Palladium-Catalyzed and Hybrid Acids-Assisted Synthesis of [60]Fulleroazepines in One Pot
Spectral data of compound (2o): Rf =0.5 (toluene);
1H NMR (300 MHz, CDCl3): d=7.33 (d, J=7.8 Hz, 1H),
7.42–7.79 (m, 7H), 7.92–7.94 (m, 3H), 8.51 (d, J=7.7 Hz,
142.5, 142.54, 142.6, 142.66, 142.7, 143.1, 144.2, 144.3, 144.5,
144.6, 144.8, 145.0, 145.02, 145.1, 145.2, 145.35, 145.4, 145.8,
145.9, 146.0, 146.02, 146.2, 146.4, 146.5, 147.7, 148.2, 150.0,
152.3, 154.0, 156.3; FT-IR (KBr): n=526, 667, 694, 730, 759,
1047, 1084, 1163, 1218, 1354, 1463, 1495, 1604, 2871, 2924,
2957, 3026 cmÀ1; HR-MS (APCIÀ): m/z=1105.1141, calcd.
for C84H19NO2S [MÀ]: 1105.1136.
1H); 13C NMR [150 MHz, CDCl3, with Cr
ACHTNUTRGNE(UNG acac)3 as relaxa-
tion reagent]: d=71.3, 88.8, 120.4 (q, J=257.3 Hz), 121.1,
121.6, 127.4, 129.0, 129.57, 129.6, 129.9, 132.3, 132.7, 132.74,
133.1, 135.9, 136.0, 138.9, 139.0, 139.2, 139.6, 139.7, 139.9,
140.0, 140.3, 141.1, 141.12, 141.2, 141.6, 142.1, 142.11, 142.2,
142.27, 142.3, 142.36, 142.4, 142.5, 142.52, 142.56, 142.6,
142.64, 142.7, 142.86, 142.9, 143.2, 144.1, 144.4, 144.5, 144.52,
144.7, 144.9, 145.2, 145.23, 145.26, 145.3, 145.32, 145.4, 145.5,
145.6, 145.8, 146.1, 146.15, 146.2, 146.22, 146.23, 146.3, 146.6,
146.64, 146.7, 147.9, 148.48, 149.05, 150.5, 151.4, 153.0; FT-
IR (KBr): n=527, 577, 757, 1056, 1091, 1167, 1214, 1253,
1359, 1484, 2855, 2925, 2958 cmÀ1; HR-MS (APCI+): m/z=
1112.0541, calcd. for C79H13F3NO3S [M+1]: 1112.0568.
Spectral data of compound (2p): Rf =0.69 (toluene);
1H NMR (300 MHz, CS2/CDCl3 =1:2): d=2.59 (s, 3H), 7.29
(d, J=8.2 Hz, 1H), 7.42 (dd, J=3.5, 8.1 Hz, 4H), 7.51 (t, J=
7.6 Hz, 2H), 7.87 (dd, J=2.5, 4.2 Hz, 2H), 7.91 (s, 1H), 8.34
(d, J=8.1 Hz, 1H); 13C NMR [150 MHz, CS2/CDCl3 =1:2,
Spectral data of compound (2s): Rf =0.66 (toluene);
1H NMR (300 MHz, CS2/CDCl3 =1:2): d=2.29 (s, 3H), 7.0
(d, J=8.1 Hz, 2H), 7.51–7.64 (m, 6H), 7.99 (d, J=2.3 Hz,
2H), 8.09 (d, J=9.1 Hz, 2H), 8.54 (d, J=8.8 Hz, 1H);
13C NMR [150 MHz, CS2/CDCl3 =1:2, with Cr
ACTHUNTRGNE(UGN acac)3 as re-
laxation reagent]: d=21.4, 70.8, 89.2, 125.3, 126.7, 126.8,
127.2, 127.4, 128.3, 129.1, 129.2, 130.1, 132.8, 133.2, 133.4,
133.7, 134.9, 135.3, 135.4, 135.6, 138.9, 139.0, 139.04, 139.2,
139.5, 139.8, 140.2, 140.4, 140.9, 141.1, 141.3, 141.7, 141.9,
142.1, 142.2, 142.3, 142.33, 142.4, 142.5, 142.6, 142.7, 142.8,
143.1, 143.2, 144.3, 144.35, 144.4, 144.6, 145.0, 145.1, 145.14,
145.2, 145.4, 145.5, 145.6, 145.8, 146.1, 146.13, 146.2, 146.4,
146.6, 146.64, 147.9, 148.3, 149.7, 151.9, 153.7, 156.1; FT-IR
(KBr): n=527, 573, 672, 757, 1046, 1086, 1164, 1216, 1356,
1595, 2857, 2927, 2962, 3019 cmÀ1; HR-MS (APCIÀ): m/z=
1125.0571, calcd. for C83H16ClNO2S [MÀ]: 1125.0590.
with CrACHTUNGTRENNUNG(acac)3 as relaxation reagent]: d=21.0, 70.9, 88.5,
120.3 (q, J=258.9 Hz), 120.7, 121.4, 127.3, 128.8, 129.5,
130.4, 132.2, 132.4, 132.5, 133.7, 135.8, 135.9, 138.5, 138.9,
139.0, 139.37, 139.4, 139.42, 139.5, 139.6, 139.8, 140.2, 140.9,
141.0, 141.5, 142.0, 142.02, 142.1, 142.2, 142.22, 142.3, 142.4,
142.5, 142.54, 142.76, 142.8, 143.1, 144.0, 144.3, 144.4, 144.41,
144.7, 144.8, 145.0, 145.05, 145.1, 145.2, 145.21, 145.3, 145.4,
145.5, 145.7, 146.0, 146.1, 146.13, 146.2, 146.4, 146.5, 147.7,
148.3, 149.0, 150.3, 151.5, 153.1, 156.7; FT-IR (KBr): n=527,
589, 755.6, 1054, 1091, 1168, 1217, 1253, 1358, 1493, 2919,
3026 cmÀ1; HR-MS (APCIÀ): m/z=1125.0700, calcd. for
C80H14F3NO3S [MÀ]: 1125.0646.
Spectral data of compound (2t): Rf =0.67 (toluene);
1H NMR (300 MHz, CS2/CDCl3 =1:2): d=2.31 (s, 3H), 7.01
(d, J=8.1 Hz, 2H), 7.38 (d, J=6.5 Hz, 1H), 7.56–7.67 (m,
5H), 7.86 (s, 1H), 7.97–8.1 (m, 3H), 8.52 (d, J=8.8 Hz,
1H); 13C NMR [150 MHz, CS2/CDCl3 =1:2, with Cr
ACHTUNGTRENNUNG(acac)3
as relaxation reagent]: d=21.4, 70.6, 89.0, 120.3 (q, J=
261.2 Hz), 121.2, 124.9, 125.8, 126.6, 127.0, 127.3, 128.2,
129.1, 130.1, 132.6, 132.9, 133.3, 133.5, 135.0, 135.3, 138.8,
138.9, 139.0, 139.2, 139.3, 139.6, 139.9, 140.6, 140.8, 140.9,
141.1, 141.3, 141.6, 141.7, 141.9, 141.92, 142.0, 142.1, 142.2,
142.4, 142.43, 142.5, 142.7, 142.72, 142.8, 142.9, 143.0, 144.17,
144.2, 144.23, 144.4, 144.9, 144.94, 144.98, 145.0, 145.01,
145.04, 145.1, 145.15, 145.2, 145.3, 145.4, 145.7, 145.9, 146.0,
146.02, 146.3, 146.4, 146.46, 146.5, 147.7, 148.1, 148.7, 149.4,
151.6, 153.4, 155.9; FT-IR (KBr): n=527, 573, 675, 756, 812,
920, 968, 1045, 1085, 1165, 1254, 1357, 1486, 1595, 2853,
2922, 2958 cmÀ1; HR-MS (APCIÀ): m/z=1175.0793, calcd.
for C84H16F3NO3S [MÀ]: 1175.0803.
Spectral data of compound (2q): Rf =0.5 (toluene);
1H NMR (300 MHz, CS2/CDCl3 =1:2): d=2.35 (s, 3H), 7.05
(d, J=8.0 Hz, 2H), 7.57–7.71 (m, 6H), 7.81 (td, J=1.4,
8.3 Hz, 1H), 8.01–8.13 (m, 4H), 8.58 (d, J=8.8 Hz, 1H);
13C NMR [150 MHz, CS2/CDCl3 =1:2, with Cr
ACTHUNTRGNE(UGN acac)3 as re-
laxation reagent]: d=21.4, 70.8, 88.9, 125.8, 126.4, 126.7,
126.8, 127.1, 128.1, 128.8, 128.9, 129.1, 129.5, 131.8, 133.0,
133.3, 133.6, 133.7, 135.2, 135.4, 136.9, 138.7, 138.8, 138.9,
139.0, 139.1, 139.3, 139.5, 139.6, 140.1, 140.8, 141.0, 141.2,
141.6, 141.9, 141.91, 142.1, 142.2, 142.3, 142.4, 142.5, 142.6,
142.7, 142.73, 143.1, 144.25, 144.3, 144.5, 144.6, 144.9, 145.0,
145.1, 145.17, 145.2, 145.21, 145.23, 145.4, 145.41, 145.8,
145.9, 146.0, 146.1, 146.3, 146.5, 146.53, 147.7, 148.2, 149.8,
152.1, 153.9, 156.3; FT-IR (KBr): n=526, 675, 755, 815,
1048, 1087, 1165, 1355, 1595, 2850, 2918 cmÀ1; HR-MS
(APCIÀ): m/z=1091.0955, calcd. for C83H17NO2S [MÀ]:
1091.0980.
Spectral data of compound (2u): Rf =0.72 (toluene);
1H NMR (300 MHz, CS2/CDCl3 =1:2): d=2.29 (s, 3H), 6.97
(d, J=8.2 Hz, 2H), 7.30 (d, J=8.6 Hz, 1H), 7.48 (d, J=
8.6 Hz, 1H), 7.56–7.64 (m, 4H), 7.93 (d, J=7.8 Hz, 1H), 8.0
(dd, J=1.8, 9.8 Hz, 2H), 8.04 (s, 1H), 8.76 (s, 1H);
13C NMR [150 MHz, CS2/CDCl3 =1:2, with Cr
ACTHUNTRGNE(UGN acac)3 as re-
laxation reagent]: d=21.4, 71.2, 87.4, 120.2 (q, J=258.0 Hz),
120.6, 121.0, 127.2, 127.4, 127.7, 128.2, 128.9, 129.2, 132.6,
132.97, 133.0, 133.3, 135.5, 135.8, 136.1, 138.8, 138.9, 139.0,
139.01, 139.5, 139.54, 139.7, 140.1, 140.8, 141.1, 141.2, 141.5,
141.9, 142.0, 142.1, 142.15, 142.18, 142.19, 142.2, 142.3, 142.4,
142.5, 142.7, 142.8, 143.0, 143.1, 144.0, 144.1, 144.2, 144.3,
144.4, 144.8, 145.0, 145.03, 145.1, 145.13, 145.17, 145.2,
145.24, 145.4, 145.41, 145.7, 145.96, 145.98, 146.0, 146.03,
146.05, 146.1, 146.4, 146.5, 146.53, 147.7, 148.2, 149.6, 150.2,
151.6, 152.9, 156.4; FT-IR (KBr): n=527, 675, 754, 1048,
Spectral data of compound (2r): Rf =0.58 (toluene);
1H NMR (300 MHz, CS2/CDCl3 =1:2): d=2.29 (s, 3H), 2.64
(s, 3H), 6.98 (d, J=8.2 Hz, 2H), 7.33 (d, J=8.2 Hz, 1H),
7.50 (d, J=8.3 Hz, 2H), 7.56 (d, J=7.8 Hz, 1H), 7.62 (d, J=
8.3 Hz, 2H), 7.79 (s, 1H), 7.95 (d, J=7.6 Hz, 1H), 8.03 (d,
J=8.9 Hz, 1H), 8.09 (d, J=8.2 Hz, 1H), 8.51 (d, J=8.7 Hz,
1H); 13C NMR [150 MHz, CS2/CDCl3 =1:2, with Cr
ACTHNUTRGNEN(UG acac)3
as relaxation reagent]: d=21.4, 21.7, 70.8, 88.9, 125.9, 126.4,
126.7, 126.8, 127.1, 128.0, 129.0, 129.4, 129.6, 131.6, 133.0,
133.4, 133.7, 134.0, 135.2, 135.4, 137.0, 138.4, 138.6, 138.7,
138.87, 138.9, 139.0, 139.3, 139.6, 140.1, 140.14, 140.8, 141.0,
141.2, 141.6, 141.8, 141.9, 142.1, 142.2, 142.3, 142.32, 142.34,
1090, 1166, 1215, 1253, 1356, 1489, 2850, 2919, 3030 cmÀ1
;
HR-MS (APCIÀ): m/z=1175.0800, calcd. for C84H16F3NO3S
[MÀ]: 1175.0803.
Spectral data of compound (2v): Rf =0.55 (toluene);
1H NMR (300 MHz, CDCl3): d=7.21–7.41 (m, 4H), 7.55 (d,
Adv. Synth. Catal. 0000, 000, 0 – 0
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