The Journal of Organic Chemistry
Article
13C NMR (126 MHz, CDCl3) δ 159.3, 141.0, 133.9, 128.9, 128.3,
127.96, 127.2, 126.2, 123.5, 51.3, 20.7; HRMS (CI+) calcd for
C15H15O2 (M+ + H) 227.1072, found 227.1073.
126.9, 126.8, 114.4, 55.5.
Methyl 4′-Methoxy-[1,1′-biphenyl]-2-carboxylate25 (3k).
3-Methoxy-1,1′-biphenyl34 (3z). Colorless oil. H NMR (500
1
1
Colorless oil. H NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.7, 1H),
MHz, CDCl3) δ 7.58 (dd, J = 5.2, 3.3, 2H), 7.41 (dd, J = 10.4, 4.9,
2H), 7.33 (td, J = 7.6, 3.5, 2H), 7.15 (dt, J = 4.1, 2.9, 2H), 6.88 (dd, J =
8.2, 2.5, 1H), 3.83 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 160.1,
142.9, 141.2, 129.9, 128.9, 127.5, 127.3, 119.8, 113.0, 112.8, 100.0,
55.4.
7.50 (td, J = 7.6, 1.4, 1H), 7.37 (t, J = 7.9, 2H), 7.24 (d, J = 8.7, 2H),
6.93 (d, J = 8.8, 2H), 3.84 (s, 3H), 3.66 (s, 3H); 13C NMR (126 MHz,
CDCl3) δ 169.5, 159.1, 142.1, 133.8, 131.3, 131.0, 130.9, 129.9, 129.6,
126.9, 113.7, 55.4, 52.1.
Dimethyl [1,1′-Biphenyl]-2,4′-dicarboxylate26 (3l). White
2-Methoxy-1,1′-biphenyl34 (3aa). Colorless oil. H NMR (500
1
1
solid, mp 56−58 °C. H NMR (500 MHz, CDCl3) δ 8.16−8.04 (m,
MHz, CDCl3) δ 7.52 (d, J = 7.8, 2H), 7.39 (t, J = 7.6, 2H), 7.33−7.28
(m, J = 7.2, 3H), 7.02 (t, J = 7.4, 1H), 6.97 (d, J = 8.6, 1H), 3.79 (s,
3H); 13C NMR (126 MHz, CDCl3) δ 156.6, 138.7, 131.0, 130.9,
129.7, 128.7, 128.1, 127.0, 121.0, 111.4, 55.7.
2H), 7.88 (dd, J = 7.8, 1.1, 1H), 7.55 (td, J = 7.6, 1.4, 1H), 7.45 (td, J =
7.6, 1.3, 1H), 7.37 (td, J = 8.1, 1.4, 3H), 3.94 (s, 3H), 3.63 (s, 3H); 13
C
NMR (126 MHz, CDCl3) δ 168.7, 167.1, 146.4, 141.8, 131.6, 130.70,
130.68, 130.3, 129.5, 129.0, 128.6, 128.0, 52.3, 52.1.
Methyl 4-(Thiophen-2-yl)benzoate (3ac). Pale yellow solid, mp
138−139 °C (lit.35 139−140 °C). 1H NMR (500 MHz, CDCl3) δ 8.07
(d, J = 8.5, 2H), 7.66 (d, J = 8.5, 2H), 7.57 (dd, J = 2.7, 1.5, 1H),
7.45−7.39 (m, 2H), 3.93 (s, 3H); 13C NMR (126 MHz, CDCl3) δ
166.1, 140.4, 139.2, 129.4, 127.8, 125.8, 125.4, 125.3, 121.0, 51.2.
1-(4-(Thiophen-2-yl)phenyl)ethanone (3ad). Pale yellow solid,
mp 121 °C (lit.36 124−126 °C). 1H NMR (500 MHz, CDCl3) δ 7.97
(d, J = 8.4, 2H), 7.70 (d, J = 8.4, 2H), 7.44 (dd, J = 3.6, 1.0, 1H), 7.37
(dd, J = 5.1, 1.0, 1H), 7.12 (dd, J = 5.0, 3.7, 1H), 2.62 (s, 3H); 13C
NMR (126 MHz, CDCl3) δ 138.0, 134.9, 128.3, 127.5, 125.6, 124.8,
123.8, 25.7.
Methyl 4-(Thiophen-3-yl)benzoate (3ae). Pale yellow solid,
mp 160−161 °C. 1H NMR (500 MHz, CDCl3) δ 8.07 (d, J = 8.3, 2H),
7.67 (d, J = 8.2, 2H), 7.57 (dd, J = 2.7, 1.5, 1H), 7.46−7.40 (m, 2H),
3.93 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 166.1, 140.4, 139.2,
129.4, 127.8, 125.8, 125.4, 125.3, 121.0, 51.3; HRMS (CI+) calcd for
C12H11O2S (M+ + H) 219.0480, found 219.0480.
8-(4-Methoxyphenyl)quinoline (3af). White solid, mp 113−
114 °C (lit.37 117−118 °C). 1H NMR (500 MHz, CDCl3) δ 8.95 (dd,
J = 4.1, 1.7, 1H), 8.18 (dd, J = 8.2, 1.5, 1H), 7.78 (d, J = 8.1, 1H), 7.71
(dd, J = 7.1, 1.2, 1H), 7.66 (d, J = 8.7, 2H), 7.58 (t, J = 7.6, 1H), 7.39
(dd, J = 8.2, 4.1, 1H), 7.04 (d, J = 8.7, 2H), 3.87 (s, 3H); 13C NMR
(126 MHz, CDCl3) δ 159.2, 150.3, 146.3, 140.7, 136.4, 132.1, 131.9,
130.1, 128.9, 127.2, 126.4, 121.0, 113.7, 55.5.
Methyl 4-(Quinolin-8-yl)benzoate (3ag). White solid, mp 92−
93 °C. 1H NMR (500 MHz, CDCl3) δ 8.94 (dd, J = 4.1, 1.7, 1H), 8.21
(dd, J = 8.3, 1.6, 1H), 8.17 (d, J = 8.4, 2H), 7.86 (d, J = 8.1, 1H), 7.78
(d, J = 8.4, 2H), 7.74 (dd, J = 7.1, 1.3, 1H), 7.62 (t, J = 7.6, 1H), 7.43
(dd, J = 8.2, 4.1, 1H), 3.95 (s, 3H); 13C NMR (126 MHz, CDCl3) δ
167.3, 150.6, 146.0, 144.5, 140.0, 136.5, 130.8, 130.5, 129.4, 129.1,
128.9, 128.4, 126.4, 121.4, 52.2; HRMS (CI+) calcd for C17H14NO2
(M+ + H) 264.1025, found 264.1030.
Methyl 4′-Methoxy-[1,1′-biphenyl]-3-carboxylate (3m).
White solid, mp 68−70 °C (lit.27 71−73 °C). H NMR (500 MHz,
1
CDCl3) δ 8.24 (d, J = 1.7, 1H), 7.97 (d, J = 7.7, 1H), 7.75 (d, J = 7.7,
1H), 7.57 (d, J = 8.7, 2H), 7.49 (t, J = 7.7, 1H), 7.00 (d, J = 8.7, 2H),
3.95 (s, 3H), 3.87 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 166.3,
158.7, 140.2, 131.8, 130.2, 129.8, 128.0, 127.4, 127.0, 126.9, 113.5,
54.5, 51.3.
Dimethyl [1,1′-Biphenyl]-3,4′-dicarboxylate (3n). White
1
solid, mp 95 °C. H NMR (500 MHz, CDCl3) δ 8.31 (t, J = 1.7,
1H), 8.16−8.10 (m, 2H), 8.09−8.03 (m, 1H), 7.86−7.77 (m, 1H),
7.71−7.65 (m, 2H), 7.54 (t, J = 7.8, 1H), 3.96 (s, 3H), 3.94 (s, 3H);
13C NMR (126 MHz, CDCl3) δ 167.01, 166.98, 144.6, 140.4, 131.8,
131.0, 130.4, 129.5, 129.3, 129.2, 128.5, 127.3, 52.4, 52.3; HRMS (CI
+) calcd for C16H15O4 (M+ + H) 271.0970, found 271.0974.
2,2′-Dimethoxy-1,1′-biphenyl (3o). White solid, mp 152−154
°C (lit.28 154−155 °C). H NMR (500 MHz, CDCl3) δ 7.38 (td, J =
1
8.2, 1.7, 2H), 7.31 (dd, J = 7.4, 1.6, 2H), 7.06 (t, J = 7.4, 2H), 7.03 (d, J
= 8.3, 2H), 3.82 (s, 6H); 13C NMR (126 MHz, CDCl3) δ 157.2, 131.6,
128.7, 128.0, 120.5, 111.2, 55.8.
Methyl 2′-Methoxy-[1,1′-biphenyl]-2-carboxylate29 (3p).
1
Colorless liquid. H NMR (500 MHz, CDCl3) δ 7.86 (dd, J = 7.8,
1.3, 1H), 7.54 (td, J = 7.6, 1.4, 1H), 7.39 (td, J = 7.6, 1.3, 1H), 7.33
(tdd, J = 6.0, 4.3, 1.7, 2H), 7.27−7.22 (m, 1H), 7.03 (td, J = 7.4, 1.0,
1H), 6.90 (d, J = 8.2, 1H), 3.71 (s, 3H), 3.65 (s, 3H); 13C NMR (126
MHz, CDCl3) δ 168.8, 156.2, 138.9, 131.74, 131.68, 131.5, 130.7,
130.1, 129.5, 129.0, 127.2, 120.9, 110.3, 55.4, 51.8.
2′-Methoxy-2,6-dimethyl-1,1′-biphenyl (3q). Not isolated.
4′-Methoxy-2,6-dimethyl-1,1′-biphenyl (3r). White solid, mp
46−48 °C (lit.30 50.3−50.9 °C). 1H NMR (500 MHz, CDCl3) δ
7.19−7.02 (m, 5H), 6.96 (d, J = 8.7, 2H), 3.85 (s, 3H), 2.04 (s, 6H);
13C NMR (126 MHz, CDCl3) δ 158.4, 141.7, 136.7, 133.5, 130.2,
127.4, 127.0, 114.0, 55.4, 21.0.
Dimethyl [1,1′-Biphenyl]-4,4′-dicarboxylate (3u). White
solid, mp 212−214 °C (lit.28 215.5−216.5 °C). 1H NMR (500
MHz, CDCl3) δ 8.13 (d, J = 8.2, 4H), 7.69 (d, J = 8.2, 4H), 3.95 (s,
6H); 13C NMR (126 MHz, CDCl3) δ 166.9, 144.5, 130.3, 129.9,
127.4, 52.3.
3-(4-Methoxyphenyl)pyridine (3ah). White solid, mp 60−61
°C (lit.38 62−63 °C). H NMR (500 MHz, CDCl3) δ 8.81 (s, 1H),
1
8.54 (d, J = 4.7, 1H), 7.83 (ddd, J = 7.9, 2.3, 1.7, 1H), 7.52 (d, J = 8.8,
2H), 7.33 (dd, J = 7.9, 4.8, 1H), 7.01 (d, J = 8.8, 2H), 3.86 (s, 3H); 13
C
NMR (126 MHz, CDCl3) δ 158.9, 147.1, 147.0, 135.4, 133.0, 129.4,
127.4, 122.6, 113.7, 54.5.
Methyl [1,1′-Biphenyl]-4-carboxylate (3v). White solid, mp
110 °C (lit.31 110−112 °C). 1H NMR (500 MHz, CDCl3) δ 8.11 (d, J
= 8.1, 2H), 7.67 (d, J = 8.2, 2H), 7.63 (d, J = 7.4, 2H), 7.47 (t, J = 7.7,
2H), 7.40 (t, J = 7.1, 1H), 3.95 (s, 3H); 13C NMR (126 MHz, CDCl3)
δ 166.1, 144.8, 139.2, 129.2, 128.1, 127.3, 126.4 126.2, 51.3.
Methyl [1,1′-Biphenyl]-3-carboxylate32 (3w). Colorless oil. 1H
NMR (500 MHz, CDCl3) δ 8.28 (t, J = 1.5, 1H), 8.01 (d, J = 7.8, 1H),
7.77 (d, J = 7.8, 1H), 7.65−7.58 (m, 2H), 7.49 (t, J = 7.7, 1H), 7.45 (t,
J = 7.6, 2H), 7.36 (t, J = 7.4, 1H), 3.93 (s, 3H); 13C NMR (126 MHz,
CDCl3) δ 167.2, 141.6, 140.2, 131.6, 130.8, 129.01, 128.97, 128.5,
128.4, 127.9, 127.3, 52.3.
3-(Thiophen-2-yl)pyridine (3ai). Light brown oil. 1H NMR (500
MHz, CDCl3) δ 8.89 (s, 1H), 8.52 (s, 1H), 7.87 (d, J = 7.4, 1H), 7.36
(d, J = 4.3, 2H), 7.31 (s, 1H), 7.14−7.10 (m, 1H); 13C NMR (126
MHz, CDCl3) δ 148.5, 147.1, 140.6, 133.1, 130.6, 128.4, 126.2, 124.4,
123.8. The 1H NMR and 13C NMR are comparable to the literature.39
3-(Thiophen-3-yl)pyridine (3aj). White solid, mp 76−77 °C
(lit.40 75−77 °C). H NMR (500 MHz, CDCl3) δ 8.88 (s, 1H), 8.54
1
(d, J = 3.7, 1H), 7.86 (d, J = 7.9, 1H), 7.52 (d, J = 1.8, 1H), 7.45 (dd, J
= 4.8, 3.1, 1H), 7.40 (d, J = 5.0, 1H), 7.32 (dd, J = 7.8, 4.8, 1H); 13C
NMR (126 MHz, CDCl3) δ 148.4, 147.9, 139.0, 133.6, 131.7, 127.1,
126.1, 123.8, 121.6.
Methyl [1,1′-Biphenyl]-2-carboxylate33 (3x). Colorless oil. H
1
8-(Thiophen-2-yl)quinoline41 (3ak). Pale yellow oil. H NMR
1
NMR (500 MHz, CDCl3) δ 7.82 (d, J = 7.8, 1H), 7.52 (td, J = 7.6, 1.4,
1H), 7.43−7.33 (m, 5H), 7.33−7.28 (m, 2H), 3.63 (s, 3H); 13C NMR
(126 MHz, CDCl3) δ 169.3, 142.6 141.5, 131.4, 131.0, 130.8, 129.9,
128.5, 128.2 127.4, 127.3, 52.1.
(500 MHz, CDCl3) δ 9.02 (dd, J = 4.1, 1.8, 1H), 8.19 (dd, J = 8.2, 1.7,
1H), 8.08 (dd, J = 7.3, 1.3, 1H), 7.79 (dd, J = 3.7, 1.1, 1H), 7.76 (dd, J
= 8.1, 1.1, 1H), 7.57 (t, J = 7.7, 1H), 7.49 (dd, J = 5.1, 1.1, 1H), 7.45
(dd, J = 8.3, 4.1, 1H), 7.18 (dd, J = 5.1, 3.7, 1H). 13C NMR (126 MHz,
CDCl3) δ 148.7, 143.9, 138.9, 135.5, 132.3, 128.0, 127.2, 127.1, 126.3,
125.9, 125.8, 125.6, 120.4.
4-Methoxy-1,1′-biphenyl (3y). White solid, mp 85 °C (lit.4b
85−87 °C). 1H NMR (500 MHz, CDCl3) δ 7.58−7.50 (m, 4H), 7.41
(t, J = 7.7, 2H), 7.30 (t, J = 7.4, 1H), 7.01−6.95 (m, 2H), 3.85 (s, 3H);
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dx.doi.org/10.1021/jo202037x | J. Org. Chem. 2011, 76, 9946−9955