The Journal of Organic Chemistry
Note
Typical Procedure for the Reaction of C60 and 1a with
TEMPO (Scheme 5). A magnetic stirring bar, C60 solution in ODCB
(25 mM, 2 mL, 50 μmol), 1a (19.3 mg, 55 μmol), ODCB (4 mL),
and DMSO (0.67 mL) were placed in a Pyrex vial under Ar. Then,
Et3N (25.3 mg, 34.8 μL, 250 μmol) and TEMPO (0.0 to 200.0
mmol) were added. The solution was irradiated with a white LED (22
W) with violent stirring for 1.0 h. After diluting the reaction solution,
the yields were determined by HPLC.
cm−1; HRMS (MALDI-TOF) m/z calcd for C67H10O4 [M]+
878.0579, found 878.0582.
[5,6]Fullereno-C60-Ih-[1,9-b]benzofuran-4′(5′H)-one, 6′,7′-dihy-
dro-6′,6′-dimethyl (3).34 The compound was obtained using
ODCB as an eluent and silica gel column chromatography: 14.4
1
mg, 34%, dark brown powder; H NMR (CDCl3, 600 MHz) δ 3.01
(s, 2H), 2.64 (s, 2H), 1.45 (s, 6H); 13C{1H} NMR (CDCl3, 150
MHz) δ 193.9, 175.6, 148.3, 148.1, 147.2, 146.8, 146.5, 146.4, 146.1,
146.1, 145.6, 145.5, 145.3, 145.1, 144.8, 144.6, 144.1, 143.7, 142.9,
142.8, 142.7, 142.6, 142.5, 142.3, 142.2, 141.8, 141.4, 140.3, 139.8,
137.9, 135.1, 129.7, 128.6, 126.4, 112.6, 51.9, 38.5, 34.5, 28.9; IR
(KBr) 2956 cm−1, 2924 cm−1, 1655 cm−1, 1638 cm−1, 1489 cm−1,
1377 cm−1, 1237 cm−1, 1177 cm−1, 1063 cm−1, 903 cm−1, 853 cm−1,
753 cm−1; HRMS (MALDI-TOF) m/z calcd for C68H10O2 [M]+
858.0681, found 858.0686.
Spectrum Data. [6,6]-Phenyl-C61-Butyric Acid Methyl Ester:
PC61BM (2a).6 The compound was obtained using ODCB as an
eluent and silica gel column chromatography: 79.4 mg, 70%, dark
1
brown powder; H NMR (CDCl3, 600 MHz) δ 7.94−7.92 (m, 2H),
7.56−7.53 (m, 2H), 7.49−7.46 (m, 1H), 3.68 (s, 3H), 2.93−2.90 (m,
2H), 2.53 (t, J = 7.6 Hz, 2H), 2.21−2.17 (m, 2H); 13C{1H} NMR
(CDCl3, 150 MHz) δ 173.5, 148.8, 147.8, 145.8, 145.2, 145.2, 145.1,
145.0, 144.8, 144.7, 144.5, 144.4, 144.0, 143.8, 143.1, 143.0, 143.0,
142.9, 142.2, 142.2, 142.1, 142.1, 141.0, 140.7, 138.0, 137.6, 136.7,
132.1, 128.4, 128.2, 79.9, 51.8, 51.7, 33.9, 33.7, 22.4; IR (KBr) 3448
cm−1, 2941 cm−1, 1736 cm−1, 1428 cm−1, 1249 cm−1, 1186 cm−1,
1155 cm−1, 765 cm−1, 712 cm−1; HRMS (MALDI-TOF) m/z calcd
for C72H14O2 [M]+ 910.0994, found 910.0955.
Phenyl-C71-Butyric Acid Methyl Ester: PC71BM Contained
[5,6]Open Fulleroid (4′).6 The compound was obtained using
ODCB as an eluent and silica gel column chromatography: dark
brown powder; 1H NMR (CDCl3, 600 MHz) δ 7.94−7.91 (m,
0.86H), 7.79−7.77 (m, 0.37H), 7.57−7.49 (m, 1.6H), 7.45−7.40 (m,
1.01H), 7.23−7.19 (m, 0.67H), 7.03 (d, J = 7.2 Hz, 0.18H), 6.67−
6.66 (m, 00.12H), 3.74−3.51 (m, 3H), 2.52−2.43 (m, 3H), 2.20−
2.15 (m, 0.81H), 2.12−2.08 (m, 0.80H), 2.04−1.99 (m, 0.59H), 1.90
(t, J = 7.4 Hz, 0.15H), 1.81−1.78 (m, 0.36H); 13C{1H} NMR
(CDCl3, 150 MHz) δ 173.5, 173.4, 156.0, 155.3, 153.2, 152.1, 151.9,
151.5, 151.4, 151.2, 151.1, 150.9, 150.8, 150.6, 150.5, 150.0, 149.9,
149.7, 149.7, 149.5, 149.4, 149.4, 149.3, 149.2, 149.1, 148.8, 148.6,
148.5, 148.5, 148.4, 148.3, 148.2, 148.2, 148.0, 148.0, 147.9, 147.6,
147.5, 147.4, 147.4, 147.2, 147.0, 147.0, 146.8, 146.8, 146.5, 146.3,
146.3, 146.1, 145.9, 145.8, 145.6, 145.5, 145.3, 144.9, 144.8, 144.5,
144.4, 144.2, 144.1, 143.9, 143.9, 143.7, 143.6, 143.5, 143.3, 143.2,
143.1, 143.0, 142.9, 142.6, 142.6, 142.5, 141.8, 141.7, 141.6, 141.5,
141.4, 141.3, 140.9, 140.1, 139.7, 139.3, 138.9, 137.9, 137.3, 134.0,
133.8, 132.8, 132.5, 132.2, 131.8, 131.7, 131.6, 131.5, 131.2, 130.9,
130.8, 130.6, 130.6, 130.4, 128.9, 128.6, 128.5, 128.3, 128.2, 127.9,
127.8, 127.0, 71.9, 69.8, 65.6, 65.3, 51.8, 51.7, 51.5, 37.8, 37.4, 35.9,
35.2, 34.1, 33.8, 33.8, 33.5, 33.4, 22.1, 21.7, 21.6.
[6,6]-Phenyl-C61-Butyric Acid: PC61BA (2b).2b The compound was
obtained using ODCB/EtOAc (5:1) as an eluent and silica gel
column chromatography: 26.7 mg, 60%, dark brown powder; 1H
NMR (CDCl3/DMSO-d6, 600 MHz) δ 11.48 (br, 1H), 7.57 (d, J =
6.7 Hz, 2H), 7.18 (dd, J = 7.5, 5.6 Hz, 2H), 7.10 (dd, J = 8.4, 6.7 Hz,
1H), 2.56 (dd, J = 8.2, 5.4 Hz, 2H), 2.10 (dd, J = 7.3, 5.2 Hz, 2H),
1.79 (dd, J = 7.5, 4.4 Hz, 2H); 13C{1H} NMR (CDCl3/DMSO-d6,
150 MHz) δ 174.0, 148.1, 147.0, 145.0, 144.2, 144.2, 144.0, 143.8,
143.6, 143.5, 143.4, 143.0, 142.8, 142.1, 141.9, 141.3, 141.1, 139.9,
139.7, 137.1, 136.5, 135.8, 131.2, 127.5, 127.3, 79.1, 51.3, 39.7, 39.6,
39.5, 39.3, 39.2, 39.1, 38.9, 38.8, 33.1, 32.8, 21.5, −0.8 (TMS); IR
(KBr) 3454 cm−1, 2922 cm−1, 1717 cm−1, 1702 cm−1, 1541 cm−1,
1727 cm−1, 1298 cm−1, 1152 cm−1, 1023 cm−1, 818 cm−1; HRMS
(MALDI-TOF) m/z calcd for C71H11O2 [M − H]− 895.0759, found
895.0772.
[6,6]-3-Pyridyl-C61-Butyric Acid Methyl Ester: 3-PyC61BM (2c).
The compound was obtained using ODCB/EtOAc (10:1) as an
eluent and silica gel column chromatography: 20.8 mg, 46%, dark
[6,6]-Phenyl-C71-Butyric Acid Methyl Ester: PC71BM (4).6 The
compound was obtained using ODCB as an eluent and silica gel
column chromatography: 34.6 mg, 67%, dark brown powder; 1H
NMR (CDCl3, 600 MHz) δ 7.95−7.91 (m, 0.94H, br), 7.79−7.77 (m,
0.44H), 7.57−7.49 (m, 1.75H), 7.46−7.37 (m, 1.07H), 7.24−7.18
(m, 0.75H), 3.74 (s, 0.72H, β-type), 3.68 (s, 1.64H, α-type), 3.51 (s,
0.65H, β-type), 2.53−2.41 (m, 3H), 2.22−2.14 (m, 1.02H), 2.13−
2.06 (m, 0.98H), 2.04−1.99 (m, 0.50H), 1.82−1.77 (m, 0.43H);
13C{1H} NMR (CDCl3, 150 MHz) δ 173.5, 173.4, 173.2, 156.0,
155.3, 153.2, 152.1, 151.9, 151.5, 151.4, 151.2, 151.1, 150.9, 150.8,
150.6, 150.5, 150.0, 149.9, 149.7, 149.7, 149.4, 149.3, 149.2, 149.1,
148.8, 148.6, 148.6, 148.5, 148.5, 148.4, 148.3, 148.2, 148.2, 148.1,
148.0, 148.0, 147.9, 147.6, 147.5, 147.4, 147.4, 147.2, 147.0, 147.0,
147.0, 146.8, 146.8, 146.5, 146.3, 146.3, 146.1, 145.9, 145.8, 145.6,
145.5, 145.3, 144.9, 144.8, 144.5, 144.4, 144.2, 144.1, 143.9, 143.9,
143.7, 143.6, 143.5, 143.3, 143.2, 143.1, 143.0, 142.9, 142.6, 142.6,
142.5, 141.7, 141.6, 141.5, 141.4, 141.3, 140.9, 140.1, 139.7, 139.3,
138.9, 137.9, 137.3, 134.0, 133.8, 132.8, 132.5, 132.2, 131.8, 131.7,
131.6, 131.5, 131.2, 130.9, 130.8, 130.6, 130.4, 128.5, 128.3, 128.2,
127.9, 127.8, 127.0, 71.9, 69.8, 65.6, 65.3, 51.8, 51.7, 51.6, 37.8, 37.4,
35.9, 35.2, 34.1, 33.8, 33.8, 33.5, 33.4, 22.1, 21.7, 21.6; IR (KBr) 2923
cm−1, 1736 cm−1, 1429 cm−1, 1155 cm−1, 1075 cm−1, 904 cm−1, 730
cm−1; HRMS (MALDI-TOF) m/z calcd for C82H14O2 [M]+
1030.0994, found 1030.0994.
1
brown powder; H NMR (CDCl3, 600 MHz) δ 9.23 (d, J = 2.4 Hz,
1H), 8.74 (dd, J = 4.8, 2.4 Hz, 1H), 8.28 (dt, J = 7.8, 2.4 Hz, 1H),
7.51 (dd, J = 7.8, 4.8 Hz, 1H), 3.69 (s, 3H), 2.94−2.91 (m, 2H), 2.55
(t, J = 7.4 Hz, 2H), 2.22−2.17 (m, 2H); 13C{1H} NMR (CDCl3, 150
MHz) δ 173.2, 152.9, 149.5, 147.8, 147.2, 145.6, 145.2, 145.2, 145.1,
144.9, 144.8, 144.7, 144.6, 144.5, 144.2, 143.8, 143.7, 143.1, 143.0,
143.0, 142.2, 142.1, 142.1, 142.1, 141.1, 140.9, 139.5, 138.2, 137.5,
132.9, 123.2, 78.5, 51.7, 48.6, 33.7, 33.3, 22.2; IR (KBr) 3454 cm−1
,
2947 cm−1, 1736 cm−1, 1431 cm−1, 1181 cm−1, 906 cm−1, 739 cm−1;
HRMS (MALDI-TOF) m/z calcd for C71H14NO2 [M + H]+
912.1019, found 912.1020.
3′H-Cyclopropa[1,9][5,6]fullerene-C60-Ih-3′-carboxylic acid, 3′-
Acetyl-, Methyl Ester (2d).19d The compound was obtained using
ODCB as an eluent and silica gel column chromatography: 18.3 mg,
1
44%, bark brown powder; H NMR (CDCl3, 600 MHz) δ 4.13 (s,
3H), 2.89 (s, 3H); 13C{1H} NMR (CDCl3, 150 MHz) δ 193.7, 164.5,
145.4, 145.3, 145.2, 145.2, 145.0, 144.8, 144.7, 144.6, 143.9, 143.8,
143.1, 143.1, 143.0, 143.0, 142.7, 142.2, 141.9, 141.9, 141.1, 141.0,
139.5, 138.0, 72.3, 59.0, 54.1, 28.9; IR (KBr) 2922 cm−1, 1752 cm−1,
1719 cm−1, 1429 cm−1, 1265 cm−1, 1232 cm−1, 1185 cm−1, 1097
cm−1, 813 cm−1, 754 cm−1; HRMS (MALDI-TOF) m/z calcd for
C65H6O3 [M]+ 834.0317, found 834.0298.
3′H-Cyclopropa[1,9][5,6]fullerene-C60-Ih-3′3′-dicarboxylic Acid,
3′3′-Dethyl Ester (2e).33 The compound was obtained using
ODCB as an eluent and silica gel column chromatography: 23.3
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
■
sı
1
mg, 59%, bark brown powder; H NMR (CDCl3, 600 MHz) δ 4.57
(q, J = 7.10 Hz, 4H), 1.49 (t, J = 7.10 Hz, 6H); 13C{1H} NMR
(CDCl3, 150 MHz) δ 163.6, 145.3, 145.2, 145.2, 144.9, 144.7, 144.6,
143.9, 143.1, 143.0, 143.0, 142.2, 141.9, 140.9, 139.0, 71.6, 63.4, 52.2,
14.2; IR (KBr) 3454 cm−1, 2979 cm−1, 2925 cm−1, 1745 cm−1, 1428
cm−1, 1365 cm−1, 1234 cm−1, 1095 cm−1, 1061 cm−1, 1020 cm−1, 703
Detailed information of light sources, photoirradiation
conditions, HPLC charts, and copies of 1H and 13C{1H}
8505
J. Org. Chem. 2021, 86, 8500−8507