The Journal of Organic Chemistry
Note
(s, 1H), 7.05 (s, 2H), 6.33 (s, 1H), 2.40 (s, 6H); 13C NMR (100 MHz,
naphthaleneylboronic acid to give a colorless solid, 44.1 mg, 54%
yield: mp 171−172 °C; H NMR (400 MHz, CDCl3) δ 8.01 (d, J =
8.5 Hz, 1H), 7.98−7.91 (m, 3H), 7.64−7.53 (m, 5H), 7.47−7.43 (m,
1H), 7.24 (dd, J = 11.7, 4.8 Hz, 1H), 6.50 (s, 1H); 13C NMR (100
MHz, CDCl3) δ 161.0, 155.9, 154.4, 133.8, 133.2, 132.8, 132.2, 128.8,
128.6, 128.3, 128.1, 127.5, 127.3, 127.2, 125.9, 124.4, 119.3, 117.6,
115.7; GC−MS (EI) m/z = 272 [M]+.
1
CDCl3) δ 161.0, 156.2, 154.2, 138.7, 135.2, 131.9, 131.4, 127.3, 126.3,
+
124.2, 119.2, 117.3, 115.0, 21.5; GC−MS (EI) m/z = 250 [M] .
4-(4-tert-Butylphenyl)-2H-chromen-2-one (3d, CAS No.
852171-80-3).19a The title compound was prepared according to
the general procedure for 4-arylated of coumarin with 4-tert-
butylphenylboronic acid to give a colorless solid, 59.3 mg, 71%
yield: mp 109−110 °C; 1H NMR (400 MHz, CDCl3) δ 7.59−7.52 (m,
4H), 7.40 (dd, J = 8.3, 1.8 Hz, 3H), 7.26−7.21 (m, 1H), 6.38 (s, 1H),
1.39 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 161.0, 155.8, 154.3,
153.2, 132.4, 132.0, 128.4, 127.3, 126.0, 124.2, 119.2, 117.4, 115.0,
35.0, 31.4; GC−MS (EI) m/z = 278 [M]+.
6,8-Dimethyl-4-phenyl-2H-chromen-2-one (3l, CAS No.
859821-52-6).23 The title compound was prepared according to
the general procedure for 4-arylated of 6,8-dimethylcoumarin with
phenylboronic acid to give a colorless solid, 67.6 mg, 90% yield: mp
107−108 °C; 1H NMR (400 MHz, CDCl3) δ 7.51 (dd, J = 6.4, 3.7 Hz,
3H), 7.39−7.45 (m, 2H), 7.21 (s, 1H), 7.07 (s, 1H), 6.32 (s, 1H), 2.46
(s, 3H), 2.28 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 161.2, 156.1,
150.7, 135.8, 134.5, 133.3, 129.6, 128.9, 128.5, 126.4, 124.6, 118.5,
114.9, 21.0, 15.8; GC−MS (EI) m/z = 250 [M]+; HRMS (ESI-TOF)
calcd. for C17H14O2Na [M + Na]+ 273.0891, found 273.0886.
6-Methyl-4-phenyl-2H-chromen-2-one (3m, CAS No. 16299-
22-2).13 The title compound was prepared according to the general
procedure for 4-arylated of 6-methylcoumarin with phenylboronic acid
4-(3-Methoxyphenyl)-2H-chromen-2-one (3e, CAS No.
131575-58-1).19a The title compound was prepared according to
the general procedure for 4-arylated of coumarin with 3-
methoxyphenylboronic acid to give a colorless solid, 49.9 mg, 66%
yield: mp 145−146 °C; 1H NMR (400 MHz, CDCl3) δ 7.50−7.58 (m,
2H), 7.38−7.46 (m, 2H), 7.26−7.20 (m, 1H), 7.08−7.00 (m, 2H),
6.99−6.95 (m, 1H), 6.38 (s, 1H), 3.86 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 160.9, 159.9, 155.7, 154.3, 136.6, 132.1, 130.1, 127.2, 124.3,
120.9, 119.1, 117.4, 115.2, 115.2, 114.2, 55.6; GC−MS (EI) m/z = 252
[M]+.
1
to give a colorless solid, 61.7 mg, 87% yield: mp 127−129 °C; H
NMR (400 MHz, CDCl3) δ 7.56−7.50 (m, 3H), 7.44 (dd, J = 6.6, 3.0
Hz, 2H), 7.35 (dd, J = 8.4, 1.6 Hz, 1H), 7.28 (d, J = 8.4 Hz, 1H), 7.25
(s, 1H), 6.33 (s, 1H), 2.33 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
161.0, 155.7, 152.4, 135.4, 134.0, 133.0, 129.7, 128.9, 128.5, 126.8,
118.7, 117.1, 115.2, 21.0; GC−MS (EI) m/z = 236 [M]+.
4-(Biphenyl-4-yl)-2H-chromen-2-one (3f, CAS No. 864354-
17-6).19a The title compound was prepared according to the general
procedure for 4-arylated of coumarin with 4-biphenylboronic acid to
1
give a white solid, 56.4 mg, 63% yield: mp 138−139 °C; H NMR
(400 MHz, CDCl3) δ 7.77−7.72 (m, 2H), 7.66 (dd, J = 5.2, 3.2 Hz,
2H), 7.61−7.45 (m, 6H), 7.43−7.38 (m, 2H), 7.25 (td, J = 7.8, 1.2 Hz,
1H), 6.42 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 160.9, 155.5,
154.3, 142.8, 140.1, 134.1, 132.1, 129.1, 129.0, 128.1, 127.7, 127.3,
127.2, 124.4, 119.1, 117.5, 115.2; GC−MS (EI) m/z = 298 [M]+.
4-(o-Tolyl)-2H-chromen-2-one (3g, CAS No. 852171-79-
0).19b The title compound was prepared according to the general
procedure for 4-arylated of coumarin with 2-methylphenylboronic acid
7-(Diethylamino)-4-phenyl-2H-chromen-2-one (3n, CAS No.
154869-90-6).22 The title compound was prepared according to the
general procedure for 4-arylated of 7-diethylaminocoumarin with
phenylboronic acid to give a melicera orange oil, 46.6 mg, 53% yield.
1H NMR (400 MHz, CDCl3) δ 7.52−7.40 (m, 5H), 7.29−7.22 (m,
1H), 6.57 (d, J = 2.5 Hz, 1H), 6.52 (dd, J = 9.0, 2.6 Hz, 1H), 6.01 (s,
1H), 3.41 (q, J = 7.1 Hz, 4H), 1.20 (t, J = 7.1 Hz, 6H); 13C NMR (100
MHz, CDCl3) δ 162.2, 156.9, 156.2, 150.7, 136.3, 129.3, 128.7, 128.5,
128.0, 108.6, 108.4, 108.0, 97.9, 44.9, 12.6; GC−MS (EI) m/z = 293
[M]+.
1
to give a white solid, 56.7 mg, 80% yield: mp 98−99 °C; H NMR
(400 MHz, CDCl3) δ 7.53 (ddd, J = 8.6, 7.3, 1.6 Hz, 1H), 7.37−7.44
(m, 2H), 7.37−7.29 (m, 2H), 7.21−7.14 (m, 2H), 7.07 (dd, J = 7.9,
1.6 Hz, 1H), 6.32 (s, 1H), 2.16 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 160.9, 156.2, 153.9, 135.4, 134.8, 132.1, 130.6, 129.4, 128.5, 127.1,
126.2, 124.4, 119.5, 117.2, 115.8, 19.9; GC−MS (EI) m/z = 236 [M]+.
4-(4-Chlorophenyl)-2H-chromen-2-one (3h, CAS No.
1092835-45-4).19b The title compound was prepared according to
the general procedure for 4-arylated of coumarin with 4-
chlorophenylboronic acid to give a colorless solid, 50.1 mg, 65%
yield: mp 186−187 °C; 1H NMR (400 MHz, CDCl3) δ 7.60−7.55 (m,
1H), 7.54−7.50 (m, 2H), 7.47−7.38 (m, 4H), 7.28−7.22 (m, 1H),
6.37 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 160.6, 154.6, 154.3,
136.1, 133.7, 132.3, 130.0, 129.4, 126.8, 124.5, 118.8, 117.6, 115.5;
GC−MS (EI) m/z = 256 [M]+.
7-Hydro-4-phenyl-2H-chromen-2-one (3o, CAS No. 2555-30-
8).19c The title compound was prepared according to the general
procedure for 4-arylated of 7-hydrocoumarin with phenylboronic acid
1
to give a colorless solid, 60.8 mg, 85% yield: mp 210−211 °C; H
NMR (400 MHz, DMSO) δ 10.70 (br, s, 1H), 7.57 (dt, J = 7.0, 3.9
Hz, 5H), 7.31 (d, J = 8.6 Hz, 1H), 6.84 (d, J = 2.2 Hz, 1H), 6.81 (dd, J
= 8.7, 2.1 Hz, 1H), 6.18 (s, 1H); 13C NMR (100 MHz, DMSO) δ
161.4, 160.2, 155.6, 155.4, 135.2, 129.6, 128.8, 128.4, 128.1, 113.2,
110.7, 110.4, 102.7; GC−MS (EI) m/z = 238 [M]+.
6-Chloro-4-phenyl-2H-chromen-2-one (3p, CAS No. 26152-
84-1).15 The title compound was prepared according to the general
procedure for 4-arylated of 6-chlorocoumarin with phenylboronic acid
1
to give a colorless solid, 67.0 mg, 87% yield: mp 151−152 °C; H
4-(4-Methoxyphenyl)-2H-chromen-2-one (3i, CAS No.
170456-76-5).19b The title compound was prepared according to
the general procedure for 4-arylated of coumarin with 4-
methoxyphenylboronic acid to give a white solid, 49.2 mg, 65%
yield: mp 128−129 °C; 1H NMR (400 MHz, CDCl3) δ 7.59−7.51 (m,
2H), 7.45−7.37 (m, 3H), 7.28−7.21 (m, 1H), 7.08−7.01 (m, 2H),
6.35 (s, 1H), 3.90 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 161.1,
161.0, 155.5, 154.4, 132.0, 130.1, 127.6, 127.2, 124.2, 119.3, 117.5,
114.8, 114.5, 55.6; GC−MS (EI) m/z = 252 [M]+.
NMR (400 MHz, CDCl3) δ 7.60−7.53 (m, 3H), 7.50 (dd, J = 8.8, 2.4
Hz, 1H), 7.41−7.47 (m, 3H), 7.35 (d, J = 8.8 Hz, 1H), 6.41 (s, 1H);
13C NMR (100 MHz, CDCl3) δ 160.2, 154.7, 152.7, 134.6, 132.0,
130.1, 129.8, 129.2, 128.4, 126.5, 120.3, 118.9, 116.3; GC−MS (EI)
m/z = 256 [M]+.
6-Nitro-4-phenyl-2H-chromen-2-one (3q). The title compound
was prepared according to the general procedure for 4-arylated of 6-
nitrocoumarin with phenylboronic acid to give a white solid, 33.7 mg,
1
42% yield: mp 217−219 °C; H NMR (400 MHz, CDCl3) δ 8.47−
4-(4-Methylthiophenyl)-2H-chromen-2-one (3j). The title
compound was prepared according to the general procedure for 4-
arylated of coumarin with 4-methylthiophenylboronic acid to give a
8.39 (m, 2H), 7.65−7.57 (m, 3H), 7.55 (d, J = 9.5 Hz, 1H), 7.48 (dd, J
= 6.5, 2.9 Hz, 2H), 6.52 (s, 1H); 13C NMR (100 MHz, CDCl3) δ
159.1, 157.9, 154.8, 144.2, 134.0, 130.7, 129.6, 128.4, 126.9, 123.2,
119.5, 118.7, 116.9; GC−MS (EI) m/z = 267 [M]+; HRMS (ESI-
TOF) calcd. for C15H9NO4Na [M + Na] 290.0429, found 290.0425.
6-Methoxy-4-phenyl-2H-chromen-2-one (3r, CAS No.
40547-03-3).24 The title compound was prepared according to the
general procedure for 4-arylated of 6-methoxycoumarin with phenyl-
boronic acid to give a colorless solid, 65.1 mg, 86% yield: mp 148−149
°C; 1H NMR (400 MHz, CDCl3) δ 7.57−7.50 (m, 3H), 7.46 (dd, J =
6.6, 2.9 Hz, 2H), 7.34 (d, J = 9.0 Hz, 1H), 7.13 (dd, J = 9.0, 2.9 Hz,
1H), 6.93 (d, J = 2.9 Hz, 1H), 6.38 (s, 1H), 3.74 (s, 3H); 13C NMR
1
colorless solid, 58.0 mg, 72% yield: mp 132−133 °C; H NMR (400
MHz, CDCl3) δ 7.57−7.50 (m, 2H), 7.41−7.34 (m, 5H), 7.26−7.20
(m, 1H), 6.34 (s, 1H), 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
160.8, 155.2, 154.3, 141.5, 132.0, 131.5, 129.0, 127.0, 126.2, 124.3,
118.9, 117.4, 114.9, 15.4; GC−MS (EI) m/z = 268 [M]+; HRMS
(ESI-TOF) calcd. for C16H12O2SNa [M + Na]+ 291.0456, found
291.0458.
4-(Naphthalene-2-yl)-2H-chromen-2-one (3k, CAS No.
76103-22-5).19b The title compound was prepared according to
the general procedure for 4-arylated of coumarin with 2-
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dx.doi.org/10.1021/jo202577m | J. Org. Chem. 2012, 77, 2053−2057