Helvetica Chimica Acta ± Vol. 84 (2001)
1131
4.54 (s, 2 H); 5.25 (m, 2 H); 6.28 (t, J 2, 1 H); 6.41 (d, J 2, 2 H). 13C-NMR (CDCl3, 50 MHz): 12.12; 18.98;
19.66; 21.33; 22.83; 23.10; 24.09; 24.56; 25.91; 2620; 28.28; 28.51; 28.75; 29.14; 29.46; 30.40; 32.15; 36.06; 36.46;
37.17; 37.55; 39.46; 39.78; 40.04; 42.59; 50.46; 56.43; 57.05; 65.70; 68.17; 79.26; 100.78; 105.31; 121.72; 141.40;
141.90; 160.76.
Propanedioic Acid {5-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}-1,3-phenylene}bis(methylene) Bis{{3,5-
bis{{6-[(3b)-cholest-5-en-3-yloxy]hexyl}oxy}phenyl}methyl} Ester (13). As described for 4, with DCC
(153 mg, 0.74 mmol), DMAP (14 mg, 0.12 mmol), HOBt (cat. amount), 9 (140 mg, 0.29 mmol), 12 (800 mg,
0.742 mmol), and CH2Cl2 (20 ml) (stirring for 24 h). CC (SiO2, CH2Cl2/AcOEt 5 :3) yielded 12 (650 mg, 85%),
which was used in the next step without further purifications. Colorless glassy solid. 1H-NMR (CDCl3,
200 MHz): 0.68 (s, 12 H); 0.85 ± 2.34 (m, 192 H); 3.13 (m, 4 H); 3.43 (s, 3 H); 3.46 (t, J 6, 8 H); 3.49 (s, 4 H);
3.52 ± 3.88 (m, 10 H); 3.91 (t, J 6, 8 H); 4.09 (t, J 6, 2 H); 5.09 (s, 4 H); 5.13 (s, 4 H); 5.34 (m, 4 H); 6.39
(t, J 2, 2 H); 6.46 (d, J 2, 4 H); 6.87 (br. s, 2 H); 6.90 (br. s, 1 H).
11''-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}-4'',15''-dioxo-3',3''-(methoxymethano[1,3]benzenomethanoxy-
methano)-3',3''-dicyclopropa[1,9 :3,15][5,6]fullerene-C60-Ih-3',3''-dicarboxylic Acid Bis {{3,5-bis{{6-[(3b)-cho-
lest-5-en-3-yloxy]hexyl}oxy}phenyl}methyl} Ester (14). As described for 6, with DBU (0.16 ml, 1.10 mmol), C60
(158 mg, 0.22 mmol), I2 (140 mg, 0.55 mmol), 13 (600 mg, 0.23 mmol), and toluene (500 ml) (SiO2-plug elution
with toluene CH2Cl2/AcOEt 1:1). CC (SiO2, CH2Cl2/AcOEt 8 :2) yielded 14 (320 mg, 44%). Dark orange
glassy product. IR (CH2Cl2): 1749 (CO). 1H-NMR (CDCl3, 200 MHz): 0.67 (s, 12 H); 0.80 ± 2.43 (m, 192 H);
3.14 (m, 4 H); 3.41 (s, 3 H); 3.45 (t, J 6, 8 H); 3.52 ± 4.15 (m, 10 H); 4.05 (t, J 6, 8 H); 4.15 (m, 2 H); 5.05
(d, J 12, 2 H); 5.15 (d, J 12, 2 H); 5.33 (m, 4 H); 5.45 (d, J 12, 2 H); 5.75 (d, J 12, 2 H); 6.33 (br. s, 2 H);
6.48 (br. s, 4 H); 6.80 (br. s, 2 H); 7.05 (br. s, 1 H). 13C-NMR (CDCl3, 50 MHz): 11.79; 18.65; 19.32; 20.98; 22.51;
22.76; 23.76; 24.21; 24.87; 25.56; 25.77; 25.90; 27.59; 27.91; 28.16; 28.40; 28.98; 29.15; 29.63; 30.07; 31.81; 31.85;
33.85; 35.70; 36.11; 36.81; 37.21; 39.12; 39.42; 39.71; 42.23; 48.94; 50.10; 56.08; 56.68; 58.96; 65.28; 66.78; 67.18;
67.50; 67.85; 68.60; 69.56; 70.50; 70.58; 70.77; 71.85; 77.21; 78.88; 101.54; 107.04; 112.41; 121.36; 135.92; 136.02;
136.46; 138.06; 139.97; 140.96; 142.21; 142.65; 142.86; 143.06; 143.48; 143.64; 143.87; 144.06; 144.24; 144.50;
144.88; 145.08; 145.26; 145.48; 145.68; 145.97; 147.22; 147.37; 148.53; 158.76; 160.25; 162.47. UV/VIS (CH2Cl2):
258 (82770), 320 (sh, 22175), 437 (2215), 464 (2020). Anal. calc. for C227H260O20 (3308.35): C 82.41, H 7.92;
found: C 82.64, H 7.98.
This work was supported by the CNRS, the French Ministry of Research, the Swiss National Science
Â
Foundation, the Swiss-French Cooperation Program (CNRS-PICS 742), a doctoral fellowship from the Region
Alsace to D. F., and a post-doctoral fellowship from DGAPA-UNAM and CONACyT to M. del P. C. We further
thank L. Oswald for technical help and Prof. J.-F. Nicoud for his support.
REFERENCES
[1] A. Hirsch, ꢁThe Chemistry of the Fullerenesꢀ, Thieme, Stuttgart, 1994; F. Diederich, C. Thilgen, Science
(Washington, D.C.) 1996, 271, 317; Y. Rubin, Chem.±Eur. J. 1997, 3, 1009; M. Prato, J. Mater. Chem. 1997, 7,
1097; L. Echegoyen, L. E. Echegoyen, Acc. Chem. Res. 1998, 31, 593; A. L. Balch, M. M. Olmstead, Chem.
Rev. 1998, 98, 2123; T. Chuard, R. Deschenaux, Chimia 1998, 52, 547; F. Diederich, R. Kessinger, Acc.
Chem. Res. 1999, 32, 537; J.-F. Nierengarten, Chem.±Eur. J. 2000, 6, 3667.
[2] U. Jonas, F. Cardullo, P. Belik, F. Diederich, A. Gügel, E. Harth, A. Herrmann, L. Isaacs, K. Müllen, H.
Ringsdorf, C. Thilgen, P. Uhlmann, A. Vasella, C. A. A. Waldraff, M. Walter, Chem.±Eur. J. 1995, 1, 243,
and ref. cit. therein.
[3] Y. S. Obeng, A. J. Bard, J. Am. Chem. Soc. 1991, 113, 6279; T. Nakamura, H. Tachibana, M. Yumura, M.
Matsumoto, R. Azumi, M. Tanaka, Y. Kawabata, Langmuir 1992, 8, 4; R. Back, R. B. Lennox, J. Phys.
Chem. 1992, 96, 8149; J. Milliken, D. D. Dominguez, H. H. Nelson, W. R. Barger, Chem. Mater. 1992, 4,
252; F. Diederich, J. Effing, U. Jonas, L. Jullien, T. Pelsnivy, H. Ringsdorf, C. Thilgen, D. Weinstein, Angew.
Chem., Int. Ed. 1992, 31, 1599; L. M. Goldenberg, G. Williams, R. M. Bryce, A. P. Monkman, M. C. Petty,
A. Hirsch, A. Soi, J. Chem. Soc., Chem. Commun. 1993, 1310; M. Maggini, A. Karisson, L. Pasimeni, G.
Scorrano, M. Prato, L. Valli, Tetrahedron Lett. 1994, 35, 2985; C. J. Hawker, P. M. Saville, J. W. White, J.
Org. Chem. 1994, 59, 3503; M. Maggini, L. Pasimeni, M. Prato, G. Scorrano, L. Valli, Langmuir 1994, 10,
4164; L. B. Gan, D. J. Zhou, C. P. Luo, C. H. Huang, T. K. Li, J. Bai, X. S. Zhao, X. H. Xia, J. Phys. Chem.
1994, 98, 12459; D. A. Leigh, A. E. Moody, F. A. Wade, T. A. King, D. West, G. S. Bahra, Langmuir 1995,
11, 2334; C. A. Mirkin, W. B. Caldwell, Tetrahedron 1996, 52, 5113, and ref. cit. therein; P. Wang, Y.
Maruyama, R. M. Metzger, Langmuir 1996, 12, 3932; C. C. Zhu, Y. Xu, Y. Q. Liu, D. B. Zhu, J. Org. Chem.