1198
Z.-H. Li, C. Zhen and W.-K. Su
Vol 45
4-Chloro-2-(2-chlorophenyl)-2H-chromene (2c). Compound
1
1H, 3-H), 6.72 (d, 1H, 8-H, J = 8.0 Hz), 6.98-7.01 (m, 1H, 5'-H),
7.25-7.35 (m, 4H, 7-, 5-, 3'-, and 4'-H); 13C-NMR (100 MHz,
CDCl3, ppm) ꢀ: 20.6, 77.7, 115.7, 119.8, 121.8, 124.8, 126.0,
126.9, 128.2, 128.5, 128.6, 130.3, 130.6, 131.2, 139.6, 151.2; MS:
m/s (%) = 258 ([M + 2]+, 18), 257 ([M + 1]+, 25), 256 (M+, 55),
255 ([M - 1]+, 60), 221 ([M - Cl]+, 100); Anal. Calcd. for
C16H13ClO: C, 74.85; H, 5.10. Found: C, 74.99; H, 5.13.
2c: Colorless oil [11]; IR (KBr, cm-1): 1629 (C=C); H-NMR
(400 MHz, CDCl3, ppm) ꢀ: 5.93 (d, 1H, 2-H, J = 3.2 Hz), 6.39 (d,
1H, 3-H, J = 3.6 Hz), 6.86 (dd, 1H, 8-H, J = 1.2, 1.2 Hz), 6.94-
6.98 (m, 1H, 6-H), 7.18-7.26 (m, 3H, 7-, 3'-, and 5'-H), 7.37-
7.39 (m, 1H, 4'-H), 7.46-7.48 (m, 1H, 6'-H), 7.56-7.58 (m, 1H,
5-H); MS: m/s (%) = 278 ([M + 2]+, 30), 277 ([M + 1]+, 23), 276
(M+, 44), 275 ([M - 1]+, 32), 241 ([M - Cl]+, 100).
4,6,8-Trichloro-2-phenyl-2H-chromene (2k). Compound
1
2k: mp 51.1-55.3 °C; IR (KBr, cm-1): 1641 (C=C); H-NMR
4-Chloro-2-(4-chlorophenyl)-2H-chromene (2d). Compound
1
2d: Colorless oil [11]; IR (KBr, cm-1): 1630 (C=C); H-NMR
(400 MHz, CDCl3, ppm) ꢀ: 6.07 (d, 1H, 2-H, J = 4.0 Hz), 6.13
(d, 1H, 3-H, J = 4.0 Hz), 7.25 (d, 1H, 8-H, J = 8.0 Hz), 7.27-
7.36 (6H, 5-, 2'-, 3'-, 4'-, 5'-, and 6'-H); 13C-NMR (100 MHz,
CDCl3, ppm) ꢀ: 77.9, 122.0, 122.4, 122.9, 123.4, 124.5, 126.0,
126.4, 126.5, 128.7, 128.9, 130.5, 133.2, 138.5, 147.8; MS: m/s
(%) = 313 ([M + 4]+, 18), 311 ([M + 2]+, 45), 310 ([M + 1]+, 49),
309 (M+, 51), 275 ([M + 1 - Cl]+, 100); Anal. Calcd. for
C15H9Cl3O: C, 57.82; H, 2.91. Found: C, 57.93; H, 3.14.
(400 MHz, CDCl3, ppm) ꢀ: 5.88 (s, 2H, 2-, and 3-H), 6.80 (d, 1H,
8-H, J = 8.4 Hz), 6.92-6.96 (m, 1H, 6-H), 7.15-7.19 (m, 1H, 7-H),
7.29-7.47 (m, 5H, 5-, 2'-, 3'-, 5'- , and 6'-H); MS: m/s (%) = 278
([M + 2]+, 33), 277 ([M + 1]+, 29), 276 (M+, 49), 275 ([M - 1]+,
33), 241 ([M - Cl]+, 100).
4-Chloro-2-(3-chlorophenyl)-2H-chromene (2e). Compound
1
2e: Colorless oil [11]; IR (KBr, cm-1): 1630 (C=C); H-NMR
4-Chloro-2-(furan-2-yl)-2H-chromene (2l). Compound 2l:
Colorless oil [11]; IR (KBr, cm-1): 1633 (C=C); H-NMR (400
(400 MHz, CDCl3, ppm) ꢀ: 5.90 (s, 2H, 2-, and 3-H), 6.82 (d, 1H,
8-H, J = 8.0Hz), 6.94-6.98 (m, 1H, 6-H), 7.17-7.21 (m, 1H, 7-H),
7.25-7.46 (m, 5H, 5-, 2'-, 4'-, 5'- , and 6'-H); MS: m/s (%) = 278
([M + 2]+, 22), 277 ([M + 1]+, 23), 276 (M+, 35), 275 ([M - 1]+,
33), 241 ([M - Cl]+, 100).
1
MHz, CDCl3, ppm) ꢀ: 5.95 (d, 1H, 2-H, J = 4.4 Hz), 5.98 (d, 1H,
J = 4.4 Hz), 6.31-6.37 (m, 1H, 3'-H), 6.37 (d, 1H, 4'-H, J = 4.4
Hz), 6.94-6.98 (m, 1H, 8-H), 7.16-7.20 (m, 1H, 6-H), 7.41-7.42
(m, 1H, 5'-H), 7.49 (dd, 1H, 5-H, J = 1.6, 1.6 Hz); MS: m/s (%)
= 234 ([M + 2]+, 6), 233 ([M + 1]+, 5), 232 (M+, 16), 231 ([M –
1]+, 9), 197 ([M - Cl]+, 100);
4-Chloro-2-(3-methoxyphenyl)-2H-chromene (2f). Compound
1
2f: Colorless oil [11]; IR (KBr, cm-1): 1627 (C=C); H-NMR
(400 MHz, CDCl3, ppm) ꢀ: 3.78 (s, 3H, OCH3), 5.89 (d, 1H,
2-H, J = 3.6 Hz), 5.93 (d, 1H, 3-H, J = 3.6 Hz), 6.78 (d, 1H, 8-H,
J = 8.4 Hz), 6.87-6.96 (m, 3H, 6-, 2'-, and 4'-H), 7.15-7.19 (m,
1H, 6'-H), 7.34-7.48 (m, 3H, 5-, 7-, and 5'-H); MS: m/s (%) =
274 ([M + 2]+, 11), 277 ([M + 1]+, 25), 276 (M+, 18), 275 ([M -
1]+, 23), 237 ([M - Cl]+, 100).
Acknowledgement. We are grateful to the National Basic
Research Program (No. 2003CB114402), National Natural
Science Foundation of China (No. 20476098 and 20676123) for
financial support.
4-Chloro-2-(3-nitrophenyl)-2H-chromene (2g). Compound
2g: Colorless oil [11]; IR (KBr, cm-1): 1633 (C=C); 1H-NMR (400
MHz, CDCl3, ppm) ꢀ: 5.97 (d, 1H, 2-H, J = 4.0 Hz), 6.04 (d, 1H, 3-
H, J = 3.6 Hz), 6.85 (d, 1H, 8-H, J = 8.0 Hz), 6.96-7.00 (m, 1H, 6-
H), 7.20-7.24 (m, 1H, 5-H), 7.47-7.56 (m, 2H, 7-, and 5'-H), 7.77
(d, 1H, 6'-H, J = 3.6 Hz), 8.17 (dd, 1H, 2'-H, J = 0.8, 0.8 Hz), 8.29
(s, 1H, 4'-H); MS: m/s (%) = 289 ([M + 2]+, 10), 288 ([M + 1]+,
12), 287 (M+, 30), 286 ([M - 1]+, 23), 252 ([M - Cl]+, 100).
4-Chloro-2-(3-fluorophenyl)-2H-chromene (2h). Compound
REFERENCES AND NOTES
[1] Cassidy, F.; Evans, J. M.; Hadley, M. S.; Haladij, A. H.;
Leach, P. E.; Stemp, G. J. Med. Chem. 1992, 35, 1623.
[2] Rimbault, C. G.; Narbel, P. M. American Patent 4,665,202,
1985; Chem. Abstr. 1985, 104, 50730.
[3] Tibor, E.; Tibor, T. Synth. Commun. 1990, 20, 3219.
[4] Bergmann, R.; Gericke, R. J. Med. Chem. 1990, 33, 492.
[5] Venkati, M.; Krupadanam, G. L. D. Synth. Commun. 2001,
31, 2589.
[6] Ishizuka, N.; Matsumura, K. I.; Sakai, K.; Fujimoto, M.;
Mihara, S. I.; Yamamori, T. J. Med. Chem., 2002, 25, 2041.
[7] Beccalli, E. M.; Contini, A.; Trimarco, P. Tetrahedron 2005,
61, 4957.
[8] Hegab, M. H.; Abdulla, M. M.; Arch. Pharm. Chem. Life.
Sci. 2006, 339, 41.
[9] Brown, P. E.; Marcus, W. Y.; Anastasis, P. J. Chem. Soc.,
Perkin Trans. 1 1985, 6, 1127.
[10] Ariamala, G.; Balasubramarian, K. K. Tetrahedron Lett.
1988, 29, 3487.
[11] Kumar, K. H.; Perumal, P. T. Chem. Lett. 2005, 34, 1346.
[12] a) Meth-Cohn, O. Heterocycles 1993, 35, 539; b) Guzman,
A.; Ronero, M.; Maddox, M. L.; Machowski, J. M. J. Org. Chem. 1990,
55, 5793; c) Sreenivasulu, M.; Krishna, R. G. S. Indian J. Chem., Sect.
B, 1989, 28, 584; d) Mahata, P. K.; Venkatesh, C.; Kumar, U. K. S.; Ila,
H.; Junjappa, H. J. Org. Chem. 2003, 68, 3966; e) Chupp, J. P. ; Metz,
S. J. Heterocycl. Chem. 1979, 16, 65; f) Katrtizky, A. R.; Arend, M. J.
Org. Chem. 1998, 63, 9989.
1
2h: Colorless oil; IR (KBr, cm-1): 1645 (C=C); H-NMR (400
MHz, CDCl3, ppm) ꢀ: 5.90 (s, 2H, 2-, and 3-H), 6.83 (d, 1H, 8-H, J
= 8.0 Hz), 6.94-7.03 (m, 2H, 6-, and 4'-H), 7.13-7.21 (m, 3H, ),
7.30-7.34 (m, 1H, 7-H), 7.46-7.47 (dd, 1H, 2'-H, J = 1.2, 1.2 Hz);
13C-NMR (100 MHz, CDCl3, ppm) ꢀ: 77.3, 113.7, 115.4, 116.0,
120.0, 121.3, 122.3, 128.5, 130.2, 130.3, 142.0, 142.1, 153.1,
161.6, 164.0; MS: m/s (%) = 262 ([M + 2]+, 15), 261 ([M + 1]+,
16), 260 (M+, 34), 259 ([M - 1]+, 36), 225 ([M - Cl]+,100); Calcd.
for C15H10ClFO: C, 69.11; H, 3.87. Found: C, 69.18; H, 3.93.
4-Chloro-2-(2-chloro-6-fluorophenyl)-2H-chromene (2i).
Compound 2i: mp 97.8-99.2 °C; IR (KBr, cm-1): 1644 (C=C); 1H-
NMR (400 MHz, CDCl3, ppm) ꢀ: 5.82 (d, 1H, 2-H, J = 2.4 Hz),
6.67 (s, 1H, 3-H), 6.78 (d, 1H, 8-H, J = 8.4 Hz), 6.95-7.06 (m, 2H,
6-, and 3'-H), 7.19-7.31 (m, 3H, 7-, 4'-, and 5'-H), 7.49 (d, 1H, 5-
H, J = 8.0 Hz); 13C-NMR (100 MHz, CDCl3, ppm) ꢀ: 13C NMR
(100 MHz, CDCl3): ꢀ = 72.6, 115.1, 115.4, 119.5, 121.4, 124.6,
125.2, 126.0, 128.2, 130.6, 130.8, 134.5, 154.0, 161.1, 163.6; MS:
m/s (%) = 296 ([M + 2]+, 24), 295 ([M + 1]+, 18), 294 (M+, 37),
293 ([M - 1]+, 25), 259 ([M - Cl]+,100); Anal. Calcd. for
C15H9Cl2FO: C, 61.04; H, 3.07. Found: C, 61.15; H, 3.11.
[13] a) Yu, C. M.; Dai, X. P.; Su, W. K. Synlett 2007, 646; b) Su,
W. K.; Jin, C. Org. Lett. 2007, 9, 993; c) Su, W. K.; Chen, J. X.; Wu, H.
Y.; Jin, C. J. Org. Chem. 2007, 72, 4524.
[14] a) Su, W. K.; Zhong, W. H.; Bian, G. F.; Shi, X. J.; Zhang,
J. P. Org. Prep. Proced. Int. 2004, 36, 499; b) Cotarca, L.; Delogu, P.;
Nardelli, A.; ꢀunjiꢁ, V. Synthesis 1996, 553.
4-Chloro-6-methyl-2-phenyl-2H-chromene (2j). Compound
1
2j: Colorless oil; IR (KBr, cm-1): 1635 (C=C); H-NMR (400
MHz, CDCl3, ppm) ꢀ: 2.30 (s, 3H, CH3), 5.91(s, 1H, 2-H), 5.95 (s,
[15] Mills, C. J.; Mateeva, N. N.; Redda, K. K. J. Heterocyclic
Chem. 2006, 43, 59.