toluene/i-hexane 1:2 and toluene gave, after washing with pentane and diethyl ether and drying in vacuo, 60 mg (37%) of monoaddition adduct. 0 /t-Bu y* 1-Bu Rf(Si02; toluene) = 0.58 MS(FAB): 934 (M6, 75%), 734 (90%), 720 (100%). -NMR (360 MHz, CDCI3): <5 = 1.68 (s) Example 8 In a 100 ml two-neck flask, 50 mg (0.054 mmol) of bis(t- butoxycarbonyDmethanofullerene from Example 7 were dissolved under an argon atmosphere in 3 0 ml of chloro- form and admixed with 650 mg (6.7 mmol) of methanesulfon- ic acid. After about 2 h, a precipitate formed. After 24 h, the solution over the precipitate was colorless. The precipitate was separated off from the solvent and washed twice with ether to remove excess acid. Drying in vacuo gave 19 mg (43%) of MS(FAB): 822 (M9, 30%), 778 (Me-C02, 30%), 734 (Me-2 CO- 100%), 720 (70%) . Example 9 236 mg (0.328 mmol) of fullerene C50 in 100 ml of toluene were placed in a 250 ml nitrogen flask and 102 mg (0.67 mmol) of DBU and 62 mg (0.412 mmol) of methyl 2- chloroacetate were injected in. After 2 h, the reaction mixture was filtered. According to HPLC, 80% of the C60 used were reacted. Chromatography over silica gel (0.063-0.2 mm) using toluene/i-hexane (1:1) and toluene gave Sot ou« in microcrystalline form (75 mg, 27%) . Rf(Si02; toluene) =0.44 MS(FAB): 834(M-) IR (on KBr) : v [cm'1] = 2996 (w), 2943 (w) , 1756 (C = 0), 1718(C = 0), 1428(Ceo), 1356(w), 1265(w), 1231 (s), 1200(m), 1185 (C60) . -NMR (360 MHz, CDCI3) : ô = 4.10 (s, 3H) , 2.87 (s, 3H) . 13C-NMR (100 MHz, CDCI3): ô = 193.64, 164.45, 145.44, 145.28, 145.28, 145.25, 145.21, 145.20, 145.08, 144.87, 144.75, 144.75, 144.74, 144.74, 144.69, 144.61, 144.61, 143.88, 143.84, 143.17, 143.12, 143.07, 143.06, 143.06, 142.98, 142.24, 142.24, 141.93, 141.90, 141.08, 141.01, 139.45, 138.03, 72.33, 54.09, no signal for methoxy C, 28.84. Analysis cale, for C65H603: C: 93.53 H: 0.72 found C: 93.4 H: 0.8 Example The procedure of Example 9 was repeated, with 0.471 g (0.654 mmol) of C60 in 200 ml of toluene being reacted with 108 mg (0.656 mmol) of ethyl 2-chloroacetate and 99.5 mg (0.654 nunol) of DBU and stirred for 2.5 h at room temperature. The reaction mixture was filtered and the solution was evaporated to from 60 to 7 0 ml. According to HPLC, only 24% of Cg0 were reacted. Chromatography over Si02 (0.063-0.2 mm) using toluene/ i-hexane 1:1 and toluene, carried out twice, gave C*o OEt in microcrystalline form (111.5 mg, 20%) and, in addition, 280 mg (59%) of C60 were recovered. Rf(Si02; toluene) = 0.36 MS(FAB): 848 (M~) H-NMR (360 MHz, CDCI3) : 3 = 4.55 (q, J = 7.1 Hz, 2H) , 2.82 (s, 3H), 1.54 (t, J = 7.1 Hz, 3H) . Example 11 151 mg (0.65 mmol) of desyl chloride and 367 mg (3.27 nunol) of potassium tert-butoxide were placed in a 250 ml 2-neck flask and a solution of 236 mg (0.328 mmol) of C60 in 100 ml of toluene was subsequently added. The mixture was stirred for 40 h at room temperature, 2 0 quenched by addition of 5 drops of 1 molar H2S04 solution, dried with MgS04 and filtered. According to HPLC, 60% of the Cg0 used were reacted. Chromatography over silica gel (0.063 - 0.2 mm) using toluene/i-hexane 2:3 and toluene gave Ph ©CO, in microcrystalline form (76 mg, 25%). Rf(Si02, toluene/i-hexane 1:1) = 0.54 MS(FAB): 914 (M") IR (on MBr) : v [cm-1] = 3051 (w), 3036 (w), 1678 (C = 0) , 1595(m), 1494(w), 1444(m) , 1427(050), 1255(m), 1187 (C60) , 697(s). H-NMR (360 MHz, CDCI3) : ô = 8.62 (m, 2H) , 8.24 (m, 2H) , 7.62-7.40 (m, 5H). 13C-NMR (100 MHz, CDCl3) ô = 190.57, 148.20, 146.31, 145.59, 145.29, 145.28, 145.21, 145.19, 145.19, 144.83, 144.81, 144.77, 144.74, 144.60, 144.50, 144.41, 143.92, 143.77, 143.17, 143.05, 143.01, 142.99, 142.97, 142.88, 142.34, 142.19, 142.19, 142.13, 141.13, 141.04, 138.51, 137.19, 134.22, 133.55, 132.21, 132.16, 130.34, 129.08, 128.99, 128.97, 75.78, 60.81. Analysis cale, for C74H10O: C: 91.6% H: 1.1% found C: 92.4% H: 1.4% Example 12 The procedure of Example 3 was repeated, with 471 mg (0.654 mmol) of C60 in 200 ml of toluene being reacted with 100 mg (0.657 mmol) of DBU and 140 mg (0.657 mmol) of a-bromoprcpiophenone. After a reaction time of 8 days at room temperature, 52% of the C60 have reacted 2 0 according to HPLC. Chromatography over Si02 (0.063-0.2 mm) using toluene/i-hexane 1:2 -» 2:1 and (30 mg, 5.4%). Rf(Si02; toluene/i-hexane 1:1) = 0.31 MS(FAB) : 852 (M~) . -NMR (360 MHz, CDC13) : ô = 8.53 (m, 2 Hortho) , 7.70 (m, 1 Hpara) , 7.64 (m, 2 HJ , 2.64 (s, 3H) . Example 13 In a 250 ml nitrogen flask, 0.236 g (0.328 mmol) of C60 were dissolved in 100 ml of toluene. 66 mg (0.331 mmol) of cj-bromoacetophenone and 0.051 g (0.334 mmol) of DBU were added and the mixture was stirred at room temperature. After 5 h, 2 drops of 2N sulfuric acid were added and the reaction mixture was dried using MgS04. After filtration and evaporation of the solution to half its volume, it was chromatographed over silica gel, after the C60 conversion had previously been determined as 72% by HPLC. Chromatography over Si02 (0.063-0.2 mm) using Ph in microcrystalline form (59 mg, 21%), and additionally 81 mg of product contaminated with Cg0. Rf(Si02, toluene) = 0.64 MS(FAB): 83 8 (M") IR (on KBr) : v [cm-1] = 3023 (w) , 1684 (C = 0), 1446 (m) , 1428(CS0), 1244(m), 1219 (s), 1185 (C60) , 1006 (s), 710 (s), 683(s) . -NMR (360 MHz, CDCI3) : ô = 8.46 (m, 2H), 7.75 (m, 1H), 7.67 (m, 2H), 5.64 (s, JCH = 162 Hz, 1H). 13C-NMR (100 MHz, CDCI3) : ô = 189.69, 148.04, 146.63, 145.58, 145.39, 145.31, 145.21, 145.20, 145.09, 144.87, 144.75, 144.69, 144.66, 144.65, 144.65, 144.37, 143.96, 143.71, 143.34, 143.18, 143.05, 142.99, 142.99, 142.80, 142.49, 142.27, 142.23, 142.11, 141.22, 140.98, 139.61, 136.65, 135.95, 134.48, 129.35, 128.94, 72.30, 44.16. Analysis cale, for C68H60: C: 97.37% H: 0.72% found C: 97.7% H: 0.8% Example 14 The procedure of Example 13 was repeated, with a mixture of 0.236 g (0.328 mmol) of C60 in 100 ml of toluene, 114 mg (0.572 mmol) of u-bromoacetophenone and 95 mg (0.62 mmol) of DBU giving 83 mg (30%) of the monoadduct 3 0 and also the diadduct, as a mixture of isomers. 216124G (54 mg, 17%) Rf : 0. MS(FAB) : 956 (M") Rf : 0.47 (toluene) In the following examples, the reactions were carried out in an argon atmosphere, while the further workup of the individual reaction mixtures was not carried out under protective gas. In each case, a solution of Cg0 in toluene was reacted with the CH acid compound and DBU as base while stirring at room temperature. After filtration of the reaction mixtures and evaporation of the solutions to half their volume, the solutions were chromatographed over silica gel. The monoaddition products isolated were washed with diethyl ether or pentane and dried in vacuo. Example 236 mg (0.33 mol) of C60 were stirred in 100 ml of toluene with 98 mg (0.33 mol) of ethyl 3 -[4-(2-bromo- acetyl)phenyl]propionate and 50 mg (0.33 mmol) of DBU for 4 h. Chromatography: 75 g of silica gel (0.063-0.2 mm); 400 ml of toluene 117 mg (38%) of v\ r—\ l C 0 , E t H '/ w ' --* R£ (Si02, toluene) = 0.2 0 MS(FAB): 938 (M8, 60%), 720 (100%) -NMR (360 MHz, CHCI3) : b = 8.38 (d, J = 8.4 Hz, 2 H) , 7.50 (d, J = 8.4 Hz, 2 H), 5.61 (s, 1 H), 4.14 (q, J = 7.1 Hz, 2 H) , 3.10 (t, J = 7.6 Hz, 2 H) , 2.71 (t, J = 7.6 Hz, 2 H) , 1.24 (t, J = 7.1 Hz, 3 H) "C-NMR (100 MHz, CDCI3) : 6 = 189.20, 172.37, 148.06, 147.99, 146.69, 145.58, 145.39, 145.28, 145.19, 145.18, 145.07, 144.86, 144.73, 144.67, 144.64, 144.62, 144.34, 143.94, 143.70, 143.32, 143.16, 143.04, 142.98, 142.97, 142.78, 142.48, 142.26, 142.21, 142.10, 141.20, 140.96, 139.57, 136.63, 134.16, 129.34, 129.25, 72.33, 60.68, 44.19, 35.21, 31.05, 15.5 Example 16 247 mg (0.34 mmol) of C60 were stirred in 100 ml of toluene with 127 mg (0.34 mmol) of diethyl 2-[4-(2-bromo- acetyl)benzyl]malonate and 52 mg (0.34 mmol) of DBU for 3 h. Chromatography: 70 g of silica gel (0.063-0.2 mm); 1000 ml of toluene 139 mg (40%) of Rf (Si02, toluene) = 0.10 MS (FAB): 1010 (M®, 45%), 720 (100%) -H-NMR (360 MHz, CD2C12) : Ô = 8.40 (d, J = 8.4 Hz, 2 H) , 7.54 (d, J = 8.4 Hz, 2 H), 5.71 (s, 1 H), 4.18 (m, 4 H), 3.75 (t, J = 7.7 Hz, 1 H) , 3.36 (d, J = 7.8 Hz, 2 H) , 1.23 (t, J = 7.1 Hz, 6 H). 13C-NMR (CD2C12) : ô = 189.1 (1C), 168.5, 148.3, 147.0, 145.7, 145.5, 145.5 (1C), 145.3, 145.2, 145.2, 145.1, 144.9 (1C), 144.8, 144.7, 144.7, 144.6, 144.4, 144.0, 143.8, 143.3, 143.2 (1C), 143.1, 143.0, 143.0, 142.9, 142.6, 142.3, 142.2, 142.2, 141.2, 141.0, 139.5, 136.8, 136.8, 134.6, 129.9, 129.2, 72.6, 61.8, 44.5, 34.7, 13.9. Example 17 123 mg (0.17 mmol) of C60 were stirred in 50 ml of toluene with 49 mg (0.17 mmol) of ethyl 4- [4- (2-broino- acetyl)phenyl]butyrate and 2 6 mg (0.17 mmol) of DBU for h. Chromatography: 40 g of silica gel (0.063-0.2 mm); 300 ml of toluene 47 mg (28%) of C02E t Rf (Si02/ toluene) = 0.27 MS (FAB): 952 (M®, 60%), 720 (100%) (360 MHz, CD2C12) : b = 8.41 (d, J = 8.3 Hz, 2 H) , 7.52 (d, J = 8.3 Hz, 2H), 5.72 (s, 1 H), 4.13 (quart., J= 7.1 Hz, 2 H), 2.83 (t, J = 7.7 Hz, 2 H) , 2.40 (t, J = 7.4 Hz, 2 H), 2.04 (quint, J = 7.6 Hz, 2 H), 1.26 (t, J = 7.1 Hz, 3H). Example 18 454 mg (0.63 mmol) of 0. were heated to about 50-60oC in 200 ml of toluene with 350 mg (0.612 mmol) of di(4- nitrophenyl) 3-[4-(2-bromoacetyl)phenyl]glutarate and stirred together with 93 mg (0.613 mmol) of DBU for hours. Chromatography: 50 g of silica gel (0.063-0.2 mm); 500 ml of toluene, 600 ml of méthylène chloride 315 mg of C50 (69% based on C60 used) 158 mg (20%/67% based on C50 used/C60 reacted) of o -CH Rf (Si02, CH2C12) = 0.30 MS (FAB): 1210 (M6, 100%), 720 (60%) 216124G 1H (360 MHz, CDCI3): ô = 8.49 (d, J = 8.3 Hz, 2 H), 8.21 (m, 4 H), 7.68 (d, J = 8.3 Hz, 2 H), 7.14 (m, 4 H), 5.61 (s, 1 H), 4.04 (quint, J = 7.4 Hz, 1 H), 3.22 (d, d, J = 16.2 Hz, Jax = 6.8 Hz, 2 H), 3.13 (d, d, J = 16.2 Hz, JBX = 8.1 Hz, 2 H) Example 19 371 mg (0.51 mmol) of Cg0 were stirred in 150 ml of toluene with 168 mg (0.44 mmol) of (2,2-dimethyl-l,3- dioxolan-4-yl)methyl 3- [4- (2-bromoacetyl)phenyl]propion- ate and 67 mg (0.44 mmol) of DBU for 15 hours. Chromatography: 25 g of silica gel (0.063-0.2 mm); 100 ml of toluene, 102 ml of toluene/ethanol 100:2, 205 ml of toluene/ethanol 100:2.5 343 mg (76% based on CH acid compound used) of .0 Rf (Si02, toluene/MeOH 20:1) = 0.68 MS (FAB): 1024 (M9, 50%), 720 (100%) -NMR (360 MHz, CDCI3) ô = 8.38 (d, J = 8.3 Hz, 2 H) , 7.50 (d, J = 8.3 Hz, 2 H), 5.61 (s, 1 H), 4.29 (m, 1 H), 4.18, 4.10 (m, 2 H) , 4.05, 3.69 (m, 2 H) , 3.11 (t, J = 7.5 Hz, 2 H), 2.78 (t, J = 7.5 Hz, 2 H) , 1.43 (s, 3 H) , 1.37 (s, 3 H) "C-NMR (100 MHz, CDCI3) ô = 189.18 (C = 0), 172.15 (C = 0), 148.04, 147.69 (1C), 146.66, 145.57, 145.38, 145.28, 145.18, 145.18, 145.07, 144.85, (1C), 144.73, 144.67, 144.64, 144.64, 144.62, 144.34, 143.93, 143.69, 143.32, 143.16 (1C), 143.03, 142.97 (1C), 142.97, 142.78, 142.47, 142.25, 142.21, 142.09, 141.20, 140.95, 139.58, 136.63, 134.24, 129.33, 129.28, 109.93, 73.56, 72.32, 66.26, 65.04, 44.16, 34.96, 30.92, 26.72, 25.37. Example 2 0 569 mg (0.79 mmol) of Cso were stirred in 230 ml of toluene with 299 mg (0.73 mmol) of menthyl 3-[4-(2- bromoacetyl)phenyl]propionate and 113 mg (0.74 mmol) of DBU for 24 h. Chromatography: 150 g of silica gel (0.063-0.2 mm); 400 ml of toluene/i-hexane 1:1, 500 ml of toluene 186 mg of C60 (33% based on C60 used) recovered 42 3 mg (55% based on CH acid compound used) of Rf (Si02/ toluene) = 0.40 MS (FAB): 1048 (M6, 40%), 720 (80%) -NMR (360 MHz, CD2C12) ô = 8.39 (d, J = 8.3 Hz, 2 H) , 7.53 (d, J = 8.3 Hz, 2 H), 5.70 (s, 1 H), 4.69 (m, 1 H), 3.11 (t, J = 7.5 Hz, 2 H), 2.72 (t, J = 7.5 Hz, 2 H) , 1.94 (m, 1 H) , 1.75 (m, 1 H) , 1.67 (m, 2 H) , 1.51-1.21 (m, 3 H), 1.11-0.8 (m, 2 H) , 0.91 (d, J = 6.5 Hz, 3 H) , 0.86 (d, J = 7.0 Hz, 3 H), 0.72 (d, J = 7.0 Hz, 3 H) 13C-NMR (100 MHz, CD2Cl2) ô = 188.6 (C = 0), 171.4 (C = 0), 148.0, 147.9 (1C), 146.7, 145.3, 145.1, 144.9, 144.8, 144.8, 144.7, 144.5 (1C), 144.4, 144.3, 144.3, 144.2, 144.0, 143.6, 143.4, 142.9, 142.8 (1C), 142.7, 142.6, 142.6, 142.5, 142.2, 141.9, 141.8, 141.8, 140.8, 140.6, 139.2, 136.4 (1C), 136.4 (1C), 133.8 (1C), 129.0, 128.8, 74.0 (1C), 72.3 (2C), 46.8 (1C), 44.2, 40.6, 35.1, 33.9, 31.1, 30.8, 26.5, 23.1, 21.5, 20.3, 15.8 Example 21 742 mg (1.03 mmol) of C60 were stirred in 300 ml of toluene with 350 mg (0.91 mmol) of (6-hydroxyhexyl) 4-[4- (2-bromoacetyl)phenyl]butyrate and 139 mg (0.91 mmol) of DBU for 24 h. Chromatography: 150 g of silica gel (0.063-0.2 mm) ; 500 ml of méthylène chloride/methane 100:1 to 100:3 359 mg of Cg0 (48% based on C60 used) recovered 53 6 mg (57% based on CH acid compound used) of MS (FAB): 1024 (M9, 50%), 734 (35%), 720 (100%) •H-NMR (360) MHz, CDCI3) : 6 = 8.38 (d, J = 8.3 Hz, 2 H) 7.48 (d, J = 8.3 Hz, 2 H) , 5.62 (s, 1 H) , 4.08 (t, J = 6.7 Hz, 2 H) , 3.63 (t, J = 6.5 Hz, 2 H) , 2.81 (t, J = 7.6 Hz, 2 H), 2.37 (t, J = 7.4 Hz, 2 H), 2.04 (quint, J = 7.5 Hz, 2 H) , 1.64 (m, 2 H) , 1.57 (m, 2 H) , 1.39 (m, 4 H) 13C-NMR (90) MHz, CDCI3) : ô = 189.2 (C = 0), 173.2 (C = 0), 149.0 (1C) , 148.1, 146.7, 145.6, 145.4, 145.3, 145.2, 145.2, 145.1, 144.9, (1C), 144.7, 144.7, 144.6, 144.6, 144.4, 143.9, 143.7, 143.3, 143.2 (1C), 143.0, 143.0, 143.0, 142.8, 142.5, 142.3, 142.2, 142.1, 141.2, 141.0, 139.6, 136.6, 136.6, 134.0, 129.5, 129.2, 72.4, 64.5, 62.8, 44.2, 35.3, 33.6, 32.6, 28.7, 26.1, 25.8, 25.4. Example 2 2 247 mg (0.34 mmol) of C60 were stirred in 100 ml of toluene with 155 mg (0.33 mmol) of 3-[4-(2-bromoacetyl)- phenyl] -1-(1,4,7,10-tetraoxa-13-azacyclodec-13-yl)propan- 1-one and 50 mg (0.33 mmol) of DBU for 24 h. Chromatography: a) 35 g of silica gel (0.063-0.2 mm); 100 ml of toluene, 315 ml of toluene/ethanol 100:5, 55 ml of toluene/ethanol 100:10, 100 ml of méthylène chloride/ethanol 95:5 b) 25 g of silica gel (0.063-0.2 mm); 133 ml of toluene/ethanol 130:3, 132 ml of toluene/ethanol 130:2, 105 ml of toluene/ethanol 100:5, 52 ml of méthylène chloride/ethanol 50:2, 105 ml of méthylène chloride/ethanol 100:5 154 mg (42% based on CH acid compound used) of Rf (Si02/ toluene/methanol 20:1) = 0.21 MS (FAB): 1112 (MH+, 100%), 720 (85%) -NMR (360 MHz, CD2C12) Ô = 8.40 (d, J = 8.3 Hz, 2 H) , 7.56 (d, J = 8.2 Hz, 2 H), 5.72 (s, 1 H), 3.72 (t, J = 6.6 Hz, 2 H) , 3.64-3.53 (m, 16 H) , 3.49 (t, J = 6.6 Hz, 2 H) , 3.12 (t, J = 7.5 Hz, 2 H) , 2.77 (t, J = 7.5 Hz, 2 H) 13C-NMR (100 MHz, CDCI3) Ô = 189.20 (C = 0), 171.99 (C = 0), 149.22 (1C), 148.11, 146.76, 145.60, 145.41, 145.28, 145.19, 145.17, 145.07, 144.87 (1C), 144.73, 144.67, 144.65, 144.63, 144.62, 144.34, 143.94, 143.70, 143.33, 143.16 (1C) , 143.04, 142.98 (1C), 142.97, 142.78, 142.49, 142.26, 142.23, 142.10, 141.20, 140.95, 139.55, 136.62, 133.92, 129.51, 129.20, 72.40, 71.70, 70.68, 70.40, 70.20, 70.16, 70.14, 69.75, 69.64, 50.52, 49.56, 44.29, 34.24, 31.50 2 0 Example 23 940 mg (1.3 mmol) of C60 were stirred in 380 ml of toluene with 500 mg (1.27 mmol) of 4-nitrophenyl 3-[4-(2- bromoacetyl)phenyl]propionate and 194 mg (1.27 mmol) of DBU for 20 hours. Chromatography: 180 g of silica gel (0.063-0.2 mm); 1600 ml of toluene 333 mg of C60 (35% based on C60 used) 7 04 mg (53% based on CH acid compound used) of Rf (Si02/ toluene) = 0.21 MS (FAB): 1031 (M®, 50%), 720 (100%) 1H (360 MHz, CDCI3) 6 = 8.43 (d, J = 8.3 Hz, 2 H), 8.25 (m, 2 H) , 7.57 (d, J = 8.1 Hz, 2 H), 1 signal for 2 arom¬ atic protons is obscured by the toluene protons, 5.61 (s, 1 H), 3.24 (d, J = 7.3 Hz, 2 H), 3.04 (d, J = 7.3 Hz, 2 H) Example 24 1757 mg (2.44 mmol) of Cso were stirred in 710 ml of toluene with 82 3 mg (2.03 mmol) of 4-nitrophenyl 4-[4-(2- bromoacetyDphenyl] butyrate and 310 mg (2.03 mmol) of DBU for 7 h. Chromatography: 400 g of silica gel (0.063-0.2 mm); 3500 ml of toluene 112 8 mg (53% based on CH acid compound used) of Rf (Si02, toluene) = 0.2 MS (FAB): 1045 (M®, 20%), 720 (100%) -NMR (360 MHz, CD2C12) Ô = 8.43 (d, J = 8.1 Hz, 2 H) , 8.27 (d, J = 9.0 Hz, 2 H) , 7.56 (d, J = 8.1 Hz, 2 H) , 7.31 (d, J = 9.0 Hz, 2 H) , 5.72 (s, 1 H) , 2.93 (t, J = 7.6 Hz, 2 H), 2.71 (t, J = 7.4 Hz, 2 H), 2.19 (quint, 7.6 Hz, 2 H) 13C-NMR (90 MHz, CDCI3) 6 = 189.2, 170.7, 155.3 (1C) , 148.3 (1C), 148.0, 146.7, 145.6, 145.4, 145.3, 145.2, ; 2161248 145.2, 145.1, 144.9 (1C) , 144.8, 144.7, 144.7, 144.6, 144.6, 144.4, 143.9, 143.7, 143.3, 143.2 (1C), 143.1, 143.0, 143.0, 142.8, 142.5, 142.3, 142.2, 142.1, 141.2, 141.0, 139.6, 136.6, 134.2 (1C), 129.3, 129.3, 125.3, 122.3, 72.3, 44.2, 35.2, 33.5, 25.8. Example 2 471 mg (0.65 nunol) of C60 were stirred in 200 ml of toluene with 168 mg (0.65 mmol) of 3-[4-(2-bromoacetyl)- phenyl]propan-l-ol and 100 mg (0.65 mmol) of DBU for 17 h. Chromatography: a) 80 g of silica gel (0.063-0.2 mm): 300 ml of toluene/methanol 100:1, 3 00 ml of toluene/methanol 30:1, 500 ml of toluene/methanol 25:1, 200 ml of toluene/methanol 20:1 b) 60 g of silica gel (0.063-0.2 mm); 900 ml of méthylène chloride/methanol 100:1 2 90 mg (53% based on CH acid compound used) of OH ,C6o Rf (Si02 CH2Cl2/MeOH 80:1) = 0.25 MS (FAB): 896 (M0, 100%), 720 (90%) •H-NMR (360 MHz, CDCI3) ô = 8.39 (d, J = 8.3 Hz, 2 H) , 7.50 (d, J = 8.3 Hz, 2 H), 5.62 (s, 1 H), 3.73 (m, 2 H), 2.88 (t, J = 7.7 Hz, 2 H, 1.98 (m, 2 H) Example 2 6 495 mg (0.65 mmol) of C60 were stirred in 200 ml of toluene with 200 mg (0.58 mmol) of tert-butyl 4-[4-(2- bromo-2-chloroacetyl)phenyl)butyrate and 94 mg (0.62 mmol) of DBU for 17 h. Chromatography: 200 g of silica gel (0.063-0.2 mm); 10 0 0 ml of toluene 180 mg of C60 (36% based on Cso used) 370 mg (62% based on CH acid compound used) of 1-Bu Vs ft Rf (Si02/ toluene) = 0.32 MS (FAB): 1014 (M®, 100%), 720 (50%) Example 27 74 mg (0.073 mmol) of the tert-butyl ester from Example 26 were dissolved in 10 ml of méthylène chloride, and 148 mg (1.58 mmol) of methanesulfonic acid were added to this solution. After 2 minutes, 1 ml of water and 3 0 ml of méthylène chloride were added. The organic phase was separated off and dried using magnesium sulfate. Chromatography: 15 g of silica gel (0.063-0.1 mm); 140 ml of méthylène chloride/acetic acid 40:1 37.7 mg (53%) of 0. OH Rf (Si02, CH2Cl2/AcOH 20:0.5) = 0.36 MS (FAB): 958 (M*, 100%), 720 (70%) Example 2 8 0 mg (0.11 mmol) of the alcohol from Example 25 were suspended in 3 0 ml of méthylène chloride, 89 mg (0.89 mmol) of succinic anhydride and 27 mg (0.22 mmol) of DMAP were added and the reaction mixture was stirred for 1 week at room temperature. One drop of concentrated hydrochloric acid was added to the reaction mixture and the latter was dried using magnesium sulfate. Chroma tography: 50 g of silica gel (0.063-0.2 mm); 800 ml of méthylène chloride/methanol 200:1, 800 ml of méthylène chloride 200:3 56 mg (50%) of Rf (Si02, CH2Cl2/MeOH 20:1) = 0.08 MS (FAB): 997 (MHe, 25%), 720 (100%) Example 2 9 A solution of 19 mg (0.018 mmol) of the p-nitrophenyl ester from Example 23 in 18 ml of toluene was stirred at room temperature with 2.0 mg (0.018 mmol) of benzylamine for 12 days. Chromatography: 5 g of silica gel (0.063-0.2 nun); 50 ml of méthylène chloride, 52 ml of méthylène chloride/- methanol 25:1 9.5 mg (51%) of Rf (Si02, CH2C12) - 0.07 MS (FAB): 999 (M6, 70%), 720 (100%) Example A solution of 50 mg (0.048 mmol) of the p-nitrophenyl ester from Exemple 23 in 75 ml of toluene was stirred at room temperature with 20 mg (0.16 mmol) of glycine methyl ester hydrochloride and 16 mg (0.16 mmol) of triethylamine for 10 days. The reaction mixture was filtered and chromatographed. Chromatography: a) 30 g of silica gel (0.063-0.2 mm); 101 ml of méthylène chloride/methanol méthylène chloride/methanol méthylène chloride/methanol méthylène chloride/methanol/triethylamine 20:1.5:1 b) 12 g of silica gel (0.063-0.2 mm); 123 ml of méthylène chloride/methanol 100:2.5 mg (75%) of 100:1, 102 ml of 100:2, 103 ml of 100:3, 180 ml of 0 Me Rf (Si02/ CH2Cl2/MeOH 40:1) = 0.33 MS (FAB): 981 (M9) -NMR (360 MHz, CDCI3) Ô = 8.38 (d, J = 8.3 Hz, 2 H) , 7.51 (d, J = 8.3 Hz, 2 H), 5.61 (s, 1 H), 4.04 (m, 2 H), 3.75 (s, 3 H), 3.14 (t, J = 7.6 Hz, 2 H), 2.64 (t, J = 7.6 Hz, 2 H) . Example 31 A solution of 100 mg (0.097 mmol) of the p-nitrophenyl ester from Example 23 in 40 ml of toluene was stirred at room temperature with 9.9 mg (0.097 mmol) of 1,3-bis- (methylamino)propane. 100 mg (1.8 mmol) of methyl isocyanate were added to the reaction mixture and this 2 0 mixture was stirred for 6 days at room temperature. The reaction mixture was filtered and chromatographed. Chrontatography : a) 50 g of silica gel (0.053-0.2 mm); 410 ml of méthylène chloride/methanol 200:5, 210 ml of méthylène chloride/methanol 100:5 43 mg (42%) of Rf (Si02, CH2Cl2/MeOH 20:1) = 0.13 MS (FAB): 1051 (M6) Example 32 The procedure of Example 3 was repeated, with 59 mg (0.082 mmol) of C60 in 25 ml of toluene being reacted with 20.7 mg (0.163 mmol) of iodine, 22.4 mg (0.082 mmol) of tetraethyl methylenebisphosphonate and 24.9 mg of DBU. After a reaction time of 3 days at room temperature, the reaction mixture was filtered and chromatographed on 30 g of silica gel (0.063-0.2 mm) . C60 was eluted with toluene and the monoaddition product was eluted with 150 ml of méthylène chloride/ethanol 20:1. This gave 8 mg (9% based on Cg0 used) of monoaddition product. S--\ .P(0)(0Et), P(0)(OEt)2 Rf (Si02, CH2Cl2/EtOH 20:1) = 0.4 MS (FAB): 1006 (M®, 50%), 720 (100%) Example 3 3 The procedure of Example 3 was repeated, with 59 mg (0.082 mmol) of C6Q in 25 ml of toluene being reacted with 20.7 mg (0.163 mmol) of iodine, 8.1 mg (0.082 mmol) 2 0 of acetylacetone and 24.9 mg of DBU. After a reaction time of 3 days at room temperature, the reaction mixture was filtered and chromatographed over 40 g of silica gel (0.063-0.2 mm). C60 was eluted with 100 ml of toluene/ i-hexane 1:1 and the monoaddition product was eluted with 2 5 250 ml of toluene/i-hexane 2:1. This gave 12 mg 216124G (17% based on Cg0 used) of monoaddition product. =0 fe>Ç Rf (Si02/ toluene) = 0.4 MS (FAB): 818 (M®, 100%), 720 (100%) -NMR (360 MHz, CDC13) : Ô = 2.82 (s) Example 34 251 mg (0.299 mmol) of C70 in 200 ml of toluene were placed in a 2 50 ml nitrogen flask which had been evacuated and flushed with argon, and 55 mg (0.230 mmol) of diethyl bromomalonate and 35.8 mg (0.235 mmol) of DBU were injected into the suspension. After stirring for 4 h at room temperature, the suspension was filtered and the clear solution was evaporated to about 75 ml. According to HPLC, 60% of the -70 used were reacted. After chromatography over Si02 (0.063-0.2 mm) using toluene/ i-hexane and toluene, 110 mg of C70 (43% based on C70 used) were recovered and COjEt C02Et '70 was obtained in microcrystalline form (138 mg, 60% based on bromomalonate). Rf (Si02, toluene) = 0.47 MS (FAB): 998 (M®) -NMR (360 MHz, CDCI3) : Ô = 4.50 (m, 4 H) , 1.46 (t, J = 7.1 Hz, 6 H). 13C-NMR (100 MHz, CDCI3) : 6 = 163.45, 155.12, 151.38 (3C) , 151.19, 150.74, 150.60, 149.36, 149.27, 149.12, 148.72, 148.59, 148.53, 148.49, 147.67, 147.54, 147.32, 147.02, 146.47 (1C), 145.95, 145.93, 144.89; 143.96, 143.86, 143.54, 142.95, 142.85, 142.25, 141.68, 140.81, 136.98, 133.59, 132.84, 130.95, 130.91, 130.83, 66.90, 66.24, 63.47, 37.22, 14.23. 216124G 33 - PC r/E ,: C: 92.6% H: 1, .0% C: 93.7% H: 0, .9% Analysis calc. for C77H10O4 found Example 3 The procedure of Example 34 was repeated, with 250 mg (0.3 mmol) of C70 in 250 ml of toluene being reacted with 66 mg (0.31 mmol) of dimethyl bromomalonate and 48 mg (0.31 mmol) of DBU. After stirring for 3 h at room temperature, the suspension was filtered and the clear brownish violet solution was evaporated to about 60 ml and chromatographed over Si02 (0.063-0.2 mm) using toluene/i-hexane 1:1 to 3:1 and toluene. 42 mg of C70 (16.8%) were recovered and C70 C02Me COjMe was obtained in microcrystalline form (137 mg, 47%). Rf (Si02, toluene) = 0.36 MS (FAB): 970 (M®, 70%), 840 (100%) -NMR (360 MHz, CDC13/CS2) : Ô = 4.02 (s) 13C-NMR (100 MHz, CDC13/CS2) 1 5 = 163.29, 154.77, 151.19, 151.12 (1C), 150.94, 150.48, 150.35, 149.12, 149.03, 148.91, 148.54, 148.37, 148.30, 148.26, 147.38, 147.30, 147.10, 146.78, 146.14 (1C), 145.77, 145.71, 144.63, 143.77, 143.66, 143.38, 142.67, 142.56, 142.05, 141.45, 140.62, 136.64, 133.36, 132.59, 130.73 (4C), 130.60, 53.72: owing to a poor signal-to-noise ratio: no signals for the cyclopropane ring. Example 3 6 The procedure of Example 34 was repeated, with 251 mg (0.299 mmol) of C70 in 250 ml of toluene being reacted with 139 mg (0.3 mmol) of didecyl bromomalonate and 45.6 mg (0.3 mmol) of DBU. After a reaction time of 4 h at room temperature, the reaction mixture was filtered, the solvent was removed and the residue was extracted with diethyl ether. The ether solution was filtered through a short silica gel column and the solvent was removed. The residue was dissolved in about 5 ml of i-hexane/ -toluene 2:1 and chromatographed over 250 g of silica gel (0.063-0.2 mm) using 2.2 1 of i-hexane/toluene 2:1 and 1.1 1 of i-hexane/toluene 1:2. This gave 12 9 mg (3 5% based on C70 used) of monoadduct .C02Dec C C02De c and also 95 mg (19%) of diadduct as a mixture of isomers. Rf(Si02; toluene/i-hexane 1:2) = 0.18 MS (FAB): 1222 (Me, 60%), 840 (100%) -NMR (360 MHz, CDCI3) : ô = 4.42 (t, J = 6.5 Hz, 4H) , 1.81 (m, 4H), 1.46 (m, 4H), 1.25 (m, 24H), 0.86 (s, 6H) 13C-NMR (100 MHz, CDCI3) : 5 = 163.51, 155.06, 151.35, 151.32(10, 151.14, 150.69, 150.55, 149.31, 149.22, 149.08, 148.67, 148.53, 148.48, 148.45, 147.61, 147.49, 147.27, 146.97, 146.42(1C), 145.90, 145.88, 144.82, 143.91, 143.81, 143.49, 142.94, 142.79, 142.17, 141.62, 140.72, 136.98, 133.54, 132.79, 130.89, 130.85, 130.77, 67.52(2C), 66.91(10, 66.24(10, 37.39(10, 31.89, 29.63, 29.57, 29.34, 29.25, 28.58, 26.02, 22.69, 14.12. Example 37 The procedure of Example 34 was repeated, with 250 mg (0.3 mmol) of C70 in 250 ml of toluene being reacted with 139 mg (0.3 mmol) of di(2-(2-methoxyethoxy)ethyl) bromomalonate and 45.6 mg (0.3 mmol) of DBU. After a reaction time of 6 hours at room temperature (75% conversion of the C70 used according to HPLC) , the reaction mixture was filtered and chromatographed over g of silica gel (0.063-0.2 mm). C70 was eluted with toluene and the addition products were eluted with 800 ml of toluene/-diethyl ether 1:1 and 400 ml of toluene/ethanol 9:1. This gave 75 mg (14%) of C70, 139 mg (4 0%) of monoadduct 216124G and 96 mg (22%) of diadduct as a mixture of isomers. Rf(Si02; toluene/diethyl ether 1:1) = 0.25 MS (FAB) : 1146 (M®, 55%) , 840 (100%) -NMR (360 MHz, CDCI3): Ô = 4.59 (m, 4H) , 3.85 (m, 4H) , 3.68 (m, 4H), 3.54 (m, 4H), 3.37 (s, 6H). Example 38 The procedure of Example 34 was repeated, with 251 mg (0.3 minol) of C70 being suspended in 250 ml of toluene and reacted with 75 mg (0.45 minol) of ethyl 2-chloro- acetate and 60 mg (0.39 mmol) of DBU. After a reaction time of 24 h at room temperature, the reaction mixture was filtered, the conversion was determined as 64% by HPLC and the solution was evaporated to about 60 ml. Chromatography over Si02 (0.063-0.2 mm) using toluene/ i-hexane 1:1 to 4:1 gave 104 mg (35.7%) of Rf (Si02/ toluene) =0.38. MS (FAB): 968 (M"). -NMR (360 MHz, CDCI3) : Ô = 4.52 (m, 2H) , 2.82 (s, 3H) , 1.48 (t, J = 7.1 Hz, 3H). Example 3 9 The procedure of Example 34 was repeated, with 250 mg (0.3 mmol) of C70 in 250 ml of toluene being reacted with 75 mg (0.37 mmol) of w-bromoacetophenone and 50.2 mg (0.37 mmol) of DBU. After a reaction time of 22 h at room temperature (56% conversion of the C70 used according to " 216124S HPLC), the reaction mixture was filtered and the reaction solution was evaporated to 7 0 ml. Chromatography over 250 g of silica gel (0.063-0.2 mm) using toluene/i-hexane 1:3, 1:2 and 1:1, carried out three times, gave 58.2 mg (20%) of monoadduct. Rf(Si02; toluene/i-hexane 1:2) = 0.12 MS (FAB): 958 (M-, 70%), 840 (100%) H-NMR (360 MHz, CDCI3) : Ô = 8.42 (m, 2 Hortho) 7.76 (m, 1 Hpara), 7.68 (m, 2 HJ , 4.42 (s, 3H) . Example The procedure of Example 34 was repeated, with 200 mg (0.24 mmol) of C70 in 200 ml of toluene being reacted with 62.5 g (0.2 mmol) of ethyl 4-[4-(2-bromoacetyl)- phenyl]butyrate and 3 0.5 mg (0.2 mmol) of DBU. After a reaction time of 24 h at room temperature, 3 drops of 1 molar sulfuric acid were added, the mixture was dried with magnesium sulfate and filtered. The solution was evaporated to 80 ml and chromatographed over 80 g of silica gel (0.063-0.2 mm) using 600 ml of toluene. This gave 110 mg (55% based on C70 used) of C70 and 34 mg (16% based on C70 used and 2 9% based on C70 reacted) of monoadduct. C02E t R£(Si02; toluene) = 0.27 MS (FAB): 1072 (M6, 50%), 840 (100%). -H-NMR (360 MHz, CD2C12) : Ô = 8.36 (d, J = 8.3 Hz, 2H) , 7.52 (d, J = 8.3 Hz, 2H) , 4.50 (s, 1H) , 4.13 (m, 2H) , 2.84 (t, J = 7.7 Hz, 2H), 2.39 (t, J = 7.4 Hz, 2H), 2.04 (quint, J = 7.5 Hz, 2H), 1.26 (t, J = 7.1 Hz, 3H).