E. Polo, L. Prent-Peñaloza, Y.A.R. Núñez et al.
Journal of Molecular Structure 1224 (2021) 129307
161.4 (C); HRMS (ESI, m/z): Calcd for C13H14 FN2 [M+H]+ 217.1141
Yield 47%; brown solid; mp 124-126; 1H NMR (400 MHz,
CDCl3): δH = 1.85 (m, 4H), 2.62 (t, J = 6.0 Hz, 2H), 2.79 (t, J = 6.0
Hz, 2H), 6.80 (m, 2H), 7.14 (dd, J = 7.0, 2.7 Hz, 2H), 7.27 (m, 3H),
7.39 (m, 1H); 13C NMR (100 MHz, CDCl3): δC = 21.5 (CH2), 23.2
(CH2), 23.4 (CH2), 23.5 (CH2), 104.8 (CH, JC-F = 25 Hz), 111.8 (CH,
JC-F = 25 Hz), 115.9 (C), 125.1 (C, JC-F = 24.0 Hz), 127.9 (CH), 128.4
(4 x CH), 129.8 (CH, JC-F = 20.0 Hz), 140.3 (C), 151.1 (C), 154.4 (C,
JC-F = 21.0 Hz), 159.4 (C, JC-F = 24.0 Hz), 164.5 (C, JC-F = 21.0 Hz);
HRMS (ESI, m/z): Calcd for C19 H17 F2N2 [M+H]+ 311.1360 found
311.1335.
found 217.1137.
3q.
2-(2,4-difluorophenyl)-3-methyl-2,4,5,6-tetrahydro
cy-
clopenta[c]pyrazole.
Yield 98%; brown oil; IR (KBr, cm−1): 2964, 2862, 1523,
1270, 1110, 963, 837, 736, 605, 596; 1H NMR (400 MHz, CDCl3):
δH = 2.51 (s, 3H), 2.79-289 (m, 4H), 2.98-3.02 (m, 2H), 7.17-7.23
(m, 2H), 7.80-7.86 (m, 1H); 13C NMR (100 MHz, CDCl3): δC = 12.6
(CH3), 22.7 (CH2), 25.2 (CH2), 30.8 (CH2), 104.7 (CH, JC-F = 25.0
Hz), 111.7 (CH, JC-F = 21.5 Hz), 127.2 (CH, JC-F = 9.5 Hz), 144.8 (C),
151.9 (C), 153.4 (C, JC-F = 11.0 Hz), 155.9 (C, JC-F = 13.0 Hz), 159.7
(C, JC-F = 11.0 Hz), 162.2 (C, JC-F = 11.0 Hz); HRMS (ESI, m/z): Calcd
for C13H12F2N2 [M]+ 234.0969 found 234.0964
3y.
2-(naphthalen-1-yl)-3-phenyl-4,5,6,7-tetrahydro-2H-
indazole.
Yield 47%; brown solid; mp, IR (KBr, cm−1): 1H NMR (400 MHz,
CDCl3): δH = 1.97-2.06 (m, 4H), 2.82 (s, 2H), 2.97 (t, J = 6.2 Hz,
2H), 7.16-7.23 (m, 5H), 7.33-7.36 (m, 1H), 7.45 (t, J = 8.0 Hz, 1H),
7.54-7.58 (m, 2H), 7.83-7.86 (m, 1H), 7.91-7.97 (m, 2H); 13C NMR
(100 MHz, CDCl3): δC = 21.8 (CH2) 23.3 (CH2) 23.6 (2 x CH2), 115.3
(C), 123.7 (CH), 124.9 (CH), 125.5 (CH), 126.3 (CH), 126.9 (CH),
127.4 (CH), 127.9 (CH), 128.1 (2 x CH), 128.4 (2 x CH), 128.5 (CH),
130.6 (C), 134.2 (C), 137.0 (C), 140.6 (C), 150.3 (C); HRMS (ESI, m/z):
Calcd for C23H21N2 [M+H]+ 325.1705 found 325.1729.
3r. 2,3-diphenyl-4,5,6,7-tetrahydro-2H-indazole [20–26].
Yield 79%; red crystal; mp 104-106°C; 1H NMR (400 MHz,
CDCl3): δH = 1.84 (m, 4H), 2.60 (t, J = 6.0 Hz, 2H), 2.83 (t, J = 6.0
Hz, 2H), 7.21 (m, 8H), 7.49 (m, 2H); 13C NMR (100 MHz, CDCl3):
δC = 21.5 (CH2), 23.3 (CH2), 23.5 (CH2), 23.6 (CH2), 116.8 (C), 124.7
(2 x CH), 126.5 (CH), 127.7 (CH), 128.4 (2 x CH), 128.7 (2 x CH),
129.2 (2 x CH), 130.8 (C), 138.4 (C), 140.4 (C), 150.3 (C); HRMS (ESI,
m/z): Calcd for C19 H20N2 [M+H]+ 275.1548 found 275.1547.
3s. 3-phenyl-4,5,6,7-tetrahydro-2H-indazole [20,27–29].
3z. 3-methyl-4,5-dihydro-1H-benzo[g]indazole [30–33].
Yield 92 %; white solid; mp 143-145; IR (KBr, cm−1): 3136,
3057, 2919, 2883, 2827, 2799 1608, 1568, 1508; 1H NMR (400 MHz,
DMSO): δH = 2.19 (s, 3H), 2.59 (t, J =7.3 Hz, 2H), 2.86 (t, J =7.3 Hz,
2H), 3.42 (bs, 1H), 7.15 (t, J =7.4 Hz, 1H), 7.23 (t, J =7.5 Hz, 2H),
7.67 (d, J =7.5 Hz, 1H), 12.44 (bs, 1H); HRMS (ESI, m/z): Calcd for
C12H13N [M+H]+ 185.1079 found 185.1093.
Yield 99%; brown solid;mp 213-215°C; 1H NMR (400 MHz,
CDCl3): δH = 1.78 -1.83 (m, 4H), 2.64 (t, J = 5.6 Hz, 2H), 2.71 (t,
J = 5.6 Hz, 2H), 7.28 (t, J = 7.3 Hz, 1H), 7.38 (t, J = 7.6 Hz, 2H)
7.63 (d, J = 7.6 Hz, 2H), 10.87 (bs, 1H); HRMS (ESI, m/z): Calcd for
C13H15N2 [M+H]+ 199,1235 found 199,1218.
3t. 4-(3-phenyl-4,5,6,7-tetrahydro-2H-indazol-2-yl)benzonitrile.
Yield 72%; white crystal; mp 130-132°C; IR (KBr, cm−1): 3050,
2937, 2842, 2226, 1603, 1514, 1369, 1155, 970, 839, 761, 700, 544;
1H NMR (400 MHz, CDCl3): δH = 1.76- 1.80 (m, 2H), 1.87-191 (m,
2H), 2.56 (t, J = 6.0 Hz, 2H), 2.80 (t, J = 6.0 Hz, 2H), 7.18 (m,
2H), 7.31-7.36 (m, 5H), 7.53 (d, J = 8.0 Hz, 1H), 7.70 (d, J = 8.0
Hz, 1H); 13C NMR (100 MHz, CDCl3): δC = 21.1 (CH2), 23.1 (CH2),
23.2 (CH2), 23.4 (CH2), 109.3 (C), 118.4 (C), 118.5 (C), 124.1 (2 x
CH), 128.3 (CH), 128.7 (2 x CH), 129.1 (2 x CH), 130.2 (C), 132.7 (2
x CH), 138.6 (C), 143.6 (C), 151.8 (C); HRMS (ESI, m/z): Calcd for
C20H18 N3 [M+H]+ 300.1501 found 300.1520.
3aa.1-(4-bromophenyl)-3-methyl-4,5-dihydro-1H-
benzo[g]indazole.
Yield 43%; orange solid; mp 121-123; IR (KBr, cm−1): 3037,
2907,2846, 1679, 1605, 1496,1066; 1H NMR (400 MHz, DMSO-d6):
δH = 2.19 (s, 3H), 2.58 (t, J =7.3 Hz, 2H), 2.91 (t, J =7.3 Hz, 2H),
6.74 (d, J =7.5 Hz, 1H), 7.05 (t, J =7.5 Hz, 1H), 7.15 (t, J =7.3 Hz,
1H), 7.33 (d, J =7.3Hz, 1H), 7.38 (d, J =8.0 Hz, 2H), 7.68 (d, J =8.0
Hz, 2H); 13C NMR (100 MHz, DMSO-d6): δC =11.1 (CH3), 18.2 (CH2),
29.5 (CH2), 118.5 (C), 120.1 (C), 121.9 (CH), 126.0 (C), 126.1 (CH),
126.7 (2 x CH), 127.1 (CH), 128.4 (CH), 131.9 (2 x CH), 136.5 (C),
137.1 (C), 139.4 (C), 145.5 (C).
3u.
2-(4-bromophenyl)-3-phenyl-4,5,6,7-tetrahydro-2H-
indazole.
3ab. 4-(3-methyl-4,5-dihydro-1H-benzo[g]indazol-1-yl)benzoic
Yield 92%; brown solid; mp 121-123°C; IR (KBr, cm−1): 1H NMR
(400 MHz, CDCl3): δH = 1.77 (m, 2H), 1.88 (m, 2H), 2.56 (t, J = 6.0
Hz, 2H), 2.79 (t, J = 6.0 Hz, 2H), 7.11 (m, 2H), 7.15 (dd, J = 7.6,
1.8, 2H), 7.30 (m, 2H), 7.36 (m, 2H); 13C NMR (100 MHz, CDCl3):
δC = 21.4 (CH2), 23.2 (CH2), 23.4 (CH2), 23.5 (CH2), 117.3 (C), 119.9
(C), 126.0 (2 x CH), 128.0 (CH), 128.5 (2 x CH), 129.2 (2 x CH),
130.5 (C), 131.8 (2 x CH), 138.4 (C), 139.4 (C), 150.7 (C); HRMS (ESI,
m/z): Calcd for C19 H19 BrN2 [M+H]+ 353.0653 found 353.0666.
3v. 2-(4-chlorophenyl)-3-phenyl-4,5,6,7-tetrahydro-2H-indazole
acid.
Yield 43%; orange solid; mp 258-260; IR (KBr, cm−1): 3453,
3214, 2935, 2891, 2835, 2640, 1701, 1646, 1607; 1H NMR (400 MHz,
DMSO-d6): δH = 2.21 (s, 3H), 2.59 (t, J =7.3 Hz, 2H), 2.93 (t, J =7.3
Hz, 2H), 6.77 (d, J =7.5 Hz, 1H), 7.05 (t, J =7.4 Hz, 1H), 7.17 (t, J
=7.3 Hz, 1H), 7.35 (d, J =7.5 Hz, 1H), 7.55 (d, J =8.0 Hz, 2H), 8.04
(d, J =8.0 Hz, 2H), 12.07 (bs, 1H); 13C NMR (100 MHz, DMSO-d6):
δC = 11.5 (CH3), 18.7 (CH2), 29.9 (CH2), 119.7 (C), 122.6 (CH), 124.7
(2 x CH), 126.5 (CH), 127.6 (CH), 128.8 (CH), 129.7 (C), 130.6 (2 x
CH), 137.0 (C), 137.6 (C), 143.8 (C), 146.4 (C), 166.8 (C), 201.2 (C);
HRMS (ESI, m/z): Calcd for C19 H17 N2O2 [M+H]+ 305.1290 found
305.1275
Yield 98%; white solid; mp 94-96; 1H NMR (400 MHz, CDCl3):
δH = 1.84 (m, 4H), 2.59 (bs, 2H), 2.81 (bs, 2H), 7.22 (m, 6H), 7.32
(m, 3H)
3ac.
1-(4-chlorophenyl)-3-methyl-4,5-dihydro-1H-
3w.
2-(4-fluorophenyl)-3-phenyl-4,5,6,7-tetrahydro-2H-
benzo[g]indazole.
Yield 65%; yellow solid; mp 139-141; IR (KBr, cm−1): 3040,
2957, 2921, 2846 1600, 1543, 1498, 1089; 1H NMR (400 MHz,
DMSO-d6): δH = 2.19 (s, 3H), 2.59 (t, J =7.3 Hz, 2H), 2.93 (t, J =7.3
Hz, 2H), 6.73 (d, J =7.7 Hz, 1H), 7.06 (t, J =7.7 Hz, 1H), 7.16 (t, J
=7.5 Hz, 1H), 7.34 (d, J =7.5 Hz, 1H), 7.45 (d, J =8.0 Hz, 2H), 7.56
(d, J =8.0 Hz, 2H); 13C NMR (100 MHz, DMSO-d6): δC = 11.3 (CH3),
18.5 (CH2), 29.7 (CH2), 118.7 (C), 122.1 (CH), 126.3 (CH),126.8 (CH),
127.4 (2 x CH), 128.7 (CH), 129.2 (2 x CH), 132.1 (C), 136.8 (C), 137.4
(C), 139.3 (C), 145.7 (C).
indazole.
Yield 90%; brown crystal; mp 84-86°C; IR (KBr, cm−1): 3050,
2940, 15,17, 1363, 1210, 1166, 964, 845, 741, 588; 1H NMR (400
MHz, CDCl3): δH = 1.77 (m, 2H), 1.91 (m, 2H), 2.64 (t, J = 6.0 Hz,
2H), 2.85 (t, J = 6.0 Hz, 2H), 7.20 (m, 2H), 7.25 (d, J = 7.6, 2H), 7.37
(m, 2H), 7.42 (m, 2H); 13C NMR (100 MHz, CDCl3): δC =21.4 (CH2),
23.3 (CH2), 23.5 (2 x CH2), 115.5 (CH), 115.7 (CH), 116.8 (C), 126.4
(CH), 126.5 (CH), 127.8 (CH), 128.4 (2 x CH), 129.2 (2 x CH), 130.6
(C), 136.6 (C), 138.5 (C), 150.4 (C), 161.1 (C).
3x.
2-(2,4-difluorophenyl)-3-phenyl-4,5,6,7-tetrahydro-2H-
4