10.1002/ejoc.201700506
European Journal of Organic Chemistry
FULL PAPER
under argon atmosphere and the mixture was heated to 130 °C for 11 h to
745; 1H NMR (400 MHz, CDCl3) δ 2.60 (s, 3H), 7.46–7.48 (m, 2H),
7.62 (d, J = 8.7 Hz, 1H), 7.87 (s, 1H), 8.01–8.03 (m, 2H), 8.19 (s,
1H), 9.24 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 21.9, 125.4, 127.6,
128.1, 129.2, 130.0, 130.4, 132.9, 135.4, 138.8, 140.7, 141.9, 142.9,
149.6; HRMS (ESI-TOF) calcd for C15H12ClN2 (M + H)+ 255.0689, found
255.0686.
afford 4h (19.4 mg, 0.088 mmol) as a yellow solid in 81% yield; mp 92–
94 °C; Rf 0.60 (20% ethyl acetate in petroleum ether); IR νmax )
(KBr, cm−1
̃
3061, 2920, 2855, 1548, 1455, 1421, 1350, 1303, 1025, 972, 828, 765,
683; 1H NMR (400 MHz, CDCl3) δ 2.59 (s, 3H), 7.47–7.61 (m, 4H),
7.87 (s, 1H), 8.03 (d, J = 8.7 Hz, 1H), 8.15–8.17 (m,2H), 9.26 (s,
1H); 13C{1H} NMR (100 MHz, CDCl3) δ 21.9, 127.5, 128.1, 129.2, 130.1,
132.7, 137.1, 140.2, 140.8, 141.7, 143.3, 151.1; HRMS (ESI-TOF) calcd
for C15H13N2 (M + H)+ 221.1079, found 221.1074.
N-(2-((2-Bromo-4-methylphenyl)amino)-2-(3-bromophenyl)ethyl)-4-
methylbenzenesulfonamide (3l). The general method A described above
was followed when 1g (50 mg, 0.142 mmol) was reacted with 2b (53 µL,
0.425 mmol) at rt for 6 h to afford 3l (58.1 mg, 0.107 mmol) as a white solid
in 76% yield; mp 126–128 °C; Rf 0.35 (20% ethyl acetate in petroleum
2-(4-Fluorophenyl)-6-methylquinoxaline (4i). The general method B
described above was followed when 3i (50 mg, 0.106 mmol) in 1.0 mL of
DMF solvent was added to a suspension of CuI (2.0 mg, 0.011 mmol), L-
proline (2.4 mg, 0.021 mmol), and NaH (6.3 mg, 0.264 mmol) in 1.0 mL of
DMF under argon atmosphere and the mixture was heated to 130 °C for
13 h to afford 4i (19.6 mg, 0.082 mmol) as a pale yellow solid in 77% yield;
ether); IR νmax
(KBr, cm−1) 3377, 3276, 3031, 2922, 2855, 1731, 1612,
̃
1596, 1570, 1516, 1472, 1427, 1317, 1265, 1190, 1159, 1092, 1038, 1018,
997, 954, 835, 811, 786, 737, 697, 663, 550; 1H NMR (400 MHz, CDCl3)
δ 2.16 (s, 3H), 2.38 (s, 3H), 3.14–3.21 (m, 1H), 3.33–3.39 (m, 1H), 4.36–
4.38 (m, 1H), 4.75–4.78 (m, 1H), 4.85 (t, J = 6.6 Hz, 1H), 6.14 (d, J = 8.4
Hz, 1H), 6.77 (dd, J = 1.1, 8.0 Hz, 1H), 7.14–7.18 (m, 2H), 7.23–7.25 (m,
3H), 7.35–7.38 (m, 2H), 7.72 (d, J = 8.4 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 20.1, 21.6, 49.1, 57.3, 110.4, 112.8, 123.3, 125.2, 127.1, 128.6,
128.9, 129.5, 129.9, 130.7, 131.3, 132.9, 136.7, 140.8, 142.2, 143.9;
HRMS (ESI-TOF) calcd for C22H23Br2N2O2S (M + H)+ 536.9847, found
536.9846.
mp 120–122 °C; Rf 0.55 (20% ethyl acetate in petroleum ether); IR νmax
̃
(KBr, cm−1) 3053, 2928, 1601, 1541, 1498, 1459, 1366, 1271, 1057, 944,
836, 766, 619; 1H NMR (400 MHz, CDCl3) δ 2.59 (s, 3H), 7.20–7.25
(m, 2H), 7.58–7.61 (m, 1H), 7.86 (s, 1H), 8.01 (d, J = 8.2 Hz, 1H),
8.14–8.18 (m, 2H), 9.22 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
21.9, 116.1, 116.3, 128.1, 129.1, 129.4, 129.5, 132.8, 133.2, 140.3, 140.7,
1
141.6, 142.9, 150.1, 164.2 (d, JC–F = 249.8 Hz); HRMS (ESI-TOF) calcd
for C15H12FN2 (M + H)+ 239.0985, found 239.0989.
2-(3-Bromophenyl)-6-methylquinoxaline (4l). The general method B
described above was followed when 3l (50 mg, 0.093 mmol) in 1.0 mL of
DMF solvent was added to a suspension of CuI (1.8 mg, 0.009 mmol), L-
proline (2.1 mg, 0.019 mmol), and NaH (5.6 mg, 0.232 mmol) in 1.0 mL of
DMF under argon atmosphere and the mixture was heated to 130 °C for
14 h to afford 4l (21.1 mg, 0.071 mmol) as a cream brown solid in 76%
yield; mp 102–104 °C; Rf 0.55 (20% ethyl acetate in petroleum ether); IR
N-(2-((2-Bromo-4-methylphenyl)amino)-2-(4-bromophenyl)ethyl)-4-
methylbenzenesulfonamide (3j). The general method A described above
was followed when 1e (50 mg, 0.142 mmol) was reacted with 2b (53 µL,
0.426 mmol) at rt for 6 h to afford 3j (60.4 mg, 0.112 mmol) as a white solid
in 79% yield; mp 128–130 °C; Rf 0.40 (20% ethyl acetate in petroleum
ether); IR νmax
(KBr, cm−1) 3372, 3271, 3035, 2920, 2859, 1741, 1614,
̃
1597, 1579, 1517, 1472, 1321, 1268, 1193, 1155, 1097, 1032, 1017, 997,
956, 831, 812, 786, 739, 692, 664, 551; 1H NMR (400 MHz, CDCl3) δ
2.15 (s, 3H), 2.38 (s, 3H), 3.14–3.21 (m, 1H), 3.32–3.38 (m, 1H), 4.39
(br s, 1H), 4.75 (br s, 1H), 4.82 (t, J = 6.9 Hz, 1H), 6.14 (d, J = 8.0 Hz, 1H),
6.76 (dd, J = 1.5, 8.4 Hz, 1H), 7.11 (d, J = 8.4 Hz, 2H), 7.22–7.25 (m, 3H),
7.40 (d, J = 8.4 Hz, 2H), 7.70 (d, J = 8.4 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 20.1, 21.6, 48.9, 57.2, 110.4, 112.9, 121.9, 127.1, 128.3, 128.6,
128.9, 129.9, 132.2, 132.9, 136.7, 138.7, 140.8, 143.8; HRMS (ESI-TOF)
calcd for C22H23Br2N2O2S(M + H)+ 536.9847, found 536.9843.
νm̃ ax
(KBr, cm−1) 3054, 2923, 1622, 1548, 1445, 1250, 1286, 1077, 1057,
958, 840, 763, 683; 1H NMR (400 MHz, CDCl3) δ 2.61 (s, 3H), 7.41
(t, J = 7.8 Hz, 1H), 7.61–7.63 (m, 2H), 7.87 (s, 1H), 8.02–8.08
(m, 2H), 8.02 (d, J = 8.7 Hz, 1H), 8.06–8.08 (m,1H), 8.34–8.35
(m, 1H), 9.23 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 21.9, 123.5,
125.9, 128.1, 129.3, 130.5, 130.7, 132.9, 139.0, 140.7, 141.9, 142.9,
149.5; HRMS (ESI-TOF) calcd for C15H12BrN2 (M + H)+ 299.0184, found
299.0187.
N-(2-((2-Bromo-4-isopropylphenyl)amino)-2-phenylethyl)-4-
2-(4-Bromophenyl)-6-methylquinoxaline (4j). The general method B
described above was followed when 3j (50 mg, 0.093 mmol) in 1.0 mL of
DMF solvent was added to a suspension of CuI (1.8 mg, 0.009 mmol), L-
proline (2.1 mg, 0.019 mmol), and NaH (5.6 mg, 0.232 mmol) in 1.0 mL of
DMF under argon atmosphere and the mixture was heated to 130 °C for
12 h to afford 4j (21.8 mg, 0.073 mmol) as a yellow solid in 78% yield; mp
methylbenzenesulfonamide (3m). The general method A described
above was followed when 1a (50 mg, 0.183 mmol) was reacted with 2c
(87 µL, 0.549 mmol) at rt for 5 h to afford 3m (74.9 mg, 0.154 mmol) as a
white semi-solid in 84% yield; Rf 0.45 (20% ethyl acetate in petroleum
ether); IR νmax
(KBr, cm−1) 3372, 3283, 3062, 3030, 2958, 2925, 2867,
̃
1916, 1739, 1608, 1514, 1494, 1454, 1404, 1381, 1324, 1265, 1207, 1185,
1160, 1119, 1093, 1034, 954, 878, 812, 738, 702, 664, 551; 1H NMR (400
MHz, CDCl3) δ 1.13 (d, J = 6.9 Hz, 6H), 2.39 (s, 3H), 2.68–2.74 (m, 1H),
3.18–3.25 (m, 1H), 3.34–3.40 (m, 1H), 4.41–4.46 (m, 1H), 4.71–4.75 (m,
2H), 6.26 (d, J = 8.4 Hz, 1H), 6.84 (dd, J = 2.2, 8.4 Hz, 1H), 7.23–7.33 (m,
8H), 7.72 (d, J = 8.0 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 21.6, 24.1,
33.0, 49.1, 57.6, 110.4, 112.8, 126.4, 126.5, 127.2, 128.1, 129.1, 129.9,
130.4, 136.8, 139.5, 139.6, 141.3, 143.7; HRMS (ESI-TOF) calcd for
C24H28BrN2O2S (M + H)+ 487.1055, found 487.1053.
124–126 °C; Rf 0.50 (20% ethyl acetate in petroleum ether); IR νmax (KBr,
̃
cm−1) 3048, 2913, 1635, 1588, 1549, 1350, 1207, 1164, 1077, 1058, 763,
683; 1H NMR (400 MHz, CDCl3) δ 2.59 (s, 3H), 7.58–7.62 (m, 1H),
7.65–7.69 (m, 2H), 7.86 (s, 1H), 8.01 (d, J = 8.7 Hz, 1H), 8.02–
8.07 (m, 2H), 9.23 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 21.9,
124.8, 128.1, 128.9, 129.2, 132.4, 132.9, 135.9, 140.6, 140.8, 141.8, 142.8,
149.9; HRMS (ESI-TOF) calcd for C15H12BrN2 (M + H)+ 299.0184, found
299.0186.
2-(3-Chlorophenyl)-6-methylquinoxaline (4k). The general method B
described above was followed when 3k (50 mg, 0.101 mmol) in 1.0 mL of
DMF solvent was added to a suspension of CuI (1.9 mg, 0.010 mmol), L-
proline (2.3 mg, 0.020 mmol), and NaH (6.1 mg, 0.253 mmol) in 1.0 mL of
DMF under argon atmosphere and the mixture was heated to 130 °C for
14 h to afford 4k (20.1 mg, 0.079 mmol) as a yellow solid in 78% yield; mp
6-Isopropyl-2-phenylquinoxaline (4m). The general method B described
above was followed when 3m (50 mg, 0.103 mmol) in 1.0 mL of DMF
solvent was added to a suspension of CuI (2.0 mg, 0.010 mmol), L-proline
(2.4 mg, 0.021 mmol), and NaH (6.2 mg, 0.256 mmol) in 1.0 mL of DMF
under argon atmosphere and the mixture was heated to 130 °C for 12 h to
afford 4m (21.9 mg, 0.088 mmol) as a light yellow solid in 86% yield; mp
108–110 °C; Rf 0.5 (20% ethyl acetate in petroleum ether); IR νmax
̃
(KBr,
114–116 °C; Rf 0.65 (20% ethyl acetate in petroleum ether); IR νmax
̃
(KBr,
cm−1) 3050, 2915, 1456, 1621, 1488, 1378, 1207, 1250, 1166, 1072, 833,
cm−1) 3060, 2959, 2924, 2873, 1543, 1490, 1442, 1385, 1145, 1169, 1026,
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