The Journal of Organic Chemistry
Article
NMR (500 MHz, CDCl3): δ 8.82 (s, 1H), 8.55 (d, J = 4.6 Hz, 1H),
7.83 (d, J = 7.9 Hz, 1H), 7.52 (d, J = 8.6 Hz, 2H), 7.33 (dd, J = 7.8, 4.8
Hz, 1H), 7.01 (d, J = 8.6 Hz, 2H), 3.86 (s, 4H). 13C NMR (125.8
MHz, CDCl3): δ 159.9, 148.2, 148.0, 136.4, 133.9, 130.4, 128.4, 123.6,
114.7, 55.5.
3-(4-Methoxyphenyl)pyridine (Table 2, Entry 5, Aryl
Chloride in Second Step).33 General procedure A was employed.
Column chromatography (0−50% EtOAc/hexane) provided the title
compound as a pale yellow solid in 82% yield (229 mg). Spectral data
were in accordance with those of published results. Mp: 63−65 °C. 1H
NMR (500 MHz, CDCl3): δ 8.82 (d, J = 1.9 Hz, 1H), 8.55 (d, J = 3.7
Hz, 1H), 7.83 (dd, J = 7.9, 1.7 Hz, 1H), 7.52 (d, J = 8.7 Hz, 2H), 7.34
(dd, J = 7.8, 4.8 Hz, 1H), 7.02 (d, J = 8.7 Hz, 2H), 3.87 (s, 3H).13C
NMR (125.8 MHz, CDCl3): δ 159.9, 148.2, 148.0, 136.4, 134.0, 130.4,
128.4, 123.7, 114.7, 55.5.
3-(4-Methoxyphenyl)pyridine (Table 2, Entry 5, Aryl Bro-
mide in Second Step).33 General procedure A was employed.
Column chromatography (0−50% EtOAc/hexane) provided the title
compound as a pale yellow solid in 80% yield (223 mg). Spectral data
were in accordance with those of published results. Mp: 63−65 °C. 1H
NMR (500 MHz, CDCl3): δ 8.82 (d, J = 1.7 Hz, 1H), 8.55 (dd, J =
4.8, 1.6 Hz, 1H), 7.85−7.82 (m, 1 H), 7.54−7.48 (m, 2H), 7.35−7.33
(m, 1 H), 7.03−6.97 (m, 2H), 3.85 (s, 3H). 13C NMR (125.8 MHz,
CDCl3): δ 159.9, 148.1, 148.0, 136.4, 133.9, 130.4, 128.4, 123.6, 114.7,
55.5.
as pale yellow crystals in 94% yield (499 mg). Mp: =156−157 °C. 1H
NMR (500 MHz, CDCl3): δ 8.03 (s, 2H), 7.88 (s, 1H), 7.68 (d, J =
8.1 Hz, 2H), 7.54 (d, J = 8.1 Hz, 2H), 7.17 (s, 2H), 6.41 (s, 2H). 13C
NMR (125.8 MHz, CDCl3): δ 142.4, 141.3, 135.4, 132.8, 132.5, 132.3,
132.0, 128.6, 127.1, 126.8, 124.6, 122.4, 121.1, 121.1, 121.1, 121.0,
120.9, 120.3, 119.2, 111.2. IR (dry film): 3142, 3104, 3021, 1901,
1817, 1613 cm−1. HRMS (ES+): calcd for C18H12F6N (M + 1)
356.0874, found 356.0866.
1-(2′,6′-Difluoro[1,1′-biphenyl]-4-yl)-1H-pyrrole (Table 3,
Entry 6A). General procedure A was employed. Column chromatog-
raphy (1/19 EtOAc/hexane) provided the title compound as off-white
1
crystals in 86% yield (328 mg). Mp: 143−144 °C. H NMR (500
MHz, CDCl3): δ 7.55 (d, J = 8.1 Hz, 2H), 7.49 (d, J = 8.5 Hz, 2H),
7.30 (ddd, J = 14.6, 8.3, 6.5 Hz, 1H), 7.18−7.13 (m, 2H), 7.01 (t, J =
7.8 Hz, 2H), 6.41−6.35 (m, 2H). 13C NMR (125.8 MHz, CDCl3): δ
156.3, 156.2, 154.3, 154.2, 135.6, 126.7, 124.2, 124.1, 124.0, 121.5,
115.3, 114.4, 112.7, 107.0, 106.9, 106.8, 106.8, 105.8. IR (dry film):
3144, 3043, 2926, 1901, 1613, 1531 cm−1. HRMS (ES+): calcd for
C16H12F2N (M + 1) 256.0938, found 256.0949.
[1,1′-Biphenyl]-2-carbonitrile (Table 4, Entry 1, Route A).22
General procedure A was employed. Column chromatography (1/49
EtOAc/hexane) provided the title compound as a clear colorless oil in
29% yield (81 mg). Spectral data were in accordance with those of
1
published results. H NMR (500 MHz, CDCl3): δ 7.77 (dd, J = 7.5,
1.6 Hz, 1H), 7.65 (td, J = 7.7, 1.4 Hz, 1H), 7.59−7.55 (m, 2H), 7.52
(dd, J = 8.7, 1.0 Hz, 1H), 7.51−7.48 (m, 2H), 7.48−7.42 (m, 2H). 13C
NMR (125.8 MHz, CDCl3): δ 145.6, 138.3, 133.9, 132.9, 130.2, 129.6,
128.9, 128.9, 127.7, 118.8, 111.4.
4′-(1H-Pyrrol-1-yl)[1,1′-biphenyl]-2-carbonitrile (Table 3,
Entry 1A). General procedure A was employed. Column chromatog-
raphy (1/9 EtOAc/hexane) provided the title compound as off-white
[1,1′-Biphenyl]-2-carbonitrile (Table 4, Entry 1, Route B).22
General procedure A was employed. Column chromatography (1/49
→ 1/19 EtOAc/hexane) provided the title compound as a clear
colorless oil in 69% yield (185 mg). Spectral data were in accordance
with those of published results. 1H NMR (500 MHz, CDCl3): δ 7.79−
7.76 (m, 1H), 7.65 (td, J = 7.7, 1.3 Hz, 1H), 7.59−7.55 (m, 2H),
7.54−7.48 (m, 3H), 7.45 (tdd, J = 7.8, 3.4, 1.2 Hz, 2H). 13C NMR
(125.8 MHz, CDCl3): δ 145.6, 138.3, 133.9, 132.9, 130.2, 128.9, 128.8
(2), 127.7, 118.8, 111.4.
1
crystals in 80% yield (294 mg). Mp: 100−101 °C. H NMR (500
MHz, CDCl3): δ 7.79 (d, J = 7.7 Hz, 1H), 7.66 (dd, J = 16.1, 8.1 Hz,
3H), 7.53 (t, J = 9.1 Hz, 3H), 7.46 (t, J = 7.6 Hz, 1H), 7.21−7.11 (m,
2H), 6.49−6.34 (m, 2H). 13C NMR (125.8 MHz, CDCl3): δ 144.5,
141.0, 135.3, 133.9, 133.0, 130.1, 130.0, 127.8, 120.5, 119.3, 118.8,
111.2, 111.0. IR (dry film): 3144, 3058, 2882, 2359, 2225, 1608, 1524
cm−1. HRMS (ES+): calcd for C17H13N2 (M + 1) 245.1079, found
245.1074.
4′-(1H-Pyrrol-1-yl)[1,1′-biphenyl]-2-yl)(morpholino)-
methanone (Table 3, Entry 2A). General procedure A was
employed. Column chromatography (1/9 → 1/1 EtOAc/hexane)
provided the title compound as off-white crystals in 74% yield (368
[1,1′-Biphenyl]-4-amine (Table 4, Entry 2, Route A).31 General
procedure A was employed. Column chromatography (1/2 → 1/1
EtOAc/hexane) provided the title compound as pale yellow crystals in
60% yield (150 mg). Spectral data were in accordance with those of
1
mg). H NMR (500 MHz, CDCl3): δ 7.58−7.35 (m, 8H), 7.14 (s,
1
2H), 6.38 (s, 2H), 3.59 (dt, J = 35.5, 13.1 Hz, 3H), 3.36−3.25 (m,
2H), 3.05−2.95 (m, 1H), 2.81−2.62 (m, 2H). 13C NMR (125.8 MHz,
CDCl3): δ 170.4, 169.9, 140.3, 137.6, 136.9, 135.5, 134.9, 130.1, 130.0,
129.8, 129.3, 128.7, 128.1, 127.9, 127.2, 120.1, 119.2, 111.1, 66.9, 66.2,
46.9, 41.9. IR (dry film): 3101, 3041, 2986, 2851, 2320, 1618 cm−1.
HRMS (ES+): calcd for C21H21N2O2 (M + 1) 333.1603, found
333.1594.
published results. Mp: 45−49 °C. H NMR (500 MHz, CDCl3): δ
7.55 (d, J = 7.2 Hz, 2H), 7.47−7.38 (m, 4H), 7.28 (t, J = 7.4 Hz, 1H),
6.77 (d, J = 8.3 Hz, 2H), 3.69 (s, 2H). 13C NMR (125.8 MHz,
CDCl3): δ 145.9, 141.2, 131.5, 128.7, 128.0, 126.4, 126.3, 115.5.
[1,1′-Biphenyl]-4-amine (Table 4, Entry 2, Route B).31 General
procedure A was employed. Column chromatography (1/4 → 1/2
EtOAc/hexane) provided the title compound as pale brown crystals in
80% yield (200 mg). Spectral data were in accordance with those of
1-(4′-(1H-Pyrrol-1-yl)[1,1′-biphenyl]-2-yl)ethanone (Table 3,
Entry 3A). General procedure A was employed. Column chromatog-
raphy (0−10% EtOAc/hexane) provided the title compound as a
yellow solid in 59% yield (230 mg). Mp: 119−121 °C. 1H NMR (500
MHz, CDCl3): δ 7.61−7.52 (m, 2H), 7.49−7.44 (m, 3H), 7.41 (m,
3H), 7.16 (t, J = 2.2 Hz, 2H), 6.39 (t, J = 2.2 Hz, 2H), 2.12 (s, 3H).
13C NMR (125.8 MHz, CDCl3): δ 204.7, 140.9, 140.5, 139.7, 138.1,
131.0, 130.4, 130.2, 128.2, 127.8, 120.5, 119.3, 110.9, 30.7. IR (dry
film): 2977, 1673, 1613, 833, 761 cm−1. HRMS (CI+): calcd for
C18H16NO (M + H) 262.1232, found 262.1220.
1-(2′,6′-Dimethyl-[1,1′-biphenyl]-4-yl)-1H-pyrrole (Table 3,
Entry 4A). General procedure A was employed. Column chromatog-
raphy (1/19 EtOAc/hexane) provided the title compound as pale
yellow crystals in 57% yield (211 mg). Mp: 88−89 °C. 1H NMR (500
MHz, CDCl3): δ 7.46 (d, J = 8.4 Hz, 2H), 7.22−7.11 (m, 7H), 6.38 (t,
J = 2.1 Hz, 2H), 2.07 (s, 6H). 13C NMR (125.8 MHz, CDCl3): δ
141.0, 139.4, 138.5, 136.3, 130.3, 127.5, 127.4, 120.5, 119.3, 110.5,
21.0. IR (dry film): 3065, 2960, 2396, 2342, 1610, 1518 cm−1. HRMS
(ES+): calcd for C18H17N (M + 1) 248.1439, found 248.1432.
1-(3′,5′-Bis(trifluoromethyl)[1,1′-biphenyl]-4-yl)-1H-pyrrole
(Table 3, Entry 5A).34 General procedure A was employed. Column
chromatography (1/19 EtOAc/hexane) provided the title compound
1
published results. Mp: 50−51 °C. H NMR (500 MHz, CDCl3): δ
7.62 (d, J = 7.7 Hz, 2H), 7.53−7.41 (m, 4H), 7.34 (t, J = 7.2 Hz, 1H),
6.79 (d, J = 7.7 Hz, 2H), 3.74 (brs, 2H). 13C NMR (125.8 MHz,
CDCl3): δ 146.0, 141.2, 131.5, 128.7, 128.1, 126.5, 126.3, 115.4.
3-(Thiophen-3-yl)phenol (Table 4, Entry 3, Route B). General
procedure A was employed. Column chromatography (0−10%
EtOAc/hexane) provided the title compound as off-white crystals in
91% yield (240 mg). Mp: 95−97 °C. 1H NMR (500 MHz, CDCl3): δ
7.45 (dd, J = 2.8, 1.4 Hz, 1H), 7.38−7.28 (m, 2H), 7.20−7.19 (m,
1H), 7.10−7.08 (m, 1H), 6.80−6.75 (m, 1H), 4.75 (s, 1H). 13C NMR
(125.8 MHz, CDCl3): δ 155.95, 142.0, 137.7, 130.2, 126.5, 126.4,
120.8, 119.3, 114.2, 113.5. IR (dry film): 2365, 1581, 1219, 769 cm−1.
HRMS (CI+): calcd for C10H9OS (M + H) 177.0374, found 177.0370.
2-Methyl-4-(4-(trifluoromethyl)phenyl)quinolone (Table 4,
Entry 4, Route A).24 General procedure B was employed. Column
chromatography (0−5% MeOH/CH2Cl2) provided the title com-
pound as off-white crystals in 63% yield (275 mg). Spectral data were
1
in accordance with those of published results. Mp: 104−106 °C. H
NMR (500 MHz, CDCl3): δ 8.11 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 8.0
Hz, 2H), 7.78−7.70 (m, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.46 (t, J = 7.5
Hz, 1H), 7.23 (s, 1H), 2.80 (s, 3H). 13C NMR (125.8 MHz, CDCl3):
H
dx.doi.org/10.1021/jo301642v | J. Org. Chem. XXXX, XXX, XXX−XXX