P. Langer et al.
(CH3), 105.22 (C), 113.10, 119.22 (CH), 120.02 (C), 123.45 (CH), 126.09,
2-Chloro-7-hydroxy-3-methyl-6H-benzo[c]chromen-6-one
(5u):
The
ꢀ
129.61 (C), 130.08 (CH), 131.40 (C), 138.57 (CH), 148.51, 159.21 (C
starting materials 1 f (195 mg, 1.0 mmol), Me3SiOTf (289 mg, 1.3 mmol),
3a (357 mg, 1.3 mmol) and NEt3 (202 mg, 0.23 mL, 2.0 mmol) in EtOH
(8 mL) produced 5u as a colorless solid (162 mg, 62%). M.p. 2068C;
1H NMR (CDCl3, 300 MHz): d=2.32 (s, 3H; CH3), 7.12 (dd, J=8.1,
0.8 Hz, 1H; Ar), 7.51 (s, 1H; Ar), 7.82 (t, J=8.1 Hz, 1H; Ar), 7.91 (dd,
J=8.1, 0.8 Hz, 1H; Ar), 8.40 (s, 1H; Ar), 11.25 ppm (s, 1H; OH);
13C NMR (DEPT, [D6]DMSO, 75.5 MHz): d=19.15 (CH3), 104.85 (C),
111.55, 115.81 (CH), 116.54 (C), 118.63, 122.68 (CH), 130.22, 133.67 (C),
136.80 (CH), 138.36, 147.85, 161.45, 164.22 ppm (C); IR (KBr): n˜ =3430
(m), 3052 (w), 1691 (s), 1615 (s), 1586 (m), 1562 (m), 1456 (s), 1376 (m),
1277 (m), 1250 (s), 1220 (s), 1175 (m), 1163 (s), 1089 (s), 1011 (m), 811
(s), 718 (m), 690 cmꢀ1 (m); UV/Vis (CH3CN): lmax (lg e): 352 (3.98), 338
(4.02), 307 (3.61), 295 (3.56), 278 (3.98), 268 (4.02), 222 nm (4.82); fluo-
rescence (CH3CN): Flmax (lex): 485 nm (340 nm); MS (EI, 70 eV): m/z
(%): 260 (100) [M]+, 231 (5), 168 (4), 139 (7), 70 (3); HRMS (EI, 70 eV):
m/z: calcd for C14H9O3Cl: 260.0240 [M]+; found: 260.0240ꢁ2 ppm.
7-Hydroxy-3-methoxy-6H-benzo[c]chromen-6-one (5v): The starting ma-
terials 1g (234 mg, 1.6 mmol), Me3SiOTf (467 mg, 2.1 mmol), 3a (576 mg,
2.1 mmol), and NEt3 (324 mg, 0.45 mL, 3.2 mmol) in EtOH (14 mL) pro-
duced 5v as a colorless solid (265 mg, 51%). M.p. 1678C; 1H NMR
(CDCl3, 300 MHz): d=3.89 (s, 3H; OCH3), 6.86 (d, J=2.5 Hz, 1H; Ar),
6.94 (dd, J=8.8, 2.6 Hz, 1H; Ar), 6.99 (dd, J=8.3, 0.8 Hz, 1H; Ar), 7.46
(dd, J=8.0, 0.4 Hz, 1H; Ar), 7.68 (t, J=8.1 Hz, 1H; Ar), 7.92 (d, J=
8.9 Hz, 1H; Ar), 11.32 ppm (s, 1H; OH); 13C NMR (DEPT, CDCl3,
75.5 MHz): d=55.73 (OCH3), 101.49 (CH), 105.20, 111.34 (C), 111.44,
113.12, 115.19 (CH), 124.37, 135.70 (C), 137.35 (CH), 151.85, 161.62,
162.45, 165.66 ppm (C); IR (KBr): n˜ =3094 (m), 3066 (m), 3024 (w), 1682
(s), 1623 (s), 1570 (m), 1524 (w), 1488 (m), 1465 (s), 1438 (s), 1352 (m),
1314 (s), 1298 (s), 1253 (s), 1223 (m), 1169 (s), 1084 (s), 1027 (w), 856
(w), 803 (s), 724 (s), 691 cmꢀ1 (m); UV/Vis (CH3CN): lmax (lg e): 346
(4.03), 302 (3.88), 268 (4.09), 241 (4.39), 211 nm (4.54); fluorescence
(CH3CN): Flmax (lex): 407 nm (345 nm); MS (EI, 70 eV): m/z (%): 242
(100) [M]+, 198 (24), 171 (7), 114 (10), 89 (2), 64 (3); HRMS (FT-ICR):
calcd for C14H11O4: 243.06519 [M+1]+; found: 243.06537.
OH), 164.80 ppm (C=O); IR (KBr): n˜ =3437 (m), 3084 (w), 1675 (s),
1623 (m), 1435 (s), 1386 (m), 1345 (w), 1317 (m), 1265 (s), 1219 (w), 1198
(w), 1135 (s), 1097 (s), 823 (m), 808 (m), 725 (s), 642 cmꢀ1 (w); UV/Vis
(CH3CN): lmax (lg e): 341 (4.03), 308 (3.59), 297 (3.56), 281 (3.91), 267
(3.97), 234 (4.52), 215 nm (4.43); fluorescence (CH3CN): Flmax (lex):
500 nm (345 nm); MS (EI, 70 eV): m/z (%): 260 (100) [M]+, 231 (10),
197 (7), 169 (5), 139 (7), 114 (3); HRMS (EI, 70 eV): m/z: calcd for
C14H9O3Cl: 260.0240 [M]+; found: 260.0240ꢁ2 ppm.
2-Chloro-7-hydroxy-8-butyl-6H-benzo[c]chromen-6-one (5r): The start-
ing materials 1d (289 mg, 1.6 mmol), Me3SiOTf (467 mg, 2.1 mmol), 3 f
(494 mg, 2.1 mmol), and NEt3 (324 mg, 0.45 mL, 3.2 mmol) in EtOH
(15 mL) produced 5r as a colorless solid (285 mg, 59%). M.p. 1298C;
1H NMR (CDCl3, 300 MHz): d=0.96 (t, J=7.3 Hz, 3H; CH3), 1.40 (sext,
J=7.5 Hz, 2H; CH2), 1.63 (m, 2H; CH2), 2.72 (t, J=7.7 Hz, 2H; CH2),
7.23 (d, J=8.8 Hz, 1H; Ar), 7.36 (m, 2H; Ar), 7.56 ppm (d, J=8.0 Hz,
1H; Ar); 13C NMR (DEPT, CDCl3, 75.5 MHz): d=13.95 (CH3), 22.57,
29.40, 31.38 (CH2), 105.30 (C), 111.71, 118.93, 122.74, 129.89 (CH),
130.58, 131.34, 131.69 (C), 137.58 (CH), 148.62, 160.38 ( C), 165.33 ppm
(C=O); IR (KBr): n˜ =3432 (w), 3132 (m), 3105 (m), 3073 (m), 2965 (s),
2931 (s), 2890 (m), 2867 (s), 1430 (s), 1385 (m), 1345 (m), 1316 (s), 1269
(s), 1234 (s), 1217 (s), 1128 (s), 1093 (s), 837 (m), 777 (w), 742 (s), 728
(s), 643 cmꢀ1 (m); UV/Vis (CH3CN): lmax (lg e): 343 (4.06), 308 (3.72),
296 (3.71), 281 (3.99), 267 (4.02), 234 (4.56), 213 nm (4.53); fluorescence
(CH3CN): Flmax (lex): 490 nm (345 nm); MS (EI, 70 eV): m/z (%): 302
(44) [M]+, 273 (5), 258 (100), 168 (3), 151 (7), 107 (3), 74 (9); elemental
analysis calcd (%) for C17H15ClO3: C 67.44, H 4.99; found: C 67.22, H
5.28.
2-Chloro-7-hydroxy-8-hexyl-6H-benzo[c]chromen-6-one (5s): The start-
ing materials 1d (289 mg, 1.6 mmol), Me3SiOTf (467 mg, 2.1 mmol), 3g
(753 mg, 2.1 mmol) and NEt3 (324 mg, 0.45 mL, 3.2 mmol) in EtOH
(15 mL) produced 5s as a colorless solid (297 mg, 56%). M.p. 758C;
1H NMR (CDCl3, 300 MHz): d=0.90 (t, J=6.9 Hz, 3H; CH3), 1.38 (m,
6H; CH2), 1.60 (m, 2H; CH2), 2.71 (m, 2H; CH2), 7.23 (d, J=8.8 Hz,
1H; Ar), 7.36 (dd, J=8.0, 2.2 Hz, 2H; Ar), 7.56 (d, J=8.0 Hz, 1H; Ar),
7.87 (d, J=2.3 Hz, 1H; Ar), 11.49 ppm (s, 1H; OH); 13C NMR (DEPT,
CDCl3, 75.5 MHz): d=14.07 (CH3), 22.59, 29.14, 29.15, 29.66, 31.66
(CH2), 105.25 (C), 111.67, 118.88 (CH), 119.91 (C), 122.69, 129.84 (CH),
130.54, 131.28, 131.69 (C), 137.53 (CH), 148.58, 160.33 (C), 165.29 ppm
(C=O); IR (KBr): n˜ =3437 (w), 3134 (w), 3104 (w), 3074 (w), 2949 (m),
2928 (s), 2865 (m), 2852 (m), 1669 (s), 1613 (m), 1569 (w), 1479 (m), 1431
(s), 1387 (m), 1342 (w), 1317 (m), 1268 (s), 1244 (m), 1216 (s), 1130 (m),
1095 (s), 834 (m), 809 (m), 779 (w), 748 (w), 729 (s), 643 cmꢀ1 (w); UV/
Vis (CH3CN): lmax (lg e): 343 (4.09), 308 (3.58), 297 (3.56), 281 (3.94), 267
(4.01), 235 (4.58), 124 nm (4.53); fluorescence (CH3CN): Flmax (lex):
495 nm (345 nm); MS (EI, 70 eV): m/z (%): 330 (40) [M]+, 273 (7), 256
(100), 168 (2), 151 (2), 70 (2); elemental analysis calcd (%) for
C19H19ClO3: C 68.98, H 5.78; found: C 68.85, H 5.89.
3-(Benzyloxy)-7-hydroxy-6H-benzo[c]chromen-6-one (5x): The starting
materials 1h (303 mg, 1.20 mmol), Me3SiOTf (347 mg, 1.56 mmol), 3a
(428 mg, 1.56 mmol), and NEt3 (246 mg, 0.43 mL, 2.43 mmol) in EtOH
(12 mL) produced 5x as a colorless solid (128 mg, 48%). M.p. 1448C;
1H NMR (CDCl3, 300 MHz): d=2.17 (s, 3H; CH3), 5.15 (s, 2H; OCH2),
6.93 (d, J=2.5 Hz, 1H; Ar), 7.01 (m, 2H; Ar), 7.34–7.47 (brm, 5H; Ph),
7.68 (t, J=8.2 Hz, 1H; Ar), 7.92 (d, J=8.8 Hz, 1H; Ar), 11.31 ppm (s,
1H; OH); 13C NMR (DEPT, CDCl3, 75.5 MHz): d=70.50 (OCH2),
102.61 (CH), 105.25 (C), 111.50 (CH), 111.61, 113.82, 115.29, 124.44,
127.54, 128.37, 128.77 (CH), 135.68, 135.91 (C), 137.40 (CH), 151.78,
160.68, 162.47, 165.67, 173.42 ppm (C); IR (KBr): n˜ =3091 (w), 2958 (w),
2926 (m), 1688 (s), 1611 (s), 1573 (w), 1465 (m), 1438 (w), 1394 (w), 1371
(w), 1309 (w), 1290 (m), 1249 (s), 1217 (m), 1188 (m), 1170 (s), 1146 (s),
1082 (s), 1024 (m), 1010 (m), 796 (m), 749 cmꢀ1 (w); UV/Vis (CH3CN):
lmax: 346, 302, 291, 269, 237, 209 nm; fluorescence (CH3CN): Flmax (lex):
486 nm (350 nm); MS (EI, 70 eV): m/z (%): 318 (43) [M]+, 91 (100).
2-Bromo-7-hydroxy-6H-benzo[c]chromen-6-one (5t): The starting mate-
rials 1e (225 mg, 1.0 mmol), Me3SiOTf (289 mg, 1.3 mmol), 3a (357 mg,
1.3 mmol), and NEt3 (202 mg, 0.23 mL, 2.0 mmol) in EtOH (8 mL) pro-
duced 5t as a colorless solid (137 mg, 47%). M.p. 1868C; 1H NMR
(CDCl3, 300 MHz): d=7.13 (dd, J=8.2, 1.0 Hz, 1H; Ar), 7.27 (d, J=
8.7 Hz, 1H; Ar), 7.56–7.62 (m, 2H; H-3, Ar), 7.75 (t, J=8.2 Hz, 1H; Ar),
8.16 (d, J=2.2 Hz, 1H; Ar), 11.27 ppm (s, 1H; OH); 13C NMR (APT,
CDCl3, 75.5 MHz): d=105.96 (C), 112.34, 117.34 (CH), 118.17 (C),
119.41 (CH), 120.07 (C), 126.18, 133.39 (CH), 133.82 (C), 137.48 (CH),
149.37, 162.52, 164.84 ppm (C); IR (KBr): n˜ =3162 (w), 3150 (w), 2980
(w), 1691 (s), 1618 (m), 1606 (m), 1566 (m), 1450 (s), 1274 (s), 1266 (s),
1249 (m), 1238 (s), 1213 (s), 1178 (s), 1135 (m), 1108 (m), 1077 (s), 812
(s), 799 (w), 723 (w), 688 cmꢀ1 (m); UV/Vis (CH3CN): lmax (lg e): 349
(3.89), 336 (3.92), 296 (3.36), 277 (3.79), 267 (3.90), 258 (3.90), 221 nm
(4.66); fluorescence (CH3CN): Flmax (lex): 483 nm (340 nm); MS (EI,
70 eV): m/z (%): 290 (100) [M]+, 264 (12), 211 (13), 183 (16), 155 (20),
127 (9), 77(6), 63 (8); HRMS (EI, 70 eV): m/z: calcd for C13H7O3Br:
289.9579 [M]+; found: 289.9579ꢁ2 ppm.
7-Hydroxy-10-methyl-6H-benzo[c]chromen-6-one (5y): The starting ma-
terials 1i (160 mg, 1.0 mmol), Me3SiOTf (289 mg, 1.3 mmol), 3a (357 mg,
1.3 mmol), and NEt3 (202 mg, 0.23 mL, 2.0 mmol) in EtOH (8 mL) pro-
duced 5y as a colorless solid (109 mg, 48%). M.p. 1448C; 1H NMR
(CDCl3, 300 MHz): d=2.75 (s, 3H; CH3), 7.05 (d, J=8.6 Hz, 1H; Ar),
7.41–7.48 (m, 2H; Ar), 7.56–7.62 (m, 1H; Ar), 7.69 (d, J=8.6 Hz, 1H;
Ar), 8.38 (dd, J=8.0, 1.3 Hz, 1H; Ar), 11.63 ppm (s, 1H; OH); 13C NMR
(DEPT, CDCl3, 75.5 MHz): d=24.08 (CH3), 106.47 (C), 116.24, 117.37
(CH), 119.34 (C), 124.89 (CH), 125.19 (C), 127.45, 130.13 (CH), 132.56
ꢀ
(C), 142.10 (CH), 149.93 (C), 160.27 (C OH), 165.35 ppm (C=O); IR
(KBr): n˜ =3250 (w), 3002 (w), 2900 (m), 2870 (m), 1679 (s), 1599 (s),
1575 (m), 1481 (m), 1467 (s), 1446 (s), 1434 (m), 1309 (m) 1267 (s), 1236
(s) 1213 (s), 1198 (s), 1129 (m) 1082 (m), 801 (m), 760 (s), 734 (m), 674
(m), 625 cmꢀ1 (m); UV/Vis (CH3CN): lmax (lg e): 345 (3.92), 298 (3.18),
263 (4.01), 239 (4.45), 232 (4.47), 204 nm (4.42); fluorescence (CH3CN):
Flmax (lex): 493 nm (348 nm); MS (EI, 70 eV): m/z (%): 226 (100) [M]+,
1230
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 1221 – 1236