The Journal of Organic Chemistry
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mixture was purified by column chromatography using silica gel
(100−200 mesh) giving 3ah (28 mg) in 82% yield (wrt 0.108 mmol
scale of starting material 1a). Physical state: yellow solid. Mp: 193−
196 °C. Rf: 0.15 (50% EtOAc/DCM). 1H NMR (400 MHz, CDCl3):
δ 8.70 (d, J = 4.8 Hz, 1H), 7.95 (td, J = 7.6, 1.6 Hz, 1H), 7.86 (d, J =
8.0 Hz, 2H), 7.48−7.42 (m, 3H), 7.26 (d, J = 8.4 Hz, 2H), 7.05 (d, J
= 16.0 Hz, 1H), 6.64 (dd, J = 9.2, 6.0 Hz, 2H), 6.29 (d, J = 16.0 Hz,
1H), 2.56 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 197.5,
163.4, 151.8, 150.3, 145.9, 140.4, 140.1, 139.1, 137.2, 133.1, 129.1,
127.3, 124.5, 124.5, 123.6, 120.8, 104.8, 26.9. IR (KBr, cm−1): 2918,
1651, 1532, 1267.
(E)-Methyl 4-(2-(2-oxo-2H-[1,2′-bipyridin]-6-yl)vinyl)benzoate
(3ai)6b was prepared according to general procedure (b). The
crude reaction mixture was purified by column chromatography using
silica gel (100−200 mesh) giving 3ai (33 mg) in 85% yield (wrt 0.117
mmol scale of starting material 1a). Physical state: pale green solid.
Mp: 126−133 °C. Rf: 0.1 (100% EtOAc). 1H NMR (400 MHz,
CDCl3): δ 8.71 (d, J = 3.6 Hz, 1H), 7.96−7.92 (m, 3H), 7.47−7.41
(m, 3H), 7.24 (d, J = 8.0 Hz, 2H), 7.03 (d, J = 16.0 Hz, 1H), 6.66−
6.61 (m, 2H), 6.28 (d, J = 16.0 Hz, 1H), 3.90 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3): δ 166.8, 163.4, 151.9, 150.4, 146.1, 140.3, 140.2,
139.2, 133.3, 130.5, 130.4, 127.2, 124.6, 123.6, 120.9, 104.8, 52.5. IR
(KBr, cm−1): 2922, 1715, 1661, 1535, 1435, 1288, 1108. HRMS
(ESI) m/z: [M + H]+ calcd for C20H17N2O3, 333.1234; found
333.1205.
(E)-6-(3-Chlorostyryl)-2H-[1,2′-bipyridin]-2-one (3aj) was prepared
according to general procedure (b). The crude reaction mixture was
purified by column chromatography using silica gel (100−200 mesh)
giving 3aj (35 mg) in 97% yield (wrt 0.117 mmol scale of starting
material 1a). Physical state: yellow solid. Mp: 165−172 °C. Rf: 0.25
(100% EtOAc). 1H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 3.2 Hz,
1H), 7.94 (dt, J = 7.8, 1.6 Hz, 1H), 7.48−7.40 (m, 3H), 7.24−7.18
(m, 2H), 7.15 (s, 1H), 7.06 (td, J = 6.8, 1.6 Hz, 1H), 6.95 (d, J = 16.0
Hz, 1H), 6.65−6.59 (m, 2H), 6.18 (d, J = 15.6 Hz, 1H). 13C{1H}
NMR (100 MHz, CDCl3): δ 163.5, 151.9, 150.4, 146.1, 140.2, 139.2,
137.9, 135.1, 133.1, 130.3, 129.2, 127.2, 125.4, 124.6, 124.5, 122.6,
120.7, 104.7. IR (KBr, cm−1): 3063, 2929, 1670, 1577, 1540, 1432,
794. HRMS (ESI) m/z: [M + H]+ calcd for C18H14ClN2O, 309.0789;
found 309.0789.
(E)-6-(3-Methylstyryl)-2H-[1,2′-bipyridin]-2-one (3ak) was prepared
according to general procedure (b). The crude reaction mixture was
purified by column chromatography using silica gel (100−200 mesh)
giving 3ak (30 mg) in 90% yield (wrt 0.116 mmol scale of starting
material 1a). Physical state: yellow solid. Mp: 122−125 °C. Rf: 0.12
(50% EtOAc/DCM). 1H NMR (400 MHz, CDCl3): δ 8.61 (d, J = 3.6
Hz, 1H), 7.83 (t, J = 7.6 Hz, 1H), 7.36−7.27 (m, 3H), 7.09−6.88 (m,
5H), 6.53−6.48 (m, 2H), 6.08 (d, J = 15.6 Hz, 1H), 2.20 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 163.5, 152.0, 150.3, 146.7,
140.2, 139.1, 138.6, 135.9, 134.8, 130.0, 128.9, 128.2, 124.4, 124.4,
124.2, 120.9, 119.9, 104.2, 21.5. IR (KBr, cm−1): 2965, 1660, 1579,
1531, 1433. HRMS (ESI) m/z: [M + H]+ calcd for C19H17N2O,
289.1335; found, 289.1330.
mesh) giving 3am (23 mg) in 85% yield (wrt 0.113 mmol scale of
starting material 1a). Physical state: yellow liquid. Rf: 0.1 (50%
EtOAc/DCM). H NMR (400 MHz, CDCl3): δ 8.69 (d, J = 4.4 Hz,
1
1H), 7.91 (td, J = 7.6, 1.6 Hz, 1H), 7.42 (dd, J = 7.2, 4.8 Hz, 1H),
7.37−7.33 (m, 2H), 6.51 (d, J = 9.2 Hz, 1H), 6.34 (d, J = 7.2 Hz,
1H), 5.69 (dd, J = 15.2, 9.2 Hz, 1H), 5.56 (d, J = 15.6 Hz, 1H), 1.33−
1.25 (m, 1H), 0.80−0.75 (m, 2H), 0.45−0.41 (m, 2H). 13C{1H}
NMR (100 MHz, CDCl3): δ 163.6, 152.2, 150.2, 146.9, 142.6, 140.3,
139.0, 124.4, 124.3, 120.3, 118.8, 103.2, 15.2, 8.3. IR (KBr, cm−1):
3005, 1652, 1575, 1532, 1433. HRMS (ESI) m/z: [M + H]+ calcd for
C15H15N2O, 239.1179; found 239.1188.
(E)-6-(Hex-1-en-1-yl)-2H-[1,2′-bipyridin]-2-one (3an) was prepared
according to general procedure (b). The crude reaction mixture was
purified by column chromatography using silica gel (100−200 mesh)
giving 3an (25 mg) in 85% yield (wrt 0.115 mmol scale of starting
material 1a). Physical state: brown oil. Rf: 0.12 (50% EtOAc/DCM).
1H NMR (400 MHz, CDCl3): δ 8.67 (d, J = 4.0 Hz, 1H), 7.90 (td, J =
7.6, 1.6 Hz, 1H), 7.42−7.40 (m, 1H), 7.38−7.36 (m, 1H), 7.33 (d, J =
7.6 Hz, 1H), 6.55 (d, J = 9.2 Hz, 1H), 6.39 (d, J = 6.8 Hz, 1H), 6.23−
6.15 (m, 1H), 5.50 (d, J = 15.2 Hz, 1H), 1.99 (dd, J = 13.2, 6.4 Hz,
2H), 1.29−1.25 (m, 2H), 1.22−1.17 (m, 2H), 0.81 (t, J = 7.2 Hz,
3H). 13C{1H} NMR (100 MHz, CDCl3): δ 163.7, 152.1, 150.2, 147.1,
140.5, 139.0, 138.5, 124.4, 124.3, 123.3, 119.3, 103.9, 32.7, 30.8, 22.2,
14.1. IR (KBr, cm−1): 2932, 1661, 1537, 1434. HRMS (ESI) m/z: [M
+ H]+ calcd for C16H19N2O, 255.1492; found 255.1492.
(E)-6-(Hept-1-en-1-yl)-2H-[1,2′-bipyridin]-2-one (3ao)6b was pre-
pared according to general procedure (b). The crude reaction mixture
was purified by column chromatography using silica gel (100−200
mesh) giving 3ao (26 mg) in 83% yield (wrt 0.117 mmol scale of
starting material 1a). Physical state: brown oil. Rf: 0.2 (50% EtOAc/
1
DCM). H NMR (400 MHz, CDCl3): δ 8.60 (dd, J = 5.2, 2.0 Hz,
1H), 7.82 (td, J = 7.6, 2.0 Hz, 1H), 7.35−7.25 (m, 3H), 6.48 (d, J =
9.2 Hz, 1H), 6.31 (d, J = 7.2 Hz, 1H), 6.16−6.08 (m, 1H), 5.42 (d, J
= 15.6 Hz, 1H), 1.91 (q, J = 7.2 Hz, 2H), 1.25−1.18 (m, 3H), 1.16−
1.12 (m, 2H), 1.11−1.09 (m, 1H), 0.77 (t, J = 7.2 Hz, 3H). 13C{1H}
NMR (100 MHz, CDCl3): δ 163.7, 152.2, 150.2, 147.1, 140.5, 138.9,
138.6, 124.4, 124.3, 123.3, 119.3, 103.9, 33.0, 31.4, 28.4, 22.7, 14.3. IR
(KBr, cm−1): 2925, 1716, 1537, 1434.
(E)-6-(Oct-1-en-1-yl)-2H-[1,2′-bipyridin]-2-one (3ap) was prepared
according to general procedure (b). The crude reaction mixture was
purified by column chromatography using silica gel (100−200 mesh)
giving 3ap (30 mg) in 93% yield (wrt 0.114 mmol scale of starting
material 1a). Physical state: brown oil. Rf: 0.13 (50% EtOAc/DCM).
1H NMR (400 MHz, CDCl3): δ 8.60 (d, J = 4.4 Hz, 1H), 7.82 (t, J =
7.6 Hz, 1H), 7.34−7.24 (m, 3H), 6.47 (d, J = 9.2 Hz, 1H), 6.30 (d, J
= 7.2 Hz, 1H), 6.15−6.08 (m, 1H), 5.42 (d, J = 15.6 Hz, 1H), 1.90
(dd, J = 14.0, 7.2 Hz, 2H), 1.22−1.09 (m, 8H), 0.78 (t, J = 6.8 Hz,
3H). 13C{1H} NMR (100 MHz, CDCl3): δ 163.6, 152.2, 150.2, 147.1,
140.4, 138.9, 138.5, 124.4, 124.3, 123.3, 119.3, 103.9, 33.1, 31.9, 28.9,
28.7, 22.9, 14.4. IR (KBr, cm−1): 2954, 1667, 1537, 1433. HRMS
(ESI) m/z: [M + H]+ calcd for C18H23N2O, 283.1805; found
283.1802.
(E)-6-(3-(Trifluoromethyl)styryl)-2H-[1,2′-bipyridin]-2-one (3al)
was prepared according to general procedure (b). The crude reaction
mixture was purified by column chromatography using silica gel
(100−200 mesh) giving 3al (29 mg) in 75% yield (wrt 0.113 mmol
scale of starting material 1a). Physical state: yellow solid. Mp: 171−
174 °C. Rf: 0.1 (50% EtOAc/hexane). 1H NMR (400 MHz, CDCl3):
δ 8.70 (dd, J = 5.2, 1.2 Hz, 1H), 7.94 (td, J = 7.6, 2.0 Hz, 1H), 7.51−
7.34 (m, 7H), 7.02 (d, J = 16.0 Hz, 1H), 6.64 (d, J = 9.2 Hz, 1H),
6.59 (d, J = 7.2 Hz, 1H), 6.25 (d, J = 16.0 Hz, 1H). 13C{1H} NMR
(100 MHz, CDCl3): δ 163.4, 151.9, 150.3, 146.0, 140.2, 139.2, 136.8,
132.9, 131.6 (q, JC−F = 32.0 Hz), 130.0, 129.6, 125.7, 124.6, 124.2,
124.1, 124.1 (q, JC−F = 271.0 Hz), 123.1, 120.8, 104.7. 19F{1H} NMR
(CDCl3, 376 MHz): δ −62.9. IR (KBr, cm−1): 3011, 1651, 1535,
1337, 1111. HRMS (ESI) m/z: [M + H]+ calcd for C19H14F3N2O,
343.1053; found 343.1032.
(E)-6-(3,5-Difluorostyryl)-2H-[1,2′-bipyridin]-2-one (3aq) was pre-
pared according to general procedure (b). The crude reaction mixture
was purified by column chromatography using silica gel (100−200
mesh) giving 3aq (28 mg) in 77% yield (wrt 0.117 mmol scale of
starting material 1a). Physical state: yellow solid. Mp: 152−158 °C.
1
Rf: 0.5 (60% EtOAc/hexane). H NMR (400 MHz, CDCl3): δ 8.70
(d, J = 4.0 Hz, 1H), 7.95 (dt, J = 7.6, 2.0 Hz, 1H), 7.49−7.42 (m,
3H), 6.91 (d, J = 16.0 Hz, 1H), 6.73−6.65 (m, 4H), 6.61 (d, J = 6.8
Hz, 1H), 6.19 (d, J = 16.0 Hz, 1H). 13C{1H} NMR (100 MHz,
CDCl3): δ 163.5 (dd, JC−F = 247.0 Hz, JC−F = 13.0 Hz), 163.4, 151.6,
150.4, 145.7, 140.4, 139.3, 139.2 (t, JC−F = 9.0 Hz), 132.3 (t, JC−F
3.0 Hz), 124.7, 124.5, 123.7, 120.8, 110.0 (dd, JC−F = 18.0 Hz, JC−F
=
=
7.0 Hz), 105.3, 104.5 (t, JC−F = 25.0 Hz). 19F{1H} NMR (376 MHz,
CDCl3): δ −109.4. IR (KBr, cm−1): 3051, 2923, 1670, 1617, 1590,
1532, 1433, 1118, 838. HRMS (ESI) m/z: [M + H]+ calcd for
C18H13F2N2O, 311.0990; found 311.0991.
(E)-6-(2-Cyclopropylvinyl)-2H-[1,2′-bipyridin]-2-one (3am) was pre-
pared according to general procedure (b). The crude reaction mixture
was purified by column chromatography using silica gel (100−200
(E)-6-(2-(Phenanthren-9-yl)vinyl)-2H-[1,2′-bipyridin]-2-one (3ar)
was prepared according to general procedure (b). The crude reaction
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J. Org. Chem. 2021, 86, 9444−9454