CA2117861A1 - Fullerene derivatives, a process for their preparation and their use - Google Patents

Abstract

Abstract of the disclosure Fullerene derivatives, a process for their preparation, and their use A process for preparing a methano-bridged fullerene derivative is described wherein a fullerene or fullerene derivative is reacted with a phosphorus ylide in an inert organic solvent at a temperature of from -78 to 180°C.

Process products of the formula (II), (II) in which the symbols and indices have the following meanings:
F: is a fullerene radical of the formula C20 + 2m, with m = 2 to 100;
R4: is H, CH3, -phenyl or R5;
R5: is a straight-chain or branched (with or without an asymmetric carbon atom) C2-C20-alkyl group, where one or more non-adjacent CH2 groups can be replaced by -C?C, -CH=CH-, -O-, -S-, -COO-, -OOC-, -SiR?-, -CO-, phenylenediyl or cyclohexylenediyl, and where one or more hydrogen atoms can be replaced by F, Cl, Br, I, OH or a tetrahydropyranyloxy group, or R4 and R5 together are =C=X with X being O, S, NR3 or (O-R3)2:
R3: is phenyl or C1-C12-alkyl;
n: is from 1 to 6;
are novel.
Compounds according to the invention and prepared in accordance with the invention are suitable for use in optoelectrical units.

Description

. ^` 2 ~

HO~CHST ~KTI~NGESELLSCHAFT ~OE 93/F 324 Dr. RI/wo Description Fullerene derivatives, a proces3 ~or their preparation, and their u~e 5 Fullerene are cage-~haped carbon allotropes ~f the fGnmUla (C20 ~ ~m) ~ where m i8 a natural numbar. They contain twelve ~i~e-m~mbered, and al80 an arbi~rary number of~ but at least two~ aix-membered, rlngs of carbon atom~. Although thi~ ala~s of ~ompound waa firat detected by Rroto and Smalley in 1985 (Nature 318 (1985) 162), and ~rAtechmer and Human reported for the firat time in 1990 on the preparation of macroscopic quantitie~
of C60 (Natura 347 (1990) 354~, the~e rom~ound~ ha~e very rapidly evoked wide~pread intereat and within a very ahort time were the ~ub~ect o numerous research atudiea (aee, for example, G. S. Hammond, V. J. Ruck (Editors), Fullerene~, ~mexican Chemical Sociaty, Washington DC 1992 and Accou~t~ o~F Chemical Re~earch, March edition 1992).

Since high expectationa are entertained o~ the potential of thia compound clas~, ~or example in the ~pheres o~
optoelectro~ic~ and active compound xeDearch, exten~lve investigations have slready been aarried out with regard to ~pecific derivatizatio~, in particular o~ C60 and C70 ~ee, or example, R. Taylor, D~ R. M. Walton, Nature 363 ~5 (1993) 685 and A. Hlr~ch, .~ngew. Ch~m. 105 (1993) 11).
Various derivatization experiments have ~ucceeded ln isolating defined monoadduct~ of C60.

For example, cyclopropane derivative~ hava been obtained by the raactlon o~ fullerane~ with diazomethane deriva-tives, i.n 1,3-dipolar cycloaddition~ (see, or axampla, F. Wudl et ~l., Acc. Ch~m. Re~. 25 (1992) 157 and F. Diedrich et al., Helv. Chem. Acta 76 (1993) 1231), and with nucleophilic glyco~yliclene carbe~ in [2 ~
carbene addition~ ~3ea, ~or axampl~, A. Va~ella et al., .'"!
,~ 2~178~

Angew. Chem. 104 (1992) 1383) and by reaction with ~tabilized ~-halocarbanion~ (~ee, or example, C. Bingel, Chem. 8er. 126 (1993) 1957). These experiment3 were directed toward synthe~izing def~ned fullerene deriv tive~ which contain a broad spectrum of ~tructural unit~ po~sessing tho~e fu~ctional groups which can be utilized in the spheres of optoelectronic~ and actiYe - compound ~sarch or for constructing novel polymeric materials and which improve the physical propertie3, ~uch a~ ~olubility or polari~y, o~ thQ fullerene derivative~.

It i8 ~nown that activated olef-.in~ which enter in o the Michael reactions can react with ~ulfur ylide~ (sae, for example, Trost a~d Melvin, Sulfur Ylides, Acad~mic Pres~, New York 1975) and pho~phorus ylide~ (see, for ~xample, Be~tmann and Seny, AngewO Chem. Int. Ed. Engl. 1 (1962) 116) to form cyclopropane derivative~.

It ha~ now been found, surpri~ingly, that fullerenes react with pho~phoru~ ylides to Eorm m3thano-bridged fullerene dexivative~.

The inventlon thereEore relate~ to a proce~ for preparing a methano-bridged ~Eullerene derivati~a wherein a ~ullersne or ~ullerene derivative is reacted with a pho~phorus ylide in an inert organ~c ~ol~ent at a tem-perature of from -78 to 180C.
. .
Preferably, ~ullerenes of the formula C20 ~ 2m~ with m =

2....100, particularly pre~erably with m = 20, 25, 28 or 29, very particularly preferably with m = 20 or 25, are employed as starting compound~.

In particular, pure C60 and/or ~70 iB~are em~loyed a~
Eullerane(~). However ~lso crude fullerene~ which contain a m~xture o~ C60 and C70 a~ the main component~ can be used.

Such ~ullerene~ can be obtained, or example, by preparing ~ullerene black in an alectric arc prOce~B and ~ 2 1 1 ~

subse~uently extracting with a non-polar organic ~olvent (crude ullar~ne~, a~ de~cribed, for example, in WO 92/09279. ~urther ~ine fractionation ~an be ef~ected by column chromatography.

Some of the~e fullerenea are al~o commercial products.

In principle, the pho~phoru~ ylide~ which are employed are known. They may have a wide var~ety of structure~.
Po~ ible ~tructures, and th~ir ~yntheee~, are to be found, for example, in - Topic~ in Current Ch~mi~try 20 (1971) 1;
- G. M. Ko~olapo ~ a~d L. ~aier, Organic Pho~phoru Compound~, vol. 3, chap. 5, Wiley Inter~c~ence, Ne~
York 1972;
- Chemikerzeitung 96 (1972) 649;
- Carbon-Carbon-Bond Formation, vol. 1, pp. 353-426, Verlag Marcel Dekker, New York 1979;
- Angew. Chem. 77 (1985~ 651, 850;
- Angew. Chem. 89 (1977) 361;
- Synthe~i~ (1992) 7~7;
- Houben-Weyl, Methoden der Organi~chen Chemie [Method~ o Organia Cheml~t~y] ~1, Organia Pho~phoru~ Compounds I, pp. 616-782, Georg Thieme ~erlag, Stuttgart 1963;
- B. M. Tro~t (Ed.), Comprehensive Organic Synthe~
vol. 6, pp. 171-202, Pergamon Pre~, Ox~ord 1991.

Ylides whic~l are preferably ~mployed ~r~ those o~ the ~ormula (I), ~ e R3 P-CR1R2 (I) where R1 and R2: are, independently of each other, EI, a ~traight~chain or branched (with or without an asymmetric ~arbon atom) ~2-C20-alkyl group, whera one or more CH2 groups can be replaced ~ ~178~

by -C-C-, -CH=CH-, -O-, -~-, -COO-, -OOC-, -SiR3 -, -CO , phenylenediyl ox cyclohe~yl-enediyl, and where one or more hydrogen atom~
~an ba replaced by F, Cl, Br, I or a tetra-hydropyranyloxy group, or Rl and R2 together are =C=X, with X b0iny 0, S, NR3 or (o-R3)2;
R3. i~, identically or dif~ersntly, phenyl or Cl-C12-alkyl.

Tho~e phoaphoru~ ylides o~ the ~ormula (I) are -~
par~icularly preerred in which the ~ymbols have the ~ollowing meaning~
R~ H or phenyl;
R2: ia ~, a ~traight-chain or bra~ched (wlth or without an a~y~metric carbon atom) C2-C20-alkyl group, w~ere one or more C~2 group~ can bs replaced by -C C-, -C~=CH-, -O-, -S-, COO-, -OOC-, -SiR32 -, -CO-, phenylenediyl or cyalohexylenediyl, and whars ona or more hydrogen atom~ can be repla~ed by F, Cl, BrJ I
or a tetrahydropyranyloxy group, or Rl and R2 togQther are =C~X, with X being 0, S/ ~R3 or (o_R3 ) R3: i~ phenyl or Cl~C12-alkyl.

Tho~e phosphoru~ ylides of the formula (I) ara very ~articularly pra~err0d in whlch the 0y~bol~ hava the ollowing meanings:
Rl: i~ H or phenyl;
R2: i~ H~ a ~traight-chain or branched C2 C20-alkyl :~
group wher~ one or more CH2 ~roup~ ca~ be replacad ~:;
by -C~C-, -CH=CH-, -O-, -S-, -COO-~ -OOC-, phenylenediyl or cy~lohexyle~ediyl, and where a hydroge~ atom can be replaced by a tetrahydro-pyra~ylo~y group.
R3: i~ pha~yl.

The stoichlomatric ratio o~ yllde to ~ullerena i~ pree- :
rably $rom a:1 to 0.5:1, particularly prserably from 4:1 to 0.8:1, very parti~ularly preferably Erom 1.5:~ to ^ 2t~7~

O.9:1.

In order to prepare the ~onoadduct of full~rene and ylide, the rea~tio~ i~ carried out pre~erably in a temperature range ~rom room temperature to the boiling te~perature of the eolvent u~ed and under ~tandard pre~ure while employing the ~tartlng compounds in approximately ~toi~hiometria proportions.

A high degree of ~ub~titution, and thereby a large ~alue for ~, i~ ~chieved by ~mploying the ylide in oxce~s.

The reaction i~ carried out in an inert ~olv9nt. ~protic solvent~, i~ particular aro~atic hydrocarbon~, ~uch as benzene, toluene or xylene~, halogenated aromatic hydro-carbon~, ~uch as chlorobenzene, and chlorinated hydrocarbon~, such as methylene chlorida, ara preferred. Arom~tic hydrocarbon~, in part~cular benzene and toluene are particularly pre~errsd.

The process i~ carried out at a temperature of from -78 to 180C, pre~erably of fxom 0 to 150C, particularly preferably o~ from 20 to 150C.

In suitable case~, the reaction i~ carried out at room temperature (rom 20 to 30C). Insoluble zwitterionic primary adduct which in 30me cases re~ults rom the ylide and fullerene can be converted into the cyaloprop~ne derivative by, ~ox example, heating the primary adduct under high vacuum at ~rom 250 to 3S0C.

In a prefsrred variant for carrying out the proaeas according to the inventlQn, the ~ullerene iB initially introduced into th~ inert BolVent, pre~erably an arom~tic hydrocarbon, and the corre~ponding gu2ntity of pho~phorane, pr~ferably di~solved in the corre~ponding ~olvent, i~ added, preerably ~lowly whila ~tirring.
The pho~phorans may advantageously be e~ployed a~ a 2~7~

standard ~oluti~n, prepared by di~solving a weighed quantity of pho~phorane i~ a defined quantity of the corre~ponding 801vent.

The working-up i~ effected in accordancs with ~nown method~ which ~re familiar to a person skilled in the art.

For example, any precipitate re ulting in the reaction are filtered off and the ~iltrate is suhseguently concen-trated. The reaidue which remain~ ca~, ~or example, then be purified ~urthar by ~hromatographic method~ or by recrystallization.

Some of the productA o the proceR~ according to the in~ention are known and ~ome are novel.

The invention therefore al~o relates to fullerena deriva-tives of the for~ula ~II), ]
R5 n wh~re the sym~ol~ and indica~ have tha following meanings:
F: i~ a ~ullerene radical of the formula C20 ~ 2m~ with m ~ 2 to 100;
R4: i~ H, CH3, -phenyl or R5;
R5: i~ a ~traight-chain or branched (w~th or without an asymmetric carbon atom) C2-~20-alkyl group, where ona or more CH2 group~ can be repl~ced by -C~C-, -CH=C~-, -O-, -S-, -COO-, -OOC-, -SiR3 -, -CO-, phenylenediyl or cyclohexylen0diyl, and where one or more hydrogen atom~ can be replaced by F, Cl, Br, I, OH or a tetrahydropyranyloxy group, or R4 and R5 together are zC=X with X being 0, S, ~R3 or (o-R3)2;
R3~ i~ phenyl or C1-C12-alkyl;
30 n~ rom 1 to 6.

Those which are preferred ara F- i~ C60 or C70;
R4- is H or phenyl;
R5: i~ a ~traight-chain or branched (with or without an asy~metric carbon atom) ~2-C20-alkyl group, whera one or more CH2 yroup~ can ~e raplaced by -C~C-, -C~=C~ -, -S-, -COO-, -OOC-, -SiR3 -, -CO-, phenylenediyl or cyclohe~ylenediyl, and where ona or more hydrogen atom~ can be replaced by F, Cl, Br, I, OH or a tetrahydropyranyloxy group, or R~ and R5 together ara -C~X with X being O, S, NR3 or (o-R3~2g ~3: i~ phenyl or Cl C12-alkyl;
n: i8 ~o Tho~e which are particularly prefarred are :.
F: i~ C60 or C70;
R4O i~ H or phenyl;
R5: is a ~traight-chain or branched C2-C20-alkyl gro~p, where one or more C~2 groups can be rsplaced by -C-C-, -CH=C~-, -O-, ~S-, -OOC-, -COO-, phenylenedlyl or cyclohexylenediyl, and whera one hydrogen atom can ba replaced by O~ or a tatrahydro-pyranyloxy group7 n: i~

Fullerene deri~atlve~
re~pecti~ely, according to the in~ention or prepared in accordance with the in~ention, are employsd, fox example~
in optoelectr~cal ~nit~.

The invention iB explained in more ~etail by maan~ o~ the example~.

Example~:

Gen~ral Proceduxal In~truation~ (GPI) All reaation~ o~ C60 w~th tha triphenylpho~phorane~ are carried out ln benzena or to:luana. The concsntration of ~ 21 ~86~

the C60 ~olution~ i~ 1 mg/ml. In all reaction~, the C60 solutions ar~ initially i~troduced and the equimolar ~uantity ~or 10 to 30 % exce~) of the re~pective triphenylpho~phorane i~ ~lowly added dropwi~e, while ~tirring, a~ a ~tandard ~olution. In order to prepare the ~tandard solution~, preci~ely weighed guantities of the triphenylpho~phoranea are di~ol~ed in a defined quantity of the corre~ponding ~olvent (benzene or toluene).

The precipitate~ ari~ing in the reaction~ are filtered off and the ol~ent~ are ~tripped off from the filtrate~.

Example 1 Methanofullerene ~rea~tion of C60 with methylene-txiphenylpho~phorane (CH2=PPh3~) The reaction is carried out in acaordance with ~he GPI.
71 mg (0.0986 mmol) of C60 are dis~ol~ed in 70 ml of toluene and heated under reflux. A precipitate form~
i~mediately after adding 29.2 mg (0.106 mmol) of methylenetriphenylpho~phorane di0~01~ed in 3.5 ml of toluene. The reaction mixture ~ heated under re~lux for a furthex 4 hour~ and then filterad.

Working-up of the filtrate:
After the ~olvent has been stripped off, the re~idue of the filtrate (40 mg) i~ loaded onto a ~ilica gel column ~ilica gel 60, from E. Merck, Darm~tadt, Germany). The column is then eluted u~ing CS2 (~eparatio~ o~ PPh3).
dark-brown miaroary~talline residue remain~ ~rom the raction obtained ~R~:l) after stripping off the ~olvent.
Yield: 30 mg Filter residue: 60 mg The mass spectrum o~ the ~olid, and al~o of the residue of the in~pissatad filtrate, ~how~ a ~ignal at m/e = 734 = C61H2 and a further ~maller ~ignal at m/e - 748 - ~62H4.

I~ the ~olid residue i9 heated under high vacuum in a --' 2~17~
g ~ublimator at from 250 to 350C triphanylpho~phane then 8ublima~ of f . The mas~ ~pectru~ of the residue shows the abovementioned 0ignal~.

Example 2 Methylmethanofullerene (rsactio~ of ~thyliden~triphenyl-phosphorane ~CH3~-CH=PPh3) with C60):

28 mg (0.039 mmol) of C60 are di~Rolved in 25 ml of ab~olute benzans or toluene and heated under reFlux.
Through thi~, a solution of 11~3 mg (0.039 mmol) of ethylidenetriphenylpho phoran~ in 5 ml o~ abRolute benzene ~standard ~olution) i~ added drop~i~e. The formation of a precipitate may immediately be ob~er~ed.
The mixture i~ boiled or a ~urther 6 hour~ and then filtered. The re~idue weigh3 12 mg. The iltrate i~
concentrated by evapoxation.

In the ma~s ~pectrum, all the fraction~, the filter residue and al~o the in~pi0sated filtrate, ~how a ~ignal at m/e = 74a = C60C~CH3 and al~o an appre~iably ~maller ~ignal at m/e = 776 = C60(CHCH3)2.

If the filter residue i8 heated at from 250 to 350C
under high vacuum in a sublimator, triphenylpho~phane then sublime~ of. The two abovementioned ~ignal3 can once agaln be ~een in the mass spectrum of the re~idue.

Example 3 Heptylmethanoullerene (reaction of octylidenetriphenyl-phosphoran2 (CH3(CH2)6CH=PPh3) with C60):

The reactlon is carried out in accoxdance with the GPI.
100 mg (0~1388 mmol) of C60 are di~ol~d in 110 ml of toluene and heated to reflux. Following the addition of 57.14 mg (0.1528 ~ol) of octylidenetriphenyl-phosphorane, di~solved in 8 ml of toluene (~tandard solution), a slight clouding of the solution can be 2~178~
~ o ob~erv~d. The reaction mixture i~ heatad, while ctirring, for a urther 24 hour~ and then iltared~

Working-up of the filtrateo After the ~ol~ent has been stripped off, the re3idue of the filtrate (150 mg) i~ loaded onto a silica gel colum~
~ilica g~l 60, ~rom E. Merck, Darm3tadt, Garmany) and eluted u~ing hexane. Once the ~olvent has been stripped off, the red-brown fraction ~R~:1) whieh ha~ bee~
obtained ~how~ a m~9 ~pactr~ ~ignal at m/e = 832 =
C60CH(C~2)6CH3 and al~o an appreciably s~aller ~ignal at m/e = 944 = c~o~c~(cH2)6 Yield: 20.8 mg H-NMR (400 MHz, C6D6/CS2, 27C3: ~ - 3.73 (t, 3J (H, H) = 7.0 Hz, 1~, CH), 2.25 (q, 3J (H, ~) = 7.0 ~z, 2EI, CH2), 1.79 (m, 2H, CH2), 1.52 (m, 2H, C~2), 1.28 (m, 6~, CH2), 0.90 (mc, 3H, CH3);
3C-NMR (100.4 M~Iz, C6D6/CS2 1:1, 29C~: ~ = 150.60, 148.15, 146.15, 145.65, 1~5.50, 145.~4, 145.33, 1~5.06, 144.53, 144.45, 143.95, 143.04, 142.74, 141.37, 138~33, 136.27 (fullerene aignals), 77.20 (~, 2C, bridgehead Carbon atom~), 39.82 (~, lC, CH bridge Carbon atom), 32.46 (~, lC, C~), 30.38 (~, lC, CH2), 29.85 (~, lC, CH2), 29.15 (~, lC, CH2), 26~92 (5, lC, C~2), 23.41 (8, lC, CH2), 14.72 (8, lC, CH3);
EI-MS: 332 (M~), 7~0 (~-CH(CH2)6C~3j+).

E'ilter re~idue. 7 mg Exampls 4 Undecylmethano~ullerene (reaction of dodecylidene-triphenylpho~phorane (CH3(CH2)10-CH=PPh3) with C60) The reaction 1~ carried out in accorda~ce with the GPI.
45 mg (0.0625 mmol) of C60 are di~eolved in 45 ml of toluene and heated under reflux. ~ollowing the additlon of 30 mg (0.0597 ~mol) of dodecylide~etriphenylpho~-phorane, di~olved in 6 ml o toluene, a clouding of the 2117~
~o ob~erved. The reaction mixture i~ heated, while Rtirring, for a urther 24 hourR and then filtered.

Working-up of the filtrate:
After the ~olvent ha~ been ~tripped o f, the r~3idue of the filtrate (150 mg) i~ loaded onto a ~ilica gel ~olumn (silica gel 60, from E. Merck, Darm~adt~ Germany) and eluted using hexane. Once the ~ol~ent ha~ been ~tripped off, the red-brown fraction (R~:l) which ha~ been obtained Rhow~ a ma~ff ~pactrum ~ignal at m/e = 832 =
C60CH(C~2)6CH3 and al80 an appreciably s~aller ~ignal at m/e = 944 = C6ot~(CH2)6c~332-Yield: 20.8 mg H-NMR (400 MHz, C6D6/CS2, 27C): ~ = 3.73 (t, 3J (H, H~
- 7.0 Hz, lH, CH), 2.25 (q, 3J (H, H) = 7.0 Hz, 2X, CH2), 1.79 (m, 2H, CH2), 1.52 (m, 2H, CH2), 1.28 (m, 6X, C~2j, 0.90 (mc, 3H, CH3);
3C-NMR (100.4 M~Iz, C6D6/CS2 1:1, 29C): ~ = 150.60, 148.15, 146.15, 145.65, 145.50, 145.44, 145.33, 145.06, 144.53, 14~.45, 1~3.95, 143.04, 14~.74, 1~1.37, 13 a . 33, 136.27 (ullerene ~ignal~), 77.20 (B, 2C, bridgehead Carbon atoms), 39.82 (~, lC, CH bridge Carbon atom), 32.46 (8, lC, CH2), 30.38 (~, lC, CH2), 29.85 ~, lC, CH~), 29.15 (~, lC, CH2), 26.92 (~, lC, CH2), 23.41 (~, lC, CH2), 14.72 (~, lC, CH3);
EI-MS: 832 (M+), 720 (~-CH(CH2)6C~3]~).

Filter residue~ 7 mg Exampls 4 Undecylmethano~ullerena (reaction of dodecylidene-triphenylphosphorane (CH3(C~2)l0-CH=PPh3) with C60) The reaction l~ carried out in accordance with ~ha GPI.
45 mg (0.0625 mmol) of C60 are dis~olved in 45 ml of toluene and heated under reflux. Following the additior of 30 mg (0.0697 mmol) of dodecylidenetriphenylpho~-phorane, dl~solved in 6 ml of toluene, a clouding of the 21~7~

toluene and heated under reflux. Following the addition of 43.5 mg (0.105 ~mel) of undacenylidenetriphenyl-pho~phoraTle, di~solved in 7 ml o~ toluene, a clouding of the eolution may immediate~y be observed. The reaction mixture i8 heated under reflux for a further 24 hour~ and then filtered.

Working-up o the filtrata:
A ter the ~olvent ha~ been ~tripped off, the xe~idue of the filtrate (92 mg) i8 loaded onto a ~ilica gel column (~ilica gel 60, ~rom E. Msrck, Darm tadt, Germany). The colu~n i~ then eluted u~i~g CS2 (~eparation of PPh3).
dark-brown micro~ry~talline re~idue remains from the fraction oht~ined (Rf: O . 95) after strippiny o~ the solve~t.
Yield: 34 mg H-NMR (400 M~z, CS2/CSCl3, 29C): ~ = 5.78 (ddt, 3J(~, H~
= 17.9 H~, 3J(H,H) = 10.3 Hz, 3J(H,H) - 6.72 Hz, lH, CH), 4.99 (dd,3J(~,H) = 17.9 Hz, 2J(H,H) = 1.83 Hz, lH, CH), 4.92 (dd, 3J(H,H) = 10.3 Hz, 2J(H,H) = 1.83 Hz, lH, CH), 4.07 (t, 3J(H,H) = 7.63 ~z, lH, CH), 2.54 (dt, 3J(~,H) =
7.63 Hz, 3J(H,H) = 7.63 Hz, 2H, CH2), 2.06 ~o 1.96 (m, 6H, CH2), 1.8 to 1.2 (m, 8H, CH2);
3C-N~R (100.4 M~z, CS2/CDCl3 2:1, 30C): ~ = 150.09, 147.63, 145.68, 145.17, 144.97, 144.90, 14~.79, 144.53, 14~.46, 144.05, 143.95, 143.47, 142.79, 142.51, 142.19, 141.95, 141.92, 140.84, 140.80, 137.84, 135.77 (~ullerene ~ignal~), 13B.67 (~, lC, C~2), 114.23 (8, lC, =CH2), 76.80 (8, 2C, bridgehead Carbon atome), 39.42 (~, lC, CH
bridge Carbon atom), 33.89 (~, lC, CH2), 29.73 (~, lC, CH2), 29.70 (~, lC, CH2), 29.64 (8~ 2C, C~2), 29.58 (8, lC, CH2), 29.28 (8, lC, CH2), 29.05 (~, lC, C~2);
EI-MS: 872 (M+), 720 (lM-C~(CH2)8-CH=C~2] t) Filter reBidue: 3 mg r~ 211781~
~ 13 -Example 6 Phenylmethanofullere~e (reaction o~ be~zylidenetriphenyl-phosphorane (C6H5-CH=PPh33 with C60) The reaction ia carried out in accordance with the ~PI.
30 mg (0.0416 mmol) of C60 are dissolved in 30 ml o~
benzene. Foll~wing the addition of 15 mg (0.0426 mmol) of benzylidenetriphenylphosphorane, di~olvsd in 1 ml of benzene, a elouding of the ~olution may be ob~erved. The reaction mixtura ia ~tirred at room temperature ~or a further 24 houra and then filtered.

Working-up of the filtrate:
After the ~olvent ha~ been ~tripped off, the re~idue o~
the filtrate (41 mg) ia loaded onto a ~ilica gel c~lumn (~ilica gel 60, from ~. Merck, DarmRtadt, Germany).
lS Unreacted C60 i~ ~eparated off uBing hexane a~ eluent.
The column i~ then eluted u~ing benzsne. The red-brown fraction (Rf:1) which i~ obtained still contain~ PPh3.
Renewed column-chromatographic ~eparatio~ o~ this frac-tion on ~iliaa gel u~ing benzene (Rf:1) as eluent 20 re~ult~, a~ter strippi~g of~ the ~olvent, in a brown, ~;.
microcry~talline ~ubRtance remaining.
Yield: 10 mg .

1H-NMR (400 MHz, CHCl3/CS2 1:1, 27C): ~ , 7.92 (d/
3J(H,H) , 7~02 Hz, 2H, o-H(Ph)), 7.49 (t, 3J(H,H) - 7.32 2S Hz, 2H, m-H(Ph)), 7.41 ~t, 3J~H,H) o 7.02 Hz, lH, p-H(Ph)), 5.36 (~, lH, CH);
3C-NMR (100.4 MHz, CDCl3/CS2 1:1, 27C): ~ = 133 to lS0 (fullerene ~ignala), 140.93 (B, lC, C(Ph), 131.02 (~, 2C, C(Ph)), 128.62 (~, 2C, C(Ph~), 128.26 (B, lC, C(Ph)), 30 75.30 (8, 2C, bridgehead Carbon atoms), 43~37 ~, lC, CH
bridge Carbon atom);
EI-MS: 810 (M+), 720 (iM-CHPh]+) Filter re~idue: 4 mg 21178~

Example 7 Diphenylmethan~fullerene (reaction of diphenylmethylene-triphenylpho~phorane (C6H5)2C-PPh3) with C60) The reaction i8 carri%d out in accordance with tha ~PI.
28 mg (0.039 mmol) of C60 are dis~olved in 28 ml of toluene and heated under raflux. Followi~g the addition of 16.6 mg (0.039 mmol~ o~ diphsnylmet~ylen~triphenyl~
pho~phorans, di~ol~ed in 8.2 mmol oE bPnzene, a clouding of the ~olution may ba observed. The reaction miæture i~
heated under reflux for a ~urther 24 houra and then fil~ared.

Working-up of the ~iltrate:
After the ~olvent has been ~tripped o~f, ths residua of the ~iltrate (39 mg) i8 loaded onto a ~ilica gel column (~ilica gel 60, from E. Merck, Darmstadt, Germany). 5 mg of unreac~ed C60 i~ ~eparated off u~ing hexane a~ eluent.
The column i8 then elu~ed u~ing benzene. The red-brown fraction (R~: 1) which is obtained ~till contain~ PPh3.
Renewed column-chromatographic ~eparation of thi~ frac-tion on ~ilica gel using benzene (R~: 1) a~ eluent now results, after ~tri~ping off the ~olvent, in a brown, microcry~talline ~ub~tance remaining.

lH-NMR (400 M~z, CHCl3/CS2 1:1, 27C): ~ - 7.97 (d, 3J(H, H) = 7.02 Hz, o~H(Ph)), 7.36 (t, 3J~H, H) = 7.32 Hz, 4H, .
25 m-~(Ph)), 7.26 (t, 3J(H, H3 ~ 7.32 H~, 2H, ~-~(Ph));
EI-MS: 8B6 (M~), 720 ~M-CHPh2]~).

Filter ra~idue: 5.6 mg Example 8 Ekhyl propanoate methanofulleren~ (raaction o~ 3-carbo-30 athoxypropylide~etriphsnylpho~phorana (~5C2-0-CO-CH2-CH2-CH-PPh3) with C60) The reaction is carried out in accordance with the GPI.
65 mg (0.0903 mmol~ o~ C60 are di~olved in 65 ml o 2~17~
, ~

toluene and heated under reflu~. Following the addition of 35 mg (0.0931 mmol) of 3-carboethoxypropylidenetri-phenylphosphorane, di~olv~d in 10 ml of toluene, for-mation o~ a precipitate may i~mediately be observed. The reaction mixture i~ heated under reflux for a further 24 hours and then filtered.

Working-up of the filtrate:
After the solv~nt ha~ been ~tripped off, the residue of the filtrate (59 mg) i~ loaded onto a silica gel column (silica gel 60, from E. Merck, Darm~tadt, Germany).
Unreacted C60 ~R~: 1) and re~ulti~g PPh3 (R~: 0.4) are separated off uRing CS2 a~ eluent. The column i~ then eluted using C~2Cl2. Onc9 the solvent has been stripped off, a dark-brown, microcry~talline residue remains from the fraction (Rf 0.9) which ha~ heen obtained.
Yield: 15 mg lH-NMR t400 MHz, CDCl3, 28C): ~ = 4.27 (q, 3J(H, H) -7.33 Hz, 2H, OC_2CH3), 4.20 (t, 3J(H, ~I) = 7.36 Hz, lH, CH-CH2), 2.97 (t, 3J(H, H) = 7.94 Hz, 2H, CH2COOEt), 2.86 (dt, 3J(H, H) = 7.63 Hr, 3J(H, H) = 6.56 Hz, 2H, CH-CH2-CH2. 1.34 (t, 3J(H, ~) = 7.02 Hz, 3H, CH3);
3C-NMR (100.4 MHz, CDCl3, 29C): ~ = 172.63 (6, lC, COOEt), 150.03, 147.31, 145.85, 145.28, 145.20, 145.14, 145.02, 144.~2, 144.76, 144.67, 144.32, ~44.27, 144.18, 143.68, 143.11, 142.98, 142.67, 142.3~, 142.15, 142.12, 141.00, 138.10, 136.09 (Fullerene ~ignals), 76.33 (~, 2C, bridgehead Carbon atom~), 60.99 (8, lC, O-CH2CH3), 37.94 (~, lC, CH bridge Carbon atom), 33.24 (~, lC, CH2-CH2-COOEt), 22.08 (~, lC, CH2-COOEt), 14.33 (B, lC, CH3);
EI-MS: 834 (M~), 720 (~M-CH(C~2~COOEt~t).

Filter residue: 41 mg Example 9 Methyl undecanoate methanofullerene (reaction of carbo-ethoxyundecylidenetriphenylphosphorane (Hsc2ooc-(cH2)lo-,~ 2~ ~78~

CH=PPh3) with C60) The reaction i~ carried out in accordance with GPI.
65 mg (0.0903 mmol) of C60 are di~nolved in 65 ml of toluene and heated ~nder refluxO Following the addition of 35 mg (0.0931 mmol) of 3-carboethoxypropylidenetri-phenylpho~phorane di~sol~ed in 10 ml o~ toluene, for-mation of a precipitate may immediately be observed. The reaction mixture iB heated under r~flux for a further 24 hours and then filteredO

Working-up of the ~iltrate:
After the æolvent ha~ been ~tripped of~, the residue of the filtrate (59 mg) i~ loaded onto a silica gel column (~ilica gel 60, from E. Merck, DarmRtadt). Unreacted C60 (R~: 1) and resulting PPh3 (R~: 0.4) are ~eparated off using C52 as th~ eluent. The column is then eluted using CH2Cl2. Once the sol~ent has been stripped off, a dark-brown, microcrystalline residue remains from th~ fraction (R~: 0.9) which ha~ been obtained.
Yield: 15 mg lH-NMR (400 MHz, CDCl3, 28C): ~ = 4.27 (q, 3J(H, H) =
7.33 H~, 2EI, OC_2CH3), 4.20 (t, 3J(H, H) - 7.36 Hz, lH, C_-CH2), 2.97 (t, 3J(H, H) - 7.94 Hz, 2H, CH2COOEt), 2.86 (dt, 3J(H, H) = 7.63 Hr, 3J(H, H) = 6.56 Hz, 2H, CH-CH2-CH2. 1.34 (t, 3J(H, H) - 7.02 Hz, 3H, CH3);
l3C-NMR (100.4 MHz, CDCl3, 29C): ~. = 172.63 (a, lC, COOEt), 150.03, 147.31, 145.85, 145.28, 145.20, 145.14, 145.02, 1~4.82, 14~.76, 144.67, 144.32, 144.~7, 144.18, 143.68, 143.11, 142.98, 142.67, 142.38, 142.15, 142.1~, 141.00, 138.10, 136.09 (fullerene ~ignals), 76.33 (~, 2C, bridgehead Carbon atom~), 60.99 (~, lC, O-CH2CH3), 37.94 (R, lC, C~I bridge Carbon atom), 33.24 (5, lC, CH2-CH2-COOEt), 22.08 (~, lC, CH2-COOEt), 14033 (8, lC, CH3);
EI-MS: 834 (Mt), 720 (~M-CEI(CH2)2COOEt]~).

Filter residue: 41 mg 2~8~ ~

Example 10 Methyl undecanoate methanofullere~e (raaction of carbo-etho~yundecylidenetriphenylphosphora~e (H5C200C-(CH2)10-CH=PPh3~ with C60~

The reaction i8 carried out in accoxdance with the GPI.
90 mg (0.125 mmol) of C60 are di~solved in 100 ml o~
toluene and heated under re41ux. Following the addition of 70 mg (0.147 mmol) of carboethoxyundecylidenetri-phenylpho~phorane, dis~ol~ed i~ 25 ml of toluane, for-mation of a precipitate may i~mediately be obs~rved. Theraaction mixture i~ heated under reflux for a further 24 hour~ and then filtered.

Working-up of the filtrate:
After the ~ol~ent ha~ been stripped of f, the re~idue of the filtra~e (50 mg) i~ loaded onto a silica gal column (~ilica gel 60, from E. Merck, Darm~tadt, Germany).
Unraacted C60 (Rf: 1) and resulti~g PPh3 (Rf: 0.4) are separated of~ u~ing CS2 a~ eluent. The column i~ then eluted usi~y CH2Cl2. Once the solvent has been ~tripped off, a dark-brown, microcrystalline resldue remain~ from the ~raction (Rf~ 1) which has been obtained.
Yield: 14 mg .

lH-NMR (400 M~Iz, CDC13, 30C): ~ = 4.03 (t, 3~(H, H) =
7.63 Hz, lH, C-~), 3.60 (~, 3H, O-CH3), 2.49 (dt, 3~(H, H) -~ 7.63 Hz, 3J(H, ~) - 7.93 ~Iz, 2H, CH-CH2-OEI2~, 2.25 (t, 3J(H, ~) , 7.63 Hz, 2~, CH2-COOMe), 1.93 (m, 2H, CH~, 1.60 (m, 4H, C~2), 1.27 to 1.42 (m, lOH, CH2~;
l3C-NMR (100.4 ~Hz, CDCl3, 30C): ~ _ 174.34 ~, lC, COOMe), 150.47, 148.04, 145.94, 145.43, 145.17~ 145.11, 145.06, 144.73, 144.54, 144.26, 144.17, 144.11, 143.67, 142.97, 1~2.73, 1~.4~, 142.15t 142.10, 1~0.96, 138.~, 135.94 (fullerene ~ignai~), 77.74 (~, 2C, bridgehead Carbon atom~), 51.47 (~, lC, O-C~3), 39.46 (~, ~C, C-H
bridge Carbon atom), 34.12 (e, lC, CH2-COOMe), 29.61 (~, lC, C~2), 29.57 (~, lC, CH2), 29.46 (~, lC, CH2), 29.40 (~, 2C, CH2), 29.28 (B, lC, CH2), 17.57 (~, lC, CH2), 21~ 7861 28 . 87 ~R~ lC, ~2);
EI-MSO 921 ~M~), 720 ( ~M-OEI(CH2)lOCOOMa~

Re~idue: 110 mg E~ample 11 8-(Tetrahydro-~-pyranyloxy)octylmethanofullere~ and 8-hydroxyoctylmethano~ullerane Ireaction o 9-~tetra-hydro-2-py~ nyloxy)non-l-ylidenetriph~nylpho~horane (THp-o-(cH2l~-c~=pph3) with C60) The reaction is carried out in accordance with the GPI.
60 ~g (0.083 mmol) o~ C60 are dissolved in 60 ml of toluene and heatcd under ra~lux. Followlng the addition of 41 mg (0~084 mmol~ o~ 9~(tetrahydro-2-pyranyloxy)-nonylidenetriphenylpho~phorane, dissol~ed in 2 ml of toluene, khe reaction m xture i~ heated under reflux or lS a further 24 hour~, during which time the solution 810wly becomes turbid, and then filtered.

Working-up o~ the 11trate:
After the ~olvent has been stripped off, the re~idue of the filtrate (88 mg) i8 loaded onto a ~ilica gel column (8ilica gel 60, from E. Merck, Darm~tadt, Germany). 17 g o unreacted C60 (R~: 1.0) are ~eparated o~$ u~ing CS2 a~
eluent. The column i8 then eluted u~ing methylene chloride. This result~, once the ~olvent has been ~tripped o~f, in two ~ractlons being obtained, ~ix~tly 21 mg o~ a red-bxown ~raction ha~ing an R~: 0.45 (~rac-tion 1) and thcn 24 mg o~ a pale-brown ~raction havlng an R~: 0.2 (fraction 2). Whan fraction 1 i8 ~ubjected to renewed column-chromatographic ~eparation on ~ilica gel u~lng mekhylene ohlorids a~ eluent, the ~ame divis~on into two ~ractions occur~ a~ ~n the ~rst elution u~ing methylene chloride, leading to the conclu~ion that the ether i9 heing aleaved on the colu~n. For puxifica~ion, the combined fraction~ 2 were 3ubsequently wa~had three tlme~ with ~ ml o~ diethyl ether on each occa~ion, di~olved in 3 ml of CS2, a~d precipitaked out once again ~i7~

by ~lowly adding diethyl eth~r dropwi~e.

The ma~R ~pectrum of fraction 1 ~how~ a ~ignal at m/e =
862, which accords with the corre~ponding al~ohol o~ the cleaved tetrahydropyranyl ether (8-hydroxyoctylmethano-fullerene~. Howe~er, in the 1H-NMR
the signal pattern of the tetrahydro-pyranylhydroxyoc~ylme~ha~o~ullaren~ is cl~arly found- Ths chloroform-~oluble precipitate al~o show the ~ignal at m/e - R62 in tha ma~ ~pectr~m.
However, the alcohol belonging to it cannot be det~cted in the lH-NMR.

Yieldof8-(tetrahydro-2-pyranyloxy)octylmethanofullerane (fraction 1~: 21 mg lH-NMR (400 M~z, CDCl3, 29C): ~ = 4.6 (m, lH, OCHO), 4.11 (t, 3J(H, H) = 7.47 H$, lH, CH), 3.4 to 3.95 (m, 4H, CH2O), 2.56 (dt, 3J~H, H) = 7.53 Hz, 2H, CH2), 2.00 (m, 2~, CH2), 1.3 to 1.9 (m, 16H, CH2);
13C-NMR (100.4 MHz, CDCl3, 30C): ~ - 150.46, 148.02, 145.94, 145.43, 145.17, 145.06, ~44.~7, 144.71, 14~.26, 144.~7, 1~4.11, 143.66, 1~2.95, 142.71, 142,42, 142.15, 140~93, 138.00, 135.93 (fullerene ~ignal~), 98.90 (~, lC, OCHO), 77.62 (n, 2C, bridgehead Carbon atom~), 67.58 (~, lC, CH2O), 62.43 (~, lC, CH2O), 39.72 (~, lC, CH bridge Carbon atom), 29.78 (~, lC, CH2), 29.47 ~, lC, CH2), 29.35 (~, lC, CH2), 28.91 (~, lC, CH2), 28.68 (~, lC, CH2), 26.41 (~, lC, CH2)~ 26.29 (8, lC, CH2), 25.51 (~, 2C, CH2), 19.76 (~, lC, C~2);
EI-MS: 862 ~[M-C5H8(dihydropyran)~), 720 ~{M-C~(CH2)~-OTHP]+).

Yield of 8-hydroxyoctylmethano~ullerene (fraction 2~:
24 mg 1H-NMR (400 M~Iz, CH2/C6D6 5:1, 29C): ~ - 4.89 (m, lH, OH), 3.9 (t, 3J(H, EI) ~ 7.49 Hz, lH, CH), 3.41 (t, 3J~H, H) = 6.43 Hz, 2H, CH2O), 2.41 (dt, 3J(H, H) = 7.54 ~z, ~7~1 - ~o 2H, CH2), 1.8~ (m, 2H, C~2), 1.57 (m, 2EI, CH2), 1.5 to 1.2 (m, 8H, CH2);
3C-NMR (100.4 M~z, CS2/C6D6 5:1, 31C~: ~ = 150.43, 147.96, 1~6.0~ 5.56, 145.43, ~45.37, 145.2~, 144.97, S 14~.89, 14~.50, 144O4~ 3.9~ 3.~4, 142.95, 1~2.62, 142.36 141.31, 141.27, 138.26, 136.21 (fullerene 3iy~
nal~), 77~21 (9, 2C, bridgehead Carbon atoma), 62.85 (~, lC, CH2O), 39.84 (~ , CH bridge Carbon atom), 33.48 (~, lC, CH2), 30.40 (~, lC, CH2), 30.08 (~, lC, C~2), 2~.53 ~, 2C, ~2)~ 26.~8 (8, lC, C~2~, 26.51 (~, lC, C~2~;
EI-MS: 862 (M+), 720 ([M-CH(CH2)8-OH]+).

Filter residue: 15 mg Example 12 Phenylthiomethanofullerene (reactio~ o~ phenylthio-methylenetriphenylpho~phorane (C6H5SCH=PPh3) with C60~

The reaction i8 carried out in accordance wi~h the GPI.
112 mg (0.155 mmol) of C60 are dissolved in 125 ml of toluene and heated under re~lux. Following the addi~ion o 59.74 mg (0~155 ~mol) o~ phenylthiomethylenetriphenyl-pho~phorane in 10 ml o$ toluena (~tandard solution), no clouding ca~ be observed; thiA occurs, to a very limited extent, only a~tex heati~g under re~lux for 24 hour~. The reaction mixture is then filtered.

Working-up o~ the fi~trate:
A~ter the ~olvent ha3 been stripped off, the re~ldua of the filtrate (171 mg) i~ loaded onto a ~iliaa gel column (silica gal 60, ~rom E. Merck, Darm~tadt, Gexmany). The product (Rf: 0.8S) can be separat~d o~ Erom unreact~d C60 30 (Rf: 0 . 92~ and triphenylphosphane by eluting with CS2.
Once the 801~ent ha~ been ~tripped o~, a brown, miarocry~talline s~b~tanca remains.
Y~eld: 31~3 mg - 21 ~ i 7 ~ ~ ~
H-NMR (400 MXz, C6D6~CS2, 29C): ~ = 7063 (d, 3J(H, H) =
7.40 Hz, 2H, o-H(Ph)), 7.19 (t, 3J(H, H) = 7.60 Hz, 2H, m-H(Ph)), 7.07 (t, 3J~H, ~) = 7.40 Hz, lH, p-H(Ph)), 5.06 (s, lH, CH-S);
l3C-NMR (100.4 MH~, C6D6/CS2 1:1, 29C): ~ = 148.63, 146.72, 145.94, 145.64, 1~5.59, 145.50, 145.08, 145.02, 144.89, 144.12, 144.09, 143.51, 143.24, 142.85, 142.78, 142.42, 141.40, 141.31, 140.11, 137.03, 135041 (fullerene 6ignals), 129.83 (~, 2C, C(Ph)), 129.70 (8, 2C, C(Ph)), 128.56 (8, lC, C~Ph)), 127.50 (s, lC, C(Ph)), 74.43 ~s~ 2C, bridgehead Carbon atoms), 39.39 (s, lC, C~-S-bridge Carbo~ atom);
EI-MS: 842 (M~), 733 ([M-SPh~3, 720 ([M-C~SPh]').

Claims (10)

1. A process for preparing a methano-bridged fullerene derivative, wherein a fullerene or fullerene deri-vative is reacted with a phosphorus ylide in an inert organic solvent at a temperature of from -78 to 180°C.

2. The process a claimed in claim 1, wherein a fuller-ene of the formula C20+2m, with m = 2....100, is employed.

3. The process as claimed in claim 1 and/or 2, wherein an ylide of the formula (I) is employed, (I) where R1, R2: are, independently of each other, H, a straight-chain or branched (with or without an asymmetric carbon atom) C2-C20 alkyl group, where one or more CH2 groups can be replaced by -C?C-, -CH=CH-, -O-, -S-, -OOC-, -COO-, , -CO-, phenylenediyl or cyclohexylenadiyl, and where one or more hydrogen atoms can be replaced by F, Cl, Br, I or a tetrahydro-pyranyloxy group, or R1 and R2 together are =C=X, with X being O, S, NR3 or (O-R3)2;
R3: is, identically or differently, phenyl or C1-C12-alkyl.

4. The process as claimed in one or more of claims 1 to 3, wherein the stoichiometric ratio of ylide to fullerene is from 8:1 to 0.5:1.

5. The process as claimed in one or more of claims 1 to 4, wherein an inert solvent from the group benzene, toluene, chlorobenzene, and methylene chloride is used.

6. A fullerene derivative of the formula (II), (II) in which the symbols and indices have the following meanings:
F: is a fullerene radical of the formula C20 + 2m, with m = 2 to 100;
R4: is H, CH3, -phenyl or R5;
R5: is a straight-chain or branched (with or with-out an asymmetric carbon atom) C2-C20-alkyl group, where one or more CH2 groups can be replaced by -C?C-, -CH=CH-, -O-, -S-, -OOC-, -COO-, , -CO-, phenylenediyl or cyclo-hexylenediyl, and where one or more hydrogen atoms can be replaced by F, Cl, Br, I, OH or a tetrahydropyranyloxy group, or R4 and R5 together are =C=X with X being O, S, NR3 or (O-R3);
R3: is phenyl or C1-C12-alkyl;
n: is from 1 to 6.

7. A fullerene derivative as claimed in claim 6, where-in the symbols and indices in the formula (II) have the following meaning:
F: is C60 or C70;
R4: is H or phenyl;
R5: is a straight-chain or branched (with or with-out an asymmetric carbon atom) C2-C20-alkyl group, where one or more CH2 groups can be replaced by -C?C-, -CH=CH-, -O-, -S-, -COO-, -OOC-, , -CO , phenylenediyl or cyclo-hexylenediyl, and where one or more hydrogen atoms can be replaced by F, Cl, Br, I, OH or a tetrahydropyranyloxy group, or R4 and R5 together are =C=X with X being O, S, NR3 or (O-R3)2;
R3 is phenyl or C1-C12-alkyl;
n: is 1.

8. A fullerene derivative as claimed in claim 6 and/or 7, wherein the symbols and indices in the formula (II) have the following meanings:
F: is C60 or C70;
R4: is H or phenyl;
R5 is a straight-chain or branched C2-C20-alkyl group, where one or more CH2 groups can be replaced by -C?C-, -CH=CH-, -O-, -S-, -COO-, -OOC-, phenylenediyl or cyclohexylenediyl, and where one hydrogen atom can be replaced by OH or a tetrahydropyranyloxy group;
n: is 1.

9. Use of fullerene derivatives, prepared using a process as claimed in one or more of claims 1 to 5, in optoelectrical units.

10. Use of fullerene derivatives of the formula (II) as claimed in one or more of claims 6 to 8 in opto-electrical units.