T. Itoh et al. / Tetrahedron 64 (2008) 1823e1828
1827
iodomethane was removed under reduced pressure. Then, the
residue was washed with toluene (three times) and hexane
(twice). The solvent was removed under vacuum to give 4
(100 mg, 0.0826 mmol) as brownish solid in 96% yield: IR
(KBr, cmꢂ1) 3414, 3082, 2964, 2860, 1560, 1458, 1431,
1165, 768, 527; HRMS (MALDI-TOF MS, matrix: SA) found
957.2200 (C74H27Nþ3 , calcd: 957.2205). Due to poor solubility
in CDCl3, CD3OD, and DMSO-d6, no NMR spectra with good
resolution could be obtained.
142.54, 142.66, 142.70, 142.97, 143.11, 144.27, 144.38,
144.69, 145.12, 145.24, 145.26, 145.30, 145.33, 145.44,
145.50, 145.61, 145.90, 146.05, 146.16, 146.24, 146.31,
147.17, 147.24, 147.29, 152.26, 152.61, 152.77, 153.80; IR
(KBr, cmꢂ1) 2930, 2853, 1541, 1508, 1460, 1182, 1111,
833, 527; HRMS (MALDI-TOF MS, matrix: SA) found
1092.2657 (C82H34N3Oþ2 , calcd: 1092.2651).
5.8. Salt 7b
5.6. Synthesis of N-methoxyethoxyethyl-2-(4-(1H-
imidazol-1-yl)phenylfulleropyrrolidine (6)
1H NMR (500 MHz, ppm, CDCl3, J¼Hz) d 0.88 (t, 3H,
J¼7.1 Hz), 1.23 (br s, 26H), 1.98 (quin, 2H, J¼7.5 Hz), 2.92
(quin, 1H, J¼5.8 Hz), 3.37 (quin, 1H, J¼6.0 Hz), 3.45
(s, 3H), 3.68 (dt, 2H, J¼1.6 Hz, 4.8 Hz), 3.75e3.85 (m, 2H),
3.99 (quin, 1H, J¼5.2 Hz), 4.05e4.10 (m, 1H), 4.36 (d, 1H,
J¼9.6 Hz), 4.56e4.66 (m, 2H), 5.24 (d, 1H, J¼9.6 Hz), 5.27
(s, 1H), 7.40 (s, 1H), 7.62 (s, 1H), 7.93 (d, 2H, J¼9.2 Hz),
8.09 (br, 2H), 11.24 (s, 1H); 13C NMR (125 MHz, ppm,
CDCl3) d 13.91, 22.54, 25.85, 28.97, 29.22, 29.29, 29.43,
29.53, 29.56, 30.28, 31.78, 50.47, 51.94, 59.06, 67.28,
69.02, 70.03, 70.42, 71.86, 75.72, 81.09, 120.42, 121.64,
122.96, 131.45, 134.13, 135.49, 136.01, 136.19, 137.10,
139.34, 139.73, 139.89, 140.08, 141.44, 141.56, 141.60,
141.73, 141.89, 141.97, 142.09, 142.12, 142.37, 142.42,
142.54, 142.89, 142.99, 144.18, 144.29, 144.60, 145.01,
145.12, 145.15, 145.21, 145.29, 145.35, 145.40, 145.50,
145.54, 145.80, 145.95, 146.05, 146.14, 146.21, 147.13,
A solution of C60 (500 mg, 0.694 mmol), [2-(2-methoxy-
ethoxy)ethylamino]acetic acid5g (185 mg, 1.04 mmol), and
4-(imidazol-1-yl)benzaldehyde11 (358 mg, 2.08 mmol) in chlo-
robenzene (200 mL) was stirred for 0.5 h at 130 ꢀC under
argon. The solvent was evaporated under reduced pressure
and the residue purified by flash chromatography (CS2/
AcOEt¼1/0, 20/1, 2/1) affording the product 6 (272 mg,
0.270 mmol) as a dark brown solid in 39% yield: Rf 0.61 (tol-
uene/methanol¼2/1): 1H NMR (500 MHz, ppm, CDCl3,
J¼Hz) d 2.93 (quin, 1H, J¼6.2 Hz), 3.42e3.48 (m, 1H),
3.45 (s, 3H), 3.68 (sep, 2H, J¼1.9 Hz), 3.78e3.85 (m, 2H),
4.05 (dquin, 2H, J¼5.4 Hz, 34.8 Hz), 4.34 (d, 1H,
J¼9.6 Hz), 5.23 (d, 1H, J¼9.6 Hz), 5.24 (s, 2H), 7.20 (s,
1H), 7.31 (s, 1H), 7.46 (d, 2H, J¼8.7 Hz), 7.89 (s, 1H), 7.96
(br s, 2H); 13C NMR (125 MHz, ppm, CDCl3) d 52.08,
58.80, 67.37, 68.83, 70.21, 70.51, 71.93, 75.77, 81.39,
117.48, 121.05, 130.43, 130.72, 134.95, 135.33, 135.74,
136.13, 136.81, 137.04, 139.28, 139.73, 139.96, 141.29,
141.43, 141.53, 141.56, 141.65, 141.76, 141.86, 141.89,
141.96, 141.98, 142.29, 142.33, 142.35, 142.44, 142.76,
142.89, 144.04, 144.15, 144.26, 144.45, 144.87, 144.91,
145.00, 145.06, 145.11, 145.18, 145.30, 145.40, 145.63,
145.66, 145.82, 145.92, 146.01, 146.07, 146.16, 147.01,
152.44, 152.70, 153.63, 155.92; IR (KBr, cmꢂ1) 3412, 2883,
1522, 1300, 1182, 1107, 656, 527: HRMS (MALDI-TOF
MS, matrix: SA) found 1007.1621 (C76H21N3O2, calcd:
1007.1634).
147.18, 152.20, 152.52, 153.69, 156.04; IR (KBr, cmꢂ1
)
3402, 2922, 2849, 1541, 1508, 1458, 1182, 746, 527; HRMS
(MALDI-TOF MS, matrix: SA) found 1232.4151 (C92H54N3Oþ2 ,
calcd: 1232.4216).
5.9. Compound 7c
1H NMR (500 MHz, ppm, CDCl3, J¼Hz) d 0.86 (t, 3H,
J¼6.9 Hz), 1.23 (br s, 26H), 1.50 (quin, 2H, J¼6.9 Hz), 2.94
(quin, 1H, J¼6.1 Hz), 3.35e3.41 (m, 3H), 3.45 (s, 3H),
3.53e3.55 (m, 2H), 3.59e3.63 (m, 8H), 3.66e3.69 (m, 4H),
3.78e3.85 (m, 2H), 3.97e4.02 (m, 3H), 4.06e4.09 (m, 1H),
4.36 (d, 1H, J¼9.7 Hz), 4.85 (t, 2H, J¼4.4 Hz), 5.25 (d, 1H,
J¼9.7 Hz), 5.27 (s, 1H), 7.64 (s, 1H), 7.85 (t, 2H,
J¼8.7 Hz), 7.96 (s, 1H), 8.08 (br s, 2H), 10.98 (s, 1H); 13C
NMR (125 MHz, ppm, CDCl3) d 14.06, 22.59, 25.98, 29.30,
29.46, 29.53, 29.61, 29.66, 31.88, 50.04, 52.00, 59.12,
67.52, 68.93, 69.15, 69.87, 70.00, 70.09, 70.22, 70.27,
70.45, 70.54, 71.38, 71.98, 75.84, 81.27, 119.65, 121.80,
124.89, 131.54, 134.31, 135.52, 135.89, 136.07, 136.25,
137.19, 139.39, 139.97, 140.19, 141.54, 141.67, 141.78,
141.83, 141.99, 142.08, 142.14, 142.19, 142.22, 142.47,
142.54, 142.66, 142.98, 143.11, 144.27, 144.40, 144.71,
145.11, 145.21, 145.24, 145.29, 145.34, 145.37, 145.46,
145.49, 145.52, 145.59, 145.62, 145.91, 146.06, 146.14,
146.16, 146.22, 146.25, 146.30, 147.24, 147.30, 152.29,
152.62, 153.83, 156.16; IR (KBr, cmꢂ1) 3439, 2916, 2849,
1541, 1508, 1458, 1107, 527; HRMS (MALDI-TOF MS,
matrix: SA) found 1408.5262 (C100H64N3Oþ6 , calcd: 1408.5265).
5.7. Salt 7a
1H NMR (500 MHz, ppm, CDCl3, J¼Hz) d 0.88 (t, 3H,
J¼7.1 Hz), 1.29e1.36 (m, 4H), 1.39e1.43 (m, 2H), 1.99
(quin, 2H, J¼7.6 Hz), 2.91e2.95 (m, 1H), 3.36e3.39
(m, 1H), 3.46 (s, 3H), 3.68 (t, 2H, J¼4.8 Hz), 3.80e3.84
(m, 2H), 4.00 (quin, 1H, J¼5.1 Hz), 4.07 (br s, 1H), 4.36
(d, 1H, J¼8.7 Hz), 4.59 (dt, 2H, J¼2.8 Hz, 4.9 Hz), 5.24 (d,
1H, J¼9.6 Hz), 5.28 (s, 1H), 7.45 (t, 1H, J¼1.8 Hz), 7.62 (s,
1H), 7.93 (d, 2H, J¼8.2 Hz), 8.10 (br s, 2H), 10.70 (s, 1H);
13C NMR (125 MHz, ppm, CDCl3) d 13.92, 22.38, 25.88,
30.36, 31.15, 50.54, 52.06, 59.16, 69.05, 70.17, 70.65,
71.93, 75.76, 81.21, 120.22, 121.63, 122.75, 131.62, 134.16,
135.53, 136.00, 136.08, 136.28, 136.43, 137.18, 139.41,
139.96, 140.06, 140.12, 140.59, 140.98, 141.53, 141.66,
141.79, 141.83, 142.00, 142.07, 142.14, 142.18, 142.47,