UPDATES
Wen-Wen Xie et al.
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yellow solid; yield: 87% (134.2 mg); mp 100.1–101.58C;
1H NMR (400 MHz, CDCl3): d=8.83 (s, 1H), 8.76 (d, J=
1.0 Hz, 1H), 7.81–7.75 (m, 2H), 7.59 (d, J=7.2 Hz, 2H),
7.48–7.36 (m, 5H), 7.29–7.28 (m, 3H), 7.23–7.21 (m, 2H);
13C NMR (100 MHz, CDCl3): d=156.8, 155.6, 148.5, 147.8,
139.5, 138.6, 137.5, 136.6, 135.1, 134.0, 129.3, 129.2, 129.0,
128.3, 128.1, 127.2, 127.0, 124.7, 123.1; HR-ESI MS: m/z=
309.1388, calcd. for C22H16N2 ([M+H]+): 309.1386.
37.48C; H NMR (400 MHz, CDCl3): d=8.85 (s, 1H), 8.77
(d, J=4.4 Hz, 1H), 7.82–7.75 (m, 2H), 7.43–7.35 (m, 3H),
7.22–7.16 (m, 2H), 7.10 (s, 1H), 6.94 (d, J=8.0 Hz, 1H),
6.79 (t, J=7.2 Hz, 2H), 6.75 (s, 1H), 3.86 (s, 3H), 3.66 (s,
3H); 13C NMR (100 MHz, CDCl3): d=160.0, 159.3, 156.8,
155.5, 148.5, 147.8, 140.7, 138.8, 138.4, 136.4, 135.0, 134.1,
130.0, 129.3, 124.6, 123.0, 121.8, 119.5, 114.7, 113.3, 113.2,
112.8, 55.3, 55.0; HR-ESI MS: m/z=369.1596, calcd. for
C24H20N2O2 ([M+H]+): 369.1598.
3,3’-Dichloro-2,6’-bipyridine (9b):[28] column chromatogra-
phy, silica gel (petroleum ether/ethyl acetate, 10:1); pale
yellow solid; yield: 39% (43.9 mg); mp 114.7–115.98C;
1H NMR (400 MHz, CDCl3): d=8.84 (s, 1H), 8.62 (s, 1H),
7.54–7.46 (m, 3H), 7.41 (d, J=5.2 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=157.6, 154.9, 149.0, 146.1, 139.0,
132.1, 128.9, 124.8, 123.1.
3,3’-Diphenyl-2,2’-biquinoxaline (15b): column chroma-
tography, silica gel (petroleum ether/ethyl acetate, from 15/
1 to 10/1); white solid; yield: 54% (110.8 mg); mp 210.2–
211.28C; 1H NMR (400 MHz, CDCl3): d=8.39–8.37 (m,
2H), 8.19–8.17 (m, 2H), 7.88–7.85 (m, 4H), 7.21 (t, J=
7.4 Hz, 2H), 7.02 (t, J=7.6 Hz, 4H), 6.80 (d, J=7.6 Hz,
4H); 13C NMR (100 MHz, CDCl3): d=153.2, 152.0, 141.9,
141.1, 137.3, 130.9, 130.2, 129.7, 129.3, 129.0, 128.7, 128.1;
HR-ESI MS: m/z=411.1608, calcd. for C28H18N4 ([M+H]+):
411.1604.
3,3’-Di(naphthalen-2-yl)-2,6’-bipyridine (10b): column
chromatography, silica gel (petroleum ether/ethyl acetate,
3:1); pale yellow solid; yield: 16% (33 mg); mp 107.6–
1
109.98C; H NMR (400 MHz, CDCl3): d=8.93 (s, 1H), 8.82
(d, J=3.6 Hz, 1H), 8.01 (s, 1H), 7.96–7.82 (m, 7H), 7.72–
7.61 (m, 2H), 7.48 (s, 6H), 7.26–7.09 (m, 2H); 13C NMR
(100 MHz, CDCl3): d=156.6, 155.6, 148.6, 148.0, 139.0,
137.2, 136.6, 135.1, 134.7, 134.4, 133.4, 132.8, 132.3, 128.8,
128.2, 128.1, 127.7, 127.6, 126.5, 126.4, 126.3, 126.1, 124.9,
123.2; HR-ESI MS: m/z=409.1682, calcd. for C30H20N2
([M+H]+): 409.1680.
3,3’-Di-p-tolyl-2,2’-biquinoxaline (16b): column chroma-
tography, silica gel (petroleum ether/ethyl acetate, from 15/
1 to 10/1); white solid; yield: 62% (135.9 mg); mp 204.8–
205.28C; 1H NMR (400 MHz, CDCl3): d=8.37–8.34 (m,
2H), 8.18–8.15 (m, 2H), 7.86–7.84 (m, 4H), 6.84 (d, J=
7.6 Hz, 4H), 6.70 (d, J=8.0 Hz, 4H), 2.27 (s, 6H); 13C NMR
(100 MHz, CDCl3): d=153.4, 152.2, 141.9, 140.9, 138.8,
134.5, 130.7, 129.9, 129.6, 129.2, 128.9, 128.7, 21.1; HR-ESI
MS: m/z=439.1917, calcd. for C30H22N4 ([M+H]+):
439.1917.
3,3’-Bis(4-methoxyphenyl)-2,6’-bipyridine (11b): column
chromatography, silica gel (petroleum ether/ethyl acetate,
3:1); pale yellow solid; yield: 44% (81.1 mg); mp 143.8–
1
146.88C; H NMR (400 MHz, CDCl3): d=8.83 (s, 1H), 8.73
3,3’-Bis(3,5-dimethylphenyl)-2,2’-biquinoxaline
(17b):
(d, J=3.6 Hz, 1H), 7.78–7.71 (m, 2H), 7.54 (d, J=8.4 Hz,
2H), 7.40–7.37 (m, 1H), 7.31 (d, J=8.4 Hz, 1H), 7.15 (d, J=
8.0 Hz, 2H), 7.01 (d, J=8.4 Hz, 2H), 6.84 (d, J=8.4 Hz,
2H), 3.85 (s, 3H), 3.79 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=159.8, 158.9, 156.2, 148.2, 147.5, 138.5, 136.2,
134.6, 133.5, 131.8, 130.5, 129.9, 128.1, 124.7, 123.0, 114.5,
113.8, 55.3, 55.2; HR-ESI MS: m/z=369.1591, calcd. for
C24H20N2O2 ([M+H]+): 369.1593.
column chromatography, silica gel (petroleum ether/ethyl
acetate, from 15/1 to 10/1); white solid; yield: 40% (94 mg);
mp 199.6–201.38C; 1H NMR (400 MHz, CDCl3): d=8.38–
8.36 (m, 2H), 8.18–8.16 (m, 2H), 7.87–7.84 (m, 4H), 6.85 (s,
2H), 6.38 (s, 4H), 2.02 (s, 12H); 13C NMR (100 MHz,
CDCl3): d=153.7, 152.4, 141.7, 140.9, 137.4, 137.0, 130.7,
130.3, 129.9, 129.5, 129.1, 127.1, 21.0; HR-ESI MS: m/z=
467.2233, calcd for C32H26N4 ([M+H]+): 467.2230.
3,3’-Di-p-tolyl-2,6’-bipyridine (12b): column chromatogra-
phy, silica gel (petroleum ether/ethyl acetate, 3:1); pale
yellow solid; yield: 64% (107.7 mg); 78% (131.2 mg); mp
109.2–112.98C; 1H NMR (400 MHz, CDCl3): d=8.85 (s,
1H), 8.75 (d, J=3.6 Hz, 1H), 7.79–7.73 (m, 2H), 7.50 (d, J=
7.2 Hz, 2H), 7.50–7.41 (m, 1H), 7.40–7.26 (m, 3H), 7.10 (s,
4H), 2.40 (s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=156.4, 155.5, 148.3, 147.7, 138.6, 138.0, 137.0,
136.5, 135.0, 134.6, 133.8, 129.7, 129.2, 129.1, 126.8, 124.7,
123.0, 21.1; HR-ESI MS: m/z=337.1688, calcd. for C24H20N2
([M+H]+): 337.1686.
3,3’-Bis(3,5-dimethylphenyl)-2,6’-bipyridine (13b): column
chromatography, silica gel (petroleum ether/ethyl acetate,
3:1); yellow solid; yield: 42% (76.5 mg); 1H NMR
(400 MHz, CDCl3): d=8.83 (s, 1H), 8.74 (d, J=4.4 Hz, 1H),
7.79–7.74 (m, 2H), 7.39–7.33 (m, 2H), 7.19 (s, 2H), 7.03 (s,
1H), 6.90 (s, 1H), 6.82 (s, 2H), 2.38 (s, 6H), 2.22 (s, 6H);
13C NMR (100 MHz, CDCl3): d=156.6, 155.6, 148.2, 147.7,
139.3, 138.6, 138.5, 137.7, 137.5, 136.8, 135.2, 133.9, 129.7,
128.8, 127.2, 124.8, 124.6, 122.9, 21.3, 21.2; HR-ESI MS:
m/z=365.2005, calcd. for C26H24N2 ([M+H]+): 365.2012.
3,3’-Bis(3-methoxyphenyl)-2,6’-bipyridine (14b): column
chromatography, silica gel (petroleum ether/ethyl acetate,
3:1); pale yellow solid; yield: 57% (104.9 mg); mp 36.1–
3,3’-Bis(4-methoxyphenyl)-2,2’-biquinoxaline
(18b):
column chromatography, silica gel (petroleum ether/ethyl
acetate, from 10/1 to 5/1); white solid; yield: 41% (97 mg);
mp 152.5–153.58C; 1H NMR (400 MHz, CDCl3): d=8.30–
8.22 (m, 2H), 8.16–8.11 (m, 2H), 7.87–7.81 (m, 4H), 7.48 (d,
J=8.8 Hz, 4H), 6.85 (d, J=8.4 Hz, 4H), 3.79 (s, 6H);
13C NMR (100 MHz, CDCl3): d=153.3, 152.4, 141.9, 141.0,
131.3, 131.2, 130.6, 130.5, 130.4, 130.1, 130.0, 129.6, 55.3;
HR-ESI MS: m/z=471.1815 calcd. for C30H22N4O2 ([M+
H]+): 471.1813.
3,3’-Di-m-tolyl-2,2’-biquinoxaline (19b): column chroma-
tography, silica gel (petroleum ether/ethyl acetate, from 15/
1 to 10/1); white solid; yield: 56% (122.8 mg); mp 207.3–
208.08C; 1H NMR (400 MHz, CDCl3): d=8.39–8.37 (m,
2H), 8.19–8.17 (m, 2H), 7.87–7.85 (m, 4H), 7.04 (d, J=
7.6 Hz, 2H), 6.85 (t, J=7.6 Hz, 2H), 6.64 (s, 2H), 6.51 (d,
J=7.6 Hz, 2H), 2.11 (s, 6H); 13C NMR (100 MHz, CDCl3):
d=153.5, 152.2, 141.9, 141.1, 138.0, 137.1, 130.8, 130.0, 129.9,
129.7, 129.4, 129.2, 127.6, 126.0, 21.1; HR-ESI MS: m/z=
439.1923, calcd. for C30H22N4 ([M+H]+): 439.1917.
3,3’-Bis(3-fluorophenyl)-2,2’-biquinoxaline (20b): column
chromatography, silica gel (petroleum ether/ethyl acetate,
from 15/1 to 10/1); green solid; yield: 39% (104.5 mg); mp
125.6–132.48C; 1H NMR (400 MHz, CDCl3): d=8.39–8.37
1000
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 994 – 1002