The Journal of Organic Chemistry
Page 10 of 12
128.0, 127.1, 126.6, 125.0, 122.6, 118.1, 118.0, 115.0, 113.7,
2.20 Hz, 1H), 6.83 (dd, J = 2.45, 8.80 Hz, 1H), 4.14 (s, 2H),
16.0. HRMS (ESI): [MꢀH]ꢀ, C16H10ClN2, calculated: 265.0538;
found: 265.0538.
3.73 (s, 3H). 13C NMR (101 MHz, DMSOꢀd6) d 154.5, 134.5,
131.1, 129.4, 129.2, 127.2, 126.7, 125.2, 118.3, 115.0, 112.8,
112.8, 100.5, 55.8, 16.0. HRMS (ESI): [MꢀH]ꢀ, C17H13N2O,
calculated: 261.1028; found: 261.1035.
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2-(5-Flouro-3-phenyl-1H-indol-2-yl)acetonitrile (15c). Synꢀ
thesized according to the procedure described for 13c. White
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solid, 40 mg, 64% yield. Melting point 153ꢀ155 °C. H NMR
2-(1-Methyl-3-phenyl-1H-indol-2-yl)acetonitrile (17a). Synꢀ
thesized according to the procedure described for 13c. Yellow
(400 MHz, DMSOꢀd6) δ 11.73 (s, 1H), 7.44 ꢀ 7.58 (m, 6H),
7.34 ꢀ 7.41 (m, 1H), 7.24 (dd, J = 2.32, 9.90 Hz, 1H), 7.04 (dt,
J = 2.57, 9.11 Hz, 1H), 4.20 (s, 2H). 13C NMR (101 MHz,
DMSOꢀd6) δ 159.2, 156.8, 133.8, 132.7, 129.5, 129.2, 127.1,
127.0, 127.0, 126.8, 118.1, 115.4, 115.3, 113.3, 113.2, 111.0,
110.7, 103.8, 103.6, 16.0. HRMS (ESI): [M]+•, C16H11FN2,
calculated: 250.0906; found: 250.0907.
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oil, 41 mg, 67% yield. Melting point 64ꢀ66 °C. H NMR (400
MHz, DMSOꢀd6) δ 7.49 ꢀ 7.60 (m, 4H), 7.45 (d, J = 6.85 Hz,
2H), 7.34 ꢀ 7.42 (m, 1H), 7.24 ꢀ 7.30 (m, 1H), 7.07 ꢀ 7.17 (m,
1H), 4.29 (s, 2H), 3.88 (s, 3H). 13C NMR (101 MHz, DMSOꢀ
d6) δ 137.2, 134.1, 129.6, 129.5, 127.0, 126.2, 126.1, 122.9,
120.7, 119.2, 117.9, 115.7, 110.6, 30.4, 14.6. HRMS (ESI):
[M]+•, C17H14N2, calculated: 246.1157; found: 246.1162.
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Methyl
2-(Cyanomethyl)-3-phenyl-1H-indole-5-carboxylate
(15d). Synthesized according to the procedure described for
13c using DMSO instead of DCE. Yellow solid, 53 mg, 73%
yield. Melting point 235ꢀ238 °C. 1H NMR (400 MHz, DMSOꢀ
d6) δ 12.04 (s, 1H), 8.19 (s, 1H), 7.82 (dd, J = 1.47, 8.56 Hz,
1H), 7.53 ꢀ 7.61 (m, 3H), 7.46 ꢀ 7.51 (m, 2H), 7.37 ꢀ 7.45 (m,
1H), 4.23 (s, 2H), 3.83 (s, 3H). 13C NMR (101 MHz, DMSOꢀ
d6) δ 167.5, 138.7, 133.4, 129.6, 129.5, 127.3, 126.7, 126.6,
123.6, 121.8, 121.5, 118.0, 116.5, 112.2, 52.3, 15.9. HRMS
(ESI): [MꢀH]ꢀ, C18H13N2O2, calculated: 289.0977; found:
289.0984.
2-(1-Isopropyl-3-phenyl-1H-indol-2-yl)acetonitrile
(17b).
Synthesized according to the procedure described for 13c.
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Yellow solid, 32 mg, 47% yield. Melting point 67ꢀ69 °C. H
NMR (400 MHz, DMSOꢀd6) δ 7.74 (d, J = 8.31 Hz, 1H), 7.49
ꢀ 7.60 (m, 3H), 7.35 ꢀ 7.47 (m, 3H), 7.21 (t, J = 7.58 Hz, 1H),
7.09 (t, J = 7.46 Hz, 1H), 4.80 ꢀ 4.97 (m, 1H), 4.25 (s, 2H),
1.67 (d, J = 6.85 Hz, 6H). 13C NMR (101 MHz, DMSOꢀd6) δ
134.7, 134.2, 129.9, 129.5, 127.4, 127.1, 125.7, 122.6, 120.3,
119.6, 118.2, 115.8, 112.8, 48.1, 21.4, 15.0. HRMS (ESI):
[M]+•, C19H18N2, calculated: 274.1470; found: 274.1477.
2-(Cyanomethyl)-3-phenyl-1H-indole-carbonitrile (15e). Synꢀ
thesized according to the procedure described for 13c using
DMSO instead of DCE. Light brown solid, 21 mg, 33% yield.
2-(3-(4-Fluorophenyl)-1-isoropyl-1H-indol-2-yl)acetonitrile
(17c). Synthesized according to the procedure described for
13c using 2 equiv of indole 16c and 1 equiv bromoacetonitrile
2. White solid, 66 mg, 90% yield. Melting point 127ꢀ129 °C.
1H NMR (400 MHz, DMSOꢀd6) δ 7.74 (d, J = 8.56 Hz, 1H),
7.41 ꢀ 7.53 (m, 3H), 7.33 ꢀ 7.40 (m, 2H), 7.21 (dt, J = 1.22,
7.70 Hz, 1H), 7.06 ꢀ 7.12 (m, 1H), 4.87 (quin, J = 6.91 Hz,
1H), 4.25 (s, 2H), 1.66 (d, J = 6.85 Hz, 6H). 13C NMR (101
MHz, DMSOꢀd6) δ 162.8, 160.4, 134.6, 131.8, 131.8, 130.5,
130.4, 127.4, 125.8, 122.6, 120.3, 119.5, 118.1, 116.4, 116.2,
114.8, 112.8, 48.1, 21.4, 15.0. HRMS (ESI): [M]+•, C19H17FN2,
calculated: 292.1376; found: 292.1386.
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Melting point 172ꢀ174 °C. H NMR (400 MHz, DMSOꢀd6) δ
12.23 (s, 1H), 7.99 (s, 1H), 7.62 ꢀ 7.66 (m, 1H), 7.49 ꢀ 7.58
(m, 6H), 7.38 ꢀ 7.44 (m, 1H), 4.26 (s, 2H). 13C NMR (101
MHz, DMSOꢀd6) δ 137.9, 132.9, 129.6, 129.5, 127.6, 127.4,
126.7, 125.4, 124.7, 120.9, 117.8, 116.0, 113.4, 102.6, 16.0.
HRMS (ESI): [MꢀH]ꢀ, C17H10N3, calculated: 256.0875; found:
256.0876.
2-(3-phenyl-5-(trifluoromethyl)-1H-indol-2-yl)acetonitrile
(15f). Synthesized according to the procedure described for
13c using DMSO instead of DCE. White solid, 31 mg, 41%
yield. Melting point 156ꢀ158 °C. 1H NMR (400 MHz, DMSOꢀ
d6) δ 12.12 (s, 1H), 7.81 (s, 1H), 7.68 (d, J = 8.56 Hz, 1H),
7.53 ꢀ 7.60 (m, 2H), 7.47 ꢀ 7.52 (m, 3H), 7.38 ꢀ 7.44 (m, 1H),
4.25 (s, 2H). 13C NMR (101 MHz, DMSOꢀd6) δ 137.7, 133.2,
129.6, 129.5, 127.4, 127.3, 127.2, 126.3, 124.5, 121.4, 121.1,
119.1, 119.1, 117.9, 116.4, 116.3, 116.1, 113.0, 15.9. HRMS
(ESI): [MꢀH]ꢀ, C17H10F3N2, calculated: 299.0796; found:
299.0797.
2-(1-Cyclopropyl-3-phenyl-1H-indol-2-yl)acetonitrile (17d).
Synthesized according to the procedure described for 13c.
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Yellow solid, 13 mg, 19% yield. Melting point 68ꢀ71 °C. H
NMR (400 MHz, DMSOꢀd6) δ 7.66 (d, J = 8.31 Hz, 1H), 7.50
ꢀ 7.58 (m, 3H), 7.45 (d, J = 7.09 Hz, 2H), 7.37 ꢀ 7.43 (m, 1H),
7.28 (t, J = 7.21 Hz, 1H), 7.09 ꢀ 7.17 (m, 1H), 4.27 (s, 2H),
3.35 ꢀ 3.40 (m, 1H), 1.27 ꢀ 1.35 (m, 2H), 1.11 ꢀ 1.19 (m, 2H).
13C NMR (101 MHz, DMSOꢀd6) δ 137.8, 133.9, 129.7, 129.5,
127.6, 127.2, 126.3, 123.1, 120.9, 119.4, 118.1, 116.4, 111.6,
25.8, 15.3, 7.5. HRMS (ESI): [M]+•, C19H16N2, calculated:
272.1313; found: 272.1309.
2-(5-Methyl-3-phenyl-1H-indol-2-yl)acetonitrile (15g). Synꢀ
thesized according to the procedure described for 13c using
DMSO instead of DCE. Brown solid, 27 mg, 44% yield. Meltꢀ
ing point 149ꢀ151 °C. 1H NMR (400 MHz, DMSOꢀd6) δ 11.46
(s, 1H), 7.41 ꢀ 7.56 (m, 4H), 7.27 ꢀ 7.39 (m, 3H), 6.95 ꢀ 7.06
(m, 1H), 4.14 (s, 2H), 2.37 (s, 3H). 13C NMR (101 MHz,
DMSOꢀd6) d 134.5, 129.4, 128.9, 127.1, 126.7, 124.6, 124.2,
118.5, 118.3, 114.8, 111.7, 21.7, 15.9. HRMS (ESI): [MꢀH]ꢀ,
C17H13N2, calculated: 245.1079; found: 245.1079.
2-(2-methyl-1H-indol-3-yl)acetonitrile (19a). Synthesized
according to the procedure described for 13c using DMSO
instead of DCE with 3 equiv of indole 18a and 1 equiv of
bromoacetonitrile 2. Yellow solid, 17 mg, 41% yield. Melting
point 83ꢀ85 °C. Analytical data are consistent with reported
values.43 1H NMR (400 MHz, DMSOꢀd6) δ 11.12 (br s, 1H),
7.26 (d, J = 8.07 Hz, 1H), 7.00 (t, J = 7.58 Hz, 1H), 6.93 (d, J
= 7.09 Hz, 1H), 6.20 ꢀ 6.28 (m, 1H), 4.11 (s, 2H), 2.41 (s, 3H).
13C NMR (101 MHz, DMSOꢀd6) δ 136.5, 136.4, 127.8, 121.1,
120.6, 119.7, 118.6, 110.8, 97.7, 21.1, 13.9. HRMS (ESI): [Mꢀ
H]ꢀ, C11H9N2, calculated: 169.0766; found: 169.0763.
2-(5-Methoxy-3-phenyl-1H-indol-2-yl)acetonitrile (15h). Synꢀ
thesized according to the procedure described for 13c using
DMSO instead of DCE. White solid, 24 mg, 36% yield. Meltꢀ
ing point 132ꢀ134 °C. 1H NMR (400 MHz, DMSOꢀd6) δ 11.45
(s, 1H), 7.45 ꢀ 7.55 (m, 4H), 7.30 ꢀ 7.40 (m, 2H), 7.00 (d, J =
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