10.1002/ejoc.202001337
European Journal of Organic Chemistry
FULL PAPER
1446, 1385, 1356, 1313, 1266, 1233, 1196, 1151, 1116, 1094, 1063,
1043, 1010, 943, 922, 848, 831, 804, 744, 711, 632 cm‒1.
H), 2.10-2.04 (m, 2 H) ppm. 13C{1H} NMR (125 MHz, JMOD, CDCl3): δ =
161.5 (d, J = 241 Hz, C), 148.1 (C), 146.4 (d, J = 8 Hz, C), 129.6 (CH),
126.5 (d, J = 11 Hz, CH), 125.6 (CH), 124.5 (CH), 111.3 (d, J = 21 Hz, C),
110.7 (d, J = 2 Hz, CH), 104.2 (d, J = 23 Hz, CH), 50.8 (CH2), 21.6 (CH2),
20.4 (CH2) ppm. 19F NMR (470 MHz, CDCl3): δ = −117.94 ppm. GC/MS
(EI, 70 eV): m/z (%) = 227 (100) [M]+, 211 (13), 198 (18), 77 (11) [C6H5]+.
HRMS (EI): calcd. (C15H14FN) 227.1105, found 227.1098 [M]+. IR (ATR,
neat): λ−1 = 3053, 2936, 2853, 1621, 1595, 1570, 1496, 1466, 1382, 1349,
1316, 1258, 1239, 1201, 1114, 1075, 1046, 1031, 1007, 995, 913, 761,
2-Ethyl-1-phenyl-1,2,3,4-tetrahydroquinoline (61): General procedure
C was used to synthesize 61 from 36b (0.50 mmol, 137 mg). After
purification by flash chromatography (SiO2, PE/EtOAc, 60:1), 61 (119 mg,
0.50 mmol, >99 %) was isolated as a slightly yellow oil. Rf = 0.24 (SiO2,
PE/EtOAc, 60:1). 1H NMR (500 MHz, CDCl3): δ = 7.41-7.36 (m, 2 H),
7.28 (dd, J = 8.5 Hz, J = 1.1 Hz, 2 H), 7.17-7.11 (m, 2 H), 6.99 (t, J = 8.4
Hz, 1 H), 6.80-6.74 (m, 2 H), 3.73 (ddt, J = 8.2 Hz, J = 6.1 Hz, J = 4.0 Hz,
1 H), 2.97-2.88 (m, 1 H), 2.88-2.80 (m, 1 H), 2.10-2.02 (m, 1 H), 2.02-
1.95 (m, 1 H), 1.80-1.70 (m, 1 H), 1.61-1.51 (m, 1 H), 1.02 (t, J = 7.4 Hz,
3 H) ppm. 13C{1H} NMR (125 MHz, JMOD, CDCl3): δ = 148.8 (C), 143.6
(C), 129.4 (CH), 129.4 (CH), 126.4 (CH), 125.6 (CH), 124.5 (C), 123.5
(CH), 118.4 (CH), 118.0 (CH), 60.7 (CH), 25.1 (CH2), 24.1 (CH2), 23.7
(CH2), 10.8 (CH3) ppm. GC/MS (EI, 70 eV): m/z (%) = 237 (46) [M]+, 208
(100) [C15H14N]+, 193 (25), 180 (19), 77 (23) [C6H5]+. HRMS (EI): calcd.
(C17H19N) 237.1512, found 237.1522 [M]+. IR (ATR, neat): λ−1 = 3033,
2959, 2932, 2871, 1592, 1573, 1489, 1456, 1383, 1336, 1273, 1230,
1206, 1180, 1128, 1106, 1062, 1032, 1002, 937, 896, 872, 843, 745, 722,
698, 655, 617 cm‒1
.
7-(Methylthio)-1-phenyl-1,2,3,4-tetrahydroquinoline (65): General
procedure C was used to synthesize 65 from 46b (0.50 mmol, 146 mg).
After purification by flash chromatography (SiO2, PE/EtOAc, 30:1), 65 (65
mg, 0.25 mmol, 51 %) was isolated as a slightly yellow oil. Rf = 0.45
1
(SiO2, PE/EtOAc, 30:1). H NMR (500 MHz, CDCl3): δ = 7.40-7.35 (m, 2
H), 7.27-7.24 (m, 2 H), 7.14 (tt, J = 7.4 Hz, J = 1.1 Hz, 1 H), 6.98 (d, J =
7.8 Hz, 1 H), 6.68 (d, J = 1.8 Hz, 1 H), 6.65 (dd, J = 7.8 Hz, J = 1.9 Hz, 1
H), 3.65-3.61 (m, 2 H), 2.83 (t, J = 6.5 Hz, 2 H), 2.34 (s, 3 H), 2.08-2.02
(m, 2 H) ppm. 13C{1H} NMR (125 MHz, JMOD, CDCl3): δ = 148.0 (C),
144.9 (C), 135.8 (C), 129.8 (CH), 129.6 (CH), 125.0 (CH), 124.1 (CH),
121.8 (C), 117.0 (CH), 114.1 (CH), 51.0 (CH2), 27.5 (CH2), 22.7 (CH2),
16.4 (CH3) ppm. GC/MS (EI, 70 eV): m/z (%) = 255 (100) [M]+, 206 (25),
193 (8), 180 (11), 77 (13) [C6H5]+. HRMS (EI): calcd. (C16H17NS)
255.1076, found 255.1068 [M]+. IR (ATR, neat): λ−1 = 2921, 2842, 1589,
1556, 1491, 1436, 1407, 1379, 1308, 1262, 1237, 1203, 1173, 1130,
1092, 1071, 1025, 956, 891, 864, 787, 759, 696, 660, 651 cm‒1.
695, 656 cm‒1
.
2-Isopropyl-1-phenyl-1,2,3,4-tetrahydroquinoline
(62):
General
procedure C was used to synthesize 62 from 37b (0.50 mmol, 144 mg).
After purification by flash chromatography (SiO2, PE/EtOAc, 50:1), 62
(114 mg, 0.45 mmol, 91 %) was isolated as a slightly yellow oil. Rf = 0.45
1
(SiO2, PE/EtOAc, 50:1). H NMR (500 MHz, CDCl3): δ = 7.27 (t, J = 7.9
Hz, 2 H), 7.16 (d, J = 7.6 Hz, 2 H), 7.10 (d, J = 7.5 Hz, 1 H), 6.98 (t, J =
7.3 Hz, 2 H), 6.88 (d, J = 8.2 Hz, 1 H), 6.82 (t, J = 7.3 Hz, 1 H), 3.42-3.36
(m, 1 H), 2.87-2.76 (m, 2 H), 2.01-1.89 (m, 2 H), 1.87-1.78 (m, 1 H), 1.13
(d, J = 6.7 Hz, 3 H), 0.97 (d, J = 6.7 Hz, 3 H) ppm. 13C{1H} NMR (125
MHz, JMOD, CDCl3): δ = 150.8 (C), 143.2 (C), 129.6 (CH), 129.2 (CH),
127.2 (C), 126.2 (CH), 123.4 (CH), 122.0 (CH), 122.0 (CH), 120.1 (CH),
65.8 (CH), 28.2 (CH), 23.7 (CH2), 21.7 (CH2), 21.2 (CH3), 18.7 (CH3) ppm.
GC/MS (EI, 70 eV): m/z (%) = 251 (10) [M]+, 208 (100) [C15H14N]+, 77 (7)
[C6H5]+. HRMS (EI): calcd. (C18H21N) 251.1669, found 251.1676 [M]+. IR
(ATR, neat): λ−1 = 3060, 3023, 2954, 2867, 1593, 1573, 1490, 1456,
1447, 1375, 1340, 1316, 1263, 1229, 1200, 1111, 1084, 1068, 1035, 995,
8-Methoxy-1-phenyl-1,2,3,4-tetrahydroquinoline
(66):
General
procedure C was used to synthesize 66 from 47b (0.50 mmol, 138 mg).
After purification by flash chromatography (SiO2, PE/EtOAc, 30:1), 66 (46
mg, 0.19 mmol, 38 %) was isolated as a slightly yellow oil. Rf = 0.27
1
(SiO2, PE/EtOAc, 30:1). H NMR (500 MHz, CDCl3): δ = 7.21 (t, J = 7.9
Hz, 2 H), 7.00 (t, J = 7.9 Hz, 1 H), 6.92-6.86 (m, 3 H), 6.81 (d, J = 7.6 Hz,
1 H), 6.71 (d, J = 8.0 Hz, 1 H), 3.77-3.71 (m, 2 H), 3.61 (s, 3 H), 2.83 (t, J
= 6.7 Hz, 2 H), 1.87-1.81 (m, 2 H) ppm. 13C{1H} NMR (125 MHz, JMOD,
CDCl3): δ = 152.8 (C), 150.3 (C), 132.6 (C), 132.3 (C), 128.4 (CH), 122.9
(CH), 121.8 (CH), 120.6 (CH), 120.0 (CH), 109.1 (CH), 55.5 (CH3), 52.0
(CH2), 27.5 (CH2), 21.3 (CH2) ppm. GC/MS (EI, 70 eV): m/z (%) = 239
(100) [M]+, 224 [C15H14NO]+ (57), 208 [C15H14N]+ (10), 196 (24), 180 (15),
167 (19), 130 (9), 117 (8), 104 (6), 91 (12), 77 (21) [C6H5]+, 65 (10), 51
(13). HRMS (EI): calcd. (C16H17NO) 239.1305, found 239.1311 [M]+. IR
(ATR, neat): λ−1 = 3003, 2953, 2930, 2893, 2862, 2831, 2343, 1594,
1580, 1490, 1472, 1460, 1433, 1349, 1335, 1301, 1256, 1231, 1215,
1192, 1172, 1102, 1089, 1052, 1026, 963, 915, 889, 842, 768, 756, 745,
942, 864, 819, 749, 722, 694, 660, 619 cm‒1
.
7-Fluoro-1-phenyl-1,2,3,4-tetrahydroquinoline
(63):
General
procedure C was used to synthesize 63 from 44b (0.50 mmol, 132 mg).
After purification by flash chromatography (SiO2, PE/EtOAc, 50:1), 63
(105 mg, 0.46 mmol, 92 %) was isolated as a slightly yellow oil. Rf = 0.37
1
(SiO2, PE/EtOAc, 50:1). H NMR (500 MHz, CDCl3): δ = 7.39 (t, J = 7.8
700, 673, 644, 625 cm‒1
.
Hz, 2 H), 7.26 (d, J = 7.8 Hz, 2 H), 7.18 (t, J = 7.4 Hz, 1 H), 6.96 (t, J =
7.4 Hz, 1 H), 6.41-6.33 (m, 2 H), 3.65-3.60 (m, 2 H), 2.83 (t, J = 6.4 Hz, 2
H), 2.06 (quint, J = 6.0 Hz, 2 H) ppm. 13C{1H} NMR (125 MHz, JMOD,
CDCl3): δ = 162.0 (d, J = 240 Hz, C), 147.6 (C), 146.0 (d, J = 10 Hz, C),
130.2 (d, J = 10 Hz, CH), 129.8 (CH), 125.6 (CH), 124.8 (CH), 119.2 (d, J
= 2 Hz, C), 104.3 (d, J = 22 Hz, CH), 101.6 (d, J = 26 Hz, CH), 50.9
(CH2), 27.3 (CH2), 22.7 (CH2) ppm. 19F NMR (470 MHz, CDCl3): δ =
−116.08 ppm. GC/MS (EI, 70 eV): m/z (%) = 227 (100) [M]+, 211 (12),
198 (18), 77 (12) [C6H5]+. HRMS (EI): calcd. (C15H14FN) 227.1105, found
227.1108 [M]+. IR (ATR, neat): λ−1 = 3031, 2933, 2841, 1614, 1588, 1501,
1427, 1384, 1313, 1273, 1241, 1211, 1161, 1111, 1071, 1027, 938, 834,
1-Phenyl-8-(trifluoromethyl)-1,2,3,4-tetrahydroquinoline (67): General
procedure C was used to synthesize 67 from 48b (0.50 mmol, 157 mg).
After purification by flash chromatography (SiO2, PE/EtOAc, 30:1), 67
(125 mg, 0.45 mmol, 90 %) was isolated as a slightly yellow oil. Rf = 0.39
1
(SiO2, PE/EtOAc, 30:1). H NMR (500 MHz, CDCl3): δ = 7.52 (d, J = 7.8
Hz, 1 H), 7.38 (d, J = 7.5 Hz, 1 H), 7.27-7.21 (m, 2 H), 7.17 (t, J = 7.7 Hz,
1 H), 6.97 (t, J = 7.3 Hz, 1 H), 6.85 (d, J = 7.7 Hz, 2 H), 3.74-3.68 (m, 2
H), 2.87 (t, J = 6.9 Hz, 2 H), 1.97-1.90 (m, 2 H) ppm. 13C{1H} NMR (125
MHz, JMOD, CDCl3): δ = 151.8 (C), 143.4 (C), 135.3 (C), 133.1 (CH),
128.7 (CH), 125.9 (q, J = 5 Hz, CH), 125.4 (q, J = 30 Hz, C), 123.9 (q, J =
274 Hz, C), 123.3 (CH), 121.6 (CH), 121.5 (CH), 51.7 (CH2), 27.1 (CH2),
20.9 (CH2) ppm. 19F NMR (470 MHz, CDCl3): δ = −60.33 ppm. GC/MS
(EI, 70 eV): m/z (%) = 277 (100) [M]+, 262 (7), 256 (8), 242 (8), 228 (14),
208 (36) [C15H14N]+, 193 (6), 180 (72), 166 (7), 115 (5), 104 (6), 91 (8),
77 (22) [C6H5]+, 51 (17). HRMS (EI): calcd. (C16H14F3N) 277.1073, found
277.1073 [M]+. IR (ATR, neat): λ−1 = 3067, 2942, 2923, 2876, 1592, 1492,
1460, 1336, 1308, 1255, 1236, 1184, 1150, 1116, 1053, 1028, 957, 874,
785, 761, 696, 610 cm‒1
.
5-Fluoro-1-phenyl-1,2,3,4-tetrahydroquinoline
(64):
General
procedure C was used to synthesize 64 from 45b (0.50 mmol, 132 mg).
After purification by flash chromatography (SiO2, PE/EtOAc, 50:1), 64
(108 mg, 0.48 mmol, 95 %) was isolated as a slightly yellow oil. Rf = 0.41
1
(SiO2, PE/EtOAc, 50:1). H NMR (500 MHz, CDCl3): δ = 7.43-7.37 (m, 2
H), 7.29-7.25 (m, 2 H), 7.18 (tt, J = 7.4 Hz, J = 1.1 Hz, 1 H), 6.88 (q, J =
8.1 Hz, 1 H), 6.51-6.43 (m, 2 H), 3.67-3.62 (m, 2 H), 2.87 (t, J = 6.6 Hz, 2
853, 833, 786, 757, 694, 666, 650, 627, 615 cm‒1
.
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