538 JOURNAL OF CHEMICAL RESEARCH 2016
Preparation of indazole derivatives (3, 4); general procedure
128.96, 130.51, 131.24, 131.32, 132.81, 137.84, 146.72, 153.40, 161.03,
163.47.
In a test tube, a mixture of 2,6-bisbenzylidenecyclohexanone (1 mmol)
and phenyl hydrazine (3 mmol) in PEG-400 (2 mL) was stirred at 110
°C for 4 h. After completion of the reaction (monitored by TLC), the
reaction mixture was poured onto water to afford gum-like solids. The
gum was converted to powder by rubbing the gum vigorously with a
few drops of ethanol. Then, the obtained powder was recrystallised
by hot EtOH or CH2Cl2 for further purification. It should be noted that
hexahydroindazoles (3) precipitate as the first product and should be
collected immediately.
(7E)-7-benzylidene-3,3a,4,5,6,7-hexahydro-2,3-diphenyl-2H-
indazole (3a): Green crystals; m.p. 131–134 °C (lit.22 161–163 °C);
FTIR (KBr) (νmax cm−1): 1596.95 (C=N), 1496.66 (C=C), 1056.92
(C–N); 1H NMR (300 MHz, CDCl3-d): δ 1.46 (m, 1H), 1.69 (m,
1H), 1.94 (m, 1H), 2.21 (m, 1H), 2.43 (m, 1H), 3.01 (m, 2H), 4.60 (d,
J = 12.30 Hz, 1H), 6.83 (t, J = 7.17 Hz, 1H), 7.05–7.43 (m, 15H, ArH);
13C NMR (75 MHz, CDCl3-d): δ 24.44, 28.86, 29.36, 57.19, 73.92,
114.83, 120.01, 126.02, 126.43, 127.12, 127.58, 128.18, 128.71, 129.16,
129.65, 130.81, 136.72, 142.18, 146.82, 153.59.
(7E)-7-benzylidene-1,3-diphenyl-4,5,6,7-tetrahydro-1H-indazole
(4a): White powder; m.p. 174–177 °C (lit.22 175–177 °C); FTIR
(KBr) (νmax cm−1): 1596.95 (C=N), 1496.66 (C=C), 1072.35 (C–N);
1H NMR (300 MHz, CDCl3-d): δ 1.91 (quin, J = 6.16 Hz, 2H), 2.80
(t, J = 6.02 Hz, 2H), 2.93 (t, J = 6.02 Hz, 2H), 6.18 (s, 1H), 7.09–7.81
(m, 15H, ArH); 13C NMR (75 MHz, CDCl3-d): δ 22.88, 24.94, 27.64,
117.98, 125.70, 126.53, 126.62, 127.16, 127.50, 128.06, 128.20, 128.37,
128.43, 129.06, 129.28, 133.55, 136.99, 139.17, 141.63, 148.79.
(E)-7-(4-fluorobenzylidene)-3-(4-fluorophenyl)-1-phenyl-4,5,6,7-
tetrahydro-1H-indazole (4d): White powder; m.p. 213–216 °C; FTIR
(KBr) (νmax cm−1): 1596.95 (C=N), 1496.66 (C=C), 1157.21 (C–N),
1218.93 (C–F); 1H NMR (400 MHz, CDCl3-d): δ 1.94 (m, 2H),
2.76 (m, 2H), 2.91 (m, 2H), 6.12 (m, 1H), 6.97–8.14 (m, 13H, ArH);
13C NMR (100 MHz, CDCl3-d): δ 22.92, 25.00, 27.71, 113.14, 114.48,
115.00, 117.59, 118.24, 119.05, 120.48, 121.11, 121.48, 121.86, 122.01,
122.10, 123.86, 129.75, 133.45, 134.90, 141.87, 149.13, 162.24, 162.45.
Anal. calcd for C26H20F2N2 (398.45): C, 78.37; H, 5.06; N, 7.03; found:
C, 77.96; H, 5.19; N, 7.25%.
(E)-7- (2-chlorobenzylidene)-3- (2-chlorophenyl)-2-phenyl-
3,3a,4,5,6,7-hexahydro-2H-indazole (3e): Green crystals; m.p.
154–157 °C; FTIR (KBr) (νmax cm−1): 1596.95 (C=N), 1496.66 (C=C),
1033.77 (C–N), 1118.64 (C–Cl); 1H NMR (400 MHz, CDCl3-d): δ 1.49
(m, 1H), 1.79 (m, 1H), 1.92 (m, 1H), 2.39 (m, 2H), 2.83 (m, 1H), 3.07
(m, 1H), 5.29 (d, J = 12.4 Hz, 1H), 6.83 (t, J = 7.2 Hz, 1H), 6.97–7.62
(m, 13H, ArH); 13C NMR (100 MHz, CDCl3-d): δ 24.63, 29.11, 30.24,
57.43, 69.08, 114.42, 120.10, 123.20, 126.14, 127.96, 128.14, 128.48,
128.64, 128.86, 129.55, 129.75, 130.90, 132.17, 132.59, 134.58, 134.87,
139.51, 146.07, 152.45.
We thank the Department of Chemistry of Semnan University
for supporting this work.
Electronic Supplementary Information
(E)-7-(4-methylbenzylidene)-2-phenyl-3-(p-tolyl)-3,3a,4,5,6,7-
hexahydro-2H-indazole (3b): Yellow crystals; m.p. 176–179 °C; FTIR
(KBr) (νmax cm−1): 1596.95 (C=N), 1496.66 (C=C), 1026.06 (C–N),
The spectral data for the compounds and crystal information
are available in the ESI through:
stl.publisher.ingentaconnect.com/content/stl/jcr/supp-data
1
3031.89 (C–H); H NMR (300 MHz, CDCl3-d): δ 1.44 (m, 1H), 1.68
(m, 1H), 1.93 (m, 1H), 2.20 (m, 1H), 2.24 (s, 3H), 2.26 (s, 3H), 2.42
(m, 1H), 3.01 (m, 2H), 4.57 (d, J = 12.14 Hz, 1H), 6.84 (t, J = 7.10 Hz,
1H), 6.92–7.40 (m, 13H, ArH); 13C NMR (75 MHz, CDCl3-d): δ 21.40,
21.46, 24.42, 28.84, 29.25, 57.18, 73.65, 116.32, 117.00, 117.64, 122.79,
127.83, 129.04, 129.30, 130.14, 132.37, 133.44, 134.18, 139.73, 140.14,
146.18, 147.90, 151.61. Anal. calcd for C28H28N2 (392.54): C, 85.67; H,
7.19; N, 7.14; found: C, 85.89; H, 6.78; N, 7.33%.
Received 17 March 2016; accepted 11 July 2016
Published online: 26 August 2016
References
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(E)-7- (4-methylbenzylidene)-1-phenyl-3- (p-tolyl)-4,5,6,7-
tetrahydro-1H-indazole (4b): White powder; m.p. 196–198 °C; FTIR
(KBr) (νmax cm−1): 1596.95 (C=N), 1496.66 (C=C), 1157.21 (C–N),
3055.03 (C–H); 1H NMR (300 MHz, CDCl3-d): δ 1.90 (quin, J = 6.0 Hz,
2H), 2.32 (s, 3H), 2.39 (s, 3H), 2.79 (t, J = 5.5 Hz, 2H), 2.91 (t, J = 6.2 Hz,
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C28H26N2 (390.52): C, 86.12; H, 6.71; N, 7.17; found: C, 86.00; H, 6.80;
N, 7.20%.
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(E)-7-(4-methoxybenzylidene)-3-(4-methoxyphenyl)-2-phenyl-
3,3a,4,5,6,7-hexahydro-2H-indazole (3c): Green crystals; m.p.
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(C=N), 1504.37 (C=C), 1033.77 (C–N), 1242.07/1180.35 (C–O);
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1H), 2.17 (m, 1H), 2.41 (m, 1H), 2.98 (m, 2H), 3.81 (s, 3H), 3.83 (s,
3H), 4.53 (d, J = 12.32 Hz, 1H), 6.81 (t, J = 7.10 Hz, 1H), 6.90–7.37 (m,
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55.27, 57.17, 73.49, 113.62, 114.48, 114.92, 119.91, 126.00, 127.16,
128.65, 129.04, 129.45, 131.04, 134.18, 147.03, 153.91, 158.66, 158.99.
(E)-7- (4-fluorobenzylidene)-3- (4-fluorophenyl)-2-phenyl-
3,3a,4,5,6,7-hexahydro-2H-indazole (3d): Green crystals; m.p.
167–168 °C (lit.35 165.9–166.7 °C); FTIR (KBr) (νmax cm−1): 1596.95
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1
(C=N), 1496.66 (C=C), 1049.20 (C–N), 1226.64 (C–F); H NMR
(400 MHz, CDCl3-d): δ 1.48 (m, 1H), 1.67 (m, 1H), 1.96 (m, 1H),
2.20 (m, 1H), 2.41 (m, 1H), 2.96 (m, 2H), 4.58 (d, J = 12.4 Hz, 1H),
6.84 (t, J = 7.2 Hz, 1H), 7.03–7.42 (m, 13H, ArH); 13C NMR (100
MHz, CDCl3-d): δ 24.39, 28.74, 29.28, 57.17, 73.35, 114.98, 115.10,
115.32, 115.99, 116.20, 120.32, 125.20, 125.41, 127.58, 127.66, 128.76,