LETTER
Synthesis of Fullerene-Cardanol Derivatives
801
(9) Attanasi, O. A.; Filippone, P.; Balducci, S. Gazz. Chim. Ital.
1991, 121, 487.
(10) Amorati, R.; Attanasi, O. A.; El Ali, B. G.; Filippone, P.;
Mele, G.; Spadavecchia, J.; Vasapollo, G. Synthesis 2002,
2749.
spectrum of 12a in CDCl3 shows typical signals of the
pyrrolidine (C60)-fullerene system, (a singlet for H-2 at
d = 4.91 ppm and the AB system for CH2-5, two doublets
centred respectively at d = 4.26 ppm and d = 5.00 ppm
with a geminal coupling JAB = 9.4 Hz). The signals in the
13C NMR spectrum are also in agreement with the pro-
posed structures. The number of signals in the range
around 136–159 ppm of this spectrum shows the lack of
symmetry in the compound 12a which is typical of asym-
metric fulleropyrrolidine systems.
(11) Attanasi, O. A.; Ciccarella, G.; Filippone, P.; Mele, G.;
Spadavecchia, J.; Vasapollo, G. J. Porphyrins
Phthalocyanines 2003, 7, 52.
(12) Del Sole, R.; Mazzetto, S. E.; Mele, G.; Vasapollo, G.;
Attanasi, O. A.; Filippone, P. IV-INSTM Conference, Ischia
(Na), 29 June–02 July 2003, and unpublished results.
(13) Representative Procedure for the Synthesis of 1-(2-
Bromoethoxy)-3-pentadecyl-benzene (7a) is as follows:
Compound 5a (4.00 g, 13.16 mmol) was heated with stirring
at 70 °C with 1,2-dibromoethane(6) (15 mL). After complete
dissolution of 5a, potassium hydroxide (1.11 g, 19.78 mmol)
was added to the solution and the mixture was stirred for 6 h.
The progress of the reaction was monitored by TLC analysis
until the complete disappearance of 5a and then the mixture
was cooled to r.t. and filtered to remove the colorless solid
formed. The filtered solution was purified by
In conclusion, we have reported here the attractive synthe-
sis of interesting compounds formed by fullerene and sub-
stituted cardanol derivatives that represent a sustainable
combination between the diversity of natural biosynthesis
and the creativity of human chemistry. The compounds
exhibit good solubility in the common organic solvent as
well as ease of manipulation and suitability for further
transformation. In fact, the solubility in chloroform of the
fulleropyrrolidine derivatives reported in this paper rang-
es between 100–300 times more than that of the starting
fullerene [C60].1–17 This enhanced solubility permits the
easy purification, characterization, and subsequent trans-
formation of the products, as well as their scale-up and
low cost production.
chromatography on a silica gel column, eluting first with
petroleum ether (40–60 °C) to recover the unreacted 1,2-
dibromoethane, and then with Et2O/petroleum ether (3:7), to
obtain product 7a in 90% yield.
Compound 7a: colorless powder; mp 43–44 °C. FT-IR
(neat): 2922, 2852, 1603, 1584, 1487, 1447, 1255, 1157,
1024, 874 cm–1. MS (EI, 70 eV): m/z (%) = 412 (35) [M+ +
2], 410 (34) [M+], 217 (10), 216 (95), 215 (36), 214 (100).
1H NMR (CDCl3): d = 0.85 (t, J = 6.8 Hz, 3 H), 1.25–1.27
(m, 24 H), 1.57 (qn, J = 7.6 Hz, 2 H), 2.55 (t, J = 7.6 Hz, 2
H), 3.60 (t, J = 6.3 Hz, 2 H), 4.25 (t, J = 6.3 Hz, 2 H), 6.67–
6.70 (m, 1 H), 6.71–6.73 (m, 1 H), 6.76–6.80 (m, 1 H), 7.16
(t, J = 7.8 Hz, 1 H) ppm. 13C NMR (CDCl3): d = 14.58,
23.15, 29.64, 29.77, 29.78, 29.82, 29.96, 29.99, 30.04,
30.11, 30.12, 30.14, 30.15, 31.82, 32.38, 36.43, 68.17,
112.02, 115.48, 122.06, 129.69, 145.28, 158.51 ppm.
(14) Representative Procedure for the Synthesis of 4-[2-(3-
Pentadecylphenoxy)-ethoxy]-benzaldehyde (9a) is as
follows:
Acknowledgment
This work was supported by financial assistance from Consorzio
INCA (Legge 488), in part from MIUR (Fondi ex 40%), MIUR
(COFIN 2002), University of Lecce, and University of Urbino.
Prof. S. E. Mazzetto thanks CAPES for financial support.
References
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Nolte, R. J. M.; Torres, T.; Wöhrle, D. Monatsh. Chem.
2001, 132, 3; and references therein. (b) Leznoff, C. C.;
Lever, A. B. P. Phthalocyanines: Properties and
Applications, Vol. 1-4; VCH: Weinheim, 1989-1996.
(c) McKeown, N. B. Phthalocyanines Materials Synthesis
Structure and Function; Cambridge University Press:
Cambridge, 1998. (d) Hirsch, A. The Chemistry of the
Fullerenes; Georg Thieme Verlag: Stuttgart, 1994.
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1999, 40, 187. (b) D’Souza, F.; Deviprasad, G. R.; El-
Khouly, M. E.; Fujitsuka, M.; Ito, O. J. Am. Chem. Soc.
2001, 123, 5277. (c) Mele, G.; Del Sole, R.; Vasapollo, G.;
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To 7a (3.00 g, 7.30 mmol) dissolved in acetone (15 mL) 4-
hydroxybenzaldehyde (8) (1.33 g, 10.9 mmol) and
potassium carbonate (3.03 g, 21.9 mmol) were added. The
mixture was stirred under reflux for 24 h. The mixture was
cooled to r.t. and filtered to remove the colorless solid
formed. The solvent was evaporated under reduced pressure
and the crude material was purified by chromatography on a
silica gel column, eluting with Et2O/petroleum ether (3:7), to
obtain product 9a in 60% yield.
Compound 9a: colorless powder; mp 72 °C. FT-IR (neat):
2952, 2918, 2848, 1681, 1606, 1582, 1463, 1247, 1167,
1066, 929, 838 cm–1. MS (EI, 70 eV): m/z (%) = 452 (45)
[M+], 256 (16), 149 (42), 135 (59), 121 (67), 108 (100). 1H
NMR (CDCl3): d = 0.84 (t, J = 6.8 Hz, 3 H), 1.20–1.25 (m,
24 H), 1.54–1.59 (m, 2 H), 2.53 (t, J = 7.6 Hz, 2 H), 4.29–
4.38 (m, 4 H), 6.71–6.78 (m, 3 H), 7.01 (d, J = 8.7 Hz, 2 H),
7.16 (t, J = 7.7 Hz, 1 H), 7.80 (d, J = 8.7 Hz, 2 H), 9.85 (s,
1 H) ppm. 13C NMR (CDCl3): d = 14.55, 23.11, 28.90, 29.76,
29.79, 29.94, 30.02, 30.08, 30.10, 30.12, 31.81, 32.35,
66.49, 67.30, 111.90, 115.33, 121.93, 129.67, 130.62,
132.40, 145.24, 158.84, 164.09, 191.22 ppm.
(15) Representative Procedure for the Synthesis of N-Methyl-
2-{4-[2-(3-pentadecyl-phenoxy)-ethoxy]-phenyl}-
fulleropyrrolidine (12a) is as follows:
(7) Attanasi, O. A.; Buratti, S.; Filippone, P. Chim. Ind. (Milan)
1996, 78, 693.
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Proced. Int. 1995, 27, 645. (b) Attanasi, O. A.; Filippone, P.
Italian Patent PS95A000021, 1995.
Compound 9a (0.090 g, 0.2 mmol), fullerene [C60] 10 (0.144
g, 0.2 mmol) and N-methylglycine (11a) (0.018 g, 0.2 mmol)
were allowed to react in toluene (500 mL) under reflux for
Synlett 2004, No. 5, 799–802 © Thieme Stuttgart · New York