10.1002/ejoc.201900394
European Journal of Organic Chemistry
FULL PAPER
2-(3-Methoxyphenyl)-5-fluoro-1H-indole (12c): Colorless solid; m.p. 97-
98 °C, 195.6 mg; yield 82%. H NMR (300 MHz, CDCl3) 8.23 (br, 1H,
MS 225 (M+,100%). IR ATR/(cm-1): 3408.88, 3410.12 (, N-H). HRMS
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calcd. for C15H12FN [M+] 225.0954, found 225.0926.
N-H), 7.27 (t, J = 7.9 Hz, 1H), 7.22 (d, J = 4.5 Hz, 1H), 7.19 (d, J = 3.9 Hz,
1H), 7.15 (dd, J = 6.7 Hz, J = 5.7 Hz, 1H), 7.09 (m, 1H), 6.87 (dd, J = 9.1
Hz, J = 2.3 Hz, 1H), 6.81 (dd, J = 8.4 Hz, J = 1.8 Hz, 1H), 6.69 (d, J = 1.0
2-Phenyl-4-5-6-7-tetradeuterated-1H-indol (17c): Colorless solid, m.p
146.9-148.4 °C, yield (68%). 1H NMR (300 MHz, CDCl3) 8.22 (br, 1H, N-
H), 7.60-7.52 (m, 1H), 7.38-7.28 (m, 2H), 7.25 (d, J = 7.4 Hz, 1H), 7.15-
7.01 (m, 1H), 6.75 (s, 1H); 13C NMR (75 MHz, CDCl3) 137.91, 132.40,
127.75, 125.21, 125.19, 122.39, 122.28, 120.71, 120.32, 120.20, 120.09,
110.94, 110.83, 100.2, 99.98; IR (ATR)/cm-1 3440 (, N-H); EI-MS 197 (M+,
12%).
Hz, 1H3), 3.79 (s, 3H). 13C NMR (75 MHz, CDCl3) 160.1, 159.8 (1JCF
=
235), 139.6, 133.4, 133.3, 130.2, 129.6, 129.5, 117.7, 113.4, 111.6, 111.4,
111.1, 110.9 (2JCF = 26 Hz), 110.6 (2JCF = 26 Hz), 105.6 (3JCF = 24 Hz),
105.3 (3JCF = 24 Hz), 100.3, 55.4; IR (ATR)/cm-1 3423 (, N-H); EI-MS 241
(M+, 100%). HRMS calcd. for C14H10FN 241.0903, found 241.0900.
2-(4-Methylphenyl)-1H-indole (18c):19 Colorless solid; 47.9 mg; yield
96%. 1H NMR (300 MHz, CDCl3) 8.27 (br, 1H, N-H), 7.67 (d, J = 7.5 Hz,
2H), 7.51–7.40 (m, 3H), 7.33 (t, J = 8.1 Hz, 1H), 7.27 (s, 2H), 7.04 (d, J =
8.3 Hz, 1H), 6.77 (s, 1H), 2.78–2.30 (m, 3H). 13C NMR (75 MHz, CDCl3)
138.0, 137.6, 136.7, 129.7, 129.6, 129.3, 125.0, 122.1, 120.5, 120.2,
110.8, 99.4, 21.2. IR (ATR)/cm-1 3390 (, N-H); EI-MS 223 (M+, 100%).
Mixture of isomers, 2-(3-Methoxyphenyl)-6-methyl-1H-indole (13c)
and 2-(3-methoxyphenyl)-4-methyl-1H-indole (13c´):20 Yellow oil; 188.5
mg, 95%. 1H RMN (300 MHz, CDCl3) 8.27(br, N-H), 8.13 (br, N-H), 7.42
(d, J = 8.1 Hz, 1H ), 7.24-7.20 (m, 2H), 7.15-6.98 (m, 7H), 6.84 (t, J = 8.2
Hz, 2H), 6.78-6.74 (m, 3H), 6.67 (s, 1H), 3.77-3.76 (m, 6H), 2.49 (s, 3H),
2.36 (s, 3H). 13C RMN (75 MHz, CDCl3) 160.1, 137.2, 137.1, 133.9, 132.3,
130.1, 127, 122.1, 120.3, 117.4, 112.8, 110.88, 110.86, 110.8, 100.1, 55.3,
21.8.
2-(4-Methoxyphenyl)-1H-indole (19c):19 Colorless solid; 47.3 mg; yield
95%. 1H NMR (300 MHz, CDCl3) 8.27 (br, 1H, N-H), 7.91–7.56 (m, 3H),
7.41 (dq, J = 8.0, 1.0 Hz, 1H), 7.25–7.08 (m, 2H), 7.08–6.95 (m, 2H), 6.74
(s, 1H), 3.89 (s, 3H). 13C NMR (75 MHz, CDCl3) 159.4, 137.9, 136.6,
129.4, 126.5, 125.2, 121.9, 120.3, 120.1, 114.5, 110.7, 98.8, 55.4. IR
(ATR)/cm-1 3426 (, N-H); EI-MS 224 (M+, 100%).
2-(3-Methoxyphenyl)-7-methyl-1H-indole (14c): Yellow pale oil, 172.6
mg; yield 72%. 1H NMR (300 MHz, CDCl3) 8.09 (br, 1H), 7.40 (d, J = 7.5
Hz, 1H), 7.28 (t, J = 7.9 Hz, 1H), 7.19 (d, J = 7.2 Hz, 1H), 7.14 (d, J = 5.3
Hz, 1H), 6.98 (d, J = 7.2 Hz, 1H), 6.92 (t, J = 5.9 Hz, 1H), 6.82-6.76 (m,
1H), 6.74 (d, J = 1.5 Hz, 1H), 3.79 (s, 3H), 2.45 (s, 3H); 13C NMR (75 MHz,
CDCl3) 160.1, 137.5, 136.4, 134.0, 130.1, 128.8, 123.1, 120.5, 120.1,
118.5, 117.7, 113.0, 111.2, 101.0, 55.4, 16.7; IR (ATR)/cm-1 3367 (, N-
H); EI-MS 237 (M+, 100%); HRMS calcd. for C16H15NO 237.1156, found
237.1160.
2-(3-Fluorophenyl)-1H-indole (20c):24 Colorless solid; 47.9 mg; yield
96%. 1H NMR (300 MHz, CDCl3) 8.33 (br, 1H, N-H), 7.67 (d, J = 8.0 Hz,
1H), 7.47–7.35 (m, 4H), 7.26–7.18 (m, 1H), 7.15 (dd, J = 7.1, 0.9 Hz, 1H),
7.07 (t, J = 2.6 Hz, 1H), 6.88 (s, 1H). 13C NMR (75 MHz, CDCl3) 164.9,
161.6, 136.9, 136.6, 134.5 (d, J = 8.1 Hz), 130.6 (d, J = 8.6 Hz), 129.0,
122.8, 121.3–119.2 (m), 114.4 (d, J = 21.3 Hz), 112.0 (d, J = 22.9 Hz),
111.0, 100.9. IR (ATR)/cm-1 3427 (, N-H); EI-MS 212 ([M+1], 100%).
6-Chloro-2-(3-fluorophenyl)-1H-indole (15c): Colorless solid, m.p. 137-
138 °C, 149.3 mg; yield (48%). 1H NMR (300 MHz, CDCl3) 8.20 (br, 1H,
N-H), 7.45 (d, J = 8.7 Hz, 1H), 7.32 (t, J = 6.3 Hz, 3H), 7.24 (d, J = 9.7 Hz,
1H), 7.06-6.90 (m, 2H), 6.75 (s, 1H); 13C NMR (75 MHz, CDCl3) 164.9
(1JCF = 246 Hz), 161.7 (1JCF = 246 Hz), 137.3, 137.3, 137.2, 134.1, 134.0,
130.8, 130.7, 128.6, 127.6, 121.7, 121.3, 120.7, 120.7, 115.0 (3JCF = 21
Hz), 114.7 (3JCF = 21 Hz), 112.3 (2JCF = 23 Hz), 112.0 (2JCF = 23 Hz), 111.0,
100.9; IR (ATR)/cm-1 3421 , N-H); EI-MS 245 (M+,100%); HRMS calcd.
for C14H9ClFN 245.0408, found 245.0410.
2-(4-Methylphenyl)-5-methyl-1H-indole (21c):25 Colorless solid; 36.9
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mg; yield 74%. H NMR (300 MHz, CDCl3) 8.21 (br, 1H, N-H), 7.57 (d,
J = 8.2 Hz, 2H), 7.44–7.41 (m, 1H), 7.33–7.23 (m, 3H), 7.03 (d, J = 8.7 Hz,
1H), 6.73 (s, 1H), 2.47 (s, 3H), 2.41 (s, 3H). 13C NMR (75 MHz, CDCl3)
138.1, 137.5, 135.0, 129.7, 129.6, 129.6, 129.4, 124.9, 123.7, 120.1,
110.4, 98.9, 21.4, 21.2. IR (ATR)/cm-1 3403 (, N-H); EI-MS 222 ([M+1],
100%).
4-Chloro-2-(3-fluorophenyl)-1H-indole (15c´): Colorless solid, m.p. 106-
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109 °C, 86,9 mg; yield 52%. H NMR (300 MHz, CDCl3) 8.36 (br, 1H,
2-(4-Methylphenyl)-7-methyl-1H-indole (22c):26 Colorless solid; 44.9
N-H), 7.39-7.30 (m, 2H), 7.27 (d, J = 10.1 Hz, 1H), 7.24-7.16 (m, 1H), 7.10-
6.91 (m, 3H), 6.85 (s, 1H). 13C NMR (75 MHz, CDCl3) 164.9 (1JCF = 246
Hz), 161.7 (1JCF = 246 Hz), 137.4, 137.2, 137.1, 134.0, 133.9, 130.8, 130.7,
128.0, 126.1, 123.3, 120.9, 120.7, 120.2, 115.1 (3JCF = 21 Hz), 114.8 (3JCF
= 21 Hz), 112.4 (2JCF = 23 Hz), 112.0 (2JCF = 23 Hz), 109.6, 99.4; IR
(ATR)/cm-1 3463 (, N-H). EI-MS 245 (M+, 100%); HRMS calcd. for
C14H9ClFN [M+] 245.0408, found 245.0408.
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mg; yield 90%. H NMR (300 MHz, CDCl3) 8.07 (br, 1H, N-H), 7.50 (d,
J = 8.2 Hz, 2H), 7.41–7.23 (m, 1H), 7.16 (d, J = 8.8 Hz, 2H), 6.99–6.88 (m,
2H), 6.70 (d, J = 2.2 Hz, 1H), 2.45 (s, 3H), 2.31 (s, 3H). 13C NMR (75 MHz,
CDCl3) 137.8, 137.6, 136.3, 129.78, 129.72, 128.9, 125.1, 122.7, 120.4,
120.0, 118.2, 100.0, 21.2, 16.7. IR (ATR)/cm-1 3427 (, N-H); EI-MS 222
([M+1], 100%).
2-(4-Methoxyphenyl)-5-methyl-1H-indole (23c): 25 Colorless solid; 45.8
mg; yield 92%. H NMR (300 MHz, CDCl3/DMSO) 10.04 (br, 1H, N-H),
7.54 (d, J = 8.7 Hz, 2H), 7.28 (d, J = 3.9 Hz, 1H), 7.19–7.11 (m, 2H), 6.79
(t, J = 7.7 Hz, 2H), 6.43 (s, 1H), 3.69 (s, 3H), 2.27 (s, 3H). 13C NMR (75
MHz, CDCl3/DMSO) 158.8, 138.1, 135.3, 129.3, 128.4, 126.4, 125.5,
122.8, 119.5, 114.1, 110.6, 97.1, 55.2, 21.3. IR (ATR)/cm-1 3431 (, N-H);
EI-MS 238 ([M+1], 100%).
Mixture of isomers, 6-Methyl-2-(3-fluorophenyl)-1H-indole (16c) and
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4-Methyl-2-(3-fluorophenyl)-1H-indole (16c´): Colorless solid mixture,
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m.p. 117.2-121.5 °C, 193.6 mg; yield 86 %. H NMR [300 MHz, CDCl3]
8.21 (br, 1H, N-H), 8.07 (br, 1H, N-H), 7.44 (d, J = 8.1 Hz, 1H), 7.38-7.20
(m, 7H), 7.19-7.14 (m, 2H), 7.10-7.02 (m, 2H), 6.97-6.92 (m, 4H), 6.79 (s,
1H), 6.71 (s, 1H), 2.51 (s, 3H), 2.39 (s, 3H). 13C NMR [75 MHz, CDCl3]
164.99 (1JCF = 245.6 Hz), 164.94 (1JCF = 245.6 Hz), 164.69 (1JCF = 245.6
Hz), 161.69 (1JCF = 245.6 Hz), 136.85, 135.98, 134.8, 134.69, 134.74,
134.63, 134.42, 132.84, 130.67, 130.63, 130.56, 130.52, 129.06, 126.90,
123.02, 122.36, 120.66 120.63, 120.54, 120.51, 114.51 (3JCF = 21.63 Hz,),
114.36 (3JCF = 21.3 Hz), 114.23(3JCF = 21.63 Hz), 114.08 (3JCF = 21.3 Hz),
112.16 (2JCF = 22.8Hz), 112.01 (2JCF = 22.8 Hz), 111.86 (2JCF = 22.8 Hz),
111,71 (2JCF = 22.8 Hz), 111.01, 108.65, 100.79, 99.53, 28.80, 21.88. EI-
2-(3-Fluorophenyl)-5-methyl-1H-indole (24c): Colorless solid; m.p.
148.1-151.9 °C, 48.9 mg; yield 98%. 1H NMR (300 MHz, CDCl3) 8.28 (br,
1H, N-H), 7.52 (s, 1H), 7.34 (t, J = 4.8 Hz, 2H), 7.26–7.21 (m, 2H), 7.08
(dd, J = 8.6, 2.0 Hz, 1H), 6.96 (d, J = 2.7 Hz, 1H), 6.69 (s, 1H), 2.37 (s,
3H). 13C NMR (75 MHz, CDCl3) 164.9, 161.6, 137.9 (d, J = 2.8 Hz), 135.2,
134.0 (d, J = 8.2 Hz), 130.7, 130.5, 129.7, 129.3, 124.5, 120.6-120.5 (d, J
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