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Synlett 2004(5): 0799-0802  
DOI: 10.1055/s-2004-820014
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Fullerene-Cardanol Derivatives

Orazio A. Attanasia, Roberta Del Soleb, Paolino Filipponea, Roberto Ianneb, Selma E. Mazzettoc, Giuseppe Mele*b, Giuseppe Vasapollob
a Centro di Studio delle Sostanze di Origine Naturale, Università degli Studi di Urbino, Piazza della Repubblica 13, 61029 Urbino, Italy
b Dipartimento di Ingegneria dell’Innovazione, Università di Lecce, Via Arnesano, 73100 Lecce, Italy
Fax: +39(832)297279; e-Mail: giuseppe.mele@unile.it;
c Departamento de Química Orgânica e Inorgânica, Universidade Federal do Ceará-UFC, Caixa Postal 12.200, 60455-760 Fortaleza, CE - Brazil
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Publication History

Received 12 January 2004
Publication Date:
24 February 2004 (online)

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Abstract

The paper describes the synthesis of fulleropyrrolidines containing substituted derivatives of cardanol - a readily available renewable raw material.

Key words

fullerene - fulleropyrrolidines - cardanol

    References

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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E.; Mele, G.; Vasapollo, G.; Attanasi, O. A.; Filippone, P. IV-INSTM Conference, Ischia (Na), 29 June-02 July 2003, and unpublished results.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 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): δ = 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): δ = 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: 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): δ = 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): δ = 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:
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 24 h. The mixture was cooled to r.t. and the resulting solution was evaporated to dryness. The residue was purified by chromatography on a silica gel column, eluting with toluene to obtain product 12a in 40% yield.
Compound 12a: brown powder; mp 189-191 °C. FT-IR (neat): 2920, 2849, 2779, 1608, 1583, 1510, 1462, 1258, 1246, 1171, 1159, 1089, 1015, 796 cm-1. LC-MS (ESI): m/z = 1200 [M + H]+. 1H NMR (CDCl3): δ = 0.90 (t, J = 6.8 Hz, 3 H), 1.23-1.35 (m, 24 H), 1.55-1.63 (m, 2 H), 2.58 (t, J = 7.7 Hz, 2 H), 2.82 (s, 3 H), 4.26 (d, J = 9.4 Hz, 1 H), 4.32-4.36 (m, 4 H), 4.91 (s, 1 H), 5.00 (d, J = 9.4 Hz, 1 H), 6.75-6.82 (m, 3 H), 7.03 (d, J = 8.1 Hz, 2 H), 7.20 (t, J = 7.8 Hz, 1 H), 7.70-7.80 (m, 2 H) ppm. 13C NMR (CDCl3): δ = 14.11, 22.67, 23.79, 29.49, 30.37, 31.33, 31.90, 36.00, 39.94, 66.31, 66.47, 68.95, 69.97, 77.77, 83.14, 111.49, 114.93, 121.29, 129.14, 129.34, 130.50, 135.72, 136.51, 136.75, 138.04, 139.57, 140.12, 141.51, 141.65, 141.93, 142.51, 142.64, 142.95, 143.11, 144.36, 144.59, 144.68, 145.20, 145.45, 145.90, 146.10, 146.30, 146.48, 147.27, 153.60, 154.07, 156.34, 158.55, 158.66 ppm.