Macrocyclane-Fused Pyrazolo[3,4-b]pyridine Derivatives
1-Methyl-3-phenyl-5-(p-tolyl)-6,7,8,9,10,11,12,13,14,15-decahydro-
3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4ao): White solid, m.p.
(s, 2 H, ArH), 3.93 (s, 3 H, OCH3), 3.88 (s, 6 H, OCH3), 3.18–3.14
(m, 2 H, CH2), 2.80 (s, 3 H, CH3), 2.84–2.81 (m, 1 H, CH2), 1.91–
1.84 (m, 2 H, CH2), 1.68–1.43 (m, 13 H, CH2), 1.40–1.33 (m, 2 H,
CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ = 160.0, 152.8, 149.2,
146.2, 141.8, 139.8, 137.8, 128.9, 127.7, 125.0, 120.6, 120.6, 115.6,
203–204 °C. IR (KBr): ν = 2922, 2900, 2866, 2845, 1597, 1578,
˜
1564, 1504, 1487, 1411, 1379, 1357, 1115, 812, 761, 692 cm–1. 1H
NMR (CDCl3, 400 MHz): δ = 8.30 (d, J = 7.6 Hz, 2 H, ArH),
7.43–7.39 (m, 4 H, ArH), 7.26 (s, 1 H, ArH), 7.24 (s, 1 H, ArH), 113.2, 106.4, 61.0, 56.3, 31.0, 30.4, 29.1, 28.3, 28.3, 27.8, 27.7, 27.1,
7.17 (t, J = 7.6 Hz, 1 H, ArH), 3.17–3.13 (m, 2 H, CH2), 2.82–2.79 22.6, 22.5, 15.5 ppm. HRMS (ESI): calcd. for C32H40N3O3
(m, 1 H, CH2), 2.79 (s, 3 H, CH3), 2.44 (s, 3 H, CH3), 1.92–1.82 514.3065; found 514.3060.
(m, 2 H, CH2), 1.76–1.72 (m, 2 H, CH2), 1.72–1.68 (m, 4 H, CH2),
1-Methyl-5-(4-nitrophenyl)-3-phenyl-6,7,8,9,10,11,12,13,14,15-
decahydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4at): Pale-yel-
1.64–1.38 (m, 7 H, CH2), 1.35–1.27 (m, 2 H, CH2) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 155.2, 144.1, 140.7, 136.5, 134.7, 134.2,
132.1, 123.6, 123.5, 123.4, 122.6, 119.6, 115.2, 112.7, 110.2, 25.1,
23.4, 23.1, 23.0, 22.6, 22.5, 21.8, 21.6, 17.4, 17.3, 16.1, 10.2 ppm.
HRMS (ESI): calcd. for C30H36N3 438.2904; found 438.2919.
low solid, m.p. 221–224 °C. IR (KBr): ν = 2928, 2857, 1599, 1578,
˜
1571, 1507, 1416, 1347, 1132, 864, 854, 753, 691 cm–1. 1H NMR
(CDCl3, 400 MHz): δ = 8.36 (d, J = 8.8 Hz, 2 H, ArH), 8.26 (d, J
= 8.8 Hz, 2 H, ArH), 7.71 (d, J = 8.8 Hz, 2 H, ArH), 7.45 (t, J =
5-(4-Methoxyphenyl)-1-methyl-3-phenyl-6,7,8,9,10,11,12,13,14,15- 8.0 Hz, 2 H, ArH), 7.23 (t, J = 7.2 Hz, 1 H, ArH), 3.22–3.18 (m,
decahydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4ap): White
2 H, CH2), 2.83 (s, 3 H, CH3), 2.81–2.78 (m, 1 H, CH2), 1.94–1.85
(m, 2 H, CH2), 1.72–1.63 (m, 4 H, CH2), 1.63–1.49 (m, 5 H, CH2),
1.48–1.44 (m, 2 H, CH2), 1.41–1.37 (m, 2 H, CH2), 1.35–1.30 (m,
solid, m.p. 212–217 °C. IR (KBr): ν = 2933, 2919, 2864, 2844, 1575,
˜
1
1519, 1506, 1411, 1380, 1291, 1251, 1175, 1032, 753, 688 cm–1. H
NMR (CDCl3, 400 MHz): δ = 8.30 (d, J = 7.6 Hz, 2 H, ArH), 7.46 2 H, CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ = 157.7, 149.1,
(d, J = 7.6 Hz, 2 H, ArH), 7.42 (t, J = 7.6 Hz, 2 H, ArH), 7.18 (t, 148.8, 147.4, 146.8, 141.9, 139.6, 130.0, 128.9, 127.3, 125.2, 123.4,
J = 6.8 Hz, 1 H, ArH), 6.98 (d, J = 7.2 Hz, 2 H, ArH), 3.89 (s, 3 120.5, 116.1, 31.0, 30.4, 28.8, 28.2, 28.1, 27.7, 27.7, 27.0, 26.6, 22.4,
H, OCH3), 3.18–3.13 (m, 1 H, CH2), 2.86–2.81 (m, 1 H, CH2), 2.79 15.5 ppm. HRMS (ESI): calcd. for C29H33N4O2 469.2599; found
(s, 3 H, CH3), 1.90–1.83 (m, 1 H, CH2), 1.67–1.61 (m, 4 H, CH2), 469.2600.
1.60–1.56 (m, 5 H, CH2), 1.55–1.48 (m, 3 H, CH2), 1.47–1.38 (m,
1-Methyl-3-phenyl-5-(2-thienyl)-6,7,8,9,10,11,12,13,14,15-deca-
3 H, CH2), 1.34–1.29 (m, 2 H, CH2) ppm. 13C NMR (CDCl3,
hydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4au): White solid,
100 MHz): δ = 159.2, 145.9, 141.8, 139.9, 134.9, 130.1, 128.9, 27.9,
m.p. 180–181 °C. IR (KBr): ν = 2921, 2861, 2842, 1575, 1505, 1409,
˜
126.7, 124.8, 120.5, 115.4, 113.4, 55.3, 31.0, 30.4, 28.6, 28.3, 28.2,
27.8, 27.7, 27.0, 26.8, 22.6, 15.5 ppm. HRMS (ESI): calcd. for
C30H36N3O 454.2853; found 454.2833.
1
1380, 1231, 1130, 905, 852, 751, 705, 691 cm–1. H NMR (CDCl3,
400 MHz): δ = 8.38–8.36 (m, 2 H, ArH), 7.50–7.48 (m, 3 H, ArH),
7.46–7.44 (m, 2 H, thienyl-H), 7.24–7.20 (m, 1 H, ArH), 7.14–7.11
(m, 1 H, thienyl-H), 3.16–3.12 (m, 2 H, CH2), 3.10–3.05 (m, 2 H,
CH2), 2.77 (s, 3 H, CH3), 1.85–1.84 (m, 2 H, CH2), 1.75–1.68 (m,
2 H, CH2), 1.69–1.62 (m, 4 H, CH2), 1.61–1.63 (m, 2 H, CH2),
1.57–1.50 (m, 6 H, CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ =
5-(4-Bromophenyl)-1-methyl-3-phenyl-6,7,8,9,10,11,12,13,14,15-
decahydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4aq): White
solid, m.p. 218–220 °C. IR (KBr): ν = 2929, 2864, 2849, 1594, 1576,
˜
1
1506, 1415, 1382, 1352, 1124, 1012, 752, 689, 619 cm–1. H NMR
(CDCl3, 400 MHz): δ = 8.26 (d, J = 7.6 Hz, 2 H, ArH), 7.59 (d, J 151.9, 149.0, 146.6, 145.8, 141.9, 139.8, 128.9, 127.6, 127.5, 127.2,
= 8.0 Hz, 2 H, ArH), 7.44–7.38 (m, 4 H, ArH), 7.19 (t, J = 7.6 Hz, 126.7, 124.9, 120.2, 115.6, 113.2, 30.1, 28.4, 28.2, 28.2, 27.8, 27.5,
1 H, ArH), 3.18–3.14 (m, 2 H, CH2), 2.79 (s, 3 H, CH3), 2.79–2.76 27.4, 26.8, 22.5, 22.4, 15.4 ppm. HRMS (ESI): calcd. for C27H32N3
(m, 1 H, CH2), 1.90–1.82 (m, 2 H, CH2), 1.74–1.61 (m, 6 H, CH2), 430.2312; found 430.2293.
1.57–1.29 (m, 9 H, CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ =
5-(2,3-Dimethoxyphenyl)-1-methyl-3-phenyl-6,7,8,9,10,11,12,13,
159.0, 156.7, 149.2, 146.3, 141.8, 141.3, 139.8, 131.2, 130.6, 128.9,
14,15-decahydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4av):
127.6, 125.0, 122.0, 120.5, 115.7, 31.0, 30.4, 28.7, 28.3, 28.2, 27.8,
White solid, m.p. 180–181 °C. IR (KBr): ν = 2929, 2860, 2843,
˜
27.7, 27.0, 26.7, 22.5, 22.5, 15.5 ppm. HRMS (ESI): calcd. for
C29H33BrN3 502.1853; found 502.1828.
1568, 1507, 1475, 1412, 1380, 1360, 1265, 1227, 1126, 1074, 1054,
1
1011, 748, 689 cm–1. H NMR (CDCl3, 400 MHz): δ = 8.32–8.30
5-(2-Chlorophenyl)-1-methyl-3-phenyl-6,7,8,9,10,11,12,13,14,15-
decahydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4ar): White
(m, 2 H, ArH), 7.42–7.38 (m, 2 H, ArH), 7.18–7.12 (m, 2 H, ArH),
7.01–6.99 (m, 1 H, ArH), 6.91–6.89 (m, 1 H, ArH), 3.94 (s, 3 H,
OCH3), 3.64 (s, 3 H, OCH3), 3.24–3.07 (m, 2 H, CH2), 2.80 (s, 3
H, CH3), 2.77–2.73 (m, 1 H, CH2), 2.64–2.54 (m, 1 H, CH2), 1.90–
1.82 (m, 2 H, CH2), 1.67–1.37 (m, 12 H, CH2), 1.27–1.25 (m, 2 H,
CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ = 157.9, 152.7, 149.4,
146.4, 145.4, 141.8, 140.0, 136.9, 129.0, 128.8, 124.8, 123.6, 122.6,
120.4, 115.8, 111.9, 61.4, 55.8, 30.4, 28.5, 28.4, 28.2, 27.8, 27.8,
27.2, 26.8, 22.4, 22.3, 15.5 ppm. HRMS (ESI): calcd. for
C31H38N3O2 484.2959; found 484.2958.
solid, m.p. 183–184 °C. IR (KBr): ν = 2921, 2844, 1598, 1576, 1567,
˜
1505, 1411, 1353, 1136, 1118, 757, 691 cm–1. 1H NMR (CDCl3,
400 MHz): δ = 8.25 (d, J = 8.0 Hz, 2 H, ArH), 7.49–7.47 (m, 1 H,
ArH), 7.43–7.37 (m, 5 H, ArH), 7.19–7.16 (t, J = 7.2 Hz, 1 H,
ArH), 3.26–3.17 (m, 1 H, CH2), 3.16–3.08 (m, 1 H, CH2), 2.80 (s,
3 H, CH3), 2.53–2.45 (m, 1 H, CH2), 1.98–1.78 (m, 2 H, CH2),
1.72–1.57 (m, 5 H, CH2), 1.51–1.36 (m, 8 H, CH2), 1.30–1.22 (m,
2 H, CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ = 157.8, 149.2,
148.0, 146.0, 141.8, 140.6, 139.7, 133.0, 130.9, 129.4, 129.1, 128.9,
128.4, 126.4, 125.1, 120.7, 116.0, 31.0, 30.4, 28.5, 28.4, 28.1, 27.8,
27.2, 26.7, 22.4, 22.2, 15.4 ppm. HRMS (ESI): calcd. for
C29H33ClN3 458.2358; found 458.2355.
5-(4-Chlorophenyl)-1-methyl-3-phenyl-6,7,8,9,10,11,12,13,14,15-
decahydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4aw): White
solid, m.p. 225–226 °C. IR (KBr): ν = 2929, 2859, 1598, 1566, 1505,
˜
1414, 1381, 1353, 1130, 1116, 747, 687, 619 cm–1 1H NMR
.
1-Methyl-3-phenyl-5-(3,4,5-trimethoxyphenyl)-6,7,8,9,10,11,12,13, (CDCl3, 400 MHz): δ = 8.27 (d, J = 8.0 Hz, 2 H, ArH), 7.47–7.40
14,15-decahydro-3H-cyclododeca[d]pyrazolo[3,4-b]pyridine (4as):
White solid, m.p. 205–208 °C. IR (KBr): ν = 2929, 2860, 2842,
(m, 6 H, ArH), 7.19 (t, J = 7.2 Hz, 1 H, ArH), 3.18–3.14 (m, 2 H,
CH2), 2.79 (s, 3 H, CH3), 2.79–2.76 (m, 1 H, CH2), 1.90–1.82 (m,
˜
1583, 1507, 1412, 1379, 1238, 1170, 1130, 1001, 826, 750, 691 cm–1. 2 H, CH2), 1.68–1.58 (m, 6 H, CH2), 1.53–1.37 (m, 7 H, CH2),
1H NMR (CDCl3, 400 MHz): δ = 8.30 (d, J = 8.0 Hz, 2 H, ArH),
1.33–1.28 (m, 2 H, CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ =
7.43 (t, J = 8.0 Hz, 2 H, ArH), 7.19 (t, J = 7.6 Hz, 1 H, ArH), 6.73 159.0, 149.3, 146.3, 141.8, 140.8, 139.8, 133.7, 130.3, 128.9, 128.2,
Eur. J. Org. Chem. 2011, 3026–3035
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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