D. Audisio, S. Messaoudi, J.-D. Brion, M. Alami
FULL PAPER
Compound 2i: Yield 60% (182 mg); white solid, m.p. 181–183 °C.
Compound 2o: Yield 70% (216 mg); white solid, m.p. 146–148 °C.
TLC: R = 0. 46 (c-hexane/AcOEt, 9:1). IR (neat): ν = 1729, 1687,
TLC: R = 0. 42 (c-hexane/AcOEt, 95:5). IR (neat): ν = 3077, 1749,
˜
f
˜
f
1596, 1481, 1396, 1343, 1243, 1198, 1144, 1124, 1065, 964, 912, 863, 1595, 1392, 1335, 1313, 1222, 1196, 1125, 1086, 989, 950, 909, 884,
1
809, 747, 718, 683, 651, 613 cm–1. H NMR (300 MHz, CDCl3): δ
= 8.05 (s, 1 H), 7.52 (d, J = 1.6 Hz, 1 H), 7.44 (dd, J1 = 8.3, J2 =
1.6 Hz, 1 H), 7.32 (d, J = 8.3 Hz, 1 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 156.2, 153.3, 146.6, 128.4, 127.9, 125.9, 120.1, 118.2,
112.1 ppm. MS (APCI+): m/z = 303.0 [M + H]+ (79Br), 305.0 [M
853, 748, 721, 633 cm–1. 1H NMR (300 MHz, CDCl3): δ = 8.39 (d,
J = 0.5 Hz, 1 H), 7.37 (d, J = 1.9 Hz, 1 H), 7.27 (dd, J1 = 0.5, J2
= 1.9 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 155.6, 153.8,
140.1, 137.8, 132.0, 125.9, 116.6, 116.1, 113.1 ppm. MS (APCI+):
m/z = 293.0 [M + H]+ (79Br), 295.0 [M + H]+ (81Br), 297.0 [M + H]
+ H]+ (81Br), 307.0 [M + H]+ (2ϫ81Br). C9H4Br2O2 (301.86): calcd. + (2ϫ37Cl]. C9H3BrCl2O2 (291.87): calcd. C 36.78, H 1.03; found C
C 35.57, H 1.33; found C 35.92, H 1.52.
36.89, H 1.11.
Compound 6: Yield 14% (71 mg). The spectroscopic data are in
Compound 2j: Yield 76% (264 mg); white solid, m.p. 160–162 °C
(lit.: 160–162 °C).[24] TLC: Rf = 0. 39 (c-hexane/AcOEt, 9:1). IR
agreement with those published in the literature.[26]
(neat): ν = 3051, 1730, 1562, 1483, 1427, 1333, 1256, 1135, 964,
˜
Compound 7: Yield 30% (51 mg). The spectroscopic data are in
1
934, 876, 822, 747, 689, 622 cm–1. H NMR (300 MHz, CDCl3): δ
agreement with those published in the literature.[27]
= 8.07 (s, 1 H), 7.36–7.25 (m, 2 H), 7.17 (dd, J1 = 7.7, J2 = 2.7 Hz,
Supporting Information (see also the footnote on the first page of
this article): NMR spectra of all new compounds.
1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 158.9 (d, JC,F
=
245.6 Hz, 1 C), 156.6, 149.3, 143.3 (d, JC,F = 2.4 Hz, 1 C),119.9 (d,
JC,F = 9.3 Hz, 1 C), 119.5 (d, JC,F = 24.6 Hz, 1 C), 118.4 (d, JC,F
= 8.5 Hz, 1 C), 113.5, 112.4 (d, JC,F = 24.4 Hz, 1 C) ppm. MS
(APCI+): m/z = 243.0 [M + H]+ (79Br), 245.0 [M + H]+ (81Br).
C9H4BrFO2 (241.94): calcd. C 44.48, H 1.66; found C 44.62, H
1.72.
Acknowledgments
The Centre National de Recherche Scientifique (CNRS) is grate-
fully acknowledged for financial support of this research. We thank
the European Union (EU) within the EST network BIOMED-
CHEM (MEST-CT-2005-020580) for a Ph.D. grant to D. A. and
for financial support. Region Ile-de-France is also acknowledged
for its support. We also thank E. Morvan for her help in the NMR
experiments and A. Solgadi for performing mass spectra analyses
(SAMM platform, Châtenay-Malabry).
Compound 2k: Yield 62% (208 mg); white solid, m.p. 172–174 °C.
TLC: R = 0. 25 (c-hexane/AcOEt, 95:5). IR (neat): ν = 1719, 1600,
˜
f
1556, 1475, 1407, 1264, 1238, 1178, 1130, 1078, 924, 818, 751, 649,
607 cm–1. 1H NMR (300 MHz, CDCl3): δ = 8.03 (s, 1 H), 7.51 (dd,
J1 = 8.8, J2 = 2.4 Hz, 1 H), 7.44 (d, J = 2.4 Hz, 1 H), 7.29 (d, J =
8.8 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 156.4, 151.5,
143.0, 132.0, 130.3, 126.2, 120.2, 118.2, 113.4 ppm. MS (APCI+):
m/z = 259.0 [M + H]+ (79Br), 261.0 [M + H]+ (37Cl), 263.0 [M +
H]+ (37Cl, 81Br). C9H4BrClO2 (257.91): calcd. C 41.66, H 1.55;
found C 41.84, H 1.78.
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hon, R. W. Fuller, G. M. Cragg, Y. Kashman, WO/1993/
020082.
Compound 2l: Yield 72% (219 mg); white solid, m.p. 185–187 °C
(lit.: 180–183 °C).[25] TLC: Rf = 0. 33 (c-hexane/AcOEt, 8:2). IR
(neat): ν = 1721, 1597, 1551, 1470, 1402, 1330, 1264, 1234, 1138,
˜
1065, 962, 924, 840, 816, 751, 638 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 8.02 (s, 1 H), 7.65 (dd, J1 = 8.8, J2 = 2.3 Hz, 1 H),
7.60 (d, J = 2.2 Hz, 1 H), 7.24 (d, J = 8.8 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 156.4, 152.0, 142.9, 134.8, 129.3, 120.7,
118.5, 117.6, 113.4 ppm. MS (APCI+): m/z = 303.0 [M + H]+
(79Br), 305.0 [M + H]+ (81Br), 307.0 [M + H]+ (2ϫ81Br).
C9H4Br2O2 (301.86): calcd. C 35.57, H 1.33; found C 35.86, H 1.61.
Compound 2m: Yield 27% (75 mg); yellow solid, m.p. 153–155 °C.
TLC: R = 0. 30 (c-hexane/AcOEt, 95:5). IR (neat): ν = 1726, 1592,
˜
f
[7] M. G. Marcu, A. Chadli, I. Bouhouche, M. Catelli, L. M.
Neckers, J. Biol. Chem. 2000, 275, 37181–37186.
1547, 1468, 1396, 1330, 1266, 1133, 964, 922, 831, 812, 750,
632 cm–1. 1H NMR (300 MHz, CDCl3): δ = 8.00 (s, 1 H), 7.78 (dd,
J1 = 8.7, J2 = 2.0 Hz, 1 H), 7.77 (d, J = 1.6 Hz, 1 H), 7.10 (d, J =
8.7 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 156.3, 152.7,
142.8, 140.5, 135.3, 121.2, 118.7, 113.1, 87.8 ppm. MS (APCI+):
m/z = 350.9 [M + H]+ (79Br), 352.9 [M + H]+ (81Br). C9H4BrIO2
(349.84): calcd. C 30.80, H 1.15; found C 30.93, H 1.31.
[8] a) G. Le Bras, C. Radanyi, J.-F. Peyrat, J.-D. Brion, M. Alami,
V. Marsaud, B. Stella, J.-M. Renoir, J. Med. Chem. 2007, 50,
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ier, J.-F. Peyrat, J.-D. Brion, V. Marsaud, J.-M. Renoir, M. Al-
ami, Bioorg. Med. Chem. Lett. 2008, 18, 2495–2498.
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T. W. Schulte, L. Neckers, J. Natl. Cancer Inst. 2000, 92, 242–
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Cancer Agents Med. Chem. 2008, 8, 761–782.
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cer Lett. 2008, 274, 88–94; b) C. Radanyi, G. Le Bras, C. Boucl-
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Compound 2n: Yield 64% (184 mg); white solid, m.p. 175–177 °C.
TLC: R = 0. 60 (c-hexane/AcOEt, 8:2). IR (neat): ν = 1736, 1543,
˜
f
1409, 1333, 1239, 1219, 1143, 1097, 979, 925, 865, 808, 748, 679,
609 cm–1. 1H NMR (300 MHz, CDCl3): δ = 8.00 (s, 1 H), 7.75 (d, J
= 2.3 Hz, 1 H), 7.40 (d, J = 2.3 Hz, 1 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 155.5, 148.6, 142.6, 134.9, 130.5, 125.5, 120.8, 114.2,
111.1 ppm. MS (APCI+): m/z = 337.0 [M + H]+, 339.0 [M + H]+
(37Cl), 341.0 [M + H]+ (37Cl, 81Br), 343.0 [M + H]+ (37Cl, 2ϫ81Br).
C9H3Br2ClO2 (335.82): calcd. C 31.95, H 0.89; found C 32.03, H
1.01.
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