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Helvetica Chimica Acta – Vol. 94 (2011)
Ethyl 6-Bromo-2-(chloromethyl)-2-hydroxy-2H-1-benzopyran-3-carboxylate (2b). Yellow solid. M.p.
90 – 928. IR: 3427, 2923, 2854, 1732, 1631, 1460, 1378, 1219, 1100, 769. 1H-NMR: 1.40 (t, J ¼ 7.1, Me); 4.02
(d, J ¼ 11.6, 1 H, CH2Cl); 4.22 (d, J ¼ 11.6, 1 H, CH2Cl); 4.36 (q, J ¼ 7.2, CH2O); 6.90 (d, J ¼ 8.7, 1 arom.
H); 7.38 – 7.46 (m, 2 arom. H); 7.64 (s, 1 arom. H). 13C-NMR: 14.12; 49.10; 61.69; 98.21; 114.09; 118.36;
119.73; 122.93; 131.06; 135.19; 135.28; 151.30; 164.68. LC/ESI-MS: 330/332 ([M ꢀ OH þ H]þ), 353/355
([M ꢀ OH þ H þ Na]þ).
Ethyl 6-Chloro-2-(chloromethyl)-2-hydroxy-2H-1-benzopyran-3-carboxylate (2c). Yellow oil. IR:
3422, 2925, 1709, 1634, 1479, 1274, 1213, 1051, 820. 1H-NMR: 1.40 (t, J ¼ 6.9, Me); 4.02 (d, J ¼ 11.3, 1 H,
CH2Cl); 4.26 (d, J ¼ 11.3, 1 H, CH2Cl); 4.34 (q, J ¼ 6.9, CH2O); 6.94 (d, J ¼ 8.5, 1 arom. H); 7.22 – 7.32
(m, 2 arom. H); 7.60 (s, 1 arom. H). LC-MS: 285/287 ([M ꢀ OH]þ), 308/310 ([M þ Na]þ).
Ethyl 2-(Chloromethyl)-2-hydroxy-6-methoxy-2H-1-benzopyran-3-carboxylate (2d). Yellow liquid.
IR: 3433, 2922, 2852, 1707, 1633, 1495, 1219, 1041. 1H-NMR: 1.34 (t, J ¼ 7.2, Me); 3.70 (s, MeO); 3.98 (d,
J ¼ 11.1, 1 H, CH2Cl); 4.18 (d, J ¼ 11.1, 1 H, CH2Cl); 4.28 (q, J ¼ 7.2, CH2O); 6.68 (d, J ¼ 6.7, 1 arom. H);
6.82 – 6.88 (m, 2 arom. H); 7.56 (s, 1 arom. H). ESI-MS: 281/283 ([M ꢀ OH]þ), 321/323 ([M þ Na]þ).
Ethyl 2-(Chloromethyl)-2-hydroxy-7-(prop-2-en-1-yloxy)-2H-1-benzopyran-3-carboxylate (2e). Yel-
1
low liquid. IR: 3445, 2922, 2853, 1705, 1617, 1503, 1279, 1208, 1163, 930. H-NMR: 1.38 (t, J ¼ 7.1, Me ) ;
4.08 (d, J ¼ 11.6, 1 H, CH2Cl); 4.22 (d, J ¼ 11.6, 1 H, CH2Cl); 4.28 (q, J ¼ 7.2, CH2O); 4.54 (d, J ¼ 7.6,
CH2O); 5.26 – 5.32 (dd, J ¼ 1.6, 10.3, 1 olefin. H); 5.40 (dd, J ¼ 1.6, 15.8, 1 olef. H); 5.96 – 6.12 (m, 1 olef.
H); 6.50 – 6.62 (m, 2 arom. H); 7.16 (d, J ¼ 8.8, 1 arom. H); 7.68 (s, 1 arom. H). 13C-NMR: 14.14; 29.61;
49.14; 61.15; 68.95; 98.34; 101.97; 109.98; 118.10; 130.01; 132.39; 136.66; 147.25; 154.01; 162.69; 165.28.
ESI-MS: 307/309 ([M ꢀ OH]þ), 347/349 ([M þ Na]þ).
Ethyl 2-(Chloromethyl)-2-hydroxy-8-(prop-2-en-1-yl)-2H-1-benzopyran-3-carboxylate (2f). Yellow
liquid. IR: 3409, 2979, 2924, 1700, 1633, 1599, 1287, 1212, 1016, 913. 1H-NMR: 1.34 (t, J ¼ 7.0, Me); 3.44 (d,
J ¼ 6.6, CH2¼CH); 4.07 (d, J ¼ 11.2, 1 H, CH2Cl); 4.22 (d, J ¼ 11.2, 1 H, CH2Cl); 4.32 (q, J ¼ 7.0, CH2O);
5.02 – 5.16 (m, 2 olef. H); 5.92 – 6.08 (m, 1 olef. H); 6.92 (t, 1 arom. H); 7.10 (d, J ¼ 7.4, 1 arom. H); 7.18 (d,
J ¼ 7.17, 1 arom. H); 7.66 (s, 1 arom. H). 13C-NMR: 14.19; 33.59; 49.12; 61.13; 96.13; 97.92; 116.08; 117.86;
121.61; 126.97; 127.91; 133.17; 135.98; 136.86; 150.06; 164.75; 14.37; 49.39; 61.70; 98.26; 116.80; 118.22;
121.93; 122.37; 129.19; 133.12; 136.89;152.52; 165.32. ESI-MS: 291/293 ([M ꢀ OH]þ), 331/333 ([M þ
Na]þ).
Ethyl 2-(Chloromethyl)-2-hydroxy-7-[(3-methylbut-2-en-1-yl)oxy]-2H-1-benzopyran-3-carboxylate
(2g). Yellow liquid. IR: 3446, 2924, 2855, 1707, 1632, 1504, 1373, 1278, 1207, 1161, 1104, 1054.
1H-NMR: 1.40 (t, J ¼ 7.2, Me); 1.78 (s, Me); 1.82 (s, Me); 4.00 (d, J ¼ 11.1, 1 H, CH2Cl); 4.22 (d, J ¼ 11.1,
1 H, CH2Cl); 4.30 (q, J ¼ 7.2, CH2O); 4.50 (d, J ¼ 6.6, CH2), 5.42 – 5.48 (m, 1 olef. H); 6.48 – 6.56 (m, 2
arom. H); 7.14 (d, J ¼ 8.8, 1 arom. H); 7.68 (s, 1 arom. H). 13C-NMR: 13.94, 25.49, 29.38, 48.87, 60.64,
64.64, 95.81, 97.98, 101.40, 109.80, 110.85, 116.25, 118.90, 136.25, 153.85, 162.78, 167.58. ESI-MS: 335/337
([M ꢀ OH]þ), 375/377 ([M þ Na]þ).
Ethyl 7-(Benzyloxy)-2-(chloromethyl)-2-hydroxy-2H-1-benzopyran-3-carboxylate (2h). Yellow liq-
uid. IR: 3426, 2923, 1694, 1581, 1546, 1443, 1391, 1289, 1202, 1118, 991. 1H-NMR: 1.42 (t, J ¼ 7.5, Me); 4.02
(d, J ¼ 11.3, 1 H, CH2Cl); 4.20 (d, J ¼ 11.3, 1 H, CH2Cl); 4.28 (q, J ¼ 7.5, CH2O); 5.12 (s, PhCH2); 6.62
(m, 2 arom. H); 7.18 (m, 1 arom. H); 7.32 – 7.44 (m, 5 arom. H); 7.62 (s, 1 arom. H). ESI-MS: 357/359
([M ꢀ OH]þ), 397/399 ([M þ Na]þ).
Ethyl 2-(Chloromethyl)-2-hydroxy-6-phenyl-2H-1-benzopyran-3-carboxylate (2i). Yellow solid. M.p.
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112 – 1138. IR: 3435, 2921, 2851, 1714, 1462, 1262. H-NMR: 1.38 (t, J ¼ 7.1, Me); 4.00 (d, J ¼ 11.6, 1 H,
CH2Cl ), 4.30 (q, J ¼ 7.2, CH2O); 4.38 (d, J ¼ 11.6, 1 H, CH2Cl); 7.04 (d, J ¼ 10.6, 1 arom. H); 7.26 – 7.54
(m, 7 arom. H); 7.22 (s, 1 atom. H); LC/MS: 327/329 ([M ꢀ OH]þ).
Ethyl 2-(Chloromethyl)-2-hydroxy-6-(pyrimidin-2-yl)-2H-1-benzopyran-3-carboxylate (2j). Color-
less solid. M.p. 150 – 1528. IR: 3421, 2924, 2856, 1716, 1643, 1423, 1268, 1228, 1119, 1069, 1016. 1H-NMR:
1.38 (t, J ¼ 7.2, Me); 4.02 (d, J ¼ 11.1, 1 H, CH2Cl); 4.38 (q, J ¼ 7.1, CH2O); 4.54 (d, J ¼ 11.1, 1 H, CH2Cl);
7.16 (d, J ¼ 7.7, 1 arom. H); 7.24 (s, 1 arom. H); 7.42 – 7.58 (m, 2 arom. H); 7.80 (s, 1 arom. H); 8.98 (s, 1
arom. H); 9.22 (s, 1 arom. H). 13C-NMR: 14.08; 48.75; 61.27; 98.83; 117.70; 119.07; 123.76; 126.96; 127.69;
130.63; 135.25; 153.34; 154.17; 160.00; 164.19. ESI-MS: 347/349 ([M þ H]þ), 369/371 ([M þ Na]þ). HR-
ESI-MS: 346.0727 (Mþ, C17H15ClN2O4þ ; calc. 346.0720).