10.1002/adsc.201700824
Advanced Synthesis & Catalysis
1H), 1.31 (d, J = 6.8 Hz, 6H); 13C NMR (100 MHz,
CDCl3): δ 147.7, 145.7, 140.4, 137.9, 133.4, 128.8, 128.2,
127.8, 127.4, 126.9, 123.2, 123.0, 121.8, 121.5, 110.8, 33.9,
24.1; HRMS (m/z) [M + H]+ calcd for C22H21N2 313.1699,
found 313.1691.
1-(4-Nitrophenyl)-3-phenyl-1H-indazole (2j). 10 h (2
mmol of I2); eluent: CH2Cl2/PE 25:75; yield: 157 mg, 99%;
1
yellow solid, mp 162-163 ºC (lit.[9a] mp 160-162 ºC); H
NMR (400 MHz, CDCl3): δ 8.39 (d, J = 9.2 Hz, 2H), 8.09
(d, J = 8.0 Hz, 1H), 8.04-8.01 (m, 4H), 7.87 (d, J = 8.4 Hz,
1H), 7.57-7.53 (m, 3H), 7.50-7.46 (m, 1H), 7.36 (t, J = 7.6
Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 148.3, 145.4,
144.9, 140.1, 132.3, 129.0, 128.2, 127.9, 125.3, 124.3,
123.1, 122.2, 121.4, 110.9; HRMS (m/z) [M + H]+ calcd
for C19H14N3O2 316.1081, found 316.1083.
1-(4-Methoxyphenyl)-3-phenyl-1H-indazole (2d). After
the condensation of diphenyl ketone (0.5 mmol) and
hydrazine salt (0.9 mmol), prepared according to General
Procedure A was complete, the reaction mixture was
concentrated and the resulting crude hydrazone (1d) was
directly subjected to the General Procedure B. 2 h (1.5
mmol of I2); eluent: CH2Cl2/PE 35:65; yield: 110 mg, 73%;
1-(2-Chlorophenyl)-3-phenyl-1H-indazole (2k).[10b] 10 h
(2 mmol of I2); eluent: CH2Cl2/PE 20:80; yield: 149 mg,
98%; colorless oil.; 1H NMR (400 MHz, CDCl3): δ 8.10 (d,
J = 8.4 Hz, 1H), 8.05 (d, J = 7.6 Hz, 2H), 7.63-7.58 (m,
2H), 7.52 (d, J = 7.6 Hz, 2H), 7.46-7.41 (m, 4H), 7.31-7.26
(m, 2H); 13C NMR (100 MHz, CDCl3): δ 146.5, 141.9,
137.1, 133.2, 131.7, 130.8, 129.9, 129.8, 128.9, 128.4,
127.82, 127.76, 127.0, 122.2, 121.8, 121.5, 110.9; HRMS
(m/z) [M + H]+ calcd for C19H14ClN2 305.0840, found
305.0850.
1
white solid, mp 128-129 ºC (lit.[9b] mp 129-131 ºC); H
NMR (400 MHz, CDCl3): δ 8.07 (d, J = 8.0 Hz, 1H), 8.05-
8.03 (m, 2H), 7.68-7.65 (m, 3H), 7.52 (t, J = 7.6 Hz, 2H),
7.44-7.40 (m, 2H), 7.26 (m, 1H, overlapped with the peak
of chloroform), 7.08-7.04 (m, 2H), 3.87 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 158.5, 145.6, 140.6, 133.4, 133.3,
128.9, 128.2, 127.8, 126.9, 124.9, 122.7, 121.7, 121.5,
114.7, 110.5, 55.6; HRMS (m/z) [M + H]+ calcd for
C20H17N2O 301.1335, found 301.1337.
1-(3-Chlorophenyl)-3-phenyl-1H-indazole (2l).[9c] 6 h
(1.5 mmol of I2); eluent: CH2Cl2/PE 20:80; yield: 131 mg,
86%; colorless oil.; 1H NMR (400 MHz, CDCl3): δ 8.07 (d,
J = 8.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 2H), 7.84 (s, 1H),
7.77 (d, J = 8.8 Hz, 1H), 7.70 (d, J = 8.0 Hz, 1H), 7.53 (t, J
= 8.0 Hz, 2H), 7.49-7.42 (m, 3H), 7.33-7.24 (m, 2H); 13C
NMR (100 MHz, CDCl3): δ 146.8, 141.3, 140.2, 135.2,
132.9, 130.4, 128.9, 128.6, 127.9, 127.5, 126.6, 123.5,
122.9, 122.3, 121.8, 120.6, 110.6; HRMS (m/z) [M + H]+
calcd for C19H14ClN2 305.0840, found 305.0849.
1-(4-Fluorophenyl)-3-phenyl-1H-indazole (2e).[9c] 6 h (1
mmol of I2); eluent: CH2Cl2/PE 25:75; yield: 137 mg, 95%;
1
white solid, mp 114-115 ºC; H NMR (400 MHz, CDCl3):
δ 8.08 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 7.2 Hz, 2H), 7.76-
7.72 (m, 2H), 7.68 (d, J = 8.8 Hz, 1H), 7.53 (t, J = 7.2 Hz,
2H), 7.47-7.41 (m, 2H), 7.28 (t, J = 7.6 Hz, 1H), 7.26-7.21
(m, 2H, overlapped with the peak of chloroform); 13C
NMR (100 MHz, CDCl3): δ 161.2 (d, JC-F = 245.0 Hz),
146.2, 140.5, 136.3 (d, JC-F = 2.9 Hz), 133.1, 128.9, 128.4,
127.8, 127.3, 124.9 (d, JC-F = 8.3 Hz), 123.0, 122.0, 121.7,
116.4 (d, JC-F = 22.9 Hz), 110.4; HRMS (m/z) [M + H]+
calcd for C19H14FN2 289.1136, found 289.1131.
1-(2,4-Dichlorophenyl)-3-phenyl-1H-indazole (2m).[9b]
10 h (2 mmol of I2); eluent: CH2Cl2/PE 20:80; yield: 169
1
mg, 99%; colorless oil; H NMR (400 MHz, CDCl3): δ
1-(4-Chlorophenyl)-3-phenyl-1H-indazole (2f).[9c] 5 h (1
8.09 (d, J = 8.0 Hz, 1H), 8.04-8.02 (m, 2H), 7.63 (d, J =
2.0 Hz, 1H), 7.54-7.50 (m, 3H), 7.46-7.41 (m, 3H), 7.30 (t,
J = 7.2 Hz, 1H), 7.25 (d, J = 8.4 Hz, 1H, overlapped with
the peak of chloroform); 13C NMR (100 MHz, CDCl3): δ
146.9, 141.9, 135.9, 135.1, 133.0, 132.4, 130.6, 130.5,
128.9, 128.5, 128.1, 127.8, 127.2, 122.3, 122.0, 121.6,
110.7; HRMS (m/z) [M + Na]+ calcd for C19H12Cl2N2Na
361.0270, found 361.0270.
mmol of I2); eluent: CH2Cl2/PE 20:80; yield: 148 mg, 97%;
1
white solid, mp 121-122 ºC; H NMR (400 MHz, CDCl3):
δ 8.08 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 7.2 Hz, 2H), 7.76-
7.72 (m, 3H), 7.75-7.42 (m, 6H), 7.29 (d, J = 7.6 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 146.5, 140.2, 138.7, 133.0,
132.1, 129.6, 128.9, 128.5, 127.8, 127.4, 124.0, 123.3,
122.2, 121.8, 110.5; HRMS (m/z) [M + H]+ calcd for
C19H14ClN2 305.0840; found 305.0847.
1-(2,5-Dichlorophenyl)-3-phenyl-1H-indazole (2n). 10 h
(2 mmol of I2); eluent: CH2Cl2/PE 15:75; yield: 169 mg,
99%; white solid, mp 95-98 ºC; 1H NMR (400 MHz,
CDCl3): δ 8.09 (d, J = 8.4 Hz, 1H), 8.04-8.02 (m, 2H), 7.62
(d, J = 2.4 Hz, 1H), 7.53 (t, J = 8.4 Hz, 3H), 7.47-7.40 (m,
3H), 7.32-7.27 (m, 2H); 13C NMR (100 MHz, CDCl3): δ
147.1, 141.7, 138.1, 133.3, 132.9, 131.6, 129.9, 129.8,
129.7, 128.9, 128.6, 127.8, 127.3, 122.4, 122.1, 121.6,
110.9; HRMS (m/z) [M + H]+ calcd for C19H13Cl2N2
339.0450, found 339.0442.
1-(4-Bromophenyl)-3-phenyl-1H-indazole (2g).[21] 5 h (1
mmol of I2); eluent: CH2Cl2/PE 20:80; yield: 167 mg, 96%;
1
white solid, mp 123-124 ºC; H NMR (400 MHz, CDCl3):
δ 8.07 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 7.2 Hz, 2H), 7.73-
7.63 (m, 5H), 7.52 (t, J = 7.6 Hz, 2H), 7.47-7.41 (m, 2H),
7.28 (t, J = 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
146.6, 140.2, 139.3, 133.0, 132.6, 128.9, 128.5, 127.8,
127.4, 124.2, 123.4, 122.2, 121.8, 119.8, 110.5; HRMS
(m/z) [M + H]+ calcd for C19H14BrN2 349.0335, found
349.0331.
3-Phenyl-1-(2,4,6-trichlorophenyl)-1H-indazole (2o).[9c]
4-(3-Phenyl-1H-indazol-1-yl)benzonitrile (2h).[9c] 8 h
12 h (2 mmol of I2); eluent: CH2Cl2/PE 20:80; yield: 185
1
(1.5 mmol of I2); eluent: EtOAc/PE 15:85; yield: 130 mg,
mg, 99%; colorless oil; H NMR (400 MHz, CDCl3): δ
1
88%; white solid, mp 161-163 ºC; H NMR (400 MHz,
8.11 (d, J = 8.4 Hz, 1H), 8.03 (d, J = 8.0 Hz, 2H), 7.55-
7.51 (m, 4H), 7.47-7.42 (m, 2H), 7.31 (t, J = 7.6 Hz, 1H),
7.11 (d, J = 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
147.2, 141.9, 136.5, 136.1, 133.7, 132.9, 129.0, 128.9,
128.6, 127.9, 127.5, 122.1, 122.0, 121.7, 109.8; HRMS
(m/z) [M + H]+ calcd for C19H12Cl3N2 373.0061, found
373.0052.
CDCl3): δ 8.09 (d, J = 8.4 Hz, 1H), 8.03-7.97 (m, 4H),
7.85-7.81 (m, 3H), 7.57-7.45 (m, 4H), 7.35 (t, J = 7.6 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ 147.9, 143.8, 140.0,
133.6, 132.5, 129.0, 128.9, 128.0, 127.9, 124.1, 122.9,
122.1, 122.0, 118.6, 110.7, 109.2; HRMS (m/z) [M + H]+
calcd for C20H14N3 296.1182, found 296.1175.
3-Phenyl-1-(4-(trifluoromethyl)phenyl)-1H-indazole
(2i).[9b] 10 h (2 mmol of I2); eluent: CH2Cl2/PE 20:80;
yield: 160 mg, 95%; white solid, mp 137-139 ºC; 1H NMR
(400 MHz, CDCl3): δ 8.10 (d, J = 8.0 Hz, 1H), 8.04-8.02
(m, 2H), 7.97 (d, J = 8.4 Hz, 2H), 7.82 (t, J = 9.2 Hz, 3H),
7.56-7.44 (m, 4H), 7.33 (t, J = 7.6 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ 147.3, 143.1, 140.2, 132.8, 128.9, 128.7,
128.1 (q, JC-F = 32.6 Hz), 127.9, 127.7, 126.7 (q, JC-F = 3.7
Hz), 124.0 (q, JC-F = 270.3 Hz), 123.8, 122.5, 122.2, 122.0,
110.6; HRMS (m/z) [M + H]+ calcd for C20H14F3N2
339.1104, found 339.1104.
1-(Tert-butyl)-3-phenyl-1H-indazole (2p). After the
condensation of diphenyl ketone (2 mmol) and hydrazine
salt (3.6 mmol) according to General Procedure A was
complete, the reaction mixture was concentrated and the
resulting crude hydrazone (1p) was directly subjected to
the General Procedure B. 1 h (6 mmol of I2); eluent:
CH2Cl2/PE 25:75; yield: 121 mg, 24%; white solid, mp
1
104-106 ºC; H NMR (400 MHz, CDCl3): δ 8.02 (d, J =
8.4 Hz, 1H), 7.98-7.96 (m, 2H), 7.72 (d, J = 8.8 Hz, 1H),
7.48 (t, J = 8.0 Hz, 2H), 7.38-7.32 (m, 2H), 7.19-7.15 (m,
1H), 1.83 (s, 9H); 13C NMR (100 MHz, CDCl3): δ 141.9,
5
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