Helvetica Chimica Acta – Vol. 94 (2011)
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1 arom. H); 7.63 (t, J ¼ 7.7, 1 arom. H); 7.94 (d, J ¼ 7.7, 1 arom. H); 10.09 (s, NH); 12.00 (s, NH ··· O).
13C-NMR (125 MHz): 94.0; 116.4; 120.5; 123.6; 125.7; 127.2; 127.9; 130.0; 134.1; 136.5; 153.6; 161.3; 175.6;
179.6. HR-ESI-MS: 266.08135 ([M þ H]þ, C16H12NO3þ ; calc. 266.08142).
(3E)-3-[Amino(4-bromophenyl)methylene]-2H-1-benzopyran-2,4(3H)-dione (4b): Yield 283 mg
(88%). Yellow solid. M.p. 227 – 2308. IR (KBr): 3238, 1682, 1602. 1H-NMR (300 MHz): 7.25 (d, J ¼
8.1, 1 arom. H); 7.29 (t, J ¼ 8.1, 1 arom. H); 7.38 (d, J ¼ 8.5, 2 arom. H); 7.60 – 7.64 (m, 1 arom. H);
7.65 (d, J ¼ 8.5, 2 arom. H); 7.93 (dd, J ¼ 8.5, 1.4, 1 arom. H); 10.14 (s, NH); 11.94 (s, NH ··· O). 13C-NMR
(75 MHz): 95.2; 116.5; 120.4; 123.4; 123.7; 125.8; 129.4; 130.9; 134.3; 135.8; 153.6; 161.5; 174.4; 179.7. HR-
ESI-MS: 343.99195 ([M þ H]þ, C16H11BrNO3þ ; calc. 343.99203).
(3E)-3-[Amino(4-chlorophenyl)methylene]-2H-1-benzopyran-2,4(3H)-dione (4c): Yield 310 mg
(98%). Yellow solid. M.p. 218 – 2208. IR (KBr): 3254, 1682, 1611. 1H-NMR (300 MHz): 7.27 (m, 2
arom. H); 7.45 (d, J ¼ 8.4, 2 arom. H); 7.53 (d, J ¼ 8.4, 2 arom. H); 7.64 (t, J ¼ 7.6, 1 arom. H); 7.93 (d, J ¼
7.6, 1 arom. H); 10.14 (s, NH); 11.95 (s, NH ··· O). 13C-NMR (75 MHz): 95.2; 116.5; 120.5; 123.7; 125.8;
128.1; 129.3; 134.3; 134.7; 135.4; 153.6; 161.5; 174.4; 179.7. HR-ESI-MS: 300.04240 ([M þ H]þ,
C16H11ClNOþ3 ; calc. 300.04247).
(3E)-3-[Amino(4-methoxyphenyl)methylene]-2H-1-benzopyran-2,4(3H)-dione (4d): Yield 225 mg
(86%). Yellow solid. M.p. 218 – 2198. IR (KBr): 3277, 1692, 1614. 1H-NMR (300 MHz): 3.82 (s, MeO); 7.0
(d, J ¼ 8.6, 2 arom. H); 7.24 (d, J ¼ 8.5, 1 arom. H); 7.27 (t, J ¼ 7.5, 1 arom. H); 7.41 (d, J ¼ 8.7, 2 arom. H);
7.62 (td, J ¼ 7.5, 1.1, 1 arom. H); 7.93 (d, J ¼ 7.7, 1 arom. H); 9.98 (br. s, NH); 11.87 (br. s, NH ··· O).
13C-NMR (75 MHz): 55.3; 94.9; 113.4; 116.4; 120.6; 123.5; 125.7; 128.3; 129.6; 134.0; 153.6; 161.2; 161.5;
175.1; 179.4. HR-ESI-MS: 296.09200 ([M þ H]þ, C17H14NO4þ ; calc. 296.09209).
(3E)-3-[Amino(4-methylphenyl)methylene]-2H-1-benzopyran-2,4(3H)-dione (4e): Yield 255 mg
1
(93%). Yellow solid. M.p. 208 – 2108. IR (KBr): 3257, 1697, 1611. H-NMR (300 MHz): 2.48 (s, Me);
7.21 – 7.33 (m, 6 arom. H); 7.62 (dt, J ¼ 7.2, 1.2, 1 arom. H); 7.93 (d, J ¼ 7.7, 1 arom. H); 10.02 (br. s, NH);
11.94 (br. s, NH ··· O). 13C-NMR (75 MHz): 21.0; 95.1; 116.4; 120.5; 123.6; 125.7; 127.4; 128.5; 133.6;
134.1; 140.0; 153.6; 161.4; 175.7; 179.6. HR-ESI-MS: 280.09703 ([M þ H]þ, C17H13NO3þ ; calc. 280.09710).
(3E)-3-[Amino(3-nitrophenyl)methylene]-2H-1-benzopyran-2,4(3H)-dione (4f): Yield 315 mg
1
(93%). Yellow solid. M.p. 245 – 2498. IR (KBr): 3368, 1689, 1617. H-NMR (500 MHz): 7.25 (d, J ¼ 8.1,
1 arom. H); 7.29 (t, J ¼ 7.5, 1 arom. H); 7.64 (dt, J ¼ 7.6, 1.0, 1 arom. H); 7.75 (t, J ¼ 8.0, 1 arom. H); 7.91 (d,
J ¼ 7.5, 1 arom. H); 7.93 (d, J ¼ 7.5, 1 arom. H); 8.31 (s, 1 arom. H); 8.35 (d, J ¼ 8.0, 1 arom. H); 10.28 (s,
NH); 11.98 (s, NH ··· O). 13C-NMR (125 MHz): 95.4; 116.5; 120.4; 122.2; 123.8; 124.3; 125.8; 129.6; 134.0;
134.4; 138.1; 147.3; 153.6; 161.7; 172.9; 179.7. HR-ESI-MS: 311.06655 ([M þ H]þ, C16H11N2O5þ ; calc.
311.06665).
(3E)-3-[Amino(phenyl)methylene]-6-chloro-2H-1-benzopyran-2,4(3H)-dione (4g): Yield 220 mg
(75%). Yellow solid. M.p. 230 – 2358. IR (KBr): 3427, 1700, 1609. 1H-NMR (300 MHz): 7.29 (d, J ¼ 8.7, 1
arom. H); 7.41 – 7.54 (m, 5 arom. H); 7.65 (dd, J ¼ 8.7, 2.6, 1 arom. H); 7.83 (d, J ¼ 2.6, 1 arom. H); 10.23 (s,
NH); 11.88 (s, NH ··· O). 13C-NMR (75 MHz): 95.0; 118.8; 121.9; 124.8; 127.3; 127.8; 128.0; 130.2; 133.7;
136.3; 152.2; 161.0; 175.8; 178.2. HR-ESI-MS: 300.04240 ([M þ H]þ, C16H11ClNO3þ ; calc. 300.04247).
(3E)-3-[Amino(4-bromophenyl)methylene]-6-chloro-2H-1-benzopyran-2,4(3H)-dione (4h): Yield
223 mg (60%). Yellow solid. M.p. 287 – 3008. IR (KBr): 3253, 1699, 1612. 1H-NMR (300 MHz): 7.30
(d, J ¼ 8.7, 1 arom. H); 7.39 (d, J ¼ 8.4, 2 arom. H); 7.65 (d, J ¼ 8.7, 1 arom. H); 7.66 (d, J ¼ 8.7, 2 arom. H);
7.82 (d, J ¼ 2.5, 1 arom. H); 10.24 (s, NH); 11.83 (s, NH ··· O). 13C-NMR (75 MHz): 95.1; 118.8; 121.8;
123.6; 124.8; 127.9; 129.5; 131.0; 133.8; 135.5; 152.2; 161.1; 174.5; 178.2. HR-ESI-MS: 377.95300 ([M þ
H]þ, C16H10BrClNOþ3 ; calc. 377.95308).
(3E)-3-[Amino(4-chlorophenyl)methylene]-6-chloro-2H-1-benzopyran-2,4(3H)-dione (4i): Yield
1
244 mg (64%). Yellow solid. M.p. 284 – 2878. IR (KBr): 3249, 1702, 1613, 1595. H-NMR (300 MHz):
7.30 (d, J ¼ 8.7, 1 arom. H); 7.46 (d, J ¼ 8.5, 2 arom. H); 7.53 (d, J ¼ 8.5, 2 arom. H); 7.66 (dd, J ¼ 8.7, 2.6, 1
arom. H); 7.82 (d, J ¼ 2.6, 1 arom. H); 10.29 (br. s, NH); 11.75 (br. s, NH ··· O). 13C-NMR (75 MHz): 95.1;
118.8; 121.8; 124.8; 127.9; 128.1; 129.3; 133.8; 134.8; 135.1; 152.2; 161.1; 174.5; 178.2. HR-ESI-MS:
344.00355 ([M þ H]þ, C16H10Cl2NOþ3 ; calc. 334.00356).
(3E)-3-(Amino(4-methylphenyl)methylene)-6-chloro-2H-1-benzopyran-2,4(3H)-dione (4j): Yield
1
217 mg (69%). Yellow solid. M.p. 247 – 2508. IR (KBr): 3224, 1694, 1601. H-NMR (300 MHz): 2.38 (s,
Me); 7.25 (d, J ¼ 8.1, 1 arom. H); 7.30 (d, J ¼ 8.4, 1 arom. H); 7.33 (d, J ¼ 8.1, 2 arom. H); 7.66 (dd, J ¼ 8.4,