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The Journal of Organic Chemistry
MHz, CDCl3): δ 8.24 (dd, J = 2.0, 8.0 Hz, 1H), 7.90 (d, J = 7.6
1H), 7.45 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 176.9,
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7
8
Hz, 1H), 7.75 (t, J = 7.6 Hz, 1H), 7.70 (dt, J = 1.6, 7.6 Hz, 1H),
7.58 (dd, J = 0.8, 8.4 Hz, 1H), 7.48 (s, 1H), 7.42 (dt, J = 0.8,
8.0 Hz, 1H), 7.28 (d, J = 8.4 Hz, 1H), 2.63 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 178.7, 161.9, 159.2, 156.1, 148.7,
137.1, 133.7, 125.8, 125.4, 125.2, 124.5, 118.1, 118.0, 108.6,
24.6.
160.1, 154.7, 150.0, 142.5, 139.3, 137.0, 130.4, 128.6, 125.7,
120.0, 119.7, 119.0, 109.5.
2-(6-Bromopyridin-2-yl)-7-methoxychromen-4-one
(5q).
Yield = 87% (288 mg); Colorless solid; mp = 202-204 oC (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C15H11BrNO3 331.9922, found 331.9923;
1H NMR (400 MHz, CDCl3): δ 8.07 (d, J = 8.8 Hz, 1H), 7.96
(dd, J = 0.8, 7.6 Hz, 1H), 7.69 (t, J = 8.0 Hz, 1H), 7.55 (dd, J
= 0.8, 8.0 Hz, 1H), 7.30 (s, 1H), 6.95 (dd, J = 2.4, 8.8 Hz, 1H),
6.91 (d, J = 2.4 Hz, 1H), 3.91 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 177.6, 164.3, 159.4, 157.6, 150.3, 142.3,
139.2, 129.9, 127.1, 119.4, 118.2, 114.7, 109.4, 100.4, 55.9.
2-(5-Fluoropyridin-2-yl)chromen-4-one (5l). Yield = 85%
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o
(205 mg); Colorless solid; mp = 165-167 C (recrystallized
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from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C14H8FNO2 242.0617, found 242.0613; H NMR
(400 MHz, CDCl3): δ 8.59 (d, J = 2.8 Hz, 1H), 8.25 (dd, J =
1.6, 8.0 Hz, 1H), 8.13 (dd, J = 4.0, 8.8 Hz, 1H), 7.72 (dt, J =
1.6, 8.4 Hz, 1H), 7.59 (dd, J = 2.4, 8.0 Hz, 1H), 7.57 (dt, J =
1.6, 8.0 Hz, 1H), 7.44 (dt, J = 0.8, 8.0 Hz, 1H), 7.37 (s, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 178.4, 160.6, 160.4 (d, J
= 260.7 Hz), 156.0, 145.6 (d, J = 3.8 Hz), 138.9 (d, J = 24.3
Hz), 133.9, 125.9, 125.4, 124.3, 123.5 (d, J = 18.2 Hz), 122.2
(d, J = 5.3 Hz), 118.0, 108.7.
2-(6-Bromopyridin-2-yl)-6,8-difluorochromen-4-one (5r).
Yield = 84% (283 mg); Colorless solid; mp = 215-247 oC (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C14H7BrF2NO2 337.9628, found 337.9629;
1H NMR (400 MHz, CDCl3): δ 8.07 (dd, J = 0.8, 7.6 Hz, 1H),
7.76 (t, J = 8.0 Hz, 1H), 7.67-7.64 (m, 1H), 7.62 (dd, J = 0.8,
8.0 Hz, 1H), 7.45 (s, 1H), 7.28 (ddd, J = 3.2, 7.6, 10.8 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 176.3 (t, J = 2.3 Hz),
159.7, 158.6 (dd, J = 9.1, 248.7 Hz), 150.3 (dd, J = 11.4, 255.5
Hz), 149.5, 142.5, 139.4, 130.6, 126.6 (d, J = 8.3 Hz), 119.9
(dd, J = 1.6, 5.4 Hz), 119.8, 109.4 (dd, J = 19.7, 28.1 Hz),
108.8, 106.2 (dd, J = 4.6, 23.5 Hz).
2-Quinolin-2-ylchromen-4-one (5m). Yield = 84% (229 mg);
Colorless solid; mp = 199-201 oC (recrystallized from hexanes
and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd for
1
C18H12NO2 274.0868, found 274.0866; H NMR (400 MHz,
CDCl3): δ 8.36 (d, J = 8.8 Hz, 1H), 8.28 (dd, J = 1.6, 8.0 Hz,
1H), 8.20 (d, J = 8.8 Hz, 2H), 7.89 (d, J = 8.4 Hz, 1H), 7.80
(dt, J = 1.2, 8.4 Hz, 1H), 7.74 (dt, J = 1.6, 8.4 Hz, 1H), 7.67-
7.61 (m, 2H), 7.66 (s, 1H), 7.46 (dt, J = 0.8, 7.6 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 178.6, 161.8, 156.2,
149.3, 148.0, 137.3, 133.9, 130.4, 130.3, 128.7, 128.1, 127.6,
125.9, 125.4, 124.6, 118.2, 117.7, 109.4.
6-Fluoro-2-quinolin-2-ylchromen-4-one (5t). Yield = 86%
o
(250 mg); Colorless solid; mp = 219-221 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C18H11FNO2 292.0774, found 292.0778; H NMR
(400 MHz, CDCl3): δ 8.34 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 8.4
Hz, 1H), 8.15 (d, J = 8.8 Hz, 1H), 7.90-7.86 (m, 2H), 7.79 (dt,
J = 1.6, 8.4 Hz, 1H), 7.66-7.61 (m, 2H), 7.63 (s, 1H), 7.44
(ddd, J = 3.2, 7.6, 10.8 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3): δ 177.7 (d, J = 2.3 Hz), 162.0, 159.7 (d, J = 245.6 Hz),
152.3, 148.9, 147.9, 137.3, 130.5, 130.2, 128.7, 128.2, 127.6,
125.7 (d, J = 7.5 Hz), 122.0 (d, J = 25.8 Hz), 120.3 (d, J = 7.5
Hz), 117.6, 110.8 (d, J = 23.5 Hz), 108.5.
2-(6-Bromopyridin-2-yl)-6-fluorochromen-4-one
Yield = 80% (255 mg); Colorless solid; mp > 250 C (recrys-
(5n).
o
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M
1
+ H]+ calcd for C14H8BrFNO2 319.9723, found 319.9722; H
NMR (400 MHz, CDCl3 + d6-DMSO): δ 7.98 (dd, J = 0.8, 7.6
Hz, 1H), 7.77 (dd, J = 3.2, 8.0 Hz, 1H), 7.69 (t, J = 8.0 Hz,
1H), 7.56 (dd, J = 0.8, 8.0 Hz, 1H), 7.52 (dd, J = 3.2, 8.0 Hz,
1H), 7.38 (dt, J = 3.2, 7.6 Hz, 1H), 7.33 (s, 1H); 13C{1H}
NMR (100 MHz, CDCl3 + d6-DMSO): δ 177.3, 159.9, 159.5
(d, J = 245.6 Hz), 152.0, 149.8, 140.2, 139.2, 130.2, 128.5,
122.1 (d, J = 25.7 Hz), 120.1 (d, J = 7.6 Hz), 119.5, 110.5 (d, J
= 23.5 Hz), 108.4.
6-Chloro-2-quinolin-2-ylchromen-4-one (5u). Yield = 88%
o
(270 mg); Colorless solid; mp = 235-237 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C18H11ClNO2 308.0478, found 308.0477; H NMR
(400 MHz, CDCl3): δ 8.32 (d, J = 8.4 Hz, 1H), 8.18 (d, J = 2.0
Hz, 1H), 8.14 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 8.4 Hz, 1H),
7.86 (d, J = 8.4 Hz, 1H), 7.77 (dt, J = 1.6, 8.4 Hz, 1H), 7.65-
7.59 (m, 2H), 7.63 (s, 1H), 7.57 (d, J = 8.8 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 177.2, 161.9, 154.4, 148.7, 147.9,
137.3, 134.0, 131.4, 130.5, 130.2, 128.7, 128.2, 127.6, 125.4,
125.3, 119.9, 117.5, 109.1.
2-(6-Bromopyridin-2-yl)-6-chlorochromen-4-one
Yield = 86% (288 mg); Colorless solid; mp > 250 C (recrys-
(5o).
o
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M
1
+ H]+ calcd for C14H8BrClNO2 335.9427, found 335.9430; H
NMR (400 MHz, CDCl3): δ 8.20 (d, J = 2.8 Hz, 1H), 8.03 (d,
J = 7.6 Hz, 1H), 7.65 (t, J = 8.0 Hz, 1H), 7.66 (dd, J = 2.4, 8.8
Hz, 1H), 7.62 (dd, J = 0.8, 8.0 Hz, 1H), 7.54 (d, J = 8.8 Hz,
1H), 7.44 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 177.1,
160.1, 154.3, 150.0, 142.5, 139.3, 134.2, 131.5, 130.4, 125.42,
125.38, 119.8, 119.6, 109.4.
6-Bromo-2-quinolin-2-ylchromen-4-one (5v). Yield = 86%
o
(302 mg); Colorless solid; mp = 242-244 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C18H11BrNO2 351.9973, found 351.9978; H NMR
6-Bromo-2-(6-bromopyridin-2-yl)chromen-4-one
Yield = 80% (303 mg); Colorless solid; mp > 250 C (recrys-
(5p).
(400 MHz, CDCl3): δ 8.37 (d, J = 2.4 Hz, 1H), 8.35 (d, J = 8.4
Hz, 1H), 8.18 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 8.4 Hz, 1H),
7.88 (d, J = 7.6 Hz, 1H), 7.82-7.77 (m, 2H), 7.65-7.61 (m, 1H),
7.64 (s, 1H), 7.54 (d, J = 9.2 Hz, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 177.1, 161.9, 154.9, 148.7, 147.9, 137.4,
136.8, 130.6, 130.2, 128.7, 128.5, 128.3, 127.6, 125.8, 120.2,
118.9, 117.6, 109.4.
o
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M
+ H]+ calcd for C14H8Br2NO2 379.8922, found 379.8925; H
1
NMR (400 MHz, CDCl3): δ 8.37 (d, J = 2.4 Hz, 1H), 8.02 (dd,
J = 0.8, 8.0 Hz, 1H), 7.80 (dd, J = 2.4, 8.8 Hz, 1H), 7.75 (t, J =
8.0 Hz, 1H), 7.62 (dd, J = 0.8, 8.0 Hz, 1H), 6.48 (d, J = 8.8 Hz,
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