Restricted Rotation in (Phenylpyrrolidino)fullerene Derivatives
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=
2 Hz, 2 H), 7.03 (d, J = 8 Hz, 1 H), 7.49 (dd, J = 8, J = 2, 1 H),
36 H), 1.84 (m, 4 H), 3.66 (d, J = 13.5 Hz, 1 H), 3.72 (s, 3 H), 3.83
(s, 3 H),4.04 (t, J = 7 Hz, 4 H), 4.22 (d, J = 9.5 Hz, 1 H), 4.54 (d,
J = 13.5 Hz, 1 H), 4.91 (d, J = 9.5 Hz, 1 H), 5.81 (s, 1 H), 6.49 (t,
J = 2 Hz, 1 H), 6.85 (m, 4 H), 7.77 (d, J = 3 Hz, 1 H).
7
2
6
1
1
1
1
1
.59 (d, J = 2 Hz, 1 H). 13C NMR (50 MHz, CDCl
3
): 14.10, 22.65,
6.10, 29.32, 29.44, 29.60, 29.66, 31.87, 56.42, 66.37, 68.11, 68.56,
8.75, 69.05, 69.44, 69.54, 70.65, 70.74, 76.75, 80.66, 100.22,
07.20, 129.69, 135.71, 135.83, 136.32, 136.41, 139.62, 139.78,
39.98, 140.06, 141.55, 141.75, 141.84, 141.97, 142.16, 142.22,
42.47, 142.58, 142.89, 143.06, 144.32, 144.62, 145.05, 145.21,
45.43, 145.66, 145.87, 146.00, 146.05, 146.16, 146.41, 146.83,
47.22, 149.05, 153.40, 153.82, 154.05, 156.42, 160.46.
101 4 2
C H67NO ·H O (1376.7): C 88.11, H 5.05, N 1.02; found C 88.12,
H 5.43, N 1.03. FAB-MS: calcd. for C101
1359.7 [MH ].
H68NO
4
1359.65; found
+
Compound 5i: As described for 5a, with 4i (103 mg, 0.555 mmol),
60 (400 mg, 0.555 mmol) and 3 (590 mg, 1.11 mmol) in o-dichloro-
benzene (100 mL). Column chromatography (SiO , CH Cl /hex-
ane, 1:9) yielded 5i (390 mg, 51%) as a brown glassy product. UV/
C
C
109
H81NO
8
·2H
2
O (1568.9): C 83.45, H 5.46, N 0.89; found C
81NaNO 1555.84;
2
2
2
83.18, H 5.70, N 1.12. FAB-MS: calcd. for C109
H
8
+
found 1555.6 [MNa ].
1
Vis (CH
NMR (400 MHz, C
3
4
9
2
Cl
2
): 256 (128100), 309 (44500), 431 (4200), 702 (370). H
Cl ): 0.89 (t, J = 7 Hz, 6 H), 1.18–1.53 (m,
6 H), 1.83 (m, 4 H), 3.68 (d, J = 13.5 Hz, 1 H), 4.04 (m, 5 H),
2
D
2
4
Compound 5f: As described for 5a, with 4f (82 mg, 0.555 mmol),
C
60 (400 mg, 0.555 mmol) and 3 (590 mg, 1.11 mmol) in o-dichloro-
benzene (100 mL). Column chromatography (SiO , CH Cl /hex-
ane, 1:9) yielded 5f (350 mg, 47%) as a brown glassy product. UV/
.29 (d, J = 9.5 Hz, 1 H), 4.38 (d, J = 13.5 Hz, 1 H), 4.93 (d, J =
.5 Hz, 1 H), 5.86 (s, 1 H), 6.49 (broad s, 1 H), 6.79 (d, J = 2 Hz,
2
2
2
1
2 H), 7.22–7.34 (m, 1 H), 7.45–7.52 (m, 1 H), 7.66 (d, J = 8 Hz, 1
Vis (CH
2
Cl
2
): 256 (105900), 309 (36700), 431 (3700), 702 (330). H
Cl ): 0.91 (t, J = 7 Hz, 6 H), 1.21–1.44 (m,
2 H), 1.48 (m, 4 H), 1.83 (m, 4 H), 2.28 (s, 3 H), 2.62 (s, 3 H),
.24 (s, 3 H), 3.55 (d, J = 13.5 Hz, 1 H), 4.03 (t, J = 7 Hz, 4 H),
.10 (d, J = 9.5 Hz, 1 H), 4.48 (d, J = 13.5 Hz, 1 H), 4.98 (d, J =
.5 Hz, 1 H), 5.70 (s, 1 H), 6.5 (t, J = 2 Hz, 1 H), 6.78 (d, J = 2 Hz,
1
3
H), 8.30 (d, J = 8 Hz, 1 H). C NMR (50 MHz, CDCl
3
): 14.15,
NMR (400 MHz, C
2
D
2
4
2
7
1
1
2.71, 26.14, 29.36, 29.49, 29.71, 31.93, 56.51, 66.10, 68.19, 68.96,
3
3
4
9
2
2
6
1
1
1
1
1
1
1
1
6.07, 78.23, 100.30, 107.31, 125.74, 128.04, 129.85, 131.80, 133.59,
35.23, 136.16, 136.27, 136.32, 136.75, 139.70, 141.63, 141.70,
41.79, 141.94, 142.02, 142.09, 142.17, 142.21, 142.53, 142.57,
H), 6.97(s, 1 H), 6.99 (s, 1 H). 1 C NMR (50 MHz, CDCl
3
142.62, 142.99, 144.38, 144.57, 145.13, 145.32, 145.62, 145.96,
3
):
1
1
8
46.05, 146.08, 146.13, 146.20, 146.56, 146.71, 147.31, 153.27,
53.65, 153.97, 156.70, 160.56. C99 62BrNO ·H O (1395.5): C
5.21, H 4.62, N 1.00; found C 85.22, H 4.87, N 0.95. FAB-MS:
2.71, 26.14, 29.36, 29.49, 29.65, 29.71, 31.93, 57.11, 66.50, 68.19,
8.91, 76.57, 100.19, 106.94, 127.24, 127.96, 128.00, 128.13, 129.92,
30.21, 130.51, 134.13, 134.96, 135.76, 136.24, 136.97, 139.29,
39.46, 140.00, 140.04, 140.48, 141.04, 141.58, 141.62, 141.74,
41.79, 141.92, 142.01, 142.05, 142.19, 142.22, 142.49, 142.53,
42.57, 142.61, 142.84, 143.07, 144.09, 144.25, 144.33, 144.50,
44.58, 145.08, 145.21, 14537, 145.40, 145.45, 145.67, 145.89,
45.92, 146.00, 146.04, 146.08, 146.20, 146.23, 146.48, 146.87,
H
2
2
+
calcd. for C99
Compound 5j: As described for 5a, with 4j (101 mg, 0.555 mmol),
60 (400 mg, 0.555 mmol) and 3 (590 mg, 1.11 mmol) in o-dichloro-
benzene (100 mL). Column chromatography (SiO , CH Cl /hex-
ane, 1:9) yielded 5j (380 mg, 50%) as a brown glassy product. UV/
2
H63BrNO 1378.49; found 1378.7 [MH ].
C
2
2
2
47.22, 147.25. C101
.02; found C 88.14, H 5.38, N 0.98. FAB-MS: calcd. for
H67NO
2
·2H
2
O (1362.7): C 88.11, H 5.20, N
1
Vis (CH
NMR (400 MHz, C
3
9
4
7
2
Cl
2
): 256 (108500), 308 (37100), 431 (3600), 704 (250). H
Cl ): 0.89 (t, J = 7 Hz, 6 H), 1.18–1.53 (m,
6 H), 1.83 (m, 4 H), 3.53 (d, J = 13.5 Hz, 1 H), 4.00 (d, J =
2
D
2
4
+
C
101
H67NO
2
1340.68; found 1340.1 [M ].
.5 Hz, 1 H), 4.05(d, J = 7 Hz, 4 H), 4.66 (d, J = 13.5 Hz, 1 H),
.86 (d, J = 9.5 Hz, 1 H), 5.55 (s, 1 H), 6.49 (s, 1 H), 6.93 (s, 2 H),
.25–7.45 (m, 7 H), 7.54 (t, J = 7 Hz, 1 H), 8.41 (d, J = 8 Hz, 1
Compound 5g: As described for 5a, with 4g (74 mg, 0.555 mmol),
C
60 (400 mg, 0.555 mmol) and 3 (590 mg, 1.11 mmol) in o-dichloro-
benzene (100 mL). Column chromatography (SiO , CH Cl /hex-
ane, 1:9) yielded 5g (270 mg, 37%) as a brown glassy product. UV/
2
2
2
1
3
H). C NMR (50 MHz, CDCl
3
): 14.15, 22.71, 26.14, 26.36, 29.49,
1
29.65, 29.71, 30.03, 31.93, 51.11, 66.50, 68.19, 68.91, 76.57, 77.46,
Vis (CH
2
Cl
2
): 255 (147700), 305 (54400), 431 (5100), 704 (410). H
Cl ): 0.88 (t, J = 7 Hz, 6 H), 1.12–1.51 (m,
6 H), 1.83 (m, 4 H), 2.39 (s, 3 H), 2.53 (s, 3 H), 3.66 (d, J =
3.5 Hz, 1 H), 4.03 (t, J = 7 Hz, 4 H), 4.26 (d, J = 9.5 Hz, 1 H),
.41 (d, J = 13.5 Hz, 1 H), 4.93 (d, J = 9.5 Hz, 1 H), 5.49 (s, 1 H),
.49 (s, 1 H), 6.76 (s, 2 H), 7.05 (d, J = 8 Hz, 1 H), 7.14 (d, J = 8
1
1
1
1
1
00.19, 106.94, 127.24, 127.96, 128.00, 128.13, 129.92, 134.13,
34.96, 135.76, 136.24, 136.97, 139.29, 139.46, 140.00, 140.04,
40.48, 141.04, 141.58, 141.62, 141.74, 141.79, 141.92, 142.01,
42.05, 142.19, 142.22, 142.49, 142.53, 142.57, 142.61, 142.85,
43.07, 144.09, 144.25, 144.33, 144.50, 144.58, 145.08, 145.21,
NMR (400 MHz, C
2
D
2
4
3
1
4
6
13
145.37, 145.40, 145.45, 145.67, 145.89, 145.92, 146.00, 146.04,
Hz, 1 H), 8.03 (s, 1 H). C NMR (50 MHz, CDCl
3
): 14.15, 19.10,
1
1
46.08, 146.20, 146.23, 146.48, 146.87, 147.22, 147.25, 153.30,
53.55, 153.79, 156.86, 160.57. C105 ·H O (1392.7): C 90.55,
2
6
1
1
1
1
1
1
1
5
1.46, 22.71, 26.14, 29.36, 29.47, 29.65, 29.70, 31.93, 56.32, 66.27,
H
67NO
2
2
8.14, 69.02, 75.95, 76.54, 100.22, 107.48, 128.80, 130.33, 130.97,
34.27, 134.66, 135.47, 135.87, 135.95, 136.49, 136.59, 139.46,
39.65, 139.78, 140.05, 140.21, 141.52, 141.62, 141.84, 141.98,
42.01, 142.09, 142.14, 142.21, 142.33, 142.53, 142.56, 142.59,
42.62, 142.94, 143.12, 144.30, 144.38, 144.62, 145.14, 145.22,
45.26, 145.30, 145.37, 145.45, 145.49, 145.56, 145.73, 145.91,
46.07, 146.10, 146.15, 146.24, 146.42, 146.63, 147.28, 153.73,
H 5.00, N 1.01; found C 90.15, H 5.46, N 0.98. FAB-MS: calcd.
+
2
for C105H67NO 1374.69; found 1374.7 [M ].
Acknowledgments
This work was supported by the CNRS, the EU (RTN Contract
54.10, 154.16, 156.81, 160.46. C101
.09, N 1.06; found C 91.58, H 5.43, N 1.12. FAB-MS: calcd. for
2
H67NO (1326.6): C 91.44, H
“FAMOUS”, HPRN-CT-2002-00171) and a doctoral fellowship
from the EU to T. M. F. D. We further thank L. Oswald for techni-
cal help, R. Hueber for the mass spectra and M. Schmitt for high-
field NMR measurements.
+
C
101
H68NO
2
1327.65; found 1327.1 [MH ].
Compound 5h: As described for 5a, with 4h (92 mg, 0.555 mmol),
C
60 (400 mg, 0.555 mmol) and 3 (590 mg, 1.11 mmol) in o-dichloro-
benzene (100 mL). Column chromatography (SiO , CH Cl /tolu-
ene, 2:3) yielded 5h (410 mg, 54%) as a brown glassy product. UV/
2
2
2
[
1] W. Krätschmer, L. D. Lamb, K. Fostiropoulos, D. R. Huffman,
Nature 1990, 347, 354.
1
Vis (CH
NMR (400 MHz, CDCl
2 2
Cl ): 255 (141700), 320 (51400), 430 (4900), 704 (430). H [2] a) F. Wudl, Acc. Chem. Res. 1992, 25, 157–161; b) F. Diederich,
3
): 0.90 (t, J = 7 Hz, 6 H), 1.24–1.55 (m,
www.eurjoc.org
L. Isaacs, D. Philp, Chem. Soc. Rev. 1994, 23, 243–255; c) A. L.
Eur. J. Org. Chem. 2005, 3766–3774
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3773